![Gangue as Flame Retardants for Flexible Poly (Vinyl Chloride) 1
Ming Gao1,a
, Chun-guang Song 1,b
,Dan Rong1,c
,Yu-wen Ji1,d
1
School of Environmental Engineering, North China University of Science and Technology, Box
206,Yanjiao Beijing 101601, China
a
gaoming@ncist.edu.cn, b
1114149912@qq.com, c
2235697702@qq.com, d
1633910613@qq.com
Key words: Gangue, flame retardant, aluminum hydroxide ,PVC
Abstract: Gangue as flame retardant was used to PVC, the mechanical properties and flame
retardance of the samples were studied. The resultant data show that gangue little effect on the
mechanical properties of the sample, especially tensile strength, yield stress, and 10% of gangue
obtained good flame retardance. PVC treated with flame-retardants showed a high limiting oxygen
index, char yield, which indicated that the flame retardance of the treated PVC was improved.
Introduction
PVC materials or products tend to have excellent fire performance. But to make it easy to
process, semirigid and flexible PVC compound always contains a large volume of plasticizer such
as DOP [di(2-ethylhexyl)phthalate], which can deteriorate the flame retardation and smoke
suppression properties. When the PVC products contain 45 parts DOP, the limiting oxygen index
(LOI) would decrease to about 24 and the PVC would thus become a high-flammability material.
However, plasticized PVC products can still have good fire performance, particularly if additionally
fire-retarded [1,2].
In recent years, the use of metal hydroxide flame retardant and smoke suppressant in PVC has
been reported [3,4].These flame-retardants, e.g., Mg(OH)2, Al(OH)3 are required at high
concentrations (40–60%) for imparting a good degree of flame retardancy. Because of the high
loading it is essential that good degree of flame retardancy be obtained, but mechanical properties
decrease obviously. Using coupling agents and synergists are good ways to solving this problem
[5–7]. Many elements, such as alloys, organic substances and inorganic compounds including
antimony, tin, zinc, copper, iron and molybdenum, have been used in the flame retardation and
smoke suppression of PVC. Gangue contains many kinds of metal oxides, which may have the
similar effective.
The purpose of our present study is to study mechanical properties, flame retardant of the
samples treated with combinations of Al(OH)3 and gangue.
Experimental
Materials
PVC, S G Type 2, dioctyl phthalate (DOP); Tribasic lead sulfate, Dibasic lead phosphate,
commercially available; Stearic acid, industrial grade; Mg(OH)2, industrial grade; Al(OH)3, ZX-131
type.
Instrumentation
LOI values were determined in accordance with ASTM D2863-70 by means of a General Model
HC-1 LOI apparatus. The vertical burning test was conducted by a CZF-II horizontal and vertical
burning tester (Jiang Ning Analysis Instrument Company, China). The mechanical properties were
Advanced Materials Research Vol. 983 (2014) pp 3-6
© (2014) Trans Tech Publications, Switzerland
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![Fig.5 SEM photographs of sample A Fig.6 SEM photographs of sample G
Conclusions
10g gangue and 100g Al (OH) 3 were added can obtain a good flame retardant for flexible PVC,
whose LOI reached 29.8%. Gangue has little effect on the mechanical properties of the sample,
especially tensile strength, yield stress. The flame-retardant effect of Al(OH)3 in soft PVC is mainly
based on their dehydration endothermic effect, thus inhibiting soft PVC temperature from rising.
Gangue could promote the formation of effective charring layer. The structure of the intumescent
charring layer may increase the efficiency of the flame retardancy, act as heat insulation, and
protect inner matrix materials.
1
Contract grant sponsor: Fundamental research funds for the Central Universities: 3142013102.
References
[1] Hirschler, M.M. (1998). Fire Performance of Poly (Vinyl Chloride) Updated and Recent
Developments, Flame Retardants, 98: 103.
[2] Hirschler, M.M. (1982). Recent Developments in Flame-Retardant Mechanisms, Development
in Polymer Stabilisation, Vol. 5, p. 107, Applied Science Publ, London.
[3] Tong, N. and Shaoyun, G. (2000). Flame-Retardant and Smoke-Suppression Properties of Zinc
Borate and Aluminum Trihydrate-Filled Rigid PVC, J. Appl. Polym. Sci., 77: 3119.
[4] Hornsby, P.R. and Watson. C.L. (1990). A Study of the Mechanism of Flame Retardance and
Smoke Suppression in Polymers Filled with Magnesium Hydroxide, Polymer Degradation and
Stability, 30: 73.
[5] Jha, N.K., Misra, A.C. and Bajaj, P. (1984). Flame-Retardant Additives for Polypropylene, J.
Macromol Sci., Rev. Macromol. Chem. Phys., C24: 1: 69.
[6] Pearce, E.M. (1986). Flame Retardants for Polymer Systems, Pure & Appl. Chem., 58: 925.
[7] Shigco, M., Takeshi, I. and Hitoshi, A. (1980). Fire-Retarding Polypropylene with Magnesium
Hydroxide, J. Appl. Polym. Sci., 25: 415.
