![Table of Contents
Preface and Conference Organization
Chapter 1: Micro/Nano Materials Research
Electrochemical Study of Corrosion Inhibition on Copper in Base Electrolyte by 1-Phenyl-
3-hydroxy-1,2,4-triazole
Q. Li, J. Li, L.T. Hu, L. Zhu, X. Han, Z.H. Tao and W. He 3
Exploration for Identification of Sheath-Core Fiber of Ploymer
R.T. Zhu, P. Zhang and F.M. Nie 8
Mechanical and Thermal Properties of Phenolic Foams Reinforced by Hollow Glass Beads
Y.X. Zuo, Z.J. Yao and J.T. Zhou 13
Monolithic Macroporous-Mesoporous Carbon Using Ionic Liquids as Carbon Source
A.B. Chen, Y.H. Yu, Y.F. Yu, H.J. Lv, T.T. Xing, Y.T. Li and W.W. Zang 23
Strain Analysis of Bimetal Material Based on Uniaxial Tensile and ANSYS
D.H. Zhang, D.Q. Zhang, Y.Q. Li, J.X. Liu, D.P. Bai, H.H. Xia and Y. Yang 27
Study on Curing Kinetics of MEP-15/593/660 System
J.L. Song, C.C. Li, Z.M. Zhou, C.Q. Ye and W.G. Li 31
Acidification Assisted Preparation of Graphite Oxide and Graphene
Y. Lei, J. Xu, R. Li and F.F. Chen 36
Preparation and Flame Retardancy of Waterbased Phosphorous Modified Phenolic Resin
Y.J. Qiao, L.T. Wei, G.L. Xu, Y. Wang and J. Hu 40
Research on Synthesis Technology of Polyester Diol Using Vacuum Melting Method
J.G. Zou, S.Y. Liu, Y.Y. Cao and Z.H. Zhang 45
The Influence of Second Particals on Grain Boundary Sliding
J.Q. Zhang, J. Zhang, G.S. Zhu, Y.J. Zheng, S.W. Li and F.H. Wang 49
High-Energy Synthesis of Al-Ti Composite Powders and its Thermal Stability
W.D. Zhang, J. Yang, Z.M. Du, B.W. Pan, H. Xu and J.Z. Dang 56
Synthesis, Characterization and Photophysical Properties of a New CuI
Complexe Contain
Bis[2-(diphenylphosphino)phenyl]ether and 1,2-diphenyl-1H-imidazo[4,5-
f][1,10]phenanthroline
Q. Li, R.F. Zhong, L. Li, M. Wang and F. Zhao 62
Synthesis, Characterization and Photophysical Properties of Rhenium(I) Complexe with 2-
(naphthalen-2-yl)-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline
Q. Li, L. Li, R.F. Zhong, H.D. Cai and F. Zhao 66
Study on Characterization and Preparetion of Bismuth Tungstate
J.G. Sheng and Y.D. Shan 70
Inhibition of Sodium Citrate on Aggregation and Sedimentation of Nanocalcium Oxalate
Dihydrate Crystals
M. Xu, J.F. Xue, J.J. Li, X.L. Wen and J.M. Ouyang 75
Preparation and Characterization of Dialdehyde Nanocellulose
W.G. Li and Q.H. Xu 79
Preparation and Characterization of Soap-Free Cationic Polystyrene Microspheres Using a
Water Soluble Monomer
Z.Q. Zhao, B.Q. Xu, G.L. Xu, Y. Wang and J. Hu 84
Preparation of High Pure and Micron-Sized α-Al2O3 Powder by Activated Aluminium
Hydrolysis Method
R. Tao, Y.T. Zhao, Z.H. Jia and L. Xu 89
Preparation, Characterization, and In Vitro and In Vivo Evaluation of Tanshinone IIA
Lipid Microspere
X.L. Liang, J.X. Zhao, X.Q. Shi, G.W. Zhao, Z.G. Liao, J. Zhang and Z. Li 93
Research Progress in Nanocellulose Preparation
W.R. Yao and Q.H. Xu 101
Synthesis of Nano-Branched Ni/Fe Layered Double Hydroxides
T.L. Wang, M.T. Liu, X.J. Liu and H.W. Ma 106](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-12-320.jpg)
![Electrochemical study of corrosion inhibition on copper
In base electrolyte by 1-Phenyl-3-hydroxy-1,2,4-triazole
Qi Li, Jian Li, Lingtong Hu, Lei Zhu, Xiao Han, ZhihuaTaoa
and Wei Heb
School of Microelectronics and Solid-State Electronics, University of Electronic Science
and Technology of China, Chengdu 610054
a
email:Tzh3595@uestc.edu.cn,b
email:Heweiz@uestc.edu.cn
Keywords: corrosion; copper; base electrolyte; Polarization curves; EIS
Abstract. This paper presents the investigation of 1-Phenyl-3-hydroxy-1,2,4-triazole as a new green
Cu corrosion inhibitor for Electronic Circuit Board in the base electrolyte (containing 60ppm
chloride ions,0.54M H2SO4 and 0.88M CuSO4).The inhibition action was investigated by
potentiodynamic polarization and electrochemical impedance spectroscopy (EIS).The results show
that the inhibition performance depends on the concentration of the inhibitor and the inhibition
efficiency increases with increasing inhibitor concentration. Potentiodynamic polarization studies
show that 1-Phenyl-3-hydroxy-1,2,4-triazole acts as the mixed-type inhibitor.The results obtained
from EIS measurements are in good agreement with that obtained from potentiodynamic
polarization.
Introduction
Copper is widely applied to the integrated circuit (IC) chips and the printed circuit board (PCB)
in eletronic industries due to its excellent electrical property and good thermal conductivity.
However, copper is very susceptible to corrosion when long-term in the base electrolyte.The use of
the corrosion inhibitor is the most economical and practical way to reduce the corrosion attack of
strong electrolyte to the metal material[1].So looking for effective and acceptable corrosion
inhibitors instead of toxic inhibitors becomes necessary in the inhibition of copper corrosion in the
base electrolyte. Fortunately, 1-Phenyl-3-hydroxy-1,2,4-triazole as pesticide intermediates in
agriculture are mass-produced, cheap and eco-friendly. In this paper, polarization curve tests and
EIS measurements were used to study the corrosion behavior of copper in base electrolyte with
addition of 1-Phenyl-3-hydroxy-1,2,4-triazole as inhibitor.
Experimental methods
2.1 Materials and test solution
The pure copper rod (99.999%) ,embedded in epoxy resin with a exposed surface area of
0.07cm2
is employed as a working electrode(WE).The WE was abraded with silicon carbide paper
(grade P1200), degreased with AR grade ethanol and acetone, and rinsed with double-distilled
water before use.
The base electrolyte containing 60 ppm chloride ions, 0.54M H2SO4 and 0.8M CuSO4 were
prepared by dilution of analytical reagent grade sulfuric acid, hydrochloric acid and copper sulfate
pentahydrate with double distilled water.
The molecular structure of 1-Phenyl-3-hydroxy-1,2,4-triazole is shown in Fig.1.The
concentrations of the inhibitor are 1×10-5
M, 5×10-5
M, 1×10-4
M, 5×10-4
M, 1×10-3
M respectively.
Advanced Materials Research Vol. 988 (2014) pp 3-7
© (2014) Trans Tech Publications, Switzerland
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![Fig.1 The molecular structure of 1-Phenyl-3-hydroxy-1,2,4-triazole
2.2 Electrochemical experiment
The electrochemical measurements were performed in a three-electrode cell with a CHI660D
electrochemical system. A platinum electrode was taken as the auxiliary electrode,and saturated
calomel electrode (SCE) as the reference electrode.
EIS measurement was carried out at the open circuit potential (OCP), prior to the EIS
measurement, a steady-state period of 30 min was observed, which proved sufficient for OCP to
attain a stable value. The ac frequency range was from 100 kHz to 10 mHz,with a 10 mV
peak-to-peak sine wave as the excitation signal. Polarization curve was carried out from -250 to
+250 mV(versus OCP) with a scan rate of 0.5 mV/s and the data was collected and analyzed by
electrochemical software. The experimental temperature was thermostatically controlled at 293k(±1
K) .
Results and discussion
3.1 Polarization curves
Fig.2 shows the anodic and cathodic potentiodynamic polarization curves for copper in the base
electrolyte with addition of various concentrations of inhabitor at 293K.The electrochemical
parameters such as corrosion potential ( Ecorr), corrosion current density (Icorr), anodic and cathodic
Tafel slopes (ba, bc) obtained from the polarization curves are listed in Table 1. The inhibition
efficiency (η%) was calculated by Eq.1 [2]
100
I
I
-
I
%
corr
inh
corr
×
=
η (1)
where Icorr and Iinh represent the corrosion current density in the absence and presence of various
concentrations of inhabitor in the base electrolyte respectively.From Table 1,it can be seen that the
current density in solution using the inhibition decreased considerably compared with that of the
blank solution and the inhibition efficiency increased with the concentration of the inhibitor .The
highest inhibition efficiency of the inhabitor even reached 97.7% at 10-3
M in the base
electrolyte.From Table 1and Fig.2, It can be seen the corrosion inhibitor suppressed both anodic
and cathodic reaction.Only as the change in Ecorr value was more than 85 mV, a compound could be
recognized as an anodic or a cathodic type inhibitor [3].The largest displacement of Ecorr was lower
than 11 mV, so 1-Phenyl-3-hydroxy-1,2,4-triazole should be considered as a mixed-type inhibitor.
4 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-21-320.jpg)
![Table 1 Polarization parameters and corresponding inhibition efficiencies in the base electrolyte
containing various concentrations of inhabitor at 293K
-0.6 -0.5 -0.4 -0.3 -0.2 -0.1
-8
-7
-6
-5
-4
-3
-2
-1
log(i/Acm
-2
)
EvsSCE/ V
a: Blank
b: 1*10
-5
M
c: 5*10
-5
M
d: 1*10
-4
M
e: 5*10
-4
M
f: 1*10
-3
M
f
e
d
a
b
c
Fig.2 Polarization curves for copper in the base electrolyte containing various concentrations
of inhabitor at 293K
3.2 Electrochemical impedance spectroscope
Fig. 3 shows the Nyquist diagrams for the copper in the base electrolyte in absence and presence
of various concentrations of inhabitor at 293 K.The impedance spectra shows that a semicircle and
the diameter of semicircle increases with increasing inhibitor concentration which means the
impedance values have increased and corrosion was inhibited. It is also clear that these impedance
diagrams are not perfect semicircles and this difference has been attributed to frequency dispersion
[4] and the heterogeneity of the metal surface[5].
A variety of parameters such as charge-transfer resistance (Rct),double layer capacitance (Cdl) and
fmax were obtained from impedance measurements and are shown in Table 2. Rct is calculated from
the difference in impedance at lower and higher frequencies, as suggested by Harnyama and Tsuru
[6]. To obtain Cdl, the frequency at which the imaginary component of the impedance is maximum
(-Zim max), is found and Cdl values are obtained from the Eq.2 [7]
Concentration(M)
Ecorr
(mV SCE)
Icorr
(µA/cm2
)
Bc
(mV/dec)
Ba
(mV/dec)
η%
Blank -360 777.4 183.3 164.0 /
1×10-5
-357 404.7 167.0 131.6 47.9
5×10-5
-355 303.6 158.4 137.0 61.0
1×10-4
-354 207.2 168.6 159.7 73.4
5×10-4
-350 36.0 161.0 159.1 95.4
1×10-3
-349 17.6 102.0 396.8 97.7
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![ct
max
dl
R
1
f
2
1
c
π
= (2)
where f max is the frequency at which the imaginary component of impedance is maximum and Rct is
the diameter of the loop.The inhibition efficiency got from the charge-transfer resistance is
calculated by Eq.3 [8]
100
R
R
-
R
%
ct
o
ct
ct
×
=
η (3)
where Rct and Ro
ct represent the resistance of charge transfer in the presence and absence of inhibitor,
respectively.
From Table 2, it can be seen clearly that the Rct values increase and the Cdl values decrease with
increasing inhibitor concentration. The decrease in Cdl is due to the adsorption of the inhibitor at
metal/solution interface leading to a protective film which decreases the extent of dissolution
reaction [9].At the same time, the inhibition efficiency (η%) increases with increasing inhabitor
concentration and the highest inhibition efficiency of the inhabitor reached 92.5% at 10-3
M.These
results are much consistent with that obtained from polarization curve tests.
0 300 600 900 1200 1500 1800 2100 2400 2700 3000
0
200
400
600
800
1000
Blank
1*10
-5
M
5*10
-5
M
1*10
-4
M
5*10
-4
M
1*10
-3
M
-Zim/O
cm
2
Zre/Ocm
2
Fig.3 Nyquist diagrams for the copper in the base electrolyte containing various concentrations
of inhabitor at 293K.
Table 2 Corrosion parameters obtained by impedance measurements for the copper in the base
electrolyte containing various concentrations of inhabitor at 293K.
Concentration(M) Rct(Ωcm2
） fmax(Hz) Cdl(µF cm-2
) η%
Blank 196.8 3.83 211.3 /
1×10-5
753.9 1.47 143.7 73.9
5×10-5
856.1 3.16 58.9 77.0
1×10-4
1082.5 2.61 56.4 81.8
5×10-4
2045.0 3.16 24.6 90.4
1×10-3
2627.7 3.83 15.8 92.5
6 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-23-320.jpg)
![Conclusions
Electrochemical study proved that 1-Phenyl-3-hydroxy-1,2,4-triazole is an effective inhibitor for
the corrosion of copper of Electronic Circuit Board at the studied temperatures of 293K in the base
electrolyte containing 60 ppm chloride ions, 0.54M H2SO4 and 0.8M CuSO4 solution. It can be
essentially described as a mixed-type inhibitor.The results show that the inhibition efficiency
depends on the concentration of the inhibitor and increase with increasing inhibitor concentration.
Acknowledgments
The authors gratefully acknowledge the support of Guangdong Innovative Research Team
Program (NO. 2013C092) and the Open Foundation of State Key Laboratory of Electronic Thin
Films and Integrated Devices (KFJJ201211), and we also express our sincere thanks to the support
of “Ph.D Programs Foundation of Ministry of Education of China” (No: 20120185110021).
Reference
[1] K. Stanly Jacob, GeethaParameswaran, Corros. Sci. 52 (2010) 224–228.
[2] Khaled, K.F., 2008. Mater. Chem. Phys. 112, 104–111.
[3] Ying Yana, Electrochemical and quantum chemical study of purines as corrosion inhibitors for
mild steel in 1M HCl solution[J]. Electrochimica Acta, 2008, 53: 5953-5960.
[4] Mansfeld, F., Kending, M.W., Tsai, S., 1982. Corrosion 38, 570.
[5] Pajkosay, T., 1994. J. Electroanal. Chem. 364, 111
[6] T. Tsuru, S. Haruyama, B. Gijutsu, J. Jpn. Soc. Corros. Eng. 27 (1978) 573.
[7] Ross Macdonald, J., 1987. Impedance Spectroscopy. John Wiley and Sons.
[8] Abd El-Rehim, S.S., Ibrahim, Magdy A.M., Khaled, K.F., 1999. J.Appl. Electrochem. 29,
593–599.
[9] F. Bentiss, M. Traisnel, M. Lagrenée, Corros. Sci. 42 (2000) 127.
Advanced Materials Research Vol. 988 7](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-24-320.jpg)
![Exploration for Identification of Sheath-Core Fiber of Ploymer
Ruitian Zhu1 a
, Peng Zhang1
, Fengming Nie1
1
.Guangzhou Fibre Product Testing and Research Institute, Guangzhou, 510220, China
a
zhurt@gtt.net.cn
Key words: sheath-core; fiber; polymer; identification
Abstract: In this paper, microscopic method, transmission technique and attenuated total reflection
method of infrared spectroscopy and differential scanning calorimetry were investigated for
analyzing the component of inner and outer layer of sheath-core polymer fiber. Results showed that
transmission technique and attenuated total reflection method of infrared spectroscopy was a quick
and accurate method for identification of sheath-core fiber of fiber.
Introduction
Conventional chemical fibers have many advantages, but also have some drawbacks, such as
polypropylene fiber has good property of processing and tensile strength but with poor moisture
absorption, nylon fiber has good abrasion performance and high strength but with inferior resistance
to heat and light. With the difference of inner layer and outer layer materials, bicomponent polymer
fibers with sheath-core structure are provided with some special performances, such as
three-dimensional crimp structure, the advantages of both of the two components. Such functional
fibers, now get applications in many fields, such as surface materials of sanitary napkins, diapers
and other hygiene materials, whose difference of thermal response behavior of the inner and outer
layer result in a three-dimensional crimp state, and the fiber web can be reinforced at a relatively
lower temperature because of the lower melt point of sheath material, forming loose, soft nonwoven
fabrics with a certain strength. Generally, price of sheath-core fiber is higher than conventional
fiber, and the price of sheath-core fibers of different components is far away from each other.
Currently, there are some suppliers sell shoddy, fake sheath-core fibers, which seriously disrupts
the market order.
So far, there are some common testing methods for identification of fiber component, like
chemical dissolution method, thermal analysis method and transmission infrared spectroscopy
method[1]
. Chemical dissolution method only applies to the case that the inner and outer layer
material have different solubility and could not be dissolved at the same time. Thermal analysis
method usually adopts differential scanning calorimetry device to measure melting point of the two
components of sheath-core fiber, which can only be used for preliminary judgment of the two
components, but not for differentiating the inner and outer component. For the low melting point
modified fibers (such as low melting point polyester), and the result of thermal analysis method is
less reliable. Similarly, transmission infrared spectroscopy method could be take for judging the
two kinds of material without distinguishing the inner and outer components, by KBr disc technique
or the method of dissolving and casting films.
Therefore, the establishment of a method for rapid accurate identification of sheath-core fiber of
polymer, is helpful for regulating the market, and will promote research and development of
sheath-core structure bicomponent polymer fibers. In this paper, microscopic method, transmission
Advanced Materials Research Vol. 988 (2014) pp 8-12
© (2014) Trans Tech Publications, Switzerland
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![technique and attenuated total reflection method of infrared spectroscopy were investigated for
identification of sheath-core polymer fiber.
Experiment
2.1 Sample
The sample used in this investigation was sheath-core fiber from Guangzhou ES Fiber Co., Ltd.
2.2 Microscopic method[2]
The picture of cross-section of sample was obtained by the fiber slicer (Model Y172) manufactured
by Changzhou the Second Textile Machines Co., Ltd., and observed under micro scope (Model
BX51TF) manufactured by Olympus Optical Co., Ltd. of Japan.
2.3 Infrared spectroscopy test
2.3.1 Attenuated total reflection method (ATR)
After being put in the infrared drying oven about 30 to 50 seconds, A suitable amount of fiber
bundle was placed on the crystal of multiple-reflection accessory of the infrared spectrometer
(Model Nicolet 6700) manufactured by Thermo Fisher Scientific Inc., completely covering the
crystal. Parameters were set as scan range for 400 ~ 4000 cm-1
, resolution for 2 cm-1
, scan times for
32, the Angle of incidence adjusted from big to small, like 50°, 40°, 30°. A series of infrared spectra
were obtained[3]
.
2.3.2 Transmission infrared spectroscopy test
A suitable amount of representative fiber was took in the fiber slicer, being cut into 10 to 30
micrometer long fiber powder. 80-120 mg potassium bromide and 2.0-5.0 mg fiber powder were
blended and powdered in the agate mortar for 2 minutes. After being dried for 30-50s, the blends
were moved to the tabletting mould to produce a transparent disc. The disc was installed in the
transmission accessory of the infrared spectrometer. Parameters were set as scan range for 400 ~
4000 cm-1
, resolution for 2 cm-1
, scan times for 32, then started scanning and a infrared spectra
obtained.
2.4 Test of differential scanning calorimetry (DSC)
5.0-10.0 mg sample was analyzed in nitrogen atmosphere in differential scanning calorimeter
(Model DSC 204 F1) manufactured by NETZSCH-Gerätebau GmbH to determine the melt point.
The sample was first heated up from 25˚˚C to 280˚C at 10˚C/min, then cooled to 25˚C at 10˚C/min
(to eliminate thermal history of sample), last heated up again to 280˚C at 10˚C/min[4]
.
Results and discussion
3.1 Observation of cross-section of fiber
The cross-section of sample is shown as Fig. 1. Obviously, the fibers were spun by composite
spinning method and made up of sheath and core. The demarcation between sheath layer and core
layer was to be clearly defined. There were lots of small black spots in the core layer, but no in the
sheath layer.
Advanced Materials Research Vol. 988 9](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-26-320.jpg)
![Reference:
[1] FZ/T 01057.8-2012 Test Method for Identification of Textile Fibres-Part 8: Infrared Absorption
Spectrum
[2] FZ/T 01057.3-2007 Test Method for Identification of Textile Fibers-Part3: Microscopy
[3] GB/T 6040-2002 General Rules for Infrared Analysis
[4] ISO 11357-3-2011 Plastics -- Differential Scanning Calorimetry (DSC) -- Part 3: Determination
of Temperature and Enthalpy of Melting and Crystallization
12 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-29-320.jpg)
![Mechanical and thermal properties of phenolic foams reinforced by
hollow glass beads
Yuxin Zuo1, a
, Zhengjun Yao1,b
and Jintang Zhou1,c
1
College of Materials and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing
211100, China
a
zuoyuxin1314@sina.com, b
yaozj@nuaa.com, c
imzjt@126.com
Keywords: Hollow glass bead, phenolic foam, thermal performance, mechanical behavior
Abstract. Hollow glass beads / phenolic foam composites were prepared by molding method. The
influence of HGB on thermal performance and mechanical properties of phenolic foams were
investigated using thermal conductivity measurement, thermogravimetric analysis (TGA) and
compression tester. The results show that the addition of hollow glass beads lead to a significant
improvement in the compressive property of phenolic foams, with the compressive strength reaching
the maximum adding 10% HGB and HGB pretreated by silicane coupling agent further enhance the
compressive property. FT-IR spectroscopy shows the reaction between alcohol -OH groups on the
surface of HGB and methoxy (-OCH3) groups on silane coupling agent (KH560). The morphology
indicates the average cell size decreases with HGB content increasing up to 10%, and again the cell
size of foams reinforced by pretreated HGB are better. Addition of HGB improved the thermal
stability property of phenolic foams, due to the porosity was mainly responsible for thermal
conductivity property of phenolic foams, so HGB filled materials achieved higher thermal
conductivity.
Introduction
Microcellular materials are widely used in thermal insulation, energy absorption and structural uses
due to their unique properties, such as light weight, thermal and acoustic insulation, impact damping
and so on [1].
Phenolic resins are synthetic polymers in that their backbone is composed of an “organic” repeating
unit, that is, the aromatic ring. In addition, the s aromatic rings are connected by organic groups, such
as methylene. The presence of the aromatic ring and methylene units gives phenolic their unique
properties and thermal and chemical stability[2]. So far, many efforts have been done to improve
thermal properties[3-6] and mechanical properties[7-9], fire-resistant properties [10, 11]of phenolic.
Also photo-induced mechanical actuation is observed when exposed to infrared radiation.
In recent years, silica filled phenolic foams have been proverbially studied[1]. Since silica filled
phenolic have presented outstanding properties for many respects, it might be the first choice for most
cases. Nevertheless, silica has passive effects on the foaming process and result in much worse
thermal properties. That is to say, silica filled phenolic foams don’t prove to be a lightweight and heat
insulation composite.
Hollow glass bead (HGB) is a rigid porous bead containing inert gas. The main chemical
constitution is silicate like silica. The hollow core endows HGB good thermal properties and
lightweight properties[12]. In virtue of these characters, HGB was broadly used to fabricate syntactic
foams. In addition, these micro-particles do not generate important stress concentration at the
interface with the matrix owing to their smooth spherical surface. Previous attempts of HGB mostly
focused on polyurethane for damping materials[5], polypropylene materials[13, 14] for automotive
applications, epoxy resin materials[15] for adhesive glue. Nikhil Gupta [16] reported that with the
increasing content of hollow glass bead the size of cell was reduced, and the compress strength of
syntactic foam was effectively enhanced. Wang[5] also proved that modified HGB improved
mechanical properties of epoxy resin composites. However, HGB filled phenolic foams have not been
Advanced Materials Research Vol. 988 (2014) pp 13-22
© (2014) Trans Tech Publications, Switzerland
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![wt.%. However, the thermal degradation of HGB-reinforced phenolic foams produces a final ash
content more than 62 wt.%. To conclude, utilization of HGB produces foams with superior thermal
stability.