6 Advanced Materials and Engineering](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-20-320.jpg)
![Novel Thermo Thickening Smart Gel
with Interpenetrating Polymer and Surfactant Network
Jiang Yang1,2,a
, Yining Zhou2
, Yongjun Lu1
, Weixiang Cui1
,
Xiaohui Qiu1
, Baoshan Guan1
, Yunhong Ding1
1
Research Institute of Petroleum Exploration & Development-Langfang, PetroChina, Hebei, China
2
Department of Petroleum Engineering, Xi’an Petroleum University, Xi’an, Shaanxi, China
a
Corresponding author email: jyang98@126.com
Keywords: Thermo gel, Surfactant, Polymer, Wormlike Micelle
Abstract
A novel smart gel based on interpenetrating network of anionic polymer and surfactant was
investigated. A supramolecular assembly structured gel is formed by associating polymer side
chain with wormlike micelle of surfactant. The physical interaction of val der vaal and hydrogen
bonding force between surfactant and polymer gives a strong viscoelastic gel at evaluated
temperature. The viscoelastic properties and gel structure were characterized by dynamic
rheometer and cryo-TEM. The polymer and VES complex gel is highly elastic, which elastic
moduli G’ is higher than loss moduli G’’ at low angular frequency, 0.1 rad/s, in high temperature.
The total concentration of surfactant and polymer is low which is economically to use in industries.
Introduction
The smart intelligent materials which properties can be controlled by environmental changes are
much interested research areas around the world. The environmental change can be electrical,
magnetic, light, thermal and pH etc. Among these materials, the polymer could be designed from
molecular structure and form smart materials in response different environmental changes [1-4].
The small molecules such as surfactant can also form different aggregates which respond to
environmental changes [5-8]. The microstructure changes can induce major changes in the
macroscopic properties such as viscoelasticity and solid-liquid transition. The intelligent materials
have been used in pharmaceutical [9], automobile [10], drag reduction [11] and oil industry [12,13]
etc.
Thermo thickening gel is interested for application in oil and pharmaceutical industries, where
fluid has lower viscosity at low temperature and form gel at higher temperature. In oil and gas
stimulation operation, fluid is preferred to have low viscosity at low temperature for easy of
pumping with low friction pressure, and form viscoelastic gel to suspend proppant particles at high
temperature at reservoir. For example, sodium erucate as surfactant can transform from fluid to
elastic gel at high temperature above its Kraft temperature [7]. Polymer and surfactant could have
synergistic interaction at certain condition. For examples, associating polymer can interact with
spherical micelle and formed the network [14]. We hereby study a new class of surfactant with
wormlike micelle structure in combination of associating polymer. The new system forms
viscoelastic fluid at broader range of concentration and forms stronger gel at higher temperature.
The complex gel can be used in oil and gas stimulation.
Advanced Materials Research Vol. 983 (2014) pp 7-10
© (2014) Trans Tech Publications, Switzerland
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![Experiment
Materials
Amphoteric surfactant with C18 chain length and hydrophobically modified polyacrylamide
polymer with anionic group (AP) were made by our lab. Anionic surfactant, sodium lauryl sulfate,
was received from Sinopharm Chemcial Co, China. Conventional polyacrylamide with anionic
group (CP) was obtained from Beijing Henju Co. Water was deionized.
Methods
Rheological properties were measured by a Haake Mars II Rheometer Pressured Cell. Dynamic
properties were measured by cone and plate geometry on rheometer.
Cryo-transimission electron microscopy (Cryo-TEM) observation of surfactant solution was
carried out in a controlled-environment vitrification system. Samples were prepared at 25 °C and
100% RH on a Quantifoil holey carbon grid (Electron Microscopy Sciences). The grid was
quenched rapidly in liquid ethane at -180 °C and then transferred to liquid nitrogen (-196 °C) for
storage. Imageing of the samples was performed using JEM2010 cryo-microscope with a Gatan 626
cryoholder. The acceleration voltage was 200 keV, and the working temperature was kept below -
170 °C. Digital images were recorded using a charge-coupled device camera (Gatan 832).
Results and Discussions
The surfactant studied is a mixture of amphoteric and anionic surfactant (MS) similar to system
studied previously [6]. The surfactant system showed viscoelastic behavior itself above certain
concentration which forms entangled wormlike micelle structure. The viscosity of surfactant and
polymer with variation of temperature is shown in Fig. 1. It can be seen that viscosity of fluid with
single surfactant or polymer all decreases as temperature increases. The viscosity in mixture of
conventional polymer (CP) and surfactant (MS) also decreases with increasing temperature.
However, the viscosity in mixture of hydrophobically modified polymer (AP) and surfactant (MS)
increases with increasing temperature. The overall concentration of mixed AP and MS is also
higher than their individual combined. Hence, there is positive synergism interaction between these
two materials at increasing temperature. It can be seen that viscosity starts to increase above 50 °C.
This behavior could be due to the increase of solubility of longer chain surfactant at higher
temperature. The complex fluid formed between associating polymer (AP) and surfactant (MS) is a
highly elastic gel as shown in Table 1, which the storage modulus, G’, is larger than loss modulus,
G’’ at frequency 0.1-100 rad/s.
At further higher temperature above 80 °C, formation of branches along the micelles leading to a
multionconnected rather than an entangled network. Branch junction points increase the number of
possible configurations, enabling percolation, and the formation of extended micellar networks,
which leads to a multiconnected rather than an entangled network of cylindrical micelles. Hence the
visocosity decreases for branched worm-like micelles.
The driving force for this increased viscosity in mixed polymer and surfactant system is due to
physical crosslinking of polymer and surfactant through intermolecular val der vaal interaction of
hydrophobic side chain in associating polymer and surfactant micelle. In addition, hydrogen
bonding between the polymer hydrophilic and surfactant head group could also reinforce their
interaction and crosslinking. The interpenetrating network of wormlike micelle from surfactant and
hydrophobic modified polymer is graphically shown in Fig. 2a.
8 Advanced Materials and Engineering](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-22-320.jpg)
![0
20
40
60
80
100
20 30 40 50 60 70 80 90
Temperature (C)
Viscosity
(mPa.s,
100
1/s)
1% MS Surfactant
0.15% AP Polymer
1% MS+0.15%AP
0.15% CP Polymer
1% MS+0.15% CP
Figure 1. Viscosity versus temperature for polymer, surfactant and their mixture.
Table 1. Storage modulus (G’) and loss modulus (G’’) versus angular frequency for 1% mixed
surfactant (MS) and 0.15% associating polymer (AP) at 70 °C.
Augular
Frequency [rad/s]
0.10 0.40 1.58 6.31 25.10 100.00
G’ [Pa] 5.45 6.36 7.78 9.37 11.20 11.90
G’’ [Pa] 1.37 1.48 1.69 2.10 2.80 4.16
The presence of wormlike micelle structure in surfactant studied is directly confirmed by Cyro-
TEM observation as shown in Fig. 2b. It can be seen that threadlike structure with about 10nm in
diameter and >1 µm in length exists. The wormlike micelles entangle with each other as well as
polymer gives highly elastic gel.
(a) (b)
Figure 2. (a) Illustrated crosslink model of wormlike micelle and associating polymer. (b) Cryo-
TEM micrographs of wormlike micelle in mixed ampheteric and anionic surfactant (1%, wt) at 25
°C.
Advanced Materials Research Vol. 983 9](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-23-320.jpg)
![Conclusions
A novel smart gel based on interpenetrating network of anionic polymer and surfactants was
formed through physical crosslink. The val der vaal and hydrogen bonding interaction between
wormlike micelle and polymer network gives strong viscoelastic gel. The gel strength is stronger at
evaluated temperature. The smart gel is useful as stimulation fluids in oil and gas industry,
hydraulic fluid, household and personal care products.
Acknowledgement
The authors acknowledgement the supports from the National Hi-Tech Development (863) Plan
Project (2013AA064801) and National Natural Science Foundation of China (Grant No 51174163).
References
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smart polymer: Core–shell nanoparticle carrier and drug release response, Acta Biomaterialia, 3
(2007) 838-850.
[2] G. Filipcsei, I. Csetneki, A. Szilágyi, M. Zrínyi, Magnetic field-responsive smart polymer
composites, Advances in Polymer Science, 206(2007)137-189.
[3] M. S. Yavuz, Y. Cheng, J. Chen et al, Gold nanocages covered by smart polymers for
controlled release with near-infrared light, Nature Materials, 8 (2009)935-939.
[4] K. Al-Tahami, J. Singh, Smart polymer based delivery systems for peptides and proteins, Recent
Patents on Drug Delivery & Formulation, 1(2007) 65-71.
[5] J. Yang, Cur. Viscoelastic wormlike micelles and their applications, Opin. Colloid Interface
Sci., 7(2002) 276-281.
[6] J. Yang, Z. Yang, Y. Lu et al, Rheological properties of zwitterionic wormlike micelle in
presence of solvents and cosurfactant at high temperature， J. Dispersion Sci. Tech. 34 (2013)
1124-1129.
[7] Y. Zhang, Y. Han, Z. Chu, S. He, J. Zhang, Y. Feng, Thermally induced structural transitions
from fluids to hydrogels with pH-switchable anionic wormlike micelles, J. Col. Interf Sci, 394
(2013) 319–328.
[8] R. Kumar , A. M. Ketner, S. R. Raghavan, Nonaqueous photorheological fluids based on light-
responsive reverse wormlike micelles, Langmuir, 26 (2010) 5405–5411.
[9] A.S. Hoffman, “Intelligent” polymers in medicine and biotechnology, Macromolecular
Symposia, 98 (1995) 645–664.
[10] A.G. Olabi, A. Grunwald, Design and application of magneto-rheological fluid, Materials &
Design, 28(2007) 2658-2664.
[11] Y. Qi, J.L. Zakin, Chemical and rheological characterization of drag-reducing cationic
surfactant systems, Ind. Eng. Chem. Res., 41(2002) 6326-6336.