Conclusions
Mechanical and thermal performance of phenolic foams reinforced by hollow glass beads was
determined and discussed by comparing with raw phenolic foams. The significant results were as
follows:
FT-IR spectroscopy shows that condensation reaction happened between alcohol -OH groups on
the surface of HGB and methoxy (-OCH3) groups on silane coupling agent (KH560).
SEM images display the microstructure and morphology of HGB filled phenolic foams. The
average cell size decreased with higher HGB content until the HGB content reaches 10%, and the cell
size of foams reinforced by pretreated HGB are better than the foams reinforced by HGB. The results
could be explained by nucleation and gas diffusion. From images of higher resolution, we concluded
that pretreated HGB had a better adhesion with the matrix.
The compressive strength increases along with the hollow glass beads content up to 10%, and the
compressive strength of phenolic foams filled by pretreated HGB is better than filled by HGB.
The lowest thermal conductivity of HGB filled phenolic foams was 0.307 Wm−1
k−1
. And the
thermal conductivity increased with higher filler content until the filler content reaches 10%. The
results could be explained in that the porosity was mainly responsible for thermal conductivity
property of phenolic foams, resulting that HGB filled materials achieved higher thermal conductivity.
The thermal stability studied by TGA, shows that the residue rate of phenolic foam were improved
8.3%, and the thermal degradation of HGB-reinforced phenolic foams is slower. Therefore the
thermal stability property of phenolic foams were improved with the HGB filled materials.
Acknowledgements
This work is supported by “The Fundamental Research Funds for the Central Universities”,
NO.NZ2013307.
References
[1]. Gao, J., et al., Preparation and properties of hollow glass bead filled silicone rubber foams with
low thermal conductivity. Materials & Design, 2013: p. 491–496.
[2]. Wu, X., et al., Preparation and characterization of carbon foams derived from aluminosilicate and
phenolic resin. Carbon, 2011. 49(5): p. 1782–1786.
[3]. Wu, X., et al., Effect of final pyrolysis temperature on the mechanical and thermal properties of
carbon foams reinforced by aluminosilicate. Materials Science and Engineering: A, 2012: p.
446–450.
[4]. Luo, R., et al., The mechanical and thermal insulating properties of resin-derived carbon foams
reinforced by K2Ti6O13 whiskers. Materials Science and Engineering: A, 2011. 528(4–5): p.
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[5]. Wang, T., et al., Damping analysis of polyurethane/epoxy graft interpenetrating polymer network
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31(8): p. 3810–3815.
[6]. Zhou, J., et al., Thermomechanical analyses of phenolic foam reinforced with glass fiber mat.
Materials & Design, 2013: p. 131–135.
Advanced Materials Research Vol. 988 21](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-38-320.jpg)
![[7]. Alonso, M.V., M.L. Auad and S. Nutt, Short-fiber-reinforced epoxy foams. Composites Part A:
Applied Science and Manufacturing, 2006. 37(11): p. 1952–1960.
[8]. Shen, H. and S. Nutt, Mechanical characterization of short fiber reinforced phenolic foam.
Composites Part A: Applied Science and Manufacturing, 2003. 34(9): p. 899–906.
[9]. Shen, H., A.J. Lavoie and S.R. Nutt, Enhanced peel resistance of fiber reinforced phenolic foams.
Composites Part A: Applied Science and Manufacturing, 2003. 34(10): p. 941–948.
[10]. Feih, S., et al., Influence of water content on failure of phenolic composites in fire. Polymer
Degradation and Stability, 2008. 93(2): p. 376–382.
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susceptible to fire blight. Scientia Horticulturae, 2005. 105(2): p. 213–221.
[12]. Li, J., X. Luo and X. Lin, Preparation and characterization of hollow glass microsphere
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[13]. Liang, J.Z. and F.H. Li, Simulation of heat transfer in hollow-glass-bead-filled polypropylene
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22 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-39-320.jpg)
![Monolithic macroporous-mesoporous carbon using ionic liquids
as carbon source
Aibing Chen*, Yunhong Yu, Yifeng Yu, Haijun Lv, Tingting Xing, Yuetong Li,
Wenwei Zang
College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology,
Yuhua Road 70, Shijiazhuang 050018, China
Email: kdchenab@163.com
Keywords: ionic liquid, monolithic, macroporous-mesoporous carbon
Abstract. A facile approach is employed for the preparation of hierarchically porous structures
monolithic ordered macroporous-mesoporous silica materials (OMS) using the commercially
available and cheap polyurethane (PU) foam as monolithic template, triblock copolymer P123
(EO20PO70EO20) as structure-directing agent and tetraethyl orthosilicate (TEOS) as silica source, then
monolithic ordered macro porous-mesoporous carbon materials (OMC) is synthesized by using
monolithic ordered macroporous-mesoporous silica materials as hard template and ionic liquids as
the carbon source. The silica and carbon monoliths possess uniform pore sizes (3.74-3.84 nm) and
ordered mesostructure.
Introduction
Mesoporous carbons with hierarchically porous structures and high surface area are required for
practical applications in adsorption and separation [1,2]. Compared with powdered carbons, the
monolithic carbons have a certain size, shape, and high mechanical strength, which are easy to
recycle and stored [3]. There are a lot of methods to synthesize monolithic carbons. The template
method has attracted more attention. Generally, the template method can be classified hard and soft
template. The hard template for the fabrication of mesoporous carbons can avoid the organic template
agent and precursor of hydrolysis condensation copolymerization process. And the selection of
carbon sources is widespread, such as phenolic resin, furfuryl alcohol, ethylene, mesophase pitch, etc.
Guo et al. synthesized ordered mesoporous carbons whose the pore surfaces were modified and
functionalized using ordered silica as hard template[4]. Kim et al. reported direct synthesis of
uniform mesoporous carbons from the carbonization of as-synthesized silica/triblock copolymer
nanocomposites [5]. Yang et al. described the preparation of controllable morphology and
nitrogen-doped porous graphitic carbons using cheap nano-CaCO3 as template. The materials with
several unique characteristics promised for potential applications in material science [6].
Recently, ionic liquids (ILs) as carbon source for the synthesis of mesoporous carbons have made
remarkable progress in the field of sorption and adsorption due to high carbonization yields and
heteroatom doping, such as N and S. Our team reported the mesoporous structure onion-like carbon
monoliths materials are obtained by employing ILs as carbon source [7]. At the same time,
nitrogen-doping hollow carbon spheres with uniform in size and shell thickness can be adjusted
which are synthesized by using the monodisperse silica spheres as hard template [8]. Wohlgemuth et
al. reported two co-monomers, S-(2-thienyl)-L-cysteine (TC) and 2-thienyl carboxaldehyde, by
one-pot method to form nitrogen and sulfur dual doped carbon aerogels [9]. Dai et al. reported the
preparation of monolithic carbon materials using monolithic silica gels as hard template,
[Bmim][NTf2] as caron source. The silica template was eliminated by dissolving in HF to obtain the
carbons, but the carbons have partial collapse [10].
Advanced Materials Research Vol. 988 (2014) pp 23-26
© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.988.23](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-40-320.jpg)
![In this paper, the hierarchically porous monolith carbon materials were synthesized by wet
impregnation method using the monolith mesoporous-macroporous silica as the hard template and
the ionic liquids as the carbon precursors. In contrast to the other carbons, the monolithic carbons
possessed unique mechanical properties which kept the complete monolithic after carbonization and
removal of the template.
Experimental
2.1 Synthesis of ordered monolithic macroporous-mesoporous silica materials
In a typical procedure, Pluronic P123 (1.0 g) was dissolved in 0.2 M HCl (1.0 g) and ethanol (10 g),
and stirred over 2 h to afford a clear solution. TEOS (2.08 g) was then added to the solution and
continuous stirred over 3 h to get a homogeneous solution. To put 0.5 ml of the obtained
homogeneous solution coat onto polyurethane (PU) foam with a total volume of 2.5 cm3
. Put it in the
drafty closet for 5-8 h to evaporate the solvent at room temperature, and in the oven for 24 h for
thermopolymerization at 100 ˚C. Finally, the sample was calcinated at 550 ˚C for 6 h under ambient
atmosphere, followed to the synthesis of ordered monolithic macroporous-mesoporous silica
materials that was named as OMS.
2.2 Synthesis of ordered monolithic macroporous-mesoporous carbon materials
0.4 g 1 - acetonitrile-3 - methylimidazolium chloride was dissolved in 0.5 ml ethanol and stirred to
afford clear solution, the clear solution was coated onto the OMS. It took 8 h to evaporate the solvent
at room temperature, and then was calcined under N2 atmosphere at 500 ˚C for 1 h. Then 0.15 g of the
above solution was coated onto the sample again, it would be calcined under N2 atmosphere at 800 ˚C
when the solvent was evaporated completely. To recover the monolith macroporous-mesoporous
composite carbon material, the silica templates were dissolved and removed by 2 M NaOH solution.
Results and Discussion
200 400 600 800
0
20
40
60
80
100
Weight
(%)
Temperature (℃)
a
b
According to the report [11], the ionic liquids with –CN group was easier to form of 3D-connected
frameworks, which would induce nitroge-rich at elevated temperatures, and the carbonization yields
was also relative high. Herein, two species of ILs consisting of functional –CN were carried on TGA
under N2 atmosphere (Fig.1), the result indicated that carbonization yield of
1-cyanopropyl-3-methylimidazolium chloride was low that only to 2.21 wt%, on the contrary, the
high carbonization yield of 1-acetonitrile-3-methylimidazolium chloride was up to 28.64% under
600 ˚C. The following experiments selected 1-acetonitrile-3-methylimidazolium chloride as carbon
source to synthesize the monolith macroporous-mesoporous carbon materials.
Fig. 2 (a) is the light yellow PU foam, which the volume is 2.5 × 1.0 ×1.0 cm3. (b) is the OMS with
1.8 × 0.72 × 0.72 cm3, its shrinkage was calculated to be about 62 % in volume, but still maintained
the macrostructure of monolith. (c) is the OMC with 1.2 × 0.5 × 0.5 cm3, which the volume shrinkage
was about 88 %. The cause of this phenomenon was that the ILs occurred polycondensation in the
process of carbonization. However, all the samples kept the original morphologies with different
Fig.2 a) Photograph of the commercial
PU foam. b) OMS. c) OMC.
Fig.1 TGA of (a) 1-cyanopropyl-3-
methylimidazolium chloride and (b)
1-acetonitrile-3-methylimidazolium chloride
24 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-41-320.jpg)
![shrinkages, suggesting a good thermal stability for these samples. By observing the optical photos, it
can be found that the monolithic morphology was well preserved, and there was no obvious collapsed
phenomenon. At the same time the carbonization yield was high, which is the key factors to
synthesize of the monolithic carbon materials.
2 4 6 8
2 4 6 8
intensity
(a.u.)
2 theta (degree)
intensity(a.u)
2 theta(degree)
(100)
(200)
(110)
0.0 0.2 0.4 0.6 0.8 1.0
5 10 15 20 25 30 35
dV/dlog(D)
Pore size(nm)
a
b
Volume
adsorbed(cm3/g.STP)
Relative pressure(P/Po)
a
b
The monolithic OMS showed three resolved diffraction peaks in the SAXRD (Fig.3), which can be
indexed as 100, 110 and 200 diffractions of 2D hexagonal mesostructure, suggesting the
mesostructure with highly ordered [12]. Compared with the silica materials by organic-organic
self-assembly, the monolithic OMS was moved for high angles, which indicating the mesoporous
pore size gradually decreasing [4]. The SAXRD pattern of the monolithic OMC which using the
monolithic OMS as hard template showed a weak broad, as shown in the inset of Fig.3. No obvious
diffraction peaks can be observed, which may be due to the weak interaction force between Ils and the
silicon group.
Fig.4 represented typical nitrogen adsorption-desorption isotherm for the OMS and OMC which
exhibit representative type-IV curves with H3-type hysteresis loop. Meanwhile, capillary
condensation of nitrogen at P/P0=0.4-1.0, implied the presence of mesoporous in those materials.
The pore size distribution of OMS with a mean value around 3.74 nm was calculated by
Barrett-Joyner-Halenda (BJH) model (inset of Fig.4). And the OMC was around 3.84 nm which was
similar to the OMS, indicating that the carbon materials can replicate by OMS. The
Brunauer-Emment-Teller (BET) surface area was calculated to be 163 m2
/g, which was larger than
the OMS (140 m2
/g). The pore volume increased from 0.10 cm3
/g to 0.24 cm3
/g.
The scanning electron microscopy (SEM) images of the OMS showed 3D interconnecting
networks and the macropores of 200-500 um. Fig. 5 a showed the OMS which were synthesized by
removing the PU foam template has a 3D macrostructure, composed of inhomogeneity polygon
struts. It can be found in the Fig.5 b, monolithic OMC was synthesized by impregnating ILs into the
OMS which can be kept the macrostructure, but their surface was rough because during the process of
carbonization, ILs turns to be polycondensation. The transmission electron microscopy (TEM) can be
observed the internal microstructure of the monolithic OMC. Fig.5 c showed the TEM images of the
monolithic OMC, it can be seen that abundant pores can be observed on the surface of materials, the
structure was honeycomb. The pore size estimated 4 nm which was in good accordance with the
results of BET.
Fig.4 N2 adsorption-desorption isotherms and pore
size distributions of (a) OMS (b) OMC
Fig.3 SAXRD patterns of
OMS and OMC
Fig.5 a,b) SEM images of OMS and OMC c) TEM image of OMC
Advanced Materials Research Vol. 988 25](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-42-320.jpg)
![The IR spectrum of the samples around carbonization was analyzed by the change of the functional
groups. As shown in Fig. 6, the absorption band at 1340 cm-1
was attributed to C-N stretching
vibrations. The peak at 1630 cm-1
can be assigned as stretching vibrations of –NH2 and C-N group,
overlapped the adsorption of N-H stretching vibrations in the range 3500-3100 cm-1
. The Fig. 5 b had
not obvious peak at 2220 cm-1
which stretching vibrations of C≡N [13]. Therefore, the IR data
indicated the existence of N element in the OMC.
1000 2000 3000 4000
40
50
60
70
80
90
100
intensity
(a.u.)
Wavenumber (cm
-1
)
a
b
Conclusion
Monolithic OMS materials were fabricated by using PU foam as a sacrificial scaffold, which have a
3D and large interconnecting mesostructure. The monolithic macroporous-mesoporous carbon
composite materials were obtained by wet impregnation method using the monolithic OMS as hard
template, ILs as carbon source. The carbon materials exhibited total pore volumes (0.24 cm3
g-1
) and
nitrogen content.
References
[1] J. Wei, D. D. Zhou, Z. K. Sun, Y. H. Deng, Y. Y. Xia, and D. Y. Zhao: Advanced Functional
Materials. 23 (2013), 2322-2328
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[4] R. X. Guo, J. Guo, F. Q. Yu, D. D. Gang: Microporous and Mesoporous Materials. 175 (2013),
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Research Vols. 557-559 (2012), p 1518-1521
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Journal of Materials Chemistry A. 1 (2013), 1045-1047
[9] S. A. Wohlgemuth, R. J. White, M. G. Willinger, M. M. Titirici, and M. Antonietti: Green
Chemistry. 14 (2012), 1515-1523
[10] X. Q. Wang, and S. Dai: Angewandte chemie-international edition. 49 (2010), 6664-6668
[11] J. S. Lee, X. Q. Wang, H. M. Luo, and S. Dai: Advanced Materials. 22 (2010), 1004-1007
[12] B. Y. Liu, D. C. Jia, Q. C. Meng, J. C. Rao: Carbon. 45 (2007), 668-689
[13] N. N. Liu, L. W. Yin, C. X. Wang, L. Y. Zhang, N. Lun, D. Xiang, Y. X. Qi, R. Gao: Carbon. 48
(2010), 3579-3591
Fig.6 IR spectrum of around carbonization a) ILs+OMS b) OMC
26 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-43-320.jpg)
![Strain analysis of bimetal material based on uniaxial tensile and ANSYS
Dehai Zhang1, a
, Duanqin Zhang1,b
, Yanqin Li1,c
, Jianxiu Liu1,d
Daiping Bai1,e
, Houhai Xia1,f
and Yong Yang1,g
1
Mechanical and Electrical Engineering Institute，Zhengzhou University of Light Industry,China
a
zhangdehai0318@163.com, b
dqzhang2003@sina.com, c
yqli@zzuli.edu.cn, d
jianxiuliu@126.com,
e
baidaiping@163.com,f
958498228@qq.com，g
875956443@qq.com
Keywords: bimetal metal, Uniaxial tensile, ANSYS
Abstract. With a combined method of theoretic analysis, numerical simulation and uniaxial tensile
test experiment research, the properties of bimetal materials are system studied. The researches are
concentrated on the followings contexts:The fabricating method of bimetal materials by semi-solid
compressive joining is studied by ANSYS, and then the tensile property relationships of the clad
material are established. The stress and their strains along x, y and z directions of the clad material are
analyzed, respectively. The different performance of composite materials, find materials conform to
the existing problems so as to optimize treatment.
Introduction
In modern technology, bimetal materials consist of metal layers with different physical properties are
widely used in aviation, chemical engineering, automobile, electronic industries and so on. Metal
composites consisting of aluminium and copper layers are of great importance in the energy sector
and consumer electronics. Power connectors, tapes and other electric and heat conductive elements
are made from them. The advantages of using these composites are good electrical and thermal
conductivity at a reduced total weight [1]
. The application of aluminium in the bimetal structure,
instead of 100% content of stainless-steel, can reduce total cost of materials due to the lower market
price of aluminium. However, there are some key problems urgent to be solved in the structure and
properties of the clad materials, which are the main tasks of this paper. The research in this field has
great significance both in theory sense and engineering practice [2]
.
The forming ability of bimetal materials are directly determined by their mechanical performance,
so the tensile mechanical properties of cladding material were studied by many domestic and foreign
scholars. The performance and single material has very big difference due to the cladding material
mismatch, performance of components caused by partial or whole deformation behavior and fracture.
Due to the mechanical properties of each component materials vary widely, deformation yield and
destruction are difficultly to achieve synchronization during the processing of uniaxial tensile test.
Due to the different of component material poisson's ratio, such as the ratio of plastic strain
difference, the performance of material along the width direction is limited by metal on both sides of
each other will generate additional stress. This kind of additional stress can produce warping along the
specimen width direction when a certain value are reached out .
In recent years, the mechanical properties of the cladding plate are studied by scholars at home and
abroad[3]
. Their researches are mainly concentrated in the mechanical properties of cladding material
and its components of the relationships between material mechanical properties, the mechanical
properties of its constituent material to predict the mechanical properties of cladding material and the
related numerical simulation and so on. Mechanical properties of the compound layer board are
depended on the mechanical properties of component materials and their respective accounts for
thickness ratio. To predict the mechanical properties of the composite board are mainly depended on
mixing rule theory. In view of the interface problem, finite element analysis software has achieved
very good effect for the forecast of damage location, but there are problems are existed on the analysis
when the material had been yielded[4]
. Due to high flow performance of semi-solid material is used by
Advanced Materials Research Vol. 988 (2014) pp 27-30
© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.988.27](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-44-320.jpg)
![Reiner [5]
, the stainless steel bolts and semi-solid steel parts are formed by rheology and forging
forming at one time. Semi-solid slurry is possessed of good liquidity, bolts of tooth filling is good, the
bolt head of semi-solid steel slurry and the surface of the bolt formed have been welded into
microcosmic joint tissue. Its combined forging and connection are achieved in one step worker, In the
meantime the cost of assembly is reduced, respectively [6]
.The pressure compound and roll casting
process are adopted to realize melting of the composite steel and semi-solid aluminium, and the
interface structure and mechanics performance of composite plate are studied. That the relationships
including of shear strength and the solid fraction of semi-solid aluminum melt, interface structures
between semi-solid aluminum composite of are determined. The method of extrusion of package is
adopt by Tohru [7]
, semi-solid aluminum alloy aluminum-double metal rod are made. A kind of
pressure transmission medium is made through adding semi-solid materials into the metal sleeve
barrel, and the production of metal package material is achieved. Next ,the performance of the
interface and the structure of the organization are analyzed.
Many important problems of performance and the organization could not well solved until then,
but the question about how to improve the accurate evaluation of performance about the interface of
the combination between dissimilar materials is an ugrent work as well as mechanics and formability
of the cladding material.
Experiment
For bimetal cladding material, a lot of research of the preparation, recombination mechanism of
composite interface, interface evaluation method and indexes are carried out. However, due to
interface is as the connection area of different materials, its mechanical properties and tissue are
relative complex. Until now there is no unified evaluation method and index and the evaluation
criterion. So on the basis of experiment, it is necessary through a combining method of numerical
simulation and theoretical analysis to study another new preparation method and interface problem.
The uniaxial tensile test of material is the basic experiment to determine mechanics performance.
The basic performance parameters of the materials, such as the yield point, tensile strength, stiffness
index, coefficient of strength, plasticity constitutive relation and so on can be obtained. In this article,
1Cr18Ni9Ti stainless steel and aluminum bimetal plate are selected. The material mechanical
properties and basic material properties required for establishing the constitutive relation of the data
can be obtained using uniaxial tensile test.
Mechanics performance test is carried using Instron-1195 material testing machine. The machine
can complete materials of all kinds of mechanical properties testing: flexural, compressive strength,
fracture toughness, elastic modulus and so on. With reference to the metal tensile test method
(GB228-87), metal tensile test specimens (GB 6397-86) , tensile sample size is shown in Fig.1.
Fig.1 Tensile samples of stainless steel/aluminium cladding materials
Numerical simulation
When uniaxial tensile experiments are simulated, necking phenomena of the material is the most
difficult to simulate, so some problems must be pay attention when using ANSYS software. For
instance, cylinder is to not simple set up to simulating and modeling. It should be noted that there are
necking phenomenon is because the material is flawed. So it should reflect that phenomenon based on
the established model. In common, the common way is to reduce the size of the model in necking
28 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-45-320.jpg)
![ANSYS results show that stress concentration is located in the defect area of bimetal material
tension, the stress distributions of different material also have very big difference. The stress
distribution of stainless steel/aluminium bimetal material under the condition of uniaxial tensile test
show that the stress of the stainless steel side is bigger.
Conclusions
Due to the bimetal material preparation and performance study is relatively complex, the aspects
including new technology and new equipment, interface control, interface characterization,
micromechanics and interface characteristics and the overall performance of the composite material
have a lot of study to do. The studies on material and mechanics, macro and micro, theory and
numerical simulation and experimental are the important development trend in the future field.
As can be seen from ANSYS simulation, the area of stress concentration is located on the defect
area when bimetal material is under the condition of tension force. But the stress distributions of
different material also have very big difference. In this paper, these conclusions about bimetal
material analysis are arrived out using ANSYS software. The metal materials are affected by external
force, the stress is mainly concentrated in the defect area. The simulated stress distribution of stainless
steel-aluminium cladding material under the condition of uniaxial tensile shows that the stress on the
side of stainless steel side is bigger.
Acknowledgements
This work has been performed under the joint project between Research Program Project of
Foundation and Advanced Technology of Henan Province(132300410181), Key Scientific Research
Project of Henan Province (142102110151), Science and Technology Research Project of Zhengzhou
(131PPTGG411-7), Key Guidance Scientific Research Project of Henan Education Department
(13B460333), Key Scientific Research Program of Henan Education Department (13A460372) and
Dr. Research Fund Project of Zhengzhou University of Light Industry.
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30 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-47-320.jpg)
![Study on Curing Kinetics of MEP-15 /593/660 System
Jiale Song1,a
, Chanchan Li2,b
,Zhimi Zhou1,c
, Chaoqiang Ye1,d
, Weiguang Li1,e
1
School of Materials Science and Engineering, Chang’ an University, Xian, 710064, PR China
2
School of Highway, Chang’ an University, Xian, 710064, PR China
a
jlsong@chd.edu.cn(J.S.), b
1174781909@qq.com, c
bodajingshen2008@163.com(Z.Z.),
d
yechaoqiangmvp@163.com (C. Y.), e
wgli@chd.edu.cn(W. L.)
Keywords: epoxy resin. curing kinetics. DSC.
Abstract: Curing kinetics of MEP-15/593 system and MEP-15/593/660 system is studied by means
of differential scanning calorimetry (DSC). Curing kinetic parameters are evaluated and the
relationship between diluent 660 and the curing properties is investigated. The results show that the
diluent 660 can not only reduce viscosity and activation energy, but also improve the degree of cure
and conversion ratio.
Introduction
Epoxy resin mortar, as a structural material, has been put into practice for its great mechanical
property. However, due to the low toughness and easy to crack in the external forces, the
application of condensates has been largely restricted [1-3]. Therefore, our experiment use curing
system which consists of the polyether soft segment chemical modification of the epoxy
resin(MEP-15) and the amine curing agent which can be cured at room temperature to improve the
brittleness of the condensates. Besides, adding Propylene oxide-butyl ether (abbreviated 660
diluent) can not only reduce the viscosity of the curing system but also increase its toughness.