[12] L. Li, H.A.Nasr-El-Din, K.E. Cawiezel. Rheological properties of a new class of viscoelastic
surfactant, SPE Prod. Oper, 25(2010) 355-366.
[13] Y.J. Lu, B. Fang, D. Y. Fang et al, Viscoelastic surfactant micelle systems and their rheological
properties, Oilfield Chemistry, 20(2003)291-294.
[14] N. Gaillard, A.Thomas, C. Favero, Novel associative acrylamide-based polymers for proppant
transport in hydraulic fracturing fluids, SPE International Symposium on Oilfield Chemistry, SPE-
164072, 8-10 April, The Woodlands, Texas, 2013.
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![Smart and Robust Composite Tube Columns Frames for Offshore Sub-
Structure Construction
Thar M. Badri Albarodya,
*, Zahiraniza Bt Mustaffab
and Mohd Shahir Liewc
Civil Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar,
31750 Tronoh, Perak, Malaysia
a
t.albarody@ymail.com, b
zahiraniza@petronas.com.my, c
shahir_liew@petronas.com.my
Keywords: Offshore Structure; Steel-encased Composite; Nano-Hyprid Composite; FGM;
Laminated Shell theory.
Abstract. Offshore industry has been welcoming to composite material for its saliences. Features
such as corrosion and temperature resistance, construction cost reduction, and superb fatigue
performance are some of the reasons for this choice. Steel tube-encased composite is an appropriate
found composite replacement for traditional offshore construction. Regardless of all its advantages,
they suffer from the interfacing problem between composite and steel layers; however,
magnetostrictive nanofillers are proposed to increase the integration between the layers. Therefore,
current effort is discussed the vibrational behavior of the proposed robust steel tube column as well
as the actuation characteristics of the magnetostrictive nanofillers in encased composite. The result
reveals that, the steel tube-encased composite columns exhibit greater stiffness in compare with
traditional steel tube. Furthermore, magnetostrictive nanofillers have shown higher actuation
capability of vibration at seismic mode.
Introduction
Composites have found extensive applications in the oil & gas industry since last two decades.
Significant advances have been made in the areas of composite pipe work and fluid handling [1, 2].
The high cost to replace steel elements in retrofit applications and increased longevity in new
construction are driving the use of composites, which withstand severe conditions as experienced in
offshore environment [3, 4]. In the offshore oil and gas industry, the cost of manufacturing and
erecting oil rigs could be reduced significantly if heavy metal column could be replaced with lighter
ones made of composites. Composite column also could be used for:
1. Replace steel components to eliminate corrosion
2. Exhibit excellent fatigue performance, good resistance to temperature extremes and wear,
especially in offshore industrial sectors.
3. Build lighter structures to increase platform performance.
4. Improved combat survivability.
5. Produce complex structural parts at reduced cost, especially in quantity
6. The tailorability of composites to suit specific applications has been one of its greater
advantages such as imparting low thermal conductivity, low coefficient of thermal expansion,
high axial strength and stiffness etc.
Therefore, offshore engineering center in Universiti Teknologi PETRONAS (OECU) has shifted
attention to the development of composite structures of carbon and/or glasses fiber reinforced epoxy
and steel for offshore jacket sub-structure construction with the aim of becoming a medium-scale
contractor with leading-edge technology. Steel Tube-Encased Composite (STEC) column is
developed essentially as weldable tubular structural element expected to be good replacement of
traditionally steel tubes in offshore industrial facilities constructions. However, still the interfacing
problem between composite and steel layers in STEC represent a challenge to be work out.
Advanced Materials Research Vol. 983 (2014) pp 11-15
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![Therefore, a Nano-Hyprid-functionally graded composite (NHFG) proposed to increase the
integration between the layers and grading the structural properties across tube thickness using
magnetic nanoparticles as fillers. Furthermore, such functional composites could utilize the
magnetostrictive properties to actuate the vibration inside the composite tubes. Several models
have been found in the literature dealt with functional composite [5, 6]. Some of them could
specialize to demonstrate the vibrational behavior of multilayered and functionally graded
magnetostrictive composite. Albarody, et.al., [5] derived the exact solution for linearly constitutive
properties, simply supported, functional composite shell subjected to static and dynamic loadings.
The authors were investigated and analyzed the effects of the material properties, lay-ups of the
constituent layers, and shell parameters under the free vibration behavior.
In this paper, a STEC columns filled with magnetic nanoparticles is modeled and the vibrational
characteristic is discussed. Also, some of NHFG composite are examined.