In our experiment, non-isothermal DSC was used to contract the curing kinetics of
MEP-15/593/660 and MEP-15/593. Then the thermodynamic data were analyzed to get the reaction
dynamic equation and the order of reaction of the two systems which lay the foundation of further
optimization of the curing process and improvement of the product’s performance.
Experimental
1.1 Materials
593 curing agent (industrial products) was provided by Yueyang Petrochemical Plant， amine
value 600-700 mgKOH/g. 660 diluent (industrial products) was produced by Xin Dian Chemical
Materials (Shanghai) Co.Ltd, epoxy value 0.50 mol/100g.
Preparation of MEP-15: Making flexible segment which end group is high activity isocyanate
group by reacting toluene diisocyanate (TDI) with flexible chain polyether diols, and introducing
this segment into the molecular chain by reacting isocyanate group with epoxy-secondary hydroxyl.
1.2 Characterization
1.2.1 DSC testing
The instrument used in above test was DSC-7 thermal analyzer produced by U.S. PE
Corporation. Peak temperature of curing exothermic DSC spectrum and glass transition DSC
spectrum are processed by TA Data Analysis software.
Advanced Materials Research Vol. 988 (2014) pp 31-35
© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.988.31](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-48-320.jpg)
![1.2.2 Viscosity testing
Viscosity within a temperature range of 20 ~ 40 o
C under MEP-15/593 system was measured
by NDJ-1 viscometer produced by Shanghai Balance Instrument Factory.
Results and discussion
1.3 The influence of diluent content
According to China’s current standard “Epoxy grouting resin for concrete
crack”(JC/T1041-2007) (hereinafter using “the specification” for short) provide that mixing
viscosity of epoxy resin mixture in construction temperature is 200mPa•s.
Viscosity of curing systems which are the mixture of MEP-15 epoxy resin and 660 diluent
mixed in different mass ratio was tested respectively under three different proportions and five
different temperature conditions. Viscosity-temperature curves are shown in Figure 1.
Figure 1 Viscosity-temperature curves of MEP-15/660 system under different temperature
It can be seen from the Figure 1 that viscosity of MEP-15/660 system decreased with the
increase of temperature. While the temperature was 20~30 o
C and mass ratio was 0.3:1, viscosity of
MEP-15/660 system was larger than 200 mPa·s and did not meet the viscosity requirement of
constructive mixture. While the temperature was 30~40 o
C and mass ratio was 0.4:1 and 0.5:1,
viscosity of the system was less than 200 mPa·s which met the requirement. But from the economic
point of view, the following tests should use 0.4:1 as the diluent proportion of epoxy mortar.
1.4 Curing kinetics parameter analysis
The curing process of epoxy resin is very complex reaction. Kissinger method is the most
commonly used method to solve the dynamic equation (that is the activation energy E, reaction
order n and function). Because of its calculation is little and easy operation, it has been widely used
[4][5]
.
Curing exothermic DSC spectra of two systems under the condition that the heating rate was 5,
10, 15, 20℃/min are shown in Figure 2. The initial temperature (Ti), the peak temperature (Tp) and
the final temperature (Tf) of two curing systems’ curing reaction exothermic peak are shown in
Table1.
32 Material, Mechanical and Manufacturing Engineering II](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-49-320.jpg)
![Conclusion
1. Through viscosity tests under 3 different ratio and 5 different temperature conditions, the best
diluent incorporation of MEP-15/660 system is 0.4:1 according to results and curing system
viscosity meet constructive mixing viscosity requirement.
2. Using non-isothermal DSC method studied the curing process of MEP-15/593 system and
MEP-15/593/660 system. And using Kissinger extremum method analyzed the curing kinetics
parameters of the two systems. The result shows that adding diluent 660 decrease the reaction
activation energy and the reaction order of the system.
3. Reactive diluent 660 decreases the activation energy and practical reaction’s temperature of
MEP-15/593 system. So at the room temperature, the reaction speed is comparatively fast and
reaction between epoxy resin and condensate is easier, and these all favours construction on the
site.
Acknowledgment
The authors acknowledge Ningbo transportation committee of science and technology plan
project NO.201311 funding sources for this work.
References
[1] Cao Ruijun, Mei Dong, Yuan Jianan. Study of the rapid repair material on concrete road surface
[J]. Journal of of Xi'an Jiaotong University, 1998, 32(1) : 97-99
[2] Chi Yi, Yin Jian. Modeling analysis of crack repairing structures for asphalt concrete pavement
[J]. Journal of Advanced Materials Research, 2013, 639-640 (1) : 377-381
[3] Sun Renjuan, Ge Zhi, Li Wu, Zhou Haifang, Huang Dawei. Experimental research of the rapid
set cement concrete for rapid repair of concrete pavements [J]. Journal of Advanced Materials
Research, 2013, 634-638 (1) : 2697-2701
[4] Peng Xiaoqin, Yang Tao, Wang Kaiyu, Meng Xiangjie. Preparation of geopolymeric concrete
and its application to rapid repair of cement concrete pavement [J]. Journal of Southwest Jiaotong
University, 2011, 46(2) : 205-210
[5] Lu Zhaofeng, He Zhaoyi, Qin Min. A rapid repair technology on faulted joint slabs of cement
pavements [C]. American: American Society of Civil Engineers, 2009: 1463-1468
Advanced Materials Research Vol. 988 35](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-52-320.jpg)
![Acidification assisted preparation of graphite oxide and graphene
Yun Lei 1,a
, Jun Xu 1,b
, Rong Li 1,c
, Feifei Chen1,d
1
School of Resource and Environmental Engineering, Wuhan University of Technology, Wuhan,
430070
a
LeiYun＠whut.edu.cn
Keywords: Acidification graphite, Graphite oxide, Graphene
Abstract: Graphite oxide was prepared by acidification assisted Hummers method, which contains
acidification, medium temperature and high-temperature three stages. Traditional Hummers
low-temperature process was replaced by acidification process. The dosages of acid, graphite and
potassium permanganate were investigated, and the produced graphite oxide was treated by ultrasonic
oscillation and reduced to graphene by refluxing the reaction mixture at 100℃ under open-air
conditions. The structure of natural graphite, graphite oxide and graphene were characterized by
X-ray diffractometry and infrared spectrum, the morphology of graphene was observed on a scanning
electron microscope and the electrochemical properties of graphene were analyzed by the
three-electrode cyclic voltammetry test system.
Introduction
Graphene, the thinnest and strongest material void sp2
hybridized carbon atoms arranged in a
honeycomb lattice, becomes the rising star in material science due to its amazing characteristics such
as large surface area, excellent electrical and mechanical properties [1,2]
with promising applications in
the fields of supercapacitors [3]
, batteries [4]
, nanoelectronics [5]
and catalystsupports [6]
. Pan Y et al.
prepared graphene film by heating methane at 1000 ℃ on the metal foil of Cu and Ni [7]
. Li et al. used
chemical reduction method to get graphene sheets which were uniformly dispersed in water [8]
.
Herein, graphite oxide (GO) was obtained by acidification assisted method, and further treated
with ultrasonic oscillation to produce graphene oxide, which was reduced by hydrazine to obtain
graphene. The prepared graphene was characterized by X-ray diffraction (XRD), scanning electron
microscopy (SEM) and Infrared Spectrometer (IR), and further investigated by transient photocurrent
and cyclic voltammetry.
Experiment
Materials. The graphite was purchased from Sinopharm Chemical Reagent Co., Ltd. Sulfuric acid
(H2SO4), nitric acid (HNO3), sodium nitrate (NaNO3), potassium permanganate (KMnO4), hydrogen
peroxide (H2O2), barium (BaCl2), hydrazine (N2H4•H2O) and ethanol (CH3CH2OH) were all
commercially available products and used without further purification.
Preparation of graphite oxide. Graphite power was used to prepare graphite oxide by modified
Hummers method. Firstly, flake graphite power was mixed with sulfuric acid and nitric acid, and
stirred for 60 min to prepare acidification graphite. Secondly, sulfuric acid, sodium nitrate and
potassium permanganate were added into acidified graphite. The mixture was heated to about 35 °C
and kept at this temperature for an additional 30 min. Lastly, hydrogen peroxide were added in the
stage of high temperature reaction.
Preparation of graphene. Graphene was prepared by chemical reduction. Firstly, 0.2g graphite
oxide was added into 200mL distilled water and treated with ultrasonic oscillation for 30min. Then
50mL hydrazine was added into the above mixture and stirred. Lastly, the mixture was heated to
reflux at the temperature of 100℃ for 8h.
Characterization. X-ray diffraction (XRD) was performed on an X Pert PRO DY2198
diffractometer using the monochromatized X-ray beam from Cu Kα radiation. The morphology of
Advanced Materials Research Vol. 988 (2014) pp 36-39
© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.988.36](https://image.slidesharecdn.com/2381994-250604185648-81166a30/85/Material-Mechanical-And-Manufacturing-Engineering-Ii-Yunhae-Kim-53-320.jpg)
Material Mechanical And Manufacturing Engineering Ii Yunhae Kim
- 1. Material Mechanical And Manufacturing Engineering Ii Yunhae Kim download https://ebookbell.com/product/material-mechanical-and- manufacturing-engineering-ii-yunhae-kim-4763988 Explore and download more ebooks at ebookbell.com
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- 6. Material, Mechanical and Manufacturing Engineering II Edited by Yun-Hae Kim
- 7. Material, Mechanical and Manufacturing Engineering II Selected, peer reviewed papers from the 2nd International Conference on Material, Mechanical and Manufacturing Engineering (IC3ME 2014), May 30-31, 2014, Guangzhou, China Edited by Yun-Hae Kim
- 8. Copyright 2014 Trans Tech Publications Ltd, Switzerland All rights reserved. No part of the contents of this publication may be reproduced or transmitted in any form or by any means without the written permission of the publisher. Trans Tech Publications Ltd Churerstrasse 20 CH-8808 Pfaffikon Switzerland http://www.ttp.net Volume 988 of Advanced Materials Research ISSN print 1022-6680 ISSN cd 1022-6680 ISSN web 1662-8985 Full text available online at http://www.scientific.net Distributed worldwide by and in the Americas by Trans Tech Publications Ltd Trans Tech Publications Inc. Churerstrasse 20 PO Box 699, May Street CH-8808 Pfaffikon Enfield, NH 03748 Switzerland USA Phone: +1 (603) 632-7377 Fax: +41 (44) 922 10 33 Fax: +1 (603) 632-5611 e-mail: sales@ttp.net e-mail: sales-usa@ttp.net
- 9. Preface The 2014 2nd International Conference on Material, Mechanical and Manufacturing Engineering (IC3ME 2014) was successfully taken place in Guangzhou, China, May 30-31, 2014 and continue to be as a forum mainly for the Asia-Pacific community working in material, mechanical and manufacturing engineering field in order to facilitate aggregation and sharing interests and results for a better collaboration and activity visibility. The topics of the Conference were: (1) Synthesis and Preparation of Materials; (2) Advanced Mechanical Engineering Science; (3) Advanced Manufacturing System and Artificial Intelligence. We want to thank the Organizing Committee, the Institutions and Sponsors supporting the Conference, and everyone who contributed to the organization of this meeting, for their invaluable efforts in order to guarantee the complete success of this conference. The Committee of IC3ME 2014
- 10. 2014 2nd International Conference on Material, Mechanical and Manufacturing Engineering (IC3ME 2014) Conference Organization Chairmen Prof. Seung-Bok Choi, Inha University, Korea Prof. Yun-Hae Kim, Korea Maritime University, Korea International Scientific Committee Prof. Nabil Gindy, University of Nottingham, UK Prof. Toshio Haga, Osaka Institute of Technology, Japan Prof. Jong Kook Lee, Chosun University, Korea Prof. Yong-Lin Kuo, National Taiwan Univ. of Sci. and Tech., Taiwan Prof. Mao-Hsiung Chiang, National Taiwan University, Taiwan Prof. Yi-Sheng Huang, National Ilan University, Taiwan Prof. Chen-Chien Hsu, National Taiwan Normal University, Taiwan Prof. Chengqi Zhang, University of Technology, Australia Prof. Jianer Chen, Texas A&M University, USA Prof. Jiankun Hu, University of South Wales, Australia Prof. Yong Guan, Iowa State University, USA Prof. Yao-Wen Chang, National Taiwan University, Taiwan Prof. Wenbo Du, Beijing University of Technology, China Prof. Hongzhen Guo, Northwestern Polytechnical University, China Prof. Wenji Xu, Dalian University of Technology, China Prof. Shiming Ji, Zhejiang University of Technology, China Prof. Jianzhong Zhou, Jiangsu University, China Prof. Xiaoqin Zhou, Jilin University, China
- 11. Prof. Wenjun Meng, Taiyuan University of Sci. and Tech., China Prof. Haoran Geng, University of Jinan, China Prof. Jun Wang, Northeastern University, China Prof. Qiang Wang, Jinan University, China Prof. Sihai Jiao, Research Institute, Baosteel, China Prof. Xiaoping Zhou, Hubei University Of Technology, China Prof. Jian Gao, Guangdong University of Technology, China Prof. Jun Xiao, Wuhan University of Technology, China Prof. Ligang Yao, Fuzhou University, China Prof. Zhaohui Zhang, Beijing Jiaotong University, China Prof. Xiaobo Zhou, University of Colorado at Colorado Springs, USA Prof. Yun-Hae Kim, Korea Maritime University, Korea Prof. Carlos Caceres, The University of Queensland, Australia Prof. Shahrum Abdullah, University Kebangsaan Malaysia Dr. Xiangping Bu, Wayne State University, USA Prof. Sagar Kamarthi, Northeastern University, USA Prof. Zhengyi Jiang, University of Wollongong, AU Prof. Cesar de Sa, Jose, University of Porto, Portugal Prof. Nabil Gindy, University of Nottingham, UK Prof. Walid Mahmoud Shewakh, Beni Suef university, Egypt
- 12. Table of Contents Preface and Conference Organization Chapter 1: Micro/Nano Materials Research Electrochemical Study of Corrosion Inhibition on Copper in Base Electrolyte by 1-Phenyl- 3-hydroxy-1,2,4-triazole Q. Li, J. Li, L.T. Hu, L. Zhu, X. Han, Z.H. Tao and W. He 3 Exploration for Identification of Sheath-Core Fiber of Ploymer R.T. Zhu, P. Zhang and F.M. Nie 8 Mechanical and Thermal Properties of Phenolic Foams Reinforced by Hollow Glass Beads Y.X. Zuo, Z.J. Yao and J.T. Zhou 13 Monolithic Macroporous-Mesoporous Carbon Using Ionic Liquids as Carbon Source A.B. Chen, Y.H. Yu, Y.F. Yu, H.J. Lv, T.T. Xing, Y.T. Li and W.W. Zang 23 Strain Analysis of Bimetal Material Based on Uniaxial Tensile and ANSYS D.H. Zhang, D.Q. Zhang, Y.Q. Li, J.X. Liu, D.P. Bai, H.H. Xia and Y. Yang 27 Study on Curing Kinetics of MEP-15/593/660 System J.L. Song, C.C. Li, Z.M. Zhou, C.Q. Ye and W.G. Li 31 Acidification Assisted Preparation of Graphite Oxide and Graphene Y. Lei, J. Xu, R. Li and F.F. Chen 36 Preparation and Flame Retardancy of Waterbased Phosphorous Modified Phenolic Resin Y.J. Qiao, L.T. Wei, G.L. Xu, Y. Wang and J. Hu 40 Research on Synthesis Technology of Polyester Diol Using Vacuum Melting Method J.G. Zou, S.Y. Liu, Y.Y. Cao and Z.H. Zhang 45 The Influence of Second Particals on Grain Boundary Sliding J.Q. Zhang, J. Zhang, G.S. Zhu, Y.J. Zheng, S.W. Li and F.H. Wang 49 High-Energy Synthesis of Al-Ti Composite Powders and its Thermal Stability W.D. Zhang, J. Yang, Z.M. Du, B.W. Pan, H. Xu and J.Z. Dang 56 Synthesis, Characterization and Photophysical Properties of a New CuI Complexe Contain Bis[2-(diphenylphosphino)phenyl]ether and 1,2-diphenyl-1H-imidazo[4,5- f][1,10]phenanthroline Q. Li, R.F. Zhong, L. Li, M. Wang and F. Zhao 62 Synthesis, Characterization and Photophysical Properties of Rhenium(I) Complexe with 2- (naphthalen-2-yl)-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline Q. Li, L. Li, R.F. Zhong, H.D. Cai and F. Zhao 66 Study on Characterization and Preparetion of Bismuth Tungstate J.G. Sheng and Y.D. Shan 70 Inhibition of Sodium Citrate on Aggregation and Sedimentation of Nanocalcium Oxalate Dihydrate Crystals M. Xu, J.F. Xue, J.J. Li, X.L. Wen and J.M. Ouyang 75 Preparation and Characterization of Dialdehyde Nanocellulose W.G. Li and Q.H. Xu 79 Preparation and Characterization of Soap-Free Cationic Polystyrene Microspheres Using a Water Soluble Monomer Z.Q. Zhao, B.Q. Xu, G.L. Xu, Y. Wang and J. Hu 84 Preparation of High Pure and Micron-Sized α-Al2O3 Powder by Activated Aluminium Hydrolysis Method R. Tao, Y.T. Zhao, Z.H. Jia and L. Xu 89 Preparation, Characterization, and In Vitro and In Vivo Evaluation of Tanshinone IIA Lipid Microspere X.L. Liang, J.X. Zhao, X.Q. Shi, G.W. Zhao, Z.G. Liao, J. Zhang and Z. Li 93 Research Progress in Nanocellulose Preparation W.R. Yao and Q.H. Xu 101 Synthesis of Nano-Branched Ni/Fe Layered Double Hydroxides T.L. Wang, M.T. Liu, X.J. Liu and H.W. Ma 106
- 13. b Material, Mechanical and Manufacturing Engineering II Chapter 2: Film and Surface Technology Analysis the Influence Law of Process Parameters on the Deposition Rate of SiC Thin Film Q.M. Xiao, B. Xu and J.F. Xu 113 Research on Preparation and Properties of Antiwear and Anticorrosion Composite Coating Ni-P-SiC Y.M. Li, X. Zhang, A. Wang and H.J. Liu 117 The Performance Research of Different Concentrations of Methyl Adsorption on Si (110) Surface Z.X. Yan, D.Z. Yan, Q. Chen, A. Gong and Q. Liao 121 Effect of Atmosphere Temperature on Physical Properties of ZnO/Ag/ZnO on PET Films Y.H. Kim, J.W. Lee, R. Murakami, D.M. Lee, J.C. Ha and P.P. Wang 125 Research of CoSiN Film as Diffusion Barrier in ULSI-Cu Metallization Z.Y. Zhang, M.J. Wu and X.H. Chen 130 Measurement Studies on Superhydrophobic Materials S. Devasahayam and P. Yarlagadda 134 Chapter 3: Metallic Materials, Alloys and its Application Comparative Study on the Properties of CuCoBe Alloy and CuNiCoBe Alloy J. Chen, M. Zhang, D. Yang and H. Liang 145 Effect of Continuous Heating on Grain Growth in Fe-40Ni-Ti Alloy S.Q. Yuan, Y.H. Yang and Z.L. Wang 151 Microstructure and Mechanical Properties of an Al-Cu-Mg-Fe-Ni Alloy H.W. Liu, F. Wang, B.Q. Xiong, Y.A. Zhang, Z.H. Li, X.W. Li and S.H. Huang 156 The Effect of Doping Lanthanum on Phlogopite-Iron Pearlescent Pigments Y. Fu, X. Pang and M.T. Liu 161 The Research on Grind Coefficient of Stainless Steel on Inverse Analysis for Prediction Z.J. Liu 165 A Combined Composition Design for Metallic Glasses from Thermodynamic and Structure Rules S.Z. Yang, X. Han, J. Zhao and X. Ji 169 Study on the Microstructure Control and the Variation of Mechanical Properties of Pearlitic Steel L.Y. Li, Y. Liang, Z.M. Wei and H. Xiong 173 Research on Nitrogen Control Technology of High-Pressure Bottle Steel J. Chen 177 Chapter 4: Building Materials and Construction A Novel Technique for Monitoring the W-Beam Guardrails M. Guerrieri and F. Corriere 185 Estimating the Importance Degree of Influence Factors on Concrete Durability Based on Rough Set Theory X.P. Su and H.Y. Sun 191 Prediction Bond Strength between FRP and Concrete Interface by LEFM Method G.S. Tong and S.S. Chen 195 Research on Mining Water-Rich Fly-Ash-Based Filling Material W.X. Chen, F.Y. Li, X.H. Guan, L. Chen and W.B. Nie 201 Research on the History and Compositions of Concrete Z.J. Zhang 207 Supporting Technics of Easily Mudding and Ultrahigh Roadway in Soft Coal Rock Z. Zhang 211
- 14. Advanced Materials Research Vol. 988 c The Technological Study of Surface Permeable Protection Materials for Fair Faced Concrete Y. Zhang, Q.C. Wang and X.J. Su 218 Influence of Limestone Powder on the Hydration of Cement-Steel Slag Composite Binder M.T. Liu, J. Hu and Y.J. Mei 226 Studying on a New Kind of Grouting Material and its Application L.W. Wang, Y.L. Feng, J.L. Li and L.H. Duan 230 The Application of Analytic Hierarchy Process (AHP) in the Evaluation Technology Research for Lock Chamber Walls M.Y. Guo, C.C. Gao and X.L. Yang 234 Chapter 5: Forming and Processing Technologies A Study on the Numerical Simulation Method for the NC Incremental Sectional Forming H. Zhu, W.W. Lin and J.L. Bai 241 Arc Behavior of Dry Hyperbaric Gas Metal Arc Welding K. Li, H.M. Gao and H.C. Li 245 Characteristic of Interface Crack Propagation in Dissimilar Weld Joints W.B. Wang, H. Xue, F.Q. Yang and X.S. Zhou 249 Effect of Milling Parameters on Surface Roughness for High-Speed Milling of Pre-Sintering Zirconia J.W. Liu and X.J. Yang 253 FEM Analysis of Profile Control Capability during Rolling in a 6-High CVC Cold Rolling Mill K.Z. Linghu, Z.Y. Jiang, F. Li, J.W. Zhao, M. Yu and Y.Q. Wang 257 Optimal Design about Parameters of Cooling Pipes in Hot Stamping Die L. Chen, W. Chen, J.D. Li, S.N. Heng and J. Wu 263 Prospect of Thin-Walled Adjusted Pressure Casting Process for Superalloys N.S. Yan, A.P. Dong, J. Zhang, J. Wang and B.D. Sun 268 Study on Controlling Lost Circulation of Pilot Hole in Raise Boring by Using Fuzzy Ball Drilling Fluid J.R. Sun 274 The Rapid Measurement and Reconstruction Research on the Blades in the Grinding Process J. Liu, J. Zhao, X. Yang, L. Zhang and H.Z. Liu 281 Research on Selective Grinding of Yunnan Low-Grade Phosphate Rock F.K. Yan, Q.F. Xiao, T. Xiong, S.K. Ren, R. Guo and Z.Q. Zhao 286 Reason Analysis and Solutions of Low Coiling Temperature at Tail of ZSAC1 Strip during U-Type Cooling Z.M. Zhang, F.Q. Wang, F. Li, S.Z. Wang and X. Jiang 290 The Influence of Cutting Parameters on the Cutting Forces when Milling Invar36 X.W. Zheng, G.F. Ying, J. Lu, N.H. Yang, Y. Chen and Y.C. Fu 296 Comparative Study of Physicochemical Properties of Compound Danshen Powders P.Y. Hu, Y.Y. Gong, G.S. Zhang, Q. Zheng, P.F. Yue, Z.F. Wu and M. Yang 300 Research on the Interference Correction in the CNC Incremental Forming Based on Iterative Algorithm H. Zhu, H.Y. Li and W. Zhang 305 Hull Plate Bending Springback Prediction Based on Artificial Neural Network S.J. Su, Y. Hu, C.F. Wang and B. Liu 309 Chapter 6: Applied Mechanics and Dynamics DEM Analysis of Lateral Ballast Resistance of Sleeper during Dynamic Stability Process under Different Vibration Frequency B. Yan, B. Hu, Y.Y. Huang and T.Y. Zhou 315 Modal Analysis Based on UG and ANSYS for Wide-Format Inkjet Printing Machine Y.Y. Cao, H.Q. Gong and P. Gao 319
- 15. d Material, Mechanical and Manufacturing Engineering II Spatial Error Modeling and Analysis of the Glass Fillet Machine Based on the Multi-Body System Theory S.P. Li, Q. Qiu and Y.L. Yuan 324 The Elastohydrodynamic Lubrication Analysis of Journal Bearing J.Y. Zhang 328 Experimental Study of Dynamic Characteristics and Model Parameter Identification of Tensioner H.Y. Wang, X.K. Zeng and J.Y. Zhao 332 Numerical Research Methodology of Free Oscillations of Geometrically Nonlinear Shell Using the Mixed Finite Element Method L.U. Stupishin and K.E. Nikitin 338 Theoretical Mechanics Analysis of Some Basic Technologies for Billiards Sport R. Zhao 342 Experiments on Effects to Rock Bolt Pretension by Thread Rolling Accuracy L.X. Yan 346 Analysis on Transient Dynamic Load of Planetary Gear Pair X.L. Jiang, S.H. Zhang, Y.X. Jia and H. Zhang 353 Layered Geometric Nonlinear Shallow Shells for Variable Form Investigation L.U. Stupishin and A.G. Kolesnikov 359 Fracture Resistance of Bended Glued Timber Elements with Flaws L.U. Stupishin, V. Kabanov and A. Masalov 363 The Optimal Form of Shallow Shells of Revolution with a Small Flexible Stiffness L.U. Stupishin, S. Emelyanov, M.U. Pereverzev and M.L. Moshkevich 367 Study on Evaluation of High Slope Stability and Countermeasures Based on GEO-SLOPE N.Q. Wang, Q.T. Wang, Q. Pang and Q. Xue 371 Simulation Analysis of the Soft Rock Inclined Shaft Surrounding Rock Control with Different Bolt Support Patterns P.F. Jiang 377 Chapter 7: Bioresearch and Medicine Technologies Effects of Uranium(VI) Stress on Physiological Feature and its Accumulation of Chinese Cabbage L. Xie, W.L. Tang, S.B. Xie, J.S. Wang and Y.J. Liu 385 Research on the Microwave-Assisted Supercritical CO2 Extraction of Alkaloids from Gynura segetum (lour.) merr. Q.F. Lu, L.F. Pan, M. Chen, Y. Qiu and B.H. Xie 390 Application of Solid-Phase Microextraction for the Analysis of Aroma Compounds from Pineapple Fruit C.B. Wei, X.D. Ding, Y.G. Liu, W.F. Zhao and G.M. Sun 397 Natural Play Materials as Motivator for Health Restoration in Paediatric Ward of Nigerian Hospital U.B. Wakawa and I. Bin Said 407 Total and Labile Carbon in Alfisol Soil Amended with Plant Residual and Livestock Manure H. Zhou, W.T. Yu and Y. Zhao 411 A Microfluidic Device for DNA Extraction by ImpetiCbead D.L. Li, X.F. Lv and Y.L. Deng 416 Aptamer Biosensor in Microfluidic Chip for Human Thrombin Detection C.X. Zhang, X.F. Lv, H. Qing and Y.L. Deng 420 Effects of Different Fertilization Regimes on Denitrifying Bacteria in Luvisols Soil Y.G. Xu and W.T. Yu 424 Early Prediction of Urolithiasis Occurrence - An Analyzer Based on Nanotechnology J.F. Xue, C.Y. Tang, L.Q. Deng and J.M. Ouyang 430 Chapter 8: Computation Methods, Advanced Modelling and Design