Theoretical Formulation
Based on Hamilton's variational principle linked with Gibbs free energy functions, the steel tube-
encased composite model is casted according to the first-order shear deformation shell theory. The
exact solution is derived for linearly magnetostrictive constitutive properties, simply supported, and
thick shell having rectangular plane-form. Expressed in the (meter–kilogram–second) system of
units, the generation procedure of thick composite shell model, written in curvilinear coordinates
and provides the much-needed materials in state of the smart or adaptive materials are as follows;
1. Constitutive Relations: In a system gather mechanical, magnetic, and thermal influences, the
constitutive relations are expressed formally as:
S = ς ,
ε – κ χ – λ τ , (1)
2. Kinematic Relations: According to the FOSD shell theory, the following representation of the
3D displacement and magnetic potentials is postulated:
u(α, β, ζ, t) = u (α, β, t) + ζψ (α, β, t), v(α, β, ζ, t) = v (α, β, t) + ζψ (α, β, t),
w(α, β, ζ, t) = w (α, β, t), and ϑ(α, β, ζ, t) = − ϑ (α, β, t) + ζϑ (α, β, t) , (2)
where uo, vo, and wo are referred to as the mid-surface displacement functions, and ψα and ψβ are
the midsurface rotation functions of the shell, and ϑ is the magnetic potential function. The strains at
any point in the shell can be written in terms of mid-surface strains and curvature changes as:
ε = (ε + ζε ), ε = ε + ζε , ε = ε + ζ ψ R
⁄ ,
ε = ε + ζε , ε = ε + ζε , ε = ε + ζ ψ R
⁄ .
(3)
However, the mid-surface strains as well as the curvature and twist changes are extended by
Codazzi-Gauss geometric relations, as [6]. The distributions of magnetic fields at any point in the
composite shell are assumed as:
χ = (χ + ζχ ), χ = χ + ζχ . (4)
and the magnetic field changes are
χ = − , χ = − , χ = − , χ = − . (5)
3. Kinetic Relations: The elastic, electric, and magnetic force and moment resultants are obtained
by integrating the constitutive relations (1) over the shell thickness as below:
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![N , M = (1, ζ) S γ dζ + N , M , (6)
where γ = (1 + ζ R
⁄ ), the subscripts n denote either of α, β or αβ, and h is the shell thickness.
In order to gain a numerical stability and pursue a possible integration of Eq. (6) in absence of
thermal forces, the term (1 + ζ R
⁄ ) should be expanded in a geometric series as in [7, 8].
4. Variational Principle: The variational energy method via the Hamiltonian axiom has been used
by [9, 10] for coupling of the energy phenomena and to derive a consistent set of equations of
motion coupled with the free charge equation. In summary, the total energy of a shell element can
be defined as:
δ (K − P) dt = 0, (7)
where P is the total potential energy induced in the system given by:
P = ∭ ς ,
ε – κ χ – λ τ dV − ∬ t S , G , + W S , G , , (8)
where Q(S , G , T) is the thermodynamic potential. t S , G , and W(S , G ) are the tractions and
the work done by body force, and magnetic charge, respectively. The kinetic energy is given as:
K = ∬ (u + v + w ) + ζ ψ + ψ + 2ζ u ψ + v ψ
−
γ γ ABdζdA. (9)
The traction is
t(S , G ) = S δu + S δv + S δw + G δϑ + G δϑ (10)
and the external work is
W(S , G ) = F u + F v + F w + C ψ + C ψ − F ϑ + C ϑ , (11)
where F , F , and F are the distributed forces in α, β and ζ directions, respectively, while
C and C are the distributed couples about the middle surface of the shell. F and C are the
distributed forces and couples due to the magnetic charge. Hence, the temperature, τ is a known
function of position and enter the formulation only through the constitutive equations. Substituting
Eqs. (1, 10, and 11) into Eq. (8) and equating the resulting equation with Eq. (9), yields after
expanding the terms:
δ ∬
̅
(u + v + w ) +
̅
ψ + ψ
+I̅ u ψ + v ψ
ABdAdt– ∭ (ς ε − κ χ − λ τδε) dVdt
+ ∬ S δu + S δv + S δw + G δϑ + G δϑ ABdAdt
+ ∬ F u + F v + F w + C ψ + C ψ − F ϑ − C ϑ ABdAdt = 0. (12)
Replacing the constitutive terms in Eq. (12) by the kinetic relations (6), then integrating the
displacement gradients by parts to obtain only the virtual displacements, we can set the coefficients
of δuo, δvo, δwo, δψα, δψβ, δϑ0 and δϑ1 to zero, individually. The equations of motion and the
charge equilibrium equation for isothermal case are
BN + AN + N – N + Q + Q + ABF = AB I̅ + I̅ ,
Advanced Materials Research Vol. 983 13](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-27-320.jpg)
![Fig 1. The transvers stresses and magnetic induction across the composite tube thickness, at unity load.
GRFE properties are (E1/ E2=15, G12/ E2=0.5, G13/ E2=0.5, υ12=0.3, a/b=1, a/h=10, and the lamination scheme
is (0/09)S), while CoFe2O4 properties and the grading material properties model can be found in [5].
Conclusions
The evolutionary process of development of adaptive steel tube-encased composite for tubular
constructions has opened up new vistas for the several interdisciplinary applications. The benefits of
these composite tubes are expected to be enormous. The concept of a structure with capability of
automatically responding to the environment by change in the self-configuration, or by changing the
interface with the environment is one which offers the potential of extremely attractive advantages
in the design, development and operation of offshore structures. The STEC columns comprising
magnetostrictive materials have been modeled and scrutinized. The present model may serve as a
reference in developing a prototype of STEC columns for further experimentations.
Acknowledgment
Authors would like to acknowledge Universiti Teknologi PETRONAS for sponsoring this work.
References
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978-3-8465-2175-5, Saarbrücken, Germany., 2013), pp. 212 Pages.
[7] Leissa A.W., Chang J., Compos. Struct. 35, 53 (1996).
[8] T. M. Badri, H. H. Al-Kayiem, Asian Journal of Scientific Research 6, 236 (2013).
[9] Y. Bao, University of Kentucky (1996).
[10]T. M. Badri, H. H. Al-Kayiem, Journal of Applied Sciences 12, 2541 (2012).
-1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
x 10
-7
-0.15
-0.1
-0.05
0
0.05
0.1
0.15
0.2
Thickness
of
Shell
in
(mm)
Magnetic Induction
-200 0 200 400 600 800 1000 1200
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
Thickness
of
Shell
in
(mm)
Transvers Stress Mpa
GRFE NHFC
Steel Tube
Advanced Materials Research Vol. 983 15](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-29-320.jpg)
![The research process and application prospect of the smart
piezoelectric materials
Xiaoliang Fang1, a
, Weifang Zhang1, b
, Hongxun Wang 1, c
1
BeiHang University, School of Reliability and Systems Engineering, Science & Technology
Laboratory on Reliability & Environment Engineering, XueYuan Road No.37,HaiDian District,
Beijing, China.
a
bit20092110@live.cn, b
08590@buaa.edu.cn, c
wanghongxun1990@163.com
Keywords: Smart piezoelectric materials; Preparation process; Application status and prospects
Abstract: Piezoelectric material which can be used as both sensor and drive is an important kind of
smart material. Studies on piezoelectric materials are now the research focus and hotspots of smart
materials which have achieved fruitful results. This article describes the working principle of smart
piezoelectric materials, provides an overview of the preparation progresses and application status,
based on which the research and development trends are discussed.
1. Introduction
The performance requirement of the smart materials is that the perceptions, drive and
information processing should be integrated in one system, which is similar to biological materials
that have intellectual properties [1]. Smart materials system can get the outside world information
by its own perception, make judgment and processing, emit instruction, and then adjust own state
and structure to adapt to the changes in the extemal environment. Consequently, the smart materials
system fulfill various special functions, such as self-detection, self-diagnosis, self-regulation,
self-adaptive and self-repair, which are similar to biological system [2].
The smart materials are based on the function materials which can be divided into two categories
according to their different roles playing at work. These can be made into various types of sensors
are known perception materials, which are used to sense the signal of stimulation and changes from
the outside or internal, such as stress, heat, light and electricity etc. The common perception
materials include photosensitive materials, heat-sensitive materials, moisture-sensitive materials,
acoustic emission material, inductor material, shape memory materials, magnetostrictive materials,
piezoelectric materials etc. These can be made into drivers are known as actuating materials, which
can change the shape, size, location, stiffness and structure of their own according to the changes of
temperature, electric field and magnetic field etc. The common actuating materials include
shape-memory materials, electrostrictive materials, electrorheological fluids, magnetostrictive
material, magnetorheological fluid and piezoelectric materials [2, 3, 4].
With the progress of the research of the smart materials, the piezoelectric materials which can be
made into both driver and sensor drive more and more attention. Piezoelectric materials are able to
achieve mutual transformation between mechanical energy and electric energy. Transforming the
changes of the outside pressure into appropriate electric signal, piezoelectric materials fulfill the
function of being a sensor, meanwhile piezoelectric materials meet the requirement of being a
driver while transforming the electric signal of the excitation source into corresponding mechanical
signal, such as the vibration signal and deformation signal [5, 6, 7].
With the rapid development of the materials science, microelectronics and computer technology,
the piezoelectric materials show broad prospect of application which catches the interests of the
global scientists. Based on the background above, the working principle of smart piezoelectric
materials are described; an overview of the preparation progresses and application status are
provided and the research and development trends are discussed in this article [5.8].
Advanced Materials Research Vol. 983 (2014) pp 16-19
© (2014) Trans Tech Publications, Switzerland
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![2. Working principle of the smart piezoelectric materials
The working principle of the smart piezoelectric materials is based on piezoelectric effect. The
piezoelectric effect is that when there is a deformation of the materials by external forces, positive
and negative electric charges will arise in the relative two surfaces of the material due to an internal
polarization at the same time. There are direct piezoelectric effect when mechanical energy is
transformed into electrical energy and inverse piezoelectric effect electrical energy is transformed
into mechanical energy [3, 5].
3. New preparation technology of the smart piezoelectric materials
3.1 The piezoelectric coatings prepared by plasma spraying method
W Haessler et al. investigated the structure and piezoelectric properties of the PZT coatings
prepared by plasma spraying method. They found out that the heat treatment and polarization
process after spraying have a significant effect on the piezoelectric properties of the PZT coatings
[9].