- 16. Advanced Materials Research Vol. 988 e FSM Based Collaborative Design Oriented Component Agent Model C.M. Su and Z. Li 437 Analysis on Mordern Bamboo-Lamp Design H.P. Liang, F.Y. Qin and N. Qin 441 The Ply Optimum Design of Composites Wind Turbine Blade Based on the Local Stability Y.J. Wang, S.R. Zhu and J.J. Wang 445 Mechanics Characteristic Research of Human Lumbar Spine Based on the Changed Gradient for 3-D Printer B. Zhang, H.Z. Cai, G. Zhou, Y.J. Zhang and J. Zhuang 449 Study on the Chaotic Behavior of Smoke Plumes and Fire Trends F. Yang, J.Y. Pu and X.J. Wu 453 Double Pulse Modulation on Current Ripple Suppression J. Li, J.H. Zhang and W. Gao 457 Nonparametric Control Charts Design and Analysis for Small Lot Production Based on the Moving Average Y.H. Deng, H.P. Zhu, G.J. Zhang, H. Yin and F.M. Liu 461 A Method of Point Cloud Stitching Based on the Mechanical Arm and Laser L. Liu and S.G. Dai 467 Numerical Examples of Variable Three-Node Beam Elements Based on Positional FEM L.Z. Ma, Y.Q. Yan, X.L. Diao and J. Liu 471 Simulation of Particle Impact Drilling Nozzles Based on FLUENT F.S. Ren, R.X. Ma and X.Z. Cheng 475 The Application of Finite Element Method in Calculating Two-Dimensional Heat Conduction in the Ground H. Zhang and J. Zhang 479 Numerical Simulation of Erosion Wear of Liquid-Solid Two-Phase Flow in Sliding Sleeve of Horizontal Well K. Ding, J.M. Li, W.X. Yang, J. Hu and W. Zeng 483 3-Dimensional Localization System Based on Extension of Beacon Nodes and Segmentation of Coordinate Space D.M. Lee, H.C. Lee and Y.H. Kim 489 Infiltration Characteristics of Topsoil in Reclamation Farmland Filled with Yellow River Sediment F. Shao, D. Liu, S. Jiang, Z.Y. Qiao and S. Lin 498 Analytical Study of Cylindrical P-Wave Propagation across Jointed Rock Masses S.B. Chai, J.C. Li, H.B. Li and Y.Q. Liu 502 Chapter 9: Data and Signal Processing, Identification and Recognition Chinese Sentiment Classifier Machine Learning Based on Optimized Information Gain Feature Selection J.T. Shi, H.L. Liu, Y. Xu, J.F. Yan and J.F. Xu 511 Optimization of Signal Intersection with the Combination of VISSIM and SYNCHRO Y.C. Wang 517 The Research on Correction Method of Capacitance Signal Drift for Drop Analysis System Q. Song, S.H. Zhang and M.Y. Qiao 521 Use of the Principal Component Analysis (PCA) to Reduce Data Complexity in Qualitative Research: An Electro-Electronics Case Study F.P. Lopes, A. de Paula Lacerda Santos and N.C. Sotsek 526 A Neutral Framework for Feature Definition and a Generic Algorithm for Feature Recognition D.B. Zeng, S.M. Wan, C.L. Zeng, G.L. Zheng and D.M. Li 530 The Defect Diagnosis of Sheet Drawing on Self-Associate with Memory of Boltzmann Network Z.J. Liu 540 A High Speed and Ultra Long-Haul Radio-Over-Fiber System Employing Dual Photoelectric Arms Coherent Modulation and Optical Duo-Binary Coding G. Li 544
- 17. f Material, Mechanical and Manufacturing Engineering II Finger Vein Identification Based on 2DPCA H. Ma 548 Nondestructive Detection of Soluble Solids Content in Navel Orange Based on GEP Algorithm L.S. Huang, W.X. Yang, Y.B. Liao and Q. Zhong 552 Chapter 10: Mechanical Engineering, Tools and Devices Development of a Powertrain Real-Time Model Based on the Assembly Characteristic L. Xu, D. Wang, R. Guo and H. Guan 559 Energy Consumption Analysis of Pulverizing System in Coal-Fired Power Plant J. Li and J. Wei 564 Fuzzy PID Control of the Integrated System of Electromagnetic Brake and Friction Brake of Car Q. Zhao, R. He and D.H. Hu 568 Research on Diesel Engine Rotate Speed Fluctuation Fuzzy Fault Diagnosis J.K. Xiao and X.L. Lu 576 Research on Effect of Locking Ratio of Limit-Slip Differential on Handling Stability of FSAE Racing Car Y.Z. Cai, J.H. Wang, W.L. Dong and Z.F. Liu 582 Research on Intelligent Shift Strategy of Automatic Transmission G.X. Zhang, M. Li and X. Wei 586 Research on Pump-Controlled Servo Hydraulic Press and its Energy Consumption Experiments H.B. Zheng and Y.S. Sun 590 Simulation of Steering System for a Certain Type of Amphibious Armored Vehicle Based on AMESim L.Q. Duan, L.G. Su and Q. Chen 597 The Prediction of the Maintainability of Armored Vehicle Engine Based on Failure Model Effectiveness Analysis L.J. Zhu and H. Cong 601 The State Assessment of Armored Vehicle Engine Based on Analytic Hierarchy Process and Fuzzy Synthetic Evaluation L.J. Zhu and H. Cong 606 Research of Parametric Design and outside Rearview Checking Method of Passenger Vehicle Y.Y. Xing, B. Yu and F.Q. Yang 611 Multi-Body Dynamics Analysis of V-Type Diesel Engine Crankshaft R.R. Wang, Y.M. Xu and X.B. Teng 617 Megawatt Wind Turbine Hydraulic Brake System Locking Device Modeling and Research Based on AMESim H.F. Tian, L.W. Yan, C.J. Ai and H. Xie 621 The Parameter Performances and Simulations of Nitrogen-Inflating Hydraulic Breaker Based on AMESim Y.W. Cen, L. Wu, X.H. Ye and Y. Ye 625 The Design of Explosion-Proof Machine Based on Single Chip Microcomputer F.W. Jiang and C. Hao 630 A High Speed Radio on Fiber Based on Optical Double-Sidebands via Optical Filter and Optical Phase Modulation G. Li 636 Chapter 11: Control Technology and Automation A Simple and Controllable Gas Control Device for Microfluidic Chips D.L. Li, X.F. Lv and Y.L. Deng 643 Matching on Dynamic Characteristics of Automatic Transmission Fluid with Hydraulic Control System Y.J. Cheng, Y.F. Liu and X.Y. Xu 647
- 18. Advanced Materials Research Vol. 988 g Preventive Maintenance Optimization of Availability for NC Machine G. Lei, C. Deng and B. Sheng 653 The Modeling and Simulation of Digital Lathe Based on OpenGL Y.R. Zhang, H.X. Bi, T.C. Wang and S.J. Li 659 Reliability Analysis for CNC Machining Tools during Early Failure Period W. Chen, B. Jiang and Z.C. Jia 663 Study on the Improved Fuzzy PID Controller of Flywheel Battery in the Micro-Grid X.Y. Li, L.T. Zhang and R. Dong 668 Chapter 12: Industrial Engineering and Information Technologies A Novel Approach for Ontological Representation of Analytic Hierarchy Process Y.X. Liao, E. Rocha Loures, O. Canciglieri and H. Panetto 675 Analysis Improtant Factors Influencing Driver Decision-Making Based on the Principal Component Method J.Y. Li, Q. Xue and J.X. Tong 683 Research on the Influence Factors System of Human Error in Power System J.X. Tang, L.C. Wang, P.J. Shi, Z. Li, S.H. Pang and C.X. Guo 687 Agile Product Development Model Focused on the Telecommunication Service R. Rodrigues Barrionuevo Silva, A. de Paula Lacerda Santos and O. Canciglieri 691 Collaborative Decision of Production Plan and Pricing in Cogeneration System Supply Chain: A Literature Review and Future Research Ideas H.J. Yu and S. Su 695 Study on Awareness and Willingness to Bear Cost for Introduction of Renewable Energy in the Household Sector (in Korea) A. Won and W.H. Hong 702 Design of Detection and Maintenance Platform for Radar Operation Unit Based on PC104 Z.H. Zhang, J. Wei and H. Fu 706 Development of Transmission Line Condition-Based Maintenance System Based on Expert System Y.J. Liu, S.Z. Ji and H.P. Chen 710 An New Approach of Real-Time Traffic Flow Prediction Based on Intelligent Transportation Technology J.Y. Li, Q. Xue and J.D. Liu 715 Informatization and New Urbanization Relationship in China T. Qin 719 Exploration and Practice of Self-Service in University Library - Case Study of Beijing University of Agriculture Library Y.L. Xing and L. Ning 724 The Research Progress of Cluster Based Routing Protocols in Mobile Ad-Hoc Networks J. Wu and X.J. Wang 729 Applications of Industrial Ethernet in Smart Substation: Problems and Solutions Z.J. Ma, J.Y. Zhong, F. Ma, Q.H. Wang and Q.P. Tan 734 Implementation Techniques of Modular BOM in Automobile Flexible Manufacturing J.M. Yao, C.H. Lu and Y.H. Wang 739 Importance Degree of Influencing Factors on Cloud Service Composition Flexibility Based on Bayesian Network K. Zhang and X.G. Xu 745 Production Decisions in Remanufacturing with Uncertain Return and Demand F. Zhang and K.F. Hu 751 Research on High-End Showcase Design Method of China Market - Based on the Reality Project of Kessebohmer High-End Showcase Design C. Liu, X.F. Zhu and C.M. Wu 755 Reducing Bubble Defect on the Outsole Production Process in the Footwear Manufacturing Industry M. Watcharaphassakorn and P.K.D.V. Yarlagadda 759
- 19. CHAPTER 1: Micro/Nano Materials Research
- 20. Electrochemical study of corrosion inhibition on copper In base electrolyte by 1-Phenyl-3-hydroxy-1,2,4-triazole Qi Li, Jian Li, Lingtong Hu, Lei Zhu, Xiao Han, ZhihuaTaoa and Wei Heb School of Microelectronics and Solid-State Electronics, University of Electronic Science and Technology of China, Chengdu 610054 a email:Tzh3595@uestc.edu.cn,b email:Heweiz@uestc.edu.cn Keywords: corrosion; copper; base electrolyte; Polarization curves; EIS Abstract. This paper presents the investigation of 1-Phenyl-3-hydroxy-1,2,4-triazole as a new green Cu corrosion inhibitor for Electronic Circuit Board in the base electrolyte (containing 60ppm chloride ions,0.54M H2SO4 and 0.88M CuSO4).The inhibition action was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS).The results show that the inhibition performance depends on the concentration of the inhibitor and the inhibition efficiency increases with increasing inhibitor concentration. Potentiodynamic polarization studies show that 1-Phenyl-3-hydroxy-1,2,4-triazole acts as the mixed-type inhibitor.The results obtained from EIS measurements are in good agreement with that obtained from potentiodynamic polarization. Introduction Copper is widely applied to the integrated circuit (IC) chips and the printed circuit board (PCB) in eletronic industries due to its excellent electrical property and good thermal conductivity. However, copper is very susceptible to corrosion when long-term in the base electrolyte.The use of the corrosion inhibitor is the most economical and practical way to reduce the corrosion attack of strong electrolyte to the metal material[1].So looking for effective and acceptable corrosion inhibitors instead of toxic inhibitors becomes necessary in the inhibition of copper corrosion in the base electrolyte. Fortunately, 1-Phenyl-3-hydroxy-1,2,4-triazole as pesticide intermediates in agriculture are mass-produced, cheap and eco-friendly. In this paper, polarization curve tests and EIS measurements were used to study the corrosion behavior of copper in base electrolyte with addition of 1-Phenyl-3-hydroxy-1,2,4-triazole as inhibitor. Experimental methods 2.1 Materials and test solution The pure copper rod (99.999%) ,embedded in epoxy resin with a exposed surface area of 0.07cm2 is employed as a working electrode(WE).The WE was abraded with silicon carbide paper (grade P1200), degreased with AR grade ethanol and acetone, and rinsed with double-distilled water before use. The base electrolyte containing 60 ppm chloride ions, 0.54M H2SO4 and 0.8M CuSO4 were prepared by dilution of analytical reagent grade sulfuric acid, hydrochloric acid and copper sulfate pentahydrate with double distilled water. The molecular structure of 1-Phenyl-3-hydroxy-1,2,4-triazole is shown in Fig.1.The concentrations of the inhibitor are 1×10-5 M, 5×10-5 M, 1×10-4 M, 5×10-4 M, 1×10-3 M respectively. Advanced Materials Research Vol. 988 (2014) pp 3-7 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.988.3
- 21. Fig.1 The molecular structure of 1-Phenyl-3-hydroxy-1,2,4-triazole 2.2 Electrochemical experiment The electrochemical measurements were performed in a three-electrode cell with a CHI660D electrochemical system. A platinum electrode was taken as the auxiliary electrode,and saturated calomel electrode (SCE) as the reference electrode. EIS measurement was carried out at the open circuit potential (OCP), prior to the EIS measurement, a steady-state period of 30 min was observed, which proved sufficient for OCP to attain a stable value. The ac frequency range was from 100 kHz to 10 mHz,with a 10 mV peak-to-peak sine wave as the excitation signal. Polarization curve was carried out from -250 to +250 mV(versus OCP) with a scan rate of 0.5 mV/s and the data was collected and analyzed by electrochemical software. The experimental temperature was thermostatically controlled at 293k(±1 K) . Results and discussion 3.1 Polarization curves Fig.2 shows the anodic and cathodic potentiodynamic polarization curves for copper in the base electrolyte with addition of various concentrations of inhabitor at 293K.The electrochemical parameters such as corrosion potential ( Ecorr), corrosion current density (Icorr), anodic and cathodic Tafel slopes (ba, bc) obtained from the polarization curves are listed in Table 1. The inhibition efficiency (η%) was calculated by Eq.1 [2] 100 I I - I % corr inh corr × = η (1) where Icorr and Iinh represent the corrosion current density in the absence and presence of various concentrations of inhabitor in the base electrolyte respectively.From Table 1,it can be seen that the current density in solution using the inhibition decreased considerably compared with that of the blank solution and the inhibition efficiency increased with the concentration of the inhibitor .The highest inhibition efficiency of the inhabitor even reached 97.7% at 10-3 M in the base electrolyte.From Table 1and Fig.2, It can be seen the corrosion inhibitor suppressed both anodic and cathodic reaction.Only as the change in Ecorr value was more than 85 mV, a compound could be recognized as an anodic or a cathodic type inhibitor [3].The largest displacement of Ecorr was lower than 11 mV, so 1-Phenyl-3-hydroxy-1,2,4-triazole should be considered as a mixed-type inhibitor. 4 Material, Mechanical and Manufacturing Engineering II
- 22. Table 1 Polarization parameters and corresponding inhibition efficiencies in the base electrolyte containing various concentrations of inhabitor at 293K -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 -8 -7 -6 -5 -4 -3 -2 -1 log(i/Acm -2 ) EvsSCE/ V a: Blank b: 1*10 -5 M c: 5*10 -5 M d: 1*10 -4 M e: 5*10 -4 M f: 1*10 -3 M f e d a b c Fig.2 Polarization curves for copper in the base electrolyte containing various concentrations of inhabitor at 293K 3.2 Electrochemical impedance spectroscope Fig. 3 shows the Nyquist diagrams for the copper in the base electrolyte in absence and presence of various concentrations of inhabitor at 293 K.The impedance spectra shows that a semicircle and the diameter of semicircle increases with increasing inhibitor concentration which means the impedance values have increased and corrosion was inhibited. It is also clear that these impedance diagrams are not perfect semicircles and this difference has been attributed to frequency dispersion [4] and the heterogeneity of the metal surface[5]. A variety of parameters such as charge-transfer resistance (Rct),double layer capacitance (Cdl) and fmax were obtained from impedance measurements and are shown in Table 2. Rct is calculated from the difference in impedance at lower and higher frequencies, as suggested by Harnyama and Tsuru [6]. To obtain Cdl, the frequency at which the imaginary component of the impedance is maximum (-Zim max), is found and Cdl values are obtained from the Eq.2 [7] Concentration(M) Ecorr (mV SCE) Icorr (µA/cm2 ) Bc (mV/dec) Ba (mV/dec) η% Blank -360 777.4 183.3 164.0 / 1×10-5 -357 404.7 167.0 131.6 47.9 5×10-5 -355 303.6 158.4 137.0 61.0 1×10-4 -354 207.2 168.6 159.7 73.4 5×10-4 -350 36.0 161.0 159.1 95.4 1×10-3 -349 17.6 102.0 396.8 97.7 Advanced Materials Research Vol. 988 5
- 23. ct max dl R 1 f 2 1 c π = (2) where f max is the frequency at which the imaginary component of impedance is maximum and Rct is the diameter of the loop.The inhibition efficiency got from the charge-transfer resistance is calculated by Eq.3 [8] 100 R R - R % ct o ct ct × = η (3) where Rct and Ro ct represent the resistance of charge transfer in the presence and absence of inhibitor, respectively. From Table 2, it can be seen clearly that the Rct values increase and the Cdl values decrease with increasing inhibitor concentration. The decrease in Cdl is due to the adsorption of the inhibitor at metal/solution interface leading to a protective film which decreases the extent of dissolution reaction [9].At the same time, the inhibition efficiency (η%) increases with increasing inhabitor concentration and the highest inhibition efficiency of the inhabitor reached 92.5% at 10-3 M.These results are much consistent with that obtained from polarization curve tests. 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 0 200 400 600 800 1000 Blank 1*10 -5 M 5*10 -5 M 1*10 -4 M 5*10 -4 M 1*10 -3 M -Zim/O cm 2 Zre/Ocm 2 Fig.3 Nyquist diagrams for the copper in the base electrolyte containing various concentrations of inhabitor at 293K. Table 2 Corrosion parameters obtained by impedance measurements for the copper in the base electrolyte containing various concentrations of inhabitor at 293K. Concentration(M) Rct(Ωcm2 ） fmax(Hz) Cdl(µF cm-2 ) η% Blank 196.8 3.83 211.3 / 1×10-5 753.9 1.47 143.7 73.9 5×10-5 856.1 3.16 58.9 77.0 1×10-4 1082.5 2.61 56.4 81.8 5×10-4 2045.0 3.16 24.6 90.4 1×10-3 2627.7 3.83 15.8 92.5 6 Material, Mechanical and Manufacturing Engineering II
- 24. Conclusions Electrochemical study proved that 1-Phenyl-3-hydroxy-1,2,4-triazole is an effective inhibitor for the corrosion of copper of Electronic Circuit Board at the studied temperatures of 293K in the base electrolyte containing 60 ppm chloride ions, 0.54M H2SO4 and 0.8M CuSO4 solution. It can be essentially described as a mixed-type inhibitor.The results show that the inhibition efficiency depends on the concentration of the inhibitor and increase with increasing inhibitor concentration. Acknowledgments The authors gratefully acknowledge the support of Guangdong Innovative Research Team Program (NO. 2013C092) and the Open Foundation of State Key Laboratory of Electronic Thin Films and Integrated Devices (KFJJ201211), and we also express our sincere thanks to the support of “Ph.D Programs Foundation of Ministry of Education of China” (No: 20120185110021). Reference [1] K. Stanly Jacob, GeethaParameswaran, Corros. Sci. 52 (2010) 224–228. [2] Khaled, K.F., 2008. Mater. Chem. Phys. 112, 104–111. [3] Ying Yana, Electrochemical and quantum chemical study of purines as corrosion inhibitors for mild steel in 1M HCl solution[J]. Electrochimica Acta, 2008, 53: 5953-5960. [4] Mansfeld, F., Kending, M.W., Tsai, S., 1982. Corrosion 38, 570. [5] Pajkosay, T., 1994. J. Electroanal. Chem. 364, 111 [6] T. Tsuru, S. Haruyama, B. Gijutsu, J. Jpn. Soc. Corros. Eng. 27 (1978) 573. [7] Ross Macdonald, J., 1987. Impedance Spectroscopy. John Wiley and Sons. [8] Abd El-Rehim, S.S., Ibrahim, Magdy A.M., Khaled, K.F., 1999. J.Appl. Electrochem. 29, 593–599. [9] F. Bentiss, M. Traisnel, M. Lagrenée, Corros. Sci. 42 (2000) 127. Advanced Materials Research Vol. 988 7
- 25. Exploration for Identification of Sheath-Core Fiber of Ploymer Ruitian Zhu1 a , Peng Zhang1 , Fengming Nie1 1 .Guangzhou Fibre Product Testing and Research Institute, Guangzhou, 510220, China a zhurt@gtt.net.cn Key words: sheath-core; fiber; polymer; identification Abstract: In this paper, microscopic method, transmission technique and attenuated total reflection method of infrared spectroscopy and differential scanning calorimetry were investigated for analyzing the component of inner and outer layer of sheath-core polymer fiber. Results showed that transmission technique and attenuated total reflection method of infrared spectroscopy was a quick and accurate method for identification of sheath-core fiber of fiber. Introduction Conventional chemical fibers have many advantages, but also have some drawbacks, such as polypropylene fiber has good property of processing and tensile strength but with poor moisture absorption, nylon fiber has good abrasion performance and high strength but with inferior resistance to heat and light. With the difference of inner layer and outer layer materials, bicomponent polymer fibers with sheath-core structure are provided with some special performances, such as three-dimensional crimp structure, the advantages of both of the two components. Such functional fibers, now get applications in many fields, such as surface materials of sanitary napkins, diapers and other hygiene materials, whose difference of thermal response behavior of the inner and outer layer result in a three-dimensional crimp state, and the fiber web can be reinforced at a relatively lower temperature because of the lower melt point of sheath material, forming loose, soft nonwoven fabrics with a certain strength. Generally, price of sheath-core fiber is higher than conventional fiber, and the price of sheath-core fibers of different components is far away from each other. Currently, there are some suppliers sell shoddy, fake sheath-core fibers, which seriously disrupts the market order. So far, there are some common testing methods for identification of fiber component, like chemical dissolution method, thermal analysis method and transmission infrared spectroscopy method[1] . Chemical dissolution method only applies to the case that the inner and outer layer material have different solubility and could not be dissolved at the same time. Thermal analysis method usually adopts differential scanning calorimetry device to measure melting point of the two components of sheath-core fiber, which can only be used for preliminary judgment of the two components, but not for differentiating the inner and outer component. For the low melting point modified fibers (such as low melting point polyester), and the result of thermal analysis method is less reliable. Similarly, transmission infrared spectroscopy method could be take for judging the two kinds of material without distinguishing the inner and outer components, by KBr disc technique or the method of dissolving and casting films. Therefore, the establishment of a method for rapid accurate identification of sheath-core fiber of polymer, is helpful for regulating the market, and will promote research and development of sheath-core structure bicomponent polymer fibers. In this paper, microscopic method, transmission Advanced Materials Research Vol. 988 (2014) pp 8-12 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.988.8
- 26. technique and attenuated total reflection method of infrared spectroscopy were investigated for identification of sheath-core polymer fiber. Experiment 2.1 Sample The sample used in this investigation was sheath-core fiber from Guangzhou ES Fiber Co., Ltd. 2.2 Microscopic method[2] The picture of cross-section of sample was obtained by the fiber slicer (Model Y172) manufactured by Changzhou the Second Textile Machines Co., Ltd., and observed under micro scope (Model BX51TF) manufactured by Olympus Optical Co., Ltd. of Japan. 2.3 Infrared spectroscopy test 2.3.1 Attenuated total reflection method (ATR) After being put in the infrared drying oven about 30 to 50 seconds, A suitable amount of fiber bundle was placed on the crystal of multiple-reflection accessory of the infrared spectrometer (Model Nicolet 6700) manufactured by Thermo Fisher Scientific Inc., completely covering the crystal. Parameters were set as scan range for 400 ~ 4000 cm-1 , resolution for 2 cm-1 , scan times for 32, the Angle of incidence adjusted from big to small, like 50°, 40°, 30°. A series of infrared spectra were obtained[3] . 2.3.2 Transmission infrared spectroscopy test A suitable amount of representative fiber was took in the fiber slicer, being cut into 10 to 30 micrometer long fiber powder. 80-120 mg potassium bromide and 2.0-5.0 mg fiber powder were blended and powdered in the agate mortar for 2 minutes. After being dried for 30-50s, the blends were moved to the tabletting mould to produce a transparent disc. The disc was installed in the transmission accessory of the infrared spectrometer. Parameters were set as scan range for 400 ~ 4000 cm-1 , resolution for 2 cm-1 , scan times for 32, then started scanning and a infrared spectra obtained. 2.4 Test of differential scanning calorimetry (DSC) 5.0-10.0 mg sample was analyzed in nitrogen atmosphere in differential scanning calorimeter (Model DSC 204 F1) manufactured by NETZSCH-Gerätebau GmbH to determine the melt point. The sample was first heated up from 25˚˚C to 280˚C at 10˚C/min, then cooled to 25˚C at 10˚C/min (to eliminate thermal history of sample), last heated up again to 280˚C at 10˚C/min[4] . Results and discussion 3.1 Observation of cross-section of fiber The cross-section of sample is shown as Fig. 1. Obviously, the fibers were spun by composite spinning method and made up of sheath and core. The demarcation between sheath layer and core layer was to be clearly defined. There were lots of small black spots in the core layer, but no in the sheath layer. Advanced Materials Research Vol. 988 9
- 27. Fig.1 Pictures of cross-section of sample 3.2 Testing of infrared spectroscopy Reflection and transmission infrared spectrograms of the sample are shown as Fig.2 and Fig. 3. 500 1000 1500 2000 2500 3000 3500 4000 0.00 0.04 0.08 0.12 angle of incidence 40° ° ° ° angle of incidence 50° ° ° ° angle of incidence 30° ° ° ° Absorbance Wave number / cm-1 Fig.2 Reflection infrared spectrogram of the sample with different incident angles 500 1000 1500 2000 2500 3000 3500 4000 0.0 0.1 0.2 0.3 0.4 Absorbance Wave number / cm-1 Fig.3 Transmission infrared spectrogram of the sample 10 Material, Mechanical and Manufacturing Engineering II
- 28. From Fig. 2 we can see that, with the angle of incidence from 50°to 30°, the characteristic peaks of the spectrogram are rising, such as the homologous rocking vibration absorption peak of methylene (-CH2-) at 720 cm-1 and 731 cm-1 , the homologous bending vibration absorption peak of C-H bond at 1470 cm-1 , the homologous stretching vibration absorption peak of C-H bond at 2865 cm-1 and 2920 cm-1 . According to these characteristic absorption peaks, the outer material of the fiber can be determined for polyethylene (PE). In Fig.3, besides the characteristic peaks as shown in Fig. 2, there are also the band characteristic peak of regularity of the conformation at 972 cm-1 and 998 cm-1 , the homologous stretching vibration absorption peak of C-C bond at 1168 cm-1 , the homologous bending vibration absorption peak of methyl (-CH3) at 1360 cm-1 . And the stretching vibration multi- absorption peak band at 2800 cm-1 to 3000 cm-1 is covered by the stretching vibration absorption peak of C-H bond of polyethylene. Therefore, we can judge that the inner layer of the sheath-core bicomponent fiber is polypropylene (PP). 3.3 Verification by DSC Thermal properties of sample were studied by differential scanning calorimetry (DSC) as is shown in Fig. 4. There were two components of the fiber with the melt points of 130.1℃ and 163.4℃, from which we can conclude that the fiber consists of polyethylene and polypropylene. 50 100 150 200 250 300 0.4 0.8 1.2 1.6 2.0 163.4℃ ℃ ℃ ℃ DSC / (mW/mg) Temperature / ℃ ℃ ℃ ℃ 130.1℃ ℃ ℃ ℃ Fig. 4 Melt point of the sample Summary Combining ATR and transmission IR, the components of sheath-core fiber can be easily judged. And the result could be verified by DSC. Consequently, transmission technique and attenuated total reflection method of infrared spectroscopy is a quick and accurate method for identification of sheath-core fiber of fiber. Advanced Materials Research Vol. 988 11
- 29. Reference: [1] FZ/T 01057.8-2012 Test Method for Identification of Textile Fibres-Part 8: Infrared Absorption Spectrum [2] FZ/T 01057.3-2007 Test Method for Identification of Textile Fibers-Part3: Microscopy [3] GB/T 6040-2002 General Rules for Infrared Analysis [4] ISO 11357-3-2011 Plastics -- Differential Scanning Calorimetry (DSC) -- Part 3: Determination of Temperature and Enthalpy of Melting and Crystallization 12 Material, Mechanical and Manufacturing Engineering II
- 30. Mechanical and thermal properties of phenolic foams reinforced by hollow glass beads Yuxin Zuo1, a , Zhengjun Yao1,b and Jintang Zhou1,c 1 College of Materials and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 211100, China a zuoyuxin1314@sina.com, b yaozj@nuaa.com, c imzjt@126.com Keywords: Hollow glass bead, phenolic foam, thermal performance, mechanical behavior Abstract. Hollow glass beads / phenolic foam composites were prepared by molding method. The influence of HGB on thermal performance and mechanical properties of phenolic foams were investigated using thermal conductivity measurement, thermogravimetric analysis (TGA) and compression tester. The results show that the addition of hollow glass beads lead to a significant improvement in the compressive property of phenolic foams, with the compressive strength reaching the maximum adding 10% HGB and HGB pretreated by silicane coupling agent further enhance the compressive property. FT-IR spectroscopy shows the reaction between alcohol -OH groups on the surface of HGB and methoxy (-OCH3) groups on silane coupling agent (KH560). The morphology indicates the average cell size decreases with HGB content increasing up to 10%, and again the cell size of foams reinforced by pretreated HGB are better. Addition of HGB improved the thermal stability property of phenolic foams, due to the porosity was mainly responsible for thermal conductivity property of phenolic foams, so HGB filled materials achieved higher thermal conductivity. Introduction Microcellular materials are widely used in thermal insulation, energy absorption and structural uses due to their unique properties, such as light weight, thermal and acoustic insulation, impact damping and so on [1]. Phenolic resins are synthetic polymers in that their backbone is composed of an “organic” repeating unit, that is, the aromatic ring. In addition, the s aromatic rings are connected by organic groups, such as methylene. The presence of the aromatic ring and methylene units gives phenolic their unique properties and thermal and chemical stability[2]. So far, many efforts have been done to improve thermal properties[3-6] and mechanical properties[7-9], fire-resistant properties [10, 11]of phenolic. Also photo-induced mechanical actuation is observed when exposed to infrared radiation. In recent years, silica filled phenolic foams have been proverbially studied[1]. Since silica filled phenolic have presented outstanding properties for many respects, it might be the first choice for most cases. Nevertheless, silica has passive effects on the foaming process and result in much worse thermal properties. That is to say, silica filled phenolic foams don’t prove to be a lightweight and heat insulation composite. Hollow glass bead (HGB) is a rigid porous bead containing inert gas. The main chemical constitution is silicate like silica. The hollow core endows HGB good thermal properties and lightweight properties[12]. In virtue of these characters, HGB was broadly used to fabricate syntactic foams. In addition, these micro-particles do not generate important stress concentration at the interface with the matrix owing to their smooth spherical surface. Previous attempts of HGB mostly focused on polyurethane for damping materials[5], polypropylene materials[13, 14] for automotive applications, epoxy resin materials[15] for adhesive glue. Nikhil Gupta [16] reported that with the increasing content of hollow glass bead the size of cell was reduced, and the compress strength of syntactic foam was effectively enhanced. Wang[5] also proved that modified HGB improved mechanical properties of epoxy resin composites. However, HGB filled phenolic foams have not been Advanced Materials Research Vol. 988 (2014) pp 13-22 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.988.13
- 31. studied yet. Compared with silica, HGB is a filler with similar chemical constitutions, but with inert gas in its hollow structure the thermal properties of phenolic foams may be remained. In this paper, hollow glass beads/phenolic foam composites were prepared by molding method. Mechanical tests were taken to compare the performance change of phenolic foams after reinforcement. Thermal Constant Analyzer and thermogravimetric analysis (TGA) were employed to study the thermal conductivity and thermal stability in order to infer the influence of HGB on thermal performance of phenolic foams. Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopes (SEM) were performed to investigate the interaction between HGB and phenolic foams. Materials and methods 2.1. Materials Resoles (W=85%; 2, 000 mPas to 3,000 mPas) were prepared under alkaline condition. The molar ratio of phenol to formaldehyde was 1:1.5. Silicone oil, n-pentane and phosphoric acid supplied by Sinopharm Chemical Reagent are used as the surfactant, foaming agent and curing agent respectively. The hollow glass beads supplied by 3 M India are used as reinforcement. The silane coupling agent (KH550) manufactured by Shuguang Chemical Plant Nanjing are used as the reagent with which the HGB were pretreated. 2.2. Composition and foam preparation Table. 1. Components of the samples used in this paper Samples 1 2 3 4 5 6 7 Resoles (g) 100 100 100 100 100 100 100 Silicone oil (g) 4 4 4 4 4 4 4 n-pentane (g) 8 8 8 8 8 8 8 Phosphoric acid (g) 6 6 6 6 6 6 6 HGB (g) 0 5 10 15 0 0 0 Pretreated HGB (g) 0 0 0 0 5 10 15 The phenolic compounds were mixed with ingredients according to Table1. The silicone oil as the surfactant was first blended into the phenolic resoles resin, stirring for 10 min to ensure good dispersion. For the subsequent incorporation of fillers HGB, mixing was continued for another 15 min to ensure the homogenous dispersion of ingredients in the matrix. The blowing agent was blended into the compounds along with the filler for good dispersion. The curing agent phosphoric acid was added finally. After compounding, the sheeted phenolic compounds were infused into the mould at room temperature. The foaming and curing processes were carried out simultaneously in a heated press at 90°C under pressure 10 MPa till optimum curing time. 2.3. FT-IR spectroscopy FT-IR spectroscopy is well established as methods of vibrational spectroscopy and has been used for decades as a method for the identification and characterization of polymeric materials. In this paper it was used to obtain the information about the interactions between HGB and silane coupling agent. FT-IR spectra were measured in the range 4000-500 cm−1 . 2.4. Microstructure A JSM-5800 scanning electron microscope (SEM) was employed to observe the cell size, cell structure, ratio of open-to-closed cell units and the dispersion of the HGB. The operation voltage of the SEM was 20 kV. 14 Material, Mechanical and Manufacturing Engineering II
- 32. 2.5. Compressive test Compression testing was performed in accordance with ISO 844:2004. Specimens (50mm×50mm×30mm) were compressed between two stainless steel platens, and load was applied with a crosshead speed of 3.0 mm/min. Compressive strength was determined from the maximum load. The results are based on an average of four tests. 2.6. Thermal conductivity measurement The thermal conductivity of the foams were determined by a Thermal Constant Analyser (2500, Hot Disk, Sweden). Specimens with a diameter of 30 mm and a thickness of 3–4 mm were used for testing. 2.7 Thermogravimetric analysis TG/DTG curves of the films were obtained by Shimadzu TGA-50 thermogravimetric instrument in nitrogen atmosphere. The temperature range was ranged from 30 to 800 °C with a ramp rate of 20°C/min. Results and discussion 3.1. FT-IR spectroscopy OH + Si OCH3 OCH3 H3CO O O CH2 + HO HO O HGB Silane coupling agent KH560 Phenolic resin O Si OCH3 OCH3 O CH O OH O HO O O Fig. 1. Schematic process of chemical reaction between the HGB and coupling agent. The interface between the filler and the binder plays an important role in the mechanical properties of the syntactic foam. Fig.1. illustrates the interfacial reaction between the HGB and the phenolic resin with the presence of silane coupling agent. The hydroxyl functional group was generated on the surface of the HGB. The silane coupling agent kh560, used in this study has three functional methoxy groups and one epoxy group at each ends of the molecules. The methoxy group can react with hydroxyl group which is on the surface of HGB to form silicon oxygen linkage. The epoxy group will react with phenolic resin monomers and form hemiacetal linkage with resin matrix. The formation of silicon oxygen linkage and hemiacetal linkage by the silane coupling agent kh560 results in strong adhesion between HGB and phenolic resin matrix. The FTIR spectra of HGB and pretreated HGB are illustrated in Fig. 2. As shown in Fig. 2, the four bands appearing at 3440 cm−1 , 1073 cm−1 , 792cm−1 , and 463cm−1 correspond to the O–H, Si-O-Si antisymmetric and symmetrical stretching vibrations, and bending vibration of Si-O-Si on the surface of HGB respectively. The Advanced Materials Research Vol. 988 15
- 33. 4000 3500 3000 2500 2000 1500 1000 500 C H C H 2 O Si-O-Si(792) Transmittance Wave number (cm -1 ) pretreated HGB (a) HGB (b) O-H (3440) Si-O-Si (1073) Si-O-Si(463) (a) (b) -CH3 (2973) (908) Fig.2. Fourier Transform Infrared (FTIR) spectra of hollow glass bead: (a) pretreated HGB; (b) HGB. FTIR spectrum of the pretreated HGB is presented in Fig. 2a. It is observed that the stretching vibrations peak of -CH3 at 2973 cm−1 and the asymmetric stretching vibrations peak of epoxy group at 908 cm−1 can not find in Fig.2b. This reveals that the coupling agent reacts with the –OH groups on the surface of HGB to form silicon oxygen linkages. The remaining functional group on the coupling agent will react with the phenolic resin binder to form a cross-linking structure. 3.2. Morphology (a) (b) Fig. 3. SEM images of the adhesion of HGB with phenolic foam: (a) HGB without coupling agent. (b) pretreated HGB with silane coupling agent. SEM studies demonstrate aspects of HGB bonding and the distribution of cell sizes. The interaction between matrix and HGB is shown in Fig. 3(a). In this case, Hollow glass beads (HGBs) are visible adhering to the composite, where the protruding HGB surfaces are relatively clean, with little adhering matrix material. Hollow glass beads (HGB) are dispersed and situated in the junctions of the foam. From this we can conclude that the wettability of the phenolic on HGB exists, although bonding was not particularly strong. On the other hand, the pretreated HGB shown in Fig.3(b) are HGB 16 Material, Mechanical and Manufacturing Engineering II
- 34. coated with adhering phenolic, indicating good wetting and good adhesion. These factors, combined with the mechanism of micropeel, undoubtedly contribute to the observed property enhancements. (a) (b) (c) (d) (e) (f) Advanced Materials Research Vol. 988 17
- 35. (g) Fig. 4. SEM images: (a) 5 wt.% HGB reinforced phenolic foam, (b) 5 wt.% pretreated HGB reinforced phenolic foam, (c) 10 wt.% HGB reinforced phenolic foam, (d) 10 wt.% pretreated HGB reinforced phenolic foam, (e) 15 wt.% HGB reinforced phenolic foam,(f) 15 wt.% pretreated HGB reinforced phenolic foam, and (g) unreinforced phenolic foam. The distributions of cell sizes of the different foams are measured from SEM images of the composites, and the results are summarized in Fig. 4. Pretreated HGB additions of various amounts yield cell size distributions in the composite foams that are different from each other and from the unreinforced foam. For instance, the average cell diameter in the phenolic foam reinforced with 5 wt.% HGB is 0.262mm, while the average cell diameter in the phenolic foam reinforced with 5 wt.% pretreated HGB is 0.194 mm, almost one third smaller. The unreinforced foam exhibited an average cell size 0.291 mm. It is clear that the cell sizes of foam decrease at first then reach the minimum, and increase as the content of hollow glass beads improves from 0 to 15 wt.%. The phenolic foam with 10 wt.% pretreated HGB exhibits the smallest cell size (0.138mm). The different mean cell sizes constitute an underlying cause of the observed compressive properties of the composite foams. Finer cell sizes, as shown in the pretreated HGB composite foams, translate into enhanced compression strength and modulus. 3.3. Compressive strength 0 5 10 15 0.0 0.4 0.8 1.2 1.6 Compressive Strength (MPa) Wt% hollow glass beads pretreated HGB HGB Fig. 5. Compressive strength of phenolic foams with different contents of hollow glass beads. 18 Material, Mechanical and Manufacturing Engineering II
- 36. Fig. 5 plots compressive strength as a function of HGB weight percent. It is clear that the compressive strength increases at first and then decreases with the increasing content of hollow glass beads. The compressive strength of phenolic foams with less than 15 wt.% hollow glass beads is higher than the unreinforced counterpart. The phenolic foam with 10 wt.% hollow glass beads exhibits the highest compressive strength, and the compressive strength of the foams filled by pretreated HGB (1.5MPa) are better than the foams filled by HGB (1.03MPa). It is stronger that the binding strength between HGB and matrix is in the pretreated HGB than the unreinforced counterpart. The hollow glass beads locating in the junctions (Fig. 3) stop the propagation of the cracks, by which the foams are strengthening. What’s more, the addition of HGB developing much higher compressive strength greatly improves the bearing capacity of the whole phenolic foams. When the filler is more than 10 wt%, the compressive strength will reduce. This can be ascribed to the following reasons. First, it is well known that the strength of the phenolic foams depends on the foam structure. Both cell edges and cell faces play important roles in bearing the external load. However, when the content of hollow glass beads exceed 10 wt%, much more cell openings in the cell walls appear, compared with the foam with only 10 wt% microspheres. Thus the cell structure is further broken and the foam exhibits lower compressive strength. Secondly, since phenolic foams are made from liquid resin, surface tension can draw the material into the cell edges. The solid distribution in phenolic foam structure is non-uniform, and the reuniting of HGB appear when the amount of HGB increases to 15%, which leads to the decrease of compressive strength. 3.4. Thermal conductivity Polymeric foams are thermal insulation materials. Indeed, these microcells of the material restrain the heat transfer, maintain a constant temperature and reducing the heat loss. To study thermal insulation materials, the effective thermal conductivity is an important heat transfer property of the materials. The lower thermal conductivity is, the better insulation capability is presented. However, the heat transfer process of porous materials is very complicated, especially for polymer composites. Our findings of thermal conductivity are mainly focused on the chain of causality between thermal conductivity and microstructure of the materials. 0 5% 10% 15% 0.300 0.305 0.310 0.315 0.320 0.325 0.330 Thermal conductivity ( W m -1 K -1 ) wt% Hollow Glass Beads Fig. 6. Thermal conductivity of phenolic foams with different HGB contents. Fig. 6 shows thermal conductivity of phenolic foams with different HGB contents. It can be seen that the thermal conductivity increases with higher filler content at first. The thermal conductivity is maximum (0.330Wm−1 K−1 ) when the filler content reach 10%, then it changes little with higher filler Advanced Materials Research Vol. 988 19
- 37. content. Although HGB has positive effects on reducing the thermal conductivity, as a foam material, the porosity which reflected the foaming extent is mainly responsible for thermal insulation property. This statement could be substantiated by SEM images of HGB filled phenolic foams with different content (Fig.4). These results showed that higher content filled materials produced a lower porosity up to 10% content. For the structure of HGB and the content of HGB influence on foaming process make the porosity not reduce forever, the thermal conductivity was much higher for higher HGB content before the content more than 10%. Because the thermal insulation property of their composites mainly relied on the hollow structure of HGB instead of the foaming process, the effects of HGB on morphology of the composites were eliminated. 3.5. Thermal stability Fig. 7. TGA thermograms for unreinforced phenolic foam and HGB reinforced phenolic foam. Thermogravimetric analyses were performed to determine the influence of the content of HGB on the thermal stability of HGB-reinforced phenolic foams. Fig. 7 displays a typical TGA curves for the unreinforced phenolic foam and foams containing varying HGB contents. The profiles of foam weight loss exhibit three steps, which include (a) the initial temperature (Ti), (b) temperature of maximum peak (Tp), and (c), the final temperature (Tf). Different stages of the thermal degradation process (stages 1st and 2nd) are shown in Fig. 6. The first step (at initial temperature Ti = 30°C ) represents the postcuring process of the polymeric foam. The second step, as shown in Fig. 6, results in burned fragments of foam in the range 240–400 °C (first stage of thermal degradation). This step can be observed in two stages, which indicate a complex degradation mechanism. The final step (at ~540°C ) involves degradation of aromatic groups in the polymeric foam (second stage of the degradation process). Specimens reinforced with HGB exhibit higher thermal stability than the other foam samples studied. This is shown in Fig. 7, where the thermal degradation of HGB-reinforced phenolic foams is slow, and the ash content is greater than the other foams. When 5% or more HGB was incorporated into the foams, the thermal stability improved due to the thermal insulation property of hollow glass bead. The unreinforced phenolic foams show less thermal stability than HGB-reinforced phenolic foams. For instance, the unreinforced phenolic foams (Fig. 6) show a loss of humidity ~2wt.% in the range 30–100°C , while HGB-reinforced phenolic foams are less 1wt.% of water absorption. In addition, the thermal degradation of unreinforced phenolic foams produces a final ash content of ~55 Temperature(°C) 20 Material, Mechanical and Manufacturing Engineering II
- 38. wt.%. However, the thermal degradation of HGB-reinforced phenolic foams produces a final ash content more than 62 wt.%. To conclude, utilization of HGB produces foams with superior thermal stability. Conclusions Mechanical and thermal performance of phenolic foams reinforced by hollow glass beads was determined and discussed by comparing with raw phenolic foams. The significant results were as follows: FT-IR spectroscopy shows that condensation reaction happened between alcohol -OH groups on the surface of HGB and methoxy (-OCH3) groups on silane coupling agent (KH560). SEM images display the microstructure and morphology of HGB filled phenolic foams. The average cell size decreased with higher HGB content until the HGB content reaches 10%, and the cell size of foams reinforced by pretreated HGB are better than the foams reinforced by HGB. The results could be explained by nucleation and gas diffusion. From images of higher resolution, we concluded that pretreated HGB had a better adhesion with the matrix. The compressive strength increases along with the hollow glass beads content up to 10%, and the compressive strength of phenolic foams filled by pretreated HGB is better than filled by HGB. The lowest thermal conductivity of HGB filled phenolic foams was 0.307 Wm−1 k−1 . And the thermal conductivity increased with higher filler content until the filler content reaches 10%. The results could be explained in that the porosity was mainly responsible for thermal conductivity property of phenolic foams, resulting that HGB filled materials achieved higher thermal conductivity. The thermal stability studied by TGA, shows that the residue rate of phenolic foam were improved 8.3%, and the thermal degradation of HGB-reinforced phenolic foams is slower. Therefore the thermal stability property of phenolic foams were improved with the HGB filled materials. Acknowledgements This work is supported by “The Fundamental Research Funds for the Central Universities”, NO.NZ2013307. References [1]. Gao, J., et al., Preparation and properties of hollow glass bead filled silicone rubber foams with low thermal conductivity. Materials & Design, 2013: p. 491–496. [2]. Wu, X., et al., Preparation and characterization of carbon foams derived from aluminosilicate and phenolic resin. Carbon, 2011. 49(5): p. 1782–1786. [3]. Wu, X., et al., Effect of final pyrolysis temperature on the mechanical and thermal properties of carbon foams reinforced by aluminosilicate. Materials Science and Engineering: A, 2012: p. 446–450. [4]. Luo, R., et al., The mechanical and thermal insulating properties of resin-derived carbon foams reinforced by K2Ti6O13 whiskers. Materials Science and Engineering: A, 2011. 528(4–5): p. 2023–2027. [5]. Wang, T., et al., Damping analysis of polyurethane/epoxy graft interpenetrating polymer network composites filled with short carbon fiber and micro hollow glass bead. Materials & Design, 2010. 31(8): p. 3810–3815. [6]. Zhou, J., et al., Thermomechanical analyses of phenolic foam reinforced with glass fiber mat. Materials & Design, 2013: p. 131–135. Advanced Materials Research Vol. 988 21