Songlin Gu, Guolu Li et al. fabricated PZT coatings on the surface of 45 steel by supersonic
plasma spraying method. The research results showed that the PZT coatings with a typical layered
structure had dense microstructure, of which the surface was flat and the air hole rate was 1.6%.
The PZT coating was well bonded to the substrate, which met the requirement of application at
actual work [10].
3.2 Piezoelectric ceramic materials prepared by sol-gel method
Piezoelectric ceramic materials fabricated by sol-gel method have high purity, well-distributed
chemical constituents and low temperature of reaction compared with these prepared by the
traditional solid state reaction.
Minglei Zhao et al. prepared Na0.5Bi0.5TiO3 ceramic by sol-gel method. The piezoelectric
constant d33=173×10-12
pC/N increased by 40% compared with that fabricated by traditional method.
Meanwhile the piezoelectric ceramic in this study had small coercive field and large residual
polarization [11].
Y. D. Hou et al. investigated the fabrication of (Na0.8K0.2)0.5Bi0.5TiO3 (NKBT) prepared by
sol-gel –hydrothermal method and its densification. The analysis of the morphology and structure
showed that NKBT nanowire with pure perovskite structure could be prepared by
sol-gel-hydrothermal method with the synthetic temperature of 160 ºC, of which the diameter was
50-80nm, and the length was 1.5-2.0µm. The theoretical density of the flake made of NKBT
nanowire was more than 98% [12].
3.3 Fabrication of piezoelectric composites
Lei Dai, Shan Hu et al. prepared PZN-PZT/PVDF piezoelectric composite material by solid
phase sintering combined with solution blending method, and investigated the properties of the
materials. The results revealed that the generation of pyrochlore phase could be restrained by
appropriately excessive Pb, but too much Pb would reduce the degree of crystallization of the main
crystal phase and the piezoelectric properties of the piezoelectric composite material [13].
4. Application prospect of the smart piezoelectric materials
4.1 Application in structural health monitoring
Due to chemical corrosion, stress effect, tiny impact and influence and other factors, local
damage and micro-cracks may appear on the surface of the structure of large aircraft, nuclear
Advanced Materials Research Vol. 983 17](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-31-320.jpg)
![reactors, bridges, and large pipes. On the structure of local damage, especially micro - cracks on the
surface of monitoring it is a very important part of structural health monitoring system to monitor
the local damage and micro-cracks on the surface of the vital structure [14].
A damage detection method based on an innovative 2D phased sensor array made of
piezoelectric paint is proposed for in situ damage detection of a thin isotropic panel using guided
Lamb waves. In this study, a 2D phased sensor array with a spiral configuration is fabricated using
a piezoelectric composite patch and used for detecting damages in an aluminum panel. Steered
array responses are generated from the raw sensor signals using a directional filtering algorithm
based on phased array signal processing. To enhance the proposed analysis technique, empirical
mode decomposition (EMD) and a Hilbert–Huang transform (HHT) are applied. A new damage
detection algorithm including threshold setting and damage index (DI) calculation is developed and
implemented for detecting damages in the form of holes and a simulated crack. The characteristic
damage indices consistently increase as damage size grows [15].
4.2 Application in energy converter
In order to optimize the deformation and brittleness of the piezoelectric materials, the Langley
research center of the NASA fabricated a new kind of smart piezoelectric macro fiber composite
(MFC). Tungpimoluryt K, Hatti N et.al designed an energy collection device based on MFC
materials. The main structure of the device is cantilever structure with the MFC fixed on the surface
of the cantilever. When sinusoidal excitation is applied, capacitor of the energy collection device is
used to collect the electric current generated by MFC, so that the function of collecting energy is
fulfilled. The study results showed that this device can produce up to 45. 6v voltage [16].
4.3 Application in adaptive wing
Based on the inverse piezoelectric effect, Paradies et al. designed and made an active control
wing model of which the wingspan was 500mm.The key parts of the model were seven set of MFC
modules. The wings would be controlled to auto-deform while the MFC parts were applied with
voltage. The study results showed that the deformation value of the wing end was 4.3mm when the
voltage applied was 1.5kV [17].
5. Research prospect of the smart piezoelectric materials
In this paper, new fabrication methods and application of the smart piezoelectric materials are
introduced. Although the smart piezoelectric materials have been used in many fields owing to the
big driving force and fast response speed, it should be noted that the effects to decrease the
brittleness and improve the deformation degree of the smart piezoelectric materials are still needed.
The key focus of the study of smart piezoelectric materials are to compound the structures and
increase the serviceability. As the synthesis and integration of various materials and high
technology, the research of smart piezoelectric materials is bound to have a good and broad
prospects.
References
[1] Y. Liu, K. Gall, M.L. Dunn: Mech. of Mater. Vol.36 (2004), p.929.
[2] C. Lin, F. Chen, L. Yuan, G.Z. Liang: FRP/Compo. Vol. 2 (2012), p. 74.
[3] X.M. Zhang: FRP/Compo. Vol. 6 (2013), p. 57.