- 39. [7]. Alonso, M.V., M.L. Auad and S. Nutt, Short-fiber-reinforced epoxy foams. Composites Part A: Applied Science and Manufacturing, 2006. 37(11): p. 1952–1960. [8]. Shen, H. and S. Nutt, Mechanical characterization of short fiber reinforced phenolic foam. Composites Part A: Applied Science and Manufacturing, 2003. 34(9): p. 899–906. [9]. Shen, H., A.J. Lavoie and S.R. Nutt, Enhanced peel resistance of fiber reinforced phenolic foams. Composites Part A: Applied Science and Manufacturing, 2003. 34(10): p. 941–948. [10]. Feih, S., et al., Influence of water content on failure of phenolic composites in fire. Polymer Degradation and Stability, 2008. 93(2): p. 376–382. [11]. Gunen, Y., A. Misirli and R. Gulcan, Leaf phenolic content of pear cultivars resistant or susceptible to fire blight. Scientia Horticulturae, 2005. 105(2): p. 213–221. [12]. Li, J., X. Luo and X. Lin, Preparation and characterization of hollow glass microsphere reinforced poly(butylene succinate) composites. Materials & Design, 2013: p. 902–909. [13]. Liang, J.Z. and F.H. Li, Simulation of heat transfer in hollow-glass-bead-filled polypropylene composites by finite element method. Polymer Testing, 2007. 26(3): p. 419–424. [14]. Liang, J.Z. and F.H. Li, Measurement of thermal conductivity of hollow glass-bead-filled polypropylene composites. Polymer Testing, 2006. 25(4): p. 527–531. [15]. Swetha, C. and R. Kumar, Quasi-static uni-axial compression behaviour of hollow glass microspheres/epoxy based syntactic foams. Materials & Design, 2011. 32(8–9): p. 4152–4163. [16]. Gupta, N., E. Woldesenbet and P. Mensah, Compression properties of syntactic foams: effect of cenosphere radius ratio and specimen aspect ratio. Composites Part A: Applied Science and Manufacturing, 2004. 35(1): p. 103–111. 22 Material, Mechanical and Manufacturing Engineering II
- 40. Monolithic macroporous-mesoporous carbon using ionic liquids as carbon source Aibing Chen*, Yunhong Yu, Yifeng Yu, Haijun Lv, Tingting Xing, Yuetong Li, Wenwei Zang College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Yuhua Road 70, Shijiazhuang 050018, China Email: kdchenab@163.com Keywords: ionic liquid, monolithic, macroporous-mesoporous carbon Abstract. A facile approach is employed for the preparation of hierarchically porous structures monolithic ordered macroporous-mesoporous silica materials (OMS) using the commercially available and cheap polyurethane (PU) foam as monolithic template, triblock copolymer P123 (EO20PO70EO20) as structure-directing agent and tetraethyl orthosilicate (TEOS) as silica source, then monolithic ordered macro porous-mesoporous carbon materials (OMC) is synthesized by using monolithic ordered macroporous-mesoporous silica materials as hard template and ionic liquids as the carbon source. The silica and carbon monoliths possess uniform pore sizes (3.74-3.84 nm) and ordered mesostructure. Introduction Mesoporous carbons with hierarchically porous structures and high surface area are required for practical applications in adsorption and separation [1,2]. Compared with powdered carbons, the monolithic carbons have a certain size, shape, and high mechanical strength, which are easy to recycle and stored [3]. There are a lot of methods to synthesize monolithic carbons. The template method has attracted more attention. Generally, the template method can be classified hard and soft template. The hard template for the fabrication of mesoporous carbons can avoid the organic template agent and precursor of hydrolysis condensation copolymerization process. And the selection of carbon sources is widespread, such as phenolic resin, furfuryl alcohol, ethylene, mesophase pitch, etc. Guo et al. synthesized ordered mesoporous carbons whose the pore surfaces were modified and functionalized using ordered silica as hard template[4]. Kim et al. reported direct synthesis of uniform mesoporous carbons from the carbonization of as-synthesized silica/triblock copolymer nanocomposites [5]. Yang et al. described the preparation of controllable morphology and nitrogen-doped porous graphitic carbons using cheap nano-CaCO3 as template. The materials with several unique characteristics promised for potential applications in material science [6]. Recently, ionic liquids (ILs) as carbon source for the synthesis of mesoporous carbons have made remarkable progress in the field of sorption and adsorption due to high carbonization yields and heteroatom doping, such as N and S. Our team reported the mesoporous structure onion-like carbon monoliths materials are obtained by employing ILs as carbon source [7]. At the same time, nitrogen-doping hollow carbon spheres with uniform in size and shell thickness can be adjusted which are synthesized by using the monodisperse silica spheres as hard template [8]. Wohlgemuth et al. reported two co-monomers, S-(2-thienyl)-L-cysteine (TC) and 2-thienyl carboxaldehyde, by one-pot method to form nitrogen and sulfur dual doped carbon aerogels [9]. Dai et al. reported the preparation of monolithic carbon materials using monolithic silica gels as hard template, [Bmim][NTf2] as caron source. The silica template was eliminated by dissolving in HF to obtain the carbons, but the carbons have partial collapse [10]. Advanced Materials Research Vol. 988 (2014) pp 23-26 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.988.23
- 41. In this paper, the hierarchically porous monolith carbon materials were synthesized by wet impregnation method using the monolith mesoporous-macroporous silica as the hard template and the ionic liquids as the carbon precursors. In contrast to the other carbons, the monolithic carbons possessed unique mechanical properties which kept the complete monolithic after carbonization and removal of the template. Experimental 2.1 Synthesis of ordered monolithic macroporous-mesoporous silica materials In a typical procedure, Pluronic P123 (1.0 g) was dissolved in 0.2 M HCl (1.0 g) and ethanol (10 g), and stirred over 2 h to afford a clear solution. TEOS (2.08 g) was then added to the solution and continuous stirred over 3 h to get a homogeneous solution. To put 0.5 ml of the obtained homogeneous solution coat onto polyurethane (PU) foam with a total volume of 2.5 cm3 . Put it in the drafty closet for 5-8 h to evaporate the solvent at room temperature, and in the oven for 24 h for thermopolymerization at 100 ˚C. Finally, the sample was calcinated at 550 ˚C for 6 h under ambient atmosphere, followed to the synthesis of ordered monolithic macroporous-mesoporous silica materials that was named as OMS. 2.2 Synthesis of ordered monolithic macroporous-mesoporous carbon materials 0.4 g 1 - acetonitrile-3 - methylimidazolium chloride was dissolved in 0.5 ml ethanol and stirred to afford clear solution, the clear solution was coated onto the OMS. It took 8 h to evaporate the solvent at room temperature, and then was calcined under N2 atmosphere at 500 ˚C for 1 h. Then 0.15 g of the above solution was coated onto the sample again, it would be calcined under N2 atmosphere at 800 ˚C when the solvent was evaporated completely. To recover the monolith macroporous-mesoporous composite carbon material, the silica templates were dissolved and removed by 2 M NaOH solution. Results and Discussion 200 400 600 800 0 20 40 60 80 100 Weight (%) Temperature (℃) a b According to the report [11], the ionic liquids with –CN group was easier to form of 3D-connected frameworks, which would induce nitroge-rich at elevated temperatures, and the carbonization yields was also relative high. Herein, two species of ILs consisting of functional –CN were carried on TGA under N2 atmosphere (Fig.1), the result indicated that carbonization yield of 1-cyanopropyl-3-methylimidazolium chloride was low that only to 2.21 wt%, on the contrary, the high carbonization yield of 1-acetonitrile-3-methylimidazolium chloride was up to 28.64% under 600 ˚C. The following experiments selected 1-acetonitrile-3-methylimidazolium chloride as carbon source to synthesize the monolith macroporous-mesoporous carbon materials. Fig. 2 (a) is the light yellow PU foam, which the volume is 2.5 × 1.0 ×1.0 cm3. (b) is the OMS with 1.8 × 0.72 × 0.72 cm3, its shrinkage was calculated to be about 62 % in volume, but still maintained the macrostructure of monolith. (c) is the OMC with 1.2 × 0.5 × 0.5 cm3, which the volume shrinkage was about 88 %. The cause of this phenomenon was that the ILs occurred polycondensation in the process of carbonization. However, all the samples kept the original morphologies with different Fig.2 a) Photograph of the commercial PU foam. b) OMS. c) OMC. Fig.1 TGA of (a) 1-cyanopropyl-3- methylimidazolium chloride and (b) 1-acetonitrile-3-methylimidazolium chloride 24 Material, Mechanical and Manufacturing Engineering II
- 42. shrinkages, suggesting a good thermal stability for these samples. By observing the optical photos, it can be found that the monolithic morphology was well preserved, and there was no obvious collapsed phenomenon. At the same time the carbonization yield was high, which is the key factors to synthesize of the monolithic carbon materials. 2 4 6 8 2 4 6 8 intensity (a.u.) 2 theta (degree) intensity(a.u) 2 theta(degree) (100) (200) (110) 0.0 0.2 0.4 0.6 0.8 1.0 5 10 15 20 25 30 35 dV/dlog(D) Pore size(nm) a b Volume adsorbed(cm3/g.STP) Relative pressure(P/Po) a b The monolithic OMS showed three resolved diffraction peaks in the SAXRD (Fig.3), which can be indexed as 100, 110 and 200 diffractions of 2D hexagonal mesostructure, suggesting the mesostructure with highly ordered [12]. Compared with the silica materials by organic-organic self-assembly, the monolithic OMS was moved for high angles, which indicating the mesoporous pore size gradually decreasing [4]. The SAXRD pattern of the monolithic OMC which using the monolithic OMS as hard template showed a weak broad, as shown in the inset of Fig.3. No obvious diffraction peaks can be observed, which may be due to the weak interaction force between Ils and the silicon group. Fig.4 represented typical nitrogen adsorption-desorption isotherm for the OMS and OMC which exhibit representative type-IV curves with H3-type hysteresis loop. Meanwhile, capillary condensation of nitrogen at P/P0=0.4-1.0, implied the presence of mesoporous in those materials. The pore size distribution of OMS with a mean value around 3.74 nm was calculated by Barrett-Joyner-Halenda (BJH) model (inset of Fig.4). And the OMC was around 3.84 nm which was similar to the OMS, indicating that the carbon materials can replicate by OMS. The Brunauer-Emment-Teller (BET) surface area was calculated to be 163 m2 /g, which was larger than the OMS (140 m2 /g). The pore volume increased from 0.10 cm3 /g to 0.24 cm3 /g. The scanning electron microscopy (SEM) images of the OMS showed 3D interconnecting networks and the macropores of 200-500 um. Fig. 5 a showed the OMS which were synthesized by removing the PU foam template has a 3D macrostructure, composed of inhomogeneity polygon struts. It can be found in the Fig.5 b, monolithic OMC was synthesized by impregnating ILs into the OMS which can be kept the macrostructure, but their surface was rough because during the process of carbonization, ILs turns to be polycondensation. The transmission electron microscopy (TEM) can be observed the internal microstructure of the monolithic OMC. Fig.5 c showed the TEM images of the monolithic OMC, it can be seen that abundant pores can be observed on the surface of materials, the structure was honeycomb. The pore size estimated 4 nm which was in good accordance with the results of BET. Fig.4 N2 adsorption-desorption isotherms and pore size distributions of (a) OMS (b) OMC Fig.3 SAXRD patterns of OMS and OMC Fig.5 a,b) SEM images of OMS and OMC c) TEM image of OMC Advanced Materials Research Vol. 988 25
- 43. The IR spectrum of the samples around carbonization was analyzed by the change of the functional groups. As shown in Fig. 6, the absorption band at 1340 cm-1 was attributed to C-N stretching vibrations. The peak at 1630 cm-1 can be assigned as stretching vibrations of –NH2 and C-N group, overlapped the adsorption of N-H stretching vibrations in the range 3500-3100 cm-1 . The Fig. 5 b had not obvious peak at 2220 cm-1 which stretching vibrations of C≡N [13]. Therefore, the IR data indicated the existence of N element in the OMC. 1000 2000 3000 4000 40 50 60 70 80 90 100 intensity (a.u.) Wavenumber (cm -1 ) a b Conclusion Monolithic OMS materials were fabricated by using PU foam as a sacrificial scaffold, which have a 3D and large interconnecting mesostructure. The monolithic macroporous-mesoporous carbon composite materials were obtained by wet impregnation method using the monolithic OMS as hard template, ILs as carbon source. The carbon materials exhibited total pore volumes (0.24 cm3 g-1 ) and nitrogen content. References [1] J. Wei, D. D. Zhou, Z. K. Sun, Y. H. Deng, Y. Y. Xia, and D. Y. Zhao: Advanced Functional Materials. 23 (2013), 2322-2328 [2] E. Bayram, N. Hoda, E. Ayranci: Journal of Hazardous Materials. 168 (2009), 1459-1466 [3] Y. Huang, H. Q. Cai, D. Feng, D. Gu, Y. H. Deng, B. Tu, H. T. Wang, P. A. Webley, and D. Y. Zhao: Chemical communications. (2008), 2641-2643 [4] R. X. Guo, J. Guo, F. Q. Yu, D. D. Gang: Microporous and Mesoporous Materials. 175 (2013), 141-146 [5] J. Kim, J. Lee, T. Hyeon: Carbon. 42 (2004), 2711-2719 [6] G. W. Yang, H. Y. Han, T. T. Li, C. Y. Du: Carbon. 50 (2012), 3753-3765 [7] A. B. Chen, W. W. Zang, C. Liu, Y. Y. Wang, M. L. Jia, B. Li, Y. F. Yu: Advanced Materials Research Vols. 557-559 (2012), p 1518-1521 [8] A. B. Chen, Y. F. Yu, H. J. Lv, Y. Y. Wang, S. F. Shen, Y. Q. Hu, B. Li, Y. Zhang, and J. Zhang: Journal of Materials Chemistry A. 1 (2013), 1045-1047 [9] S. A. Wohlgemuth, R. J. White, M. G. Willinger, M. M. Titirici, and M. Antonietti: Green Chemistry. 14 (2012), 1515-1523 [10] X. Q. Wang, and S. Dai: Angewandte chemie-international edition. 49 (2010), 6664-6668 [11] J. S. Lee, X. Q. Wang, H. M. Luo, and S. Dai: Advanced Materials. 22 (2010), 1004-1007 [12] B. Y. Liu, D. C. Jia, Q. C. Meng, J. C. Rao: Carbon. 45 (2007), 668-689 [13] N. N. Liu, L. W. Yin, C. X. Wang, L. Y. Zhang, N. Lun, D. Xiang, Y. X. Qi, R. Gao: Carbon. 48 (2010), 3579-3591 Fig.6 IR spectrum of around carbonization a) ILs+OMS b) OMC 26 Material, Mechanical and Manufacturing Engineering II
- 44. Strain analysis of bimetal material based on uniaxial tensile and ANSYS Dehai Zhang1, a , Duanqin Zhang1,b , Yanqin Li1,c , Jianxiu Liu1,d Daiping Bai1,e , Houhai Xia1,f and Yong Yang1,g 1 Mechanical and Electrical Engineering Institute，Zhengzhou University of Light Industry,China a zhangdehai0318@163.com, b dqzhang2003@sina.com, c yqli@zzuli.edu.cn, d jianxiuliu@126.com, e baidaiping@163.com,f 958498228@qq.com，g 875956443@qq.com Keywords: bimetal metal, Uniaxial tensile, ANSYS Abstract. With a combined method of theoretic analysis, numerical simulation and uniaxial tensile test experiment research, the properties of bimetal materials are system studied. The researches are concentrated on the followings contexts:The fabricating method of bimetal materials by semi-solid compressive joining is studied by ANSYS, and then the tensile property relationships of the clad material are established. The stress and their strains along x, y and z directions of the clad material are analyzed, respectively. The different performance of composite materials, find materials conform to the existing problems so as to optimize treatment. Introduction In modern technology, bimetal materials consist of metal layers with different physical properties are widely used in aviation, chemical engineering, automobile, electronic industries and so on. Metal composites consisting of aluminium and copper layers are of great importance in the energy sector and consumer electronics. Power connectors, tapes and other electric and heat conductive elements are made from them. The advantages of using these composites are good electrical and thermal conductivity at a reduced total weight [1] . The application of aluminium in the bimetal structure, instead of 100% content of stainless-steel, can reduce total cost of materials due to the lower market price of aluminium. However, there are some key problems urgent to be solved in the structure and properties of the clad materials, which are the main tasks of this paper. The research in this field has great significance both in theory sense and engineering practice [2] . The forming ability of bimetal materials are directly determined by their mechanical performance, so the tensile mechanical properties of cladding material were studied by many domestic and foreign scholars. The performance and single material has very big difference due to the cladding material mismatch, performance of components caused by partial or whole deformation behavior and fracture. Due to the mechanical properties of each component materials vary widely, deformation yield and destruction are difficultly to achieve synchronization during the processing of uniaxial tensile test. Due to the different of component material poisson's ratio, such as the ratio of plastic strain difference, the performance of material along the width direction is limited by metal on both sides of each other will generate additional stress. This kind of additional stress can produce warping along the specimen width direction when a certain value are reached out . In recent years, the mechanical properties of the cladding plate are studied by scholars at home and abroad[3] . Their researches are mainly concentrated in the mechanical properties of cladding material and its components of the relationships between material mechanical properties, the mechanical properties of its constituent material to predict the mechanical properties of cladding material and the related numerical simulation and so on. Mechanical properties of the compound layer board are depended on the mechanical properties of component materials and their respective accounts for thickness ratio. To predict the mechanical properties of the composite board are mainly depended on mixing rule theory. In view of the interface problem, finite element analysis software has achieved very good effect for the forecast of damage location, but there are problems are existed on the analysis when the material had been yielded[4] . Due to high flow performance of semi-solid material is used by Advanced Materials Research Vol. 988 (2014) pp 27-30 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.988.27
- 45. Reiner [5] , the stainless steel bolts and semi-solid steel parts are formed by rheology and forging forming at one time. Semi-solid slurry is possessed of good liquidity, bolts of tooth filling is good, the bolt head of semi-solid steel slurry and the surface of the bolt formed have been welded into microcosmic joint tissue. Its combined forging and connection are achieved in one step worker, In the meantime the cost of assembly is reduced, respectively [6] .The pressure compound and roll casting process are adopted to realize melting of the composite steel and semi-solid aluminium, and the interface structure and mechanics performance of composite plate are studied. That the relationships including of shear strength and the solid fraction of semi-solid aluminum melt, interface structures between semi-solid aluminum composite of are determined. The method of extrusion of package is adopt by Tohru [7] , semi-solid aluminum alloy aluminum-double metal rod are made. A kind of pressure transmission medium is made through adding semi-solid materials into the metal sleeve barrel, and the production of metal package material is achieved. Next ,the performance of the interface and the structure of the organization are analyzed. Many important problems of performance and the organization could not well solved until then, but the question about how to improve the accurate evaluation of performance about the interface of the combination between dissimilar materials is an ugrent work as well as mechanics and formability of the cladding material. Experiment For bimetal cladding material, a lot of research of the preparation, recombination mechanism of composite interface, interface evaluation method and indexes are carried out. However, due to interface is as the connection area of different materials, its mechanical properties and tissue are relative complex. Until now there is no unified evaluation method and index and the evaluation criterion. So on the basis of experiment, it is necessary through a combining method of numerical simulation and theoretical analysis to study another new preparation method and interface problem. The uniaxial tensile test of material is the basic experiment to determine mechanics performance. The basic performance parameters of the materials, such as the yield point, tensile strength, stiffness index, coefficient of strength, plasticity constitutive relation and so on can be obtained. In this article, 1Cr18Ni9Ti stainless steel and aluminum bimetal plate are selected. The material mechanical properties and basic material properties required for establishing the constitutive relation of the data can be obtained using uniaxial tensile test. Mechanics performance test is carried using Instron-1195 material testing machine. The machine can complete materials of all kinds of mechanical properties testing: flexural, compressive strength, fracture toughness, elastic modulus and so on. With reference to the metal tensile test method (GB228-87), metal tensile test specimens (GB 6397-86) , tensile sample size is shown in Fig.1. Fig.1 Tensile samples of stainless steel/aluminium cladding materials Numerical simulation When uniaxial tensile experiments are simulated, necking phenomena of the material is the most difficult to simulate, so some problems must be pay attention when using ANSYS software. For instance, cylinder is to not simple set up to simulating and modeling. It should be noted that there are necking phenomenon is because the material is flawed. So it should reflect that phenomenon based on the established model. In common, the common way is to reduce the size of the model in necking 28 Material, Mechanical and Manufacturing Engineering II
- 46. place, or reduce the modulus of elasticity in this area. The other way is to define hardening properties of material. Finally, the most notice way is to open the large deformation button to simulate. During the processing of sloving stage, three linear model (linear elastic stage---perfectly plastic stage---strengthening phase) are adoped, respectively. The length of the perfectly plastic stage and strengthening phase and the effect of the modulus are using by such a simple material model. Tab.1 Mechanical parameters of stainless steel-aluminum bimetal material Element Elasticity modulus（105 MPa） Poisson ratio density（g/cm2） stainless steel 1Cr18Ni9Ti 2.06 0.3 7.9 aluminum Al 0.7 0.3 2.7 Two pieces of metal sample long is 10 cm , wide is 1 cm, thick is 0.5 cm. Certain defect is existed in the gap shown in the Fig.4. Definition Element type. Element type is adopted as solid45, mechanical parameters such as densities of material are adoptedd as Tab.1 to import into ANSYS, respectively. Some key points are set up and shown in Fig.2. Area is set up and shown in Fig.3. Fig.2 Establish of key points Fig.3 Area generation in ANSYS Fig.4 Entity generation in ANSYS AS can be seen from the Fig.4, the upper and lower layer metal sheet are coupled in a body together. Figure.5 shows the mesh loaded in the body. Fig.5 Mesh Fig.6 Model constraint and load Fig.7 Deformation As shown in Fig.6, a single plane on the left is constrained, the another plane shown as Fig.7 is under tension force along x direction. It can be seen from the Fig.7, the maximum deformation of bimetal is 8.032 mm, maximum strain is 7.263, both of them are along the stretch direction. The minimum deformation of bimetal is 0.029946 mm, and its direction is opposited on the stretch direction. As can be seen from the Fig.8, the maximum stress along x direction is 2.35×1013 Pa, the minimum value is 1.14×1012 Pa. As can be seen from the Fig.9, the maximum value along y direction is 1.54×1013 Pa, the minimum value is 9.49 x1011 Pa.As can be seen from the Fig.10, the maximum value along z direction is 6.69 ×1012 Pa, the minimum value is 1.46 ×1012 Pa. Fig.8 Stress along x direction Fig.9 Stress along y direction Fig.10 Stress along z direction Advanced Materials Research Vol. 988 29
- 47. ANSYS results show that stress concentration is located in the defect area of bimetal material tension, the stress distributions of different material also have very big difference. The stress distribution of stainless steel/aluminium bimetal material under the condition of uniaxial tensile test show that the stress of the stainless steel side is bigger. Conclusions Due to the bimetal material preparation and performance study is relatively complex, the aspects including new technology and new equipment, interface control, interface characterization, micromechanics and interface characteristics and the overall performance of the composite material have a lot of study to do. The studies on material and mechanics, macro and micro, theory and numerical simulation and experimental are the important development trend in the future field. As can be seen from ANSYS simulation, the area of stress concentration is located on the defect area when bimetal material is under the condition of tension force. But the stress distributions of different material also have very big difference. In this paper, these conclusions about bimetal material analysis are arrived out using ANSYS software. The metal materials are affected by external force, the stress is mainly concentrated in the defect area. The simulated stress distribution of stainless steel-aluminium cladding material under the condition of uniaxial tensile shows that the stress on the side of stainless steel side is bigger. Acknowledgements This work has been performed under the joint project between Research Program Project of Foundation and Advanced Technology of Henan Province(132300410181), Key Scientific Research Project of Henan Province (142102110151), Science and Technology Research Project of Zhengzhou (131PPTGG411-7), Key Guidance Scientific Research Project of Henan Education Department (13B460333), Key Scientific Research Program of Henan Education Department (13A460372) and Dr. Research Fund Project of Zhengzhou University of Light Industry. References [1] J.E. Lee, D.H. Bae, W.S. Chung, K.H. Kima, J.H. Lee and Y.R. Cho: J. Mater. Process. Technol. Vol. 187(2007), p. 546 [2] H.L. Wang, T.H. Wagner and G. Eska: Physica B Vol. 284(2000), p. 2024 [3] P. He, X. Yue and J.H. Zhang: Mater. Sci. Eng. A Vol. 486(2008),p.171 [4] D.H. Zhang, X.P. Du and C. Guo :P. I. Mech. Eng. C-J. Mec. Vol. 225(2011), p.1061 [5] C.A. Leon and R.A.L: Mater. Lett. Vol. 56 (2002), p. 812 [6] T. Mori and S. Kurimoto: J. Mater. Process. Technol. Vol 56(1996), p. 242 [7] D.H. Zhang, D.P. Bai, J.B. Liu, Z. Guo and C Guo: Compos. Part B Vol 55(2013), p. 591 30 Material, Mechanical and Manufacturing Engineering II
- 48. Study on Curing Kinetics of MEP-15 /593/660 System Jiale Song1,a , Chanchan Li2,b ,Zhimi Zhou1,c , Chaoqiang Ye1,d , Weiguang Li1,e 1 School of Materials Science and Engineering, Chang’ an University, Xian, 710064, PR China 2 School of Highway, Chang’ an University, Xian, 710064, PR China a jlsong@chd.edu.cn(J.S.), b 1174781909@qq.com, c bodajingshen2008@163.com(Z.Z.), d yechaoqiangmvp@163.com (C. Y.), e wgli@chd.edu.cn(W. L.) Keywords: epoxy resin. curing kinetics. DSC. Abstract: Curing kinetics of MEP-15/593 system and MEP-15/593/660 system is studied by means of differential scanning calorimetry (DSC). Curing kinetic parameters are evaluated and the relationship between diluent 660 and the curing properties is investigated. The results show that the diluent 660 can not only reduce viscosity and activation energy, but also improve the degree of cure and conversion ratio. Introduction Epoxy resin mortar, as a structural material, has been put into practice for its great mechanical property. However, due to the low toughness and easy to crack in the external forces, the application of condensates has been largely restricted [1-3]. Therefore, our experiment use curing system which consists of the polyether soft segment chemical modification of the epoxy resin(MEP-15) and the amine curing agent which can be cured at room temperature to improve the brittleness of the condensates. Besides, adding Propylene oxide-butyl ether (abbreviated 660 diluent) can not only reduce the viscosity of the curing system but also increase its toughness. In our experiment, non-isothermal DSC was used to contract the curing kinetics of MEP-15/593/660 and MEP-15/593. Then the thermodynamic data were analyzed to get the reaction dynamic equation and the order of reaction of the two systems which lay the foundation of further optimization of the curing process and improvement of the product’s performance. Experimental 1.1 Materials 593 curing agent (industrial products) was provided by Yueyang Petrochemical Plant， amine value 600-700 mgKOH/g. 660 diluent (industrial products) was produced by Xin Dian Chemical Materials (Shanghai) Co.Ltd, epoxy value 0.50 mol/100g. Preparation of MEP-15: Making flexible segment which end group is high activity isocyanate group by reacting toluene diisocyanate (TDI) with flexible chain polyether diols, and introducing this segment into the molecular chain by reacting isocyanate group with epoxy-secondary hydroxyl. 1.2 Characterization 1.2.1 DSC testing The instrument used in above test was DSC-7 thermal analyzer produced by U.S. PE Corporation. Peak temperature of curing exothermic DSC spectrum and glass transition DSC spectrum are processed by TA Data Analysis software. Advanced Materials Research Vol. 988 (2014) pp 31-35 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.988.31
- 49. 1.2.2 Viscosity testing Viscosity within a temperature range of 20 ~ 40 o C under MEP-15/593 system was measured by NDJ-1 viscometer produced by Shanghai Balance Instrument Factory. Results and discussion 1.3 The influence of diluent content According to China’s current standard “Epoxy grouting resin for concrete crack”(JC/T1041-2007) (hereinafter using “the specification” for short) provide that mixing viscosity of epoxy resin mixture in construction temperature is 200mPa•s. Viscosity of curing systems which are the mixture of MEP-15 epoxy resin and 660 diluent mixed in different mass ratio was tested respectively under three different proportions and five different temperature conditions. Viscosity-temperature curves are shown in Figure 1. Figure 1 Viscosity-temperature curves of MEP-15/660 system under different temperature It can be seen from the Figure 1 that viscosity of MEP-15/660 system decreased with the increase of temperature. While the temperature was 20~30 o C and mass ratio was 0.3:1, viscosity of MEP-15/660 system was larger than 200 mPa·s and did not meet the viscosity requirement of constructive mixture. While the temperature was 30~40 o C and mass ratio was 0.4:1 and 0.5:1, viscosity of the system was less than 200 mPa·s which met the requirement. But from the economic point of view, the following tests should use 0.4:1 as the diluent proportion of epoxy mortar. 1.4 Curing kinetics parameter analysis The curing process of epoxy resin is very complex reaction. Kissinger method is the most commonly used method to solve the dynamic equation (that is the activation energy E, reaction order n and function). Because of its calculation is little and easy operation, it has been widely used [4][5] . Curing exothermic DSC spectra of two systems under the condition that the heating rate was 5, 10, 15, 20℃/min are shown in Figure 2. The initial temperature (Ti), the peak temperature (Tp) and the final temperature (Tf) of two curing systems’ curing reaction exothermic peak are shown in Table1. 32 Material, Mechanical and Manufacturing Engineering II
- 50. Figure 2 Dynamic curing exothermic curves of MEP-15/593 system and MEP-15/593/660 system. Table 1 Characterized curing temperature and exothermic enthalpy of curing system at different heating rates Curing system β/（o C·min-1 ） Ti/o C Tp/o C Tf/o C ΔT/o C ΔHR/（J·g-1 ） MEP-15/593/660 5 58.3 78.0 99.9 41.6 297.50 10 53.2 92.5 140.0 86.8 280.77 15 56.9 104.5 147.0 90.1 161.66 20 66.9 112.7 140.2 73.3 42.93 MEP-15/593 5 36.3 75.0 117.9 81.6 394.41 10 52.6 88.7 127.0 74.4 136.12 15 50.3 96.5 136.8 86.5 163.57 20 61.5 102.3 136.5 75.0 89.10 The activation energy E is the energy parameters which can determine that whether curing reaction could carry out. In accordance with Kissinger equation: (1) In Equation 1, 𝑇𝑝 is the peak temperature(K) of curing reaction’s exothermic peak, β is the heating rate(K/min), R is the gas constant and its value is 8.314J/mol·K. Draw the curve while is the ordinate and is the abscissa. Then linear fit them respectively and get the slope K according to fitting curves. Finally, put K into Equation 1 and get the reaction activation energy E. The system’s activation energy can be obtained according to E = - KR. Results are shown in Table 2. Table 2 Activation energy of two curing systems Curing system K Activation energy MEP-15/593 system - 4.70248 60.43kJ/mol MEP-15/593/660 system -5.91099 38.03kJ/mol Advanced Materials Research Vol. 988 33
- 51. Curing reaction order n can get by Crane equation: (2) Crane considered that when E/nR is much larger 2Tp , the latter can be neglected. Draw the curve while lnβ is the ordinate and 1/Tp is the abscissa. Then linear fit them respectively and get the linear equation. As shown in Figure 3, the curves’ slope was K’. So, ） （ R K / E - n (3) Figure 3 linear fitting curves Figure 4 linear fitting curves Known K’ and activation energy E, curing reaction orders of two systems can be obtained through Equation 3. Results are shown in Table 3. Table 3 Curing reaction orders of two systems Curing system K＇ Curing reaction order MEP-15/593 system -6.63289 1.1 MEP-15/593/660 system -5.43721 0.85 As shown in Table 4, according to activation energy, pre-exponential factor and reaction order, curing reaction kinetics model of MEP-15/593 system and MEP-15/593/660 system can be established. Table 4 uring reaction kinetics model of MEP-15/593 system and MEP-15/593/660 system Curing system activation energy E Reaction order n curing reaction kinetics model MEP-15/593 system 60.43kJ/mol 1.1 dα/dt=2.1×1010 e(-5.905/T) (1-α)1.10 MEP-15/593/660 system 38.03kJ/mol 0.85 dα/dt=6.011×103 e(-4.574/T) (1-α)0.85 According to the results, it can be known that activation energy and reaction order of MEP-15/593/660 system are lower than that of MEP-15/593 system. The reason is that diluent 660 is a kind of reactive diluent containing epoxy groups and it makes condensates’ crosslinking density decrease thus the cured become gel in advance. 34 Material, Mechanical and Manufacturing Engineering II
- 52. Conclusion 1. Through viscosity tests under 3 different ratio and 5 different temperature conditions, the best diluent incorporation of MEP-15/660 system is 0.4:1 according to results and curing system viscosity meet constructive mixing viscosity requirement. 2. Using non-isothermal DSC method studied the curing process of MEP-15/593 system and MEP-15/593/660 system. And using Kissinger extremum method analyzed the curing kinetics parameters of the two systems. The result shows that adding diluent 660 decrease the reaction activation energy and the reaction order of the system. 3. Reactive diluent 660 decreases the activation energy and practical reaction’s temperature of MEP-15/593 system. So at the room temperature, the reaction speed is comparatively fast and reaction between epoxy resin and condensate is easier, and these all favours construction on the site. Acknowledgment The authors acknowledge Ningbo transportation committee of science and technology plan project NO.201311 funding sources for this work. References [1] Cao Ruijun, Mei Dong, Yuan Jianan. Study of the rapid repair material on concrete road surface [J]. Journal of of Xi'an Jiaotong University, 1998, 32(1) : 97-99 [2] Chi Yi, Yin Jian. Modeling analysis of crack repairing structures for asphalt concrete pavement [J]. Journal of Advanced Materials Research, 2013, 639-640 (1) : 377-381 [3] Sun Renjuan, Ge Zhi, Li Wu, Zhou Haifang, Huang Dawei. Experimental research of the rapid set cement concrete for rapid repair of concrete pavements [J]. Journal of Advanced Materials Research, 2013, 634-638 (1) : 2697-2701 [4] Peng Xiaoqin, Yang Tao, Wang Kaiyu, Meng Xiangjie. Preparation of geopolymeric concrete and its application to rapid repair of cement concrete pavement [J]. Journal of Southwest Jiaotong University, 2011, 46(2) : 205-210 [5] Lu Zhaofeng, He Zhaoyi, Qin Min. A rapid repair technology on faulted joint slabs of cement pavements [C]. American: American Society of Civil Engineers, 2009: 1463-1468 Advanced Materials Research Vol. 988 35
- 53. Acidification assisted preparation of graphite oxide and graphene Yun Lei 1,a , Jun Xu 1,b , Rong Li 1,c , Feifei Chen1,d 1 School of Resource and Environmental Engineering, Wuhan University of Technology, Wuhan, 430070 a LeiYun＠whut.edu.cn Keywords: Acidification graphite, Graphite oxide, Graphene Abstract: Graphite oxide was prepared by acidification assisted Hummers method, which contains acidification, medium temperature and high-temperature three stages. Traditional Hummers low-temperature process was replaced by acidification process. The dosages of acid, graphite and potassium permanganate were investigated, and the produced graphite oxide was treated by ultrasonic oscillation and reduced to graphene by refluxing the reaction mixture at 100℃ under open-air conditions. The structure of natural graphite, graphite oxide and graphene were characterized by X-ray diffractometry and infrared spectrum, the morphology of graphene was observed on a scanning electron microscope and the electrochemical properties of graphene were analyzed by the three-electrode cyclic voltammetry test system. Introduction Graphene, the thinnest and strongest material void sp2 hybridized carbon atoms arranged in a honeycomb lattice, becomes the rising star in material science due to its amazing characteristics such as large surface area, excellent electrical and mechanical properties [1,2] with promising applications in the fields of supercapacitors [3] , batteries [4] , nanoelectronics [5] and catalystsupports [6] . Pan Y et al. prepared graphene film by heating methane at 1000 ℃ on the metal foil of Cu and Ni [7] . Li et al. used chemical reduction method to get graphene sheets which were uniformly dispersed in water [8] . Herein, graphite oxide (GO) was obtained by acidification assisted method, and further treated with ultrasonic oscillation to produce graphene oxide, which was reduced by hydrazine to obtain graphene. The prepared graphene was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Infrared Spectrometer (IR), and further investigated by transient photocurrent and cyclic voltammetry. Experiment Materials. The graphite was purchased from Sinopharm Chemical Reagent Co., Ltd. Sulfuric acid (H2SO4), nitric acid (HNO3), sodium nitrate (NaNO3), potassium permanganate (KMnO4), hydrogen peroxide (H2O2), barium (BaCl2), hydrazine (N2H4•H2O) and ethanol (CH3CH2OH) were all commercially available products and used without further purification. Preparation of graphite oxide. Graphite power was used to prepare graphite oxide by modified Hummers method. Firstly, flake graphite power was mixed with sulfuric acid and nitric acid, and stirred for 60 min to prepare acidification graphite. Secondly, sulfuric acid, sodium nitrate and potassium permanganate were added into acidified graphite. The mixture was heated to about 35 °C and kept at this temperature for an additional 30 min. Lastly, hydrogen peroxide were added in the stage of high temperature reaction. Preparation of graphene. Graphene was prepared by chemical reduction. Firstly, 0.2g graphite oxide was added into 200mL distilled water and treated with ultrasonic oscillation for 30min. Then 50mL hydrazine was added into the above mixture and stirred. Lastly, the mixture was heated to reflux at the temperature of 100℃ for 8h. Characterization. X-ray diffraction (XRD) was performed on an X Pert PRO DY2198 diffractometer using the monochromatized X-ray beam from Cu Kα radiation. The morphology of Advanced Materials Research Vol. 988 (2014) pp 36-39 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.988.36
- 54. graphene composite was observed on a scanning electron microscopy (SEM). The characteristic functional groups of graphite, graphite oxide and graphene were observed on a Nexus Fourier Transform Infrared Spectrometer (FT-IR). Cyclic voltammetry (CV) were carried out on the CHI660D electrochemical working station with a three-electrode system, which was equipped with a working electrode, a platinum foil counter electrode, and a standard calomel electrode (SCE) reference electrode. Results and Discussions XRD test of graphite oxide. Figure 1a-1c show the XRD patterns of GO prepared with acids at the dosage of H2SO4 5mL and HNO3 10mL, H2SO4 7.5mL and HNO3 7.5mL, and H2SO4 10mL and HNO3 5mL, respectively. As shown in Fig.1a and 1b, the strong peak of graphite oxide prepared with H2SO4 7.5mL and HNO3 7.5mL is stronger than that of graphite oxide prepared with H2SO4 5mL and HNO3 10mL. For GO, as shown in Fig 1c, a strong peak at 2θ =10.4° appears, which is the structure expansion as oxygen-containing groups incorporate between the carbon sheets during the course of strong oxidation. The strong peak at 10.4° becomes much stronger with the decrease of HNO3/H2SO4 ratio, and reaches the maximum at the proportion of 10mL H2SO4 and 5mL HNO3 (Fig 1c). So the results show that H2SO4 10mL and HNO3 5mL were used for the following experiment. 1 0 2 0 3 0 4 0 5 0 6 0 0 5 0 0 1 0 0 0 1 5 0 0 2 0 0 0 2 5 0 0 3 0 0 0 intensity 2 θ ( d e g re e ) a 1 0 2 0 3 0 4 0 5 0 6 0 7 0 0 5 0 0 1 0 0 0 1 5 0 0 2 0 0 0 intensity 2 θ ( d e gre e ) b 1 0 2 0 3 0 4 0 5 0 6 0 7 0 -1 0 0 0 0 1 0 0 0 2 0 0 0 3 0 0 0 4 0 0 0 5 0 0 0 6 0 0 0 intensity 2 θ ( d e g re e ) c Fig. 1 The XRD patterns of graphite oxide with different amount of acid (a) 10ml HNO3 and 5ml H2SO4，(b) 7.5ml HNO3 and 7.5ml H2SO4，(c) 5mlHNO3 and 10mlH2SO4 Figure 2a-2d show the XRD patterns of GO prepared with graphite at the dosage of 10g, 7.5g, 5g and 2.5g, respectively. As shown in figure 2a, it can be seen that a strong peak at 2θ =24.5° appears. When the dosage of graphite is decreased to 7.5g, the peak at 2θ =24.5°in Figure 2b is weaker than that in Figure 2a, and the peak at 10.4° in Figure 2b is stronger compared with that in Figure 2a. With further decrease in the amount of graphite, the peaks at 24.5° in figure 2c and 2d are much weaker than those in Figure 2b and 2a while the peaks at 10.4° display the opposite change. So graphite 5g was added in the following experiments. 10 20 30 40 50 60 70 -2000 0 2000 4000 6000 8000 10000 12000 14000 intensity 2θ( degree) d 10 20 30 40 50 60 -500 0 500 1000 1500 2000 2500 3000 intensity 2θ( degree) a 10 20 30 40 50 60 70 -500 0 500 1000 1500 2000 intensity 2θ( degree) b 10 20 30 40 50 60 70 -1000 0 1000 2000 3000 4000 5000 6000 intensity 2θ( degree) c Fig. 2 The XRD patterns of graphite oxide with different amount of graphite a) 10g，b) 7.5g，c) 5g，d) 2.5g Graphite 5g was mixed with H2SO4 10mL and HNO3 5mL, then potassium permanganate was added into the solution with different dosages (11g，13g，15g，17g). When potassium permanganate of 11g was added into the mixture, the result in Fig 3a shows that there exists two peaks at 2θ =10.4° and 2θ =24.5°. When the dosages of potassium permanganate were increased to 13g and 15g, the peaks at 24.5° in Figures 3b and 3c are weaker than those shown in Figure 3a, while the peaks at 10.4° Advanced Materials Research Vol. 988 37
- 55. Another Random Document on Scribd Without Any Related Topics
- 56. authority. There were riots in London, and the Roman Catholic chapels were sacked and destroyed. There was a general call to William to hasten his march. On the 12th, however, James was stopped near Sheerness by some fishermen and brought back to London. William had no mind to have a second royal martyr on his hands, and did everything to frighten James into another flight. On December 18 James left London and William arrived at Whitehall. On December 23, with William's connivance, James embarked for France. 21. A Convention Parliament Summoned. 1688.—Amongst the crowd which welcomed William was Sergeant Maynard, an old man of ninety. "You must," said William to him, "have survived all the lawyers of your standing." "Yes, sir," replied Maynard, "and, but for your Highness, I should have survived the laws too." He expressed the general sense of almost every Englishman. How to return to a legal system with the least possible disturbance was the problem to be faced. William consulted the House of Lords and an assembly composed of all persons who had sat in any of Charles's Parliaments, together with special representatives of the City. Members of James's one Parliament were not summoned, on the plea that the return to it of members chosen by the remodelled corporations made it no true Parliament. The body thus consulted advised William to call a Convention, which would be a Parliament in everything except that there was no king to summon it. 22. The Throne declared Vacant. 1689.—On January 22, 1689, the Convention met. The House of Commons contained a majority of Whigs, whilst the Tories were in a majority in the Lords. On the 28th the Commons resolved that "king James II., having endeavoured to subvert the constitution of the kingdom by breaking the original contract between king and people, and by the advice of Jesuits and other wicked persons having violated the fundamental laws and having withdrawn himself out of the kingdom, had abdicated the government, and that the throne had thereby become vacant." This lumbering resolution was unanimously adopted. The
- 57. Whigs were pleased with the clause which made the vacancy of the throne depend on James's misgovernment, and the Tories were pleased with the clause which made it depend on his so-called voluntary abdication. The Tories in the Lords proposed that James should remain nominally king, but that the country should be governed by a regent. Danby, however, and a small knot of Tories supported the Whigs, and the proposal was rejected. Danby had, indeed, a plan of his own. James, he held, had really abdicated, and the crown had therefore passed to the next heir. That heir was not, according to him, the supposititious infant, but the eldest daughter of James, Mary Princess of Orange, who was now in her own right queen of England. It was an ingenious theory, but two circumstances were against its being carried into practice. In the first place, Mary scolded Danby for daring to set her above her husband. In the second place William made it known that he would neither be regent nor administer the government under his wife. Danby therefore withdrew his motion, and on February 6 the Lords voted, as the Commons had voted before, that James had abdicated and the throne was vacant. 23. William and Mary to be Joint Sovereigns. 1689.—A Declaration of Rights was prepared condemning the dispensing power as lately exercised and the other extravagant actions of James II., while both Houses concurred in offering the crown to William and Mary as joint sovereigns. As long as William lived he was to administer the government, Mary only attaining to actual power in the event of her surviving her husband. After the death of both, the crown was to go first to any children which might be born to them, then to Anne and her children, and, lastly, to any children of William by a second wife in case of his surviving Mary and marrying again. As a matter of fact, William had no children by Mary, who died about eight years before him, and he never married again. On February 13 William and Mary accepted the crown on the conditions offered to them.
- 58. 24. Character of the Revolution.—The main characteristic of the revolution thus effected was that it established the supremacy of Parliament by setting up a king and queen who owed their position to a Parliamentary vote. People had been found to believe that James II. was king by a Divine right. Nobody could believe that of William. Parliament, which had set him up, could pull him down, and he would have therefore to conform his government to the will of the nation manifested in Parliament. The political revolution of 1689 succeeded, whilst the Puritan Revolution of 1641 failed, because, in 1641, the political aim of setting the Parliament above the king was complicated by an ecclesiastical dispute which had split Parliament and the nation into two hostile parties. In 1689 there was practically neither a political nor an ecclesiastical dispute. Tories and Whigs combined to support the change, and Churchmen and Dissenters made common cause against the small Roman Catholic minority which had only been dangerous because it had the Crown at its back, and because the Crown had been supported by Louis and his armies. A Revolution thus effected was, no doubt, far less complete than that which had been aimed at by the more advanced assailants of the throne of Charles I. It did not aim at changing more than a small part of the political constitution of the country, nor at changing any part whatever of its social institutions. Its programme, in short, was one for a single generation, not one, like that of the 'Heads of the Proposals' (see p. 555) or the 'Agreement of the People' (see p. 556) for several generations. Consequently it did not rouse the antagonism which had been fatal even to the best conceived plans of the Commonwealth and Protectorate. It is much to be regretted that the moral tone of the men who brought about the Revolution of 1689 was lower than that which had brought about the Revolution of 1641. That this was the case, however, was mainly the fault of the unwise attempt of the Puritans to enforce morality by law. The individual liberty which was encouraged by the later revolution would in due time work for morality as well as for political improvement. Books recommended for further study of Part VII.
- 59. Ranke, L. English History (English translation). Vol. iii. p. 310-vol. iv. p. 528. Airy, O. The English Restoration and Louis XIV. Christie, W. D. Life of A. A. Cooper, first Earl of Shaftesbury. Macaulay, Lord. History of England from the Accession of James II. Vols. i. and ii. Hallam, H. Constitutional History. Chapters XI.-XIV. Mahan, A. T. Influence of the Sea-power upon History. Chapters I.-III. Lodge, R. The Political History of England. Vol. viii. From the Restoration to the Death of William III. (1660-1702).
- 61. Abbey lands, the, distributed by Henry VIII., 400; Mary wishes for the restoration of, 422 Aberdeen, Montrose's victory at, 547 Abhorrers, party name of, 620 Addled Parliament, the, 486 Admonition to Parliament, An, 446 Adwalton Moor, battle of, 538 Agitators, choice of, 554; propose to purge the House, 556 Agreement of the People, the, drawn up by the Agitators, 556 Agriculture, More's views on the decline of, 368; progress of, in Elizabeth's reign, 464 Aix-la-Chapelle, peace of, 599 Alasco, opinions of, 418 Albemarle, George Monk, Duke of, as George Monk, commands in Scotland, 575; effects the restoration, 576; created Duke of Albemarle, 580; holds a command in the battle off the North Foreland, 592; advises Charles II. not to dissolve Parliament, 599 Alençon, Francis, Duke of, Elizabeth proposes to marry, 446; entertained by Elizabeth, 454; attacks Antwerp, 455; death of, 456 Alexander VI., Pope, character of, 375 Alford, battle of, 549 Allen, Cardinal, founds a college at Douai, 453; plots to murder Elizabeth, 454 Alva, Duke of, his tyranny in the Netherlands, 443; discusses the murder of Elizabeth, 445; fails to reduce the Dutch, 449 Amicable Loan, the, 372 Anjou, Henry, Duke of, see Henry III., king of France Annates, first Act of, 388; second Act of, 390
- 62. Anne, daughter of James II., birth of, 608; deserts James II., 645; settlement of the crown on, 647 Anne Boleyn, appears at Court, 380; is married to Henry VIII., 389; execution of, 395 Anne of Cleves married to Henry VIII., 400; divorce of, 401 Antwerp attacked by Alençon, 455; taken by Parma, 456 Appeals, Act of, 389; provision for the hearing of, 391 Architecture, Elizabethan, 465; Stuart, 631, 632 Areopagitica, 546 Argyle, Archibald Campbell, Earl of, execution of, 636 Argyle, Archibald Campbell, Marquis of, opposed to Montrose, 547; execution of, 595 Arlington, Henry Bennet, Earl of, secretary to Charles II., 599; intrigues against Clifford, 607 Armada, the Invincible, sailing of, 458; destruction of, 462 Army, the New Model, formation of, 545; attempt of Parliament to disband, 553; choice of Agitators in, 554; gains possession of the king's person, 555; the heads of the proposals presented in the name of, ib.; drives out the eleven members, ib.; turns against the king, 556, 557; expels members by Pride's Purge, ib.; its inability to reconstruct society after the king's execution, 560; overthrows Richard Cromwell, restores and expels the Rump, 575; brings back the Rump, ib.;
- 63. receives Charles II. on Blackheath, 578; paid off, 584 Army, the Royal, beginning of, 584 Army plot, the, 531 Articles, the ten, 395; the six, 399; the forty-two, 420; the thirty-nine, ib.; declaration of Charles I., prefixed to, 512 Arundel Castle taken and lost by Hopton, 542 Ashley, Lord, see Shaftesbury, Earl of Aske heads the Pilgrimage of Grace, 397 Assembly of divines, proposal to refer church questions to, 534; meeting of, 540; declares for Presbyterianism, 543 Association, the, in defence of Elizabeth, 456 Attainder, Bill of, against Thomas Cromwell, 401; nature of a, ib., note i.; against Strafford, 531 Auldearn, battle of, 547 Babington plots the murder of Elizabeth, 457 Bacon, Francis (Lord Verulam and Viscount St. Alban), scientific aspirations of, 474; advises Elizabeth as to the treatment of the Catholics, 475; his conduct to Essex, 478; gives political advice to James I., 486; his jest on Montague's promotion, 494; attacked about monopolies, 495; disgrace of, 496 Bagenal defeated by Hugh O'Neill, 475 Ballard takes part in Babington's plot, 457 Barbadoes, prisoners sent to, 564; dissenters sent to, 588
- 64. Barebone's Parliament, the, origin of the name of, 566; dissolution of, 567 Baronets, origin of the order of, 494 Barrow, Henry, a separatist, hanged, 470 Barrow, Isaac, addresses his sermons to the understanding, 598 Basing House taken by Cromwell, 549 Bastwick sentenced by the Star Chamber, 521 Bate's case, 484 Baxter, imprisoned by Jeffreys, 635 Beaton, Cardinal, burns Wishart, 412; is murdered, 414 Bedingfield, Sir Henry, takes charge of Elizabeth, 423 Benevolences raised by James I., 497 Berwick, Treaty of, 526 Bible, the, Henry VIII. authorises the translation of, 396 Bishops, nominated by congé d'élire, 391; first Bill for removing from the House of Lords, 533; impeachment of the twelve, 535; excluded from the House of Lords, 536 Bishops' War, the first, 526; the second, 529 Blackwater, the, defeat of Bagenal on, 475 Blake, defends Taunton, 548; appointed to command the fleet, 565; sent to the Mediterranean, 571; destroys Spanish ships at Santa Cruz, 573; death of, ib. Bloody Assizes, the, 637 Bocher, Joan, burnt, 419 Bohemia, outbreak of the Thirty Year War in, 490 Boleyn, Anne, see Anne Boleyn Bombay acquired by Charles II., 587 Bonner, Bishop, deprived of his see, 416 Booth, Sir George, defeated at Winnington Bridge, 575 Bothwell, James Hepburn, Earl of, career of, 439
- 65. Bothwell Bridge, defeat of the Covenanters at, 620 Boulogne, taken by Henry VIII., 405; surrendered by Warwick, 417 Bourbon, the Duke of, revolt of, 371; death of, 374 Boxley, destruction of the rood of, 398 Breda, declaration of, 576; treaty of, 593 Brentford, Charles I. at, 537 Bridgman, Sir Orlando, declares that the king's ministers are responsible, 581 Bridgwater taken by Fairfax, 549; Monmouth at, 637 Brill seized by exiles from the Netherlands, 449 Bristol stormed by Rupert, 538 Browne, Archbishop of Dublin, destroys relics and images in Ireland, 402 Browne, Robert, founder of the Separatists, 470 Brownists, see Separatists Bucer, Martin, teaches in England, 410 Buckingham, George Villiers, First Duke of, becomes Marquis of Buckingham and Lord Admiral, 488; accompanies Charles to Madrid, 497; becomes Duke of Buckingham, and advocates war with Spain, 500; promises money for foreign wars, 501; his ascendency over Charles I., 502; tries to pawn the crown jewels, 503; lends ships to fight against Rochelle, 504; impeachment of, 505; leads an expedition to Ré, 506; feeling of Wentworth towards, 508; murder of, 510 Buckingham, George Villiers, Second Duke of, in favour with Charles II., 599; his sham treaty with France, 603;
- 66. dismissal of, 608 Buckingham, Henry Stafford, Duke of, execution of, 369 Buildings, improvement in, in Elizabeth's time, 465 Bunyan writes Pilgrim's Progress, 596 Burghley, William Cecil, Lord, as Sir William Cecil becomes the chief adviser of Elizabeth, 429; urges Elizabeth to assist the Scotch Protestants, 433; becomes Lord Burghley and discovers the Ridolfi plot, 445; death of, 480 Burnet, Gilbert, his conversation with William of Orange, 645 Burton, sentenced by the Star Chamber, 521 Butler, author of Hudibras, 597 Cadiz, capture of, 464; Cecil's expedition to, 503 Calais, loss of, 427; Elizabeth's hope of regaining, 436; the Armada takes refuge in, 462; Cromwell's anxiety to recover, 571 Calvin, his work at Geneva, 430 Calvinism influences Elizabethan Protestantism, 430 Cambrai, league of, 363; treaty of, 383 Campeggio, Cardinal, appointed legate to hear the divorce case of Henry VIII., 382 Campion lands in England, 453; execution of, 454 Carberry Hill, Mary's surrender at, 439 Cardinal College founded by Wolsey, 377, 383; see Christchurch Carisbrooke Castle, detention of Charles I. in, 556 Carolina, colonisation of, 629 Cartwright advocates the Presbyterian system, 446 Casket letters, the, 440 Castlemaine, Lady, uses her influence against Clarendon, 594
- 67. Câteau Cambresis, peace of, 431 Catesby plans Gunpowder Plot, 483 Catharine of Aragon, marriage of, 363; Henry VIII. grows tired of, 379; divorce suit against, 382; is divorced, 389; the sentence of Clement VII. in favour of, 390; death of, 395 Catharine of Braganza marries Charles II., 587 Catherine de Medicis, widow of Henry II., king of France, becomes regent, 433; takes part in the massacre of St. Bartholomew, 449 Catherine Howard, marriage and execution of, 401 Catherine Parr, marriage of, 401 Catholics, Roman, laws directed against, 453, 454; their position at the end of Elizabeth's reign, 475; increased persecution of, after Gunpowder Plot, 483; negotiation between James I. and Spain for the relief of, 488; tendency of Charles II. to support, 584; declaration for the toleration of, issued by Charles II., 587; persecuted about the Popish Plot, 616; efforts of James II. in favour of, 634, 638, 640 Cecil, Sir Edward, commands the Cadiz expedition, 503 Chancery, Court of, proposal of the Barebone's Parliament to suppress, 567; reformed by Cromwell, 569; nature of the decisions of, 605 Chantries, Act for the dissolution of, 412; their income vested in the king, 415 Charles I., intention of the Gunpowder plotters to blow up, 483; proposals of marriage for, 488; visits Spain, 497; is eager for war with Spain, 500; negotiation for marriage with Henrietta Maria, 501;
- 68. becomes king and marries Henrietta Maria, 502; adjourns his first parliament to Oxford, ib.; dissolves his first parliament and sends out the Cadiz expedition, 503; meets his second Parliament, ib.; dissolves his second Parliament, 505; orders the collection of a forced loan, 506; meets his third Parliament, 508; consents to the Petition of Right, 509; claims a right to levy Tonnage and Poundage, 510; issues a declaration on the Articles, 512; dissolves his third Parliament, 513; his personal government, 514; levies knighthood fines, 515; insists on the reading of the Declaration of Sports, 517; levies fines for encroaching on forests, 523; levies ship-money, ib.; imposes a new prayer-book on Scotland, 525; leads an army against the Scots, 526; consults Wentworth, 527; makes Wentworth Earl of Strafford, and summons the Short Parliament, 528; dissolves the Short Parliament, marches again against the Scots, and summons the Long Parliament, 529; assents to the Triennial Act, 530; signs a commission for Strafford's execution, 531; visits Scotland, 532; returns to England, 534; rejects the Grand Remonstrance, 535; attempts to arrest the five members, 536; fights at Edgehill, 537; his plan of campaign, ib.; besieges Gloucester, and fights at Newbury, 539; looks to Ireland for help, 541; sends Rupert to relieve York, 543; compels Essex's infantry to surrender at Lostwithiel, and
- 69. fights again at Newbury, 544; is defeated at Naseby, 548; attempts to join Montrose, 549; sends Glamorgan to Ireland, ib.; gives himself up to the Scots, 551; negotiates at Newcastle, ib.; explains his plans to the Queen, 552; conveyed to Holmby House, 553; conducted by Joyce to Newmarket, 555; attempt of Cromwell to come to an understanding with, 555; takes refuge in the Isle of Wight, and enters into the Engagement with the Scots, 556; removed to Hurst Castle, 557; trial of, 559; execution of, 560 Charles II., as Prince of Wales, possesses himself of part of the fleet, 557; lands in Scotland, 563; escapes to France, 564; offers a reward for Cromwell's murder, 569; issues the declaration of Breda, 576; restoration of, 578; confirms Magna Carta, ib.; character of, 579; leaves the government to Hyde, 580; revenue voted to, 582; approves a scheme of modified episcopacy, 583; keeps a small armed force, 584; retains three regiments on paying off the army, ib.; profligacy of the court of, 586; issues a declaration in favour of toleration, 587; marriage of, and sale of Dunkirk by, ib.; dismisses Clarendon, 594; favours the Roman Catholics, 598; thinks of tolerating dissenters, and supports Buckingham
- 70. and Arlington, 599; agrees to the treaty of Dover, 600; supports the Cabal, 602; extravagance of, 603; issues a Declaration of Indulgence, 604; goes to war with the Dutch, 605; withdraws the Declaration of Indulgence, 606; assents to the Test Act, 607; dismisses Shaftesbury and makes peace with the Dutch, 608; supports Danby, 610; receives a pension from Louis XIV., 611; is interested in commerce, 612; refuses to make war on France, 613; threatens France with war, 614; dissolves the Cavalier Parliament, 616; dissolves the first Short Parliament, 617; supports his brother's claim to the crown, against Shaftesbury, 618; prorogues the second Short Parliament, 619; dismisses Shaftesbury, 620; dissolves the second and third Short Parliaments, 621; plot to murder, 625; death of, 627; constitutional progress in the reign of, ib. Charles II., king of Spain, bad health of, 592 Charles V., Emperor, as king of Spain becomes the rival of Francis I., 366; vast inheritance of, 369; is chosen emperor, ib.; goes to war with France, 371; captures Francis I. at Pavia, 372; liberates Francis I., 374; allies himself with Henry VIII., 405; makes peace with France at Crêpy, 406; defends Mary's mass, 417;
- 71. abdication of, 426 Charles IX., king of France, accession of, 433; takes part in the massacre of St. Bartholomew, 449; death of, 450 Charterhouse, the persecution of the monks of, 393 Chaucer, influences of the Renascence on, 367 Cheriton, battle of, 542 Chocolate, introduction of, 630 Christchurch, foundation of, 377, 383 Christian IV., king of Denmark, Buckingham's overtures to, 501, 504; defeated at Lutter, 505, 506 Church of England, see England, Church of Churchill, Lord, see Marlborough, Duke of Clarendon, Edward Hyde, first Earl of, as Edward Hyde is one of the leaders of the Anti-Presbyterian party in the Long Parliament, 533; becomes Lord Chancellor after the Restoration, 580; character of, ib.; created Earl of Clarendon, 587; is falsely supposed to be bribed, ib.; fall of, 594; escapes to France, 595 Clarendon, Henry Hyde, second Earl of, recalled from Ireland, 640 Claverhouse, see Graham, John Clement VII., Pope, forms an Italian league against Charles V., 374; appoints legates to try the divorce suit of Henry VIII., 382; revokes the cause to Rome, 383; gives sentence in favour of Catharine, 390 Clergy, the country, 633 Clifford, Thomas, Lord, a member of the Cabal, 602; probable suggester of the Stop of the Exchequer, 604; resignation of, 607 Coaches, improvement in, 633
- 72. Coffee-houses, introduction of, 630 Coinage debased by Henry VIII., 409; further debased by Somerset, 416 Coke, Sir Edward, takes part in drawing up the Petition of Right, 508 Colchester, execution of the Abbot of, 400; reduced by Fairfax, 567 Colet promotes the study of Greek, and founds St. Paul's School, 367 Coligny, murder of, 449 College invents the Protestant flail, 615; condemned to death, 622 Colonies founded in Virginia and New England, 489; in Carolina, 629 Common Prayer, the Book of, beginnings of, 409, 410; the first, of Edward VI., 415; the second, of Edward VI., 418; alterations in, in Elizabeth's reign, 429; Strickland proposes to amend, 445; generally accepted by the Parliamentary Presbyterians, 586 Commonwealth, the, establishment of, 561 Commons, the House of, Wolsey's appearance in, 371; made use of by Thomas Cromwell and Henry VIII., 389; Elizabeth's relations with, 444; Puritanism of, 445; growing strength of, 468; its tendencies to Puritanism rather than to Presbyterianism, 470; attack on monopolies by, 478; quarrels with James I., 482; anxious to go to war for the Palatinate, 490; votes a small supply, 491; brings charges against Bacon, 495; is eager for war with Spain, 500; refuses supplies to Charles I., unless spent by counsellors in whom it confides, 502;
- 73. impeaches Buckingham, 504, 505; insists on the Petition of Right, 508; claims Tonnage and Poundage, 510; religious ideas prevailing in, 511; its breach with the king, 513; violent scene before the dissolution of, 514; formation of parties in, 532; scene in, at the passing of the Grand Remonstrance, 534; Presbyterian majority in, 546; new elections to, 551; a mob in possession of, 555; the Agitators propose to purge, 556; Pride's purge of, 557; declares itself supreme, ib.; constitutes a high court of justice, 558; dissolved by Cromwell, 566; inquires into the expenditure of the crown, and impeaches Clarendon, 594; impeaches Danby, 616; the Exclusion Bill in, 617, 621; Tory majority in, 636; James II. attempts to pack, 641; discusses the abdication of James II., 646 Committee of Both Kingdoms, formation of, 542 Communion table, Laud's wish to fix at the east end, 517; decision of the Privy Council on the position of, 519; removed by the soldiers, 529 Comprehension favoured by some of the clergy, 598; attempt of Charles II. to establish, 599 Compton, Bishop of London, refuses to suspend Dr. Sharp, 639 Con, Papal agent at the court of Henrietta Maria, 521 Confederate Catholics of Ireland, the, cessation of hostilities with, 541 Congé d'élire, provision for the issue of, 391 Connaught, proposed plantation of, 528
- 74. Constantinople taken by the Turks, 366 Conventicle Act, the, 588 Convention Parliament, the first, 577; the second, 646 Convocation of province of Canterbury offers money for a pardon, 385; agrees to the submission of the clergy, 386 Cornwall, insurrection in, 415 Corporation Act, the, 585 Corporations, remodelling of the, 625 Council of State, the, appointment of, 561 Covenant, the Scottish National, 525; see Solemn League and Covenant Covenanters, the rise of, 619; insurrection of, 620 Coverdale translates the New Testament, 396 Cranfield, see Middlesex, Earl of Cranmer, Archbishop of Canterbury, pronounces Catharine's marriage to be null, 389; is forced to dismiss his wife, 400; composes the English litany, 409; character and position of, 413; wishes to preserve the revenue of the chantries for the poor clergy, 415; tries to find common ground with the Zwinglian reformers, 416; leaves his mark on the Prayer Book, 418; supports Lady Jane Grey, 420; burnt, 426 Crêpy, peace of, 406 Cromwell, Oliver, practical sagacity of, 539; introduces discipline in the Eastern Association, 540; defeats the royalists at Winceby, 542; fights at Marston Moor, 543; advocates toleration, ib.; accuses Manchester, 544;
- 75. becomes Lieutenant-General of the New Model Army, 545; cuts off the king's supplies, 547; wins the victory at Naseby, 548; reduces Winchester and Basing House, 549; proposes to leave England, 554; gives instructions to Cornet Joyce, 555; attempts to come to an understanding with Charles, ib.; puts down a mutiny in the army, 556; suppresses a rising in Wales and defeats the Scots at Preston, 557; suppresses the Levellers, 562; his campaign in Ireland, ib.; his victory at Dunbar, 563; his victory at Worcester, 564; dissolves the Long Parliament, 566; opens the Barebone's Parliament, 567; becomes Protector, 568; plots against, 569; ecclesiastical arrangements of, ib.; convenes and dissolves his first Parliament, 570; establishes major-generals, ib.; foreign policy of, 571; calls a second Parliament, 572; joins France against Spain, ib.; dissolves his second Parliament, 573; makes war against Spain, ib.; death of, 574 Cromwell, Richard, succeeds to the Protectorate, 574; abdicates, 575 Cromwell, Thomas, advises Henry VIII. to rely on the House of Commons, 385; becomes the king's secretary, and vicar-general, 393; attacks the monks of the Charterhouse, ib.; inquires into the state of the monasteries, 394; attacks the greater monasteries, 397;
- 76. execution of, 401 Cropredy Bridge, battle of, 544 Danby, Thomas Osborne, Earl of, as Sir T. Osborne, becomes Lord Treasurer, 607; policy of, 610; fails to pass a Non-resistance Bill, 611; promotes the marriage of William of Orange, 613; impeachment of, 616; imprisonment of, 617; liberated, 626; rises in support of William, 645; recommends that the crown be given to Mary, 646 Darnley, Henry Stuart, Lord, marries Mary, 438; murder of, 439 Darvel Gathern, burning of the wooden figure of, 398 Davison sends the warrant for Mary's execution, 457; dismissal of, 458 Declaration of Breda, see Breda, Declaration of Declaration of Indulgence issued by Charles II., 604; withdrawn by Charles II., 606; issued by James II., 640; reissued, 642 Declaration of Rights, the, 647 Declaration of Sports, the, ordered to be read in churches, 517 Defender of the Faith, title of, 379 Desmond, Gerald Fitzgerald, Earl of, insurrection and death of, 453 Devolution, the war of, 593 Devonshire, insurrection in, 415 Devonshire, William Cavendish, Earl of, rises in support of William of Orange, 645 Digby, John, Lord, his mission to Germany, 497 Dispensing power, the, claimed by Charles II., 604;
- 77. acknowledged by the judges, 639 Dissenters, the, origin of their name, 585; Charles II. issues a declaration for the toleration of, 587; Conventicle Act against, 588; Five-mile Act against, 590; favour of Charles II. to, 599; reception of the Declaration of Indulgence by, 640 Dissenting Brethren, the five, 543 Divine Right of Kings, doctrine of the, 619 Douai, College at, 453 Dover, treaty of, 600 Drake, Francis, lands at Nombre de Dios, 448; vows to sail on the Pacific, 449; his voyage round the world, 450; (Sir Francis) singes the king of Spain's beard, 458; has a command against the Armada, 460; pursues the Armada, 462; sacks Corunna, and fails before Lisbon, 464; death of, ib. Dramatic writers of the Restoration, 598 Dreux, battle of, 436 Drogheda, slaughter at, 562 Drumclog, skirmish at, 620 Dublin, attempt to seize, 533 Dudley, see Empson and Dudley Dudley, Lord Guilford, marries Lady Jane Grey, 420; executed, 423 Dunbar, battle of, 563 Dunes, the, battle of, 573 Dunkirk, Cromwell wishes Spain to place in his hands, 571; taken from Spain by Cromwell's troops, 573; abandoned by Charles II., 587 Dunkirk House, 587 Dunse Law, Scottish army on, 526 Dunstable, marriage of Catharine of Aragon annulled at, 389 Durham, temporary suppression of the see of, 418;
- 78. celebration of the mass in the cathedral of, 441 Dutch Republic, the, foundation of, 449; abolition of the Stadholderate in, 565; war between the English Commonwealth and, ib.; peace with, 569; first war between Charles II. and, 589; military weakness of, 591; treaty of Breda with, 593; takes part in the Triple Alliance, 599; combination of England and France against, 600; towns to be taken from, ib.; the second war between Charles II. and, 605; resists Louis XIV., ib.; animosity of Shaftesbury against, 606; peace made by England with, 608; makes peace with France at Nymwegen, 614 Eastern Association, the, formation of, 539; Cromwell's activity in, 540; Manchester in command of the army of, 542 Ecclesiastical Commission, the, established by James II., 639; abolition of, 644 Ecclesiastical Courts, the, attacks on, 385 Edgehill, battle of, 537 Edinburgh, burnt by Hertford, 409; riot in St. Giles's in, 525; Montrose executed at, 563; surrenders to Cromwell, ib. Edinburgh, treaty of, 433 Edward VI., birth of, 397; accession of, 412; precocity of, 419; death of, 420 Ejectors, Commission of, 569 Eleven Members, the, excluded from the House of Commons,
- 79. 555 Eliot, Sir John, attacks Buckingham, 504; compares Buckingham to Sejanus, 505; his policy compared with that of Wentworth, 508; vindicates the privileges of the House, 512; imprisonment and death of, 514 Elizabeth, daughter of James I., intention of the Gunpowder plotters to crown, 483; married to the Elector Palatine, 488 Elizabeth, Queen, birth of, 392; her succession acknowledged, 411; sent to the Tower and afterwards removed to Woodstock and Hatfield, 423; accession of, 428; character and policy of, ib.; modification of the title of, 429; plays off France and Spain against one another, 431; hesitates to assist the Scotch Protestants, 432; assists the Lords of the Congregation, 433; her ill-treatment of Catherine Grey, 435; contrasted with Mary, Queen of Scots, ib.; hopes to recover Calais by assisting the Huguenots, 436; appoints commissioners to examine the case against Mary, 440; detains Mary a prisoner, and suppresses a rising in the North, 441; excommunicated by Pius V., ib.; negotiates a marriage with the Duke of Anjou, 443; her attitude towards the Puritans and towards Parliament, 444; the Ridolfi plot against, 445; proposes to marry the Duke of Alençon, 446; intervenes in Scotland on behalf of James VI., 450; refuses to restore Drake's plunder, 451; her treatment of Ireland, 452; kisses the Duke of Alençon, 454;
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