[4] J.H. Xie, W.G. Zhang, D.K. Liang: Mater. Review. Vol. 20 (2006), p. 6.
[5] C. He, W.G. Chen: Jour. Fun. Mater. Vol. S1 (2010), p. 11.
18 Advanced Materials and Engineering](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-32-320.jpg)
![[6] S.R. Platt, S. Farritor, H. Haider: IEEE/ ASME Transactions on Techtronic. Vol. 10 (2005), p.
240.
[7] Y.X. Bian, C.H. Yang: Piezoelectrics & Acoustooptics, Vol. 33 (2011), p. 612.
[8] H. Takahashi, Y. Numamoto et al: Appl. Phys. Vol. 47 (2008), p. 8468.
[9] W. Haessler et al: Mater. Lett. Vol. 24 (1995), p. 387.
[10] S.L. Gu, G.L. Li et al: Mater. Sci. Eng. Powder Metall. Vol. 18 (2013), p. 560.
[11] M.L. Zhao et al: Acta. Phys. Sin. Vol. 52 (2003), p. 229.
[12] Y. D. Hou et al: J Am Ceram Soc. Vol. 90 (2007), p. 1738.
[13] L. Dai, S. Hu et al: CHN Ceram. Vol. 43 (2007), p. 47.
[14] F. Zhang et al: Chinese Journal Sensors and Actuators. Vol. 18 (2005), p. 215.
[15] B. Yoo, A.S. Purekar, Y. Zhang: Smart Mater. Struct. Vol. 19 (2010), p. 17
[16] K. Tungpimoluryt et al: IEEE International Symposium on Applications of Ferroelectrics,
2011.
[17] R. Paradies, P. Ciresa: Smart Mater. Struct. Vol. 18 (2009), p. 1.
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![Reusable and efficient polystryrene-supported acidic ionic liquid
catalyst for the synthesis of n-butyl acetate
Yuhe Cheng a
, Biao Zhang b
, Shangjiang Dai c
, Hanlin Tong d
, Lixia Li e *
1
School of environment and safety engineering, Jiangsu University, Zhenjiang 212013, PR China
a
chengyuhe@126.com, b
851974763@qq.com, c
584119471@qq.com, d
tonghanlin1@163.com,
e
*qingpipa@163.com
Keywords: Polystyrene-supported acidic ionic liquid. Esterification. n-Butyl acetate.
Abstract. A series of polystyrene-supported 1-(propyl-3-sulfonate)-3-methy-imidazolium
hydrosulfate acidic ionic liquid (PS-[SO3H-PMIM][HSO4]) catalysts with different [SO3H-PMIM]
[HSO4] contents were prepared and tested for esterification of n-butyl alcohol with acetic acid. It was
found that the reactivity of the catalyst increased with increasing [SO3H-PMIM][HSO4] content, and
best yield of n-Butyl acetate of 98% was obtained using PS-[SO3H-PMIM][HSO4]1 within 1.5h. The
catalytic activity of this catalyst decreased slightly after fifth using.
Introduction
Caboxylic esters is a important intermediates. Traditionally, they were synthesized by Fischer
esterification of carboxylic acids and alcohols under the catalyst of hydrochloric acid or sulfuric acid
[1]. Although much success has been achieved with these inorganic liquid-phase acids, some
problems still remain, for example, tedious purification procedure of the product, needing of a lot of
inorganic acids, corrosion of equipments[2,3]. Various novel catalysts have therefore been explored
in order to avoid these insufficient. Since the end of last century, with more and more recognition of
room temperature ionic liquids (TSILs), there are growing interests in using ionic liquids as solvents
or catalysts for esterification [4,5], but high costs and unendurable viscosities limited their further
applications [6].
In recent years, some researches were reported about supported acidic ionic liquid catalyst for
organic reactions [7-9]. These researches showed that the supported ionic liquid catalysts had many
advantages over their unsupported counterparts, such as separation, reusability, and the ability to
provide practical conveniences in a continuous system. Recently, Xu[10] reported a new approach of
synthesis of PS-supported acidic ionic liquid (PS-CH2-[SO3H-pIM][HSO4]) catalyst and its catalytic
performance for Fischer esterification. In the previous work, we supported a imidazole type
Brønsted-acidic TSILs, 1-(propyl-3-sulfonate)-3-methy-imidazolium hydrosulfate acidic ionic liquid
([SO3H-PMIM][HSO4]), onto three kind of chloromethylated polystyrene beads prepared in lab to
prepare a series of PS-[SO3H-PMIM][HSO4] catalysts, and studied their catalytic capability in
nitration of aromatic compounds [11, 12]. As part of our continuing interests, here, we tested for
esterification of n-butyl alcohol with acetic acid. The catalysts were characterized by FT-IR,
SEM/TEM, elements analysis, TG/DSC and acid base titration.
Experimental
Catalyst preparation. Scheme 1 showed the synthetic process of PS-[SO3H-PMIM][HSO4] [10, 13].
First, sodium methylate (0.1mol) in methanol (10mL) was added dropwise into the mixture of
imidazole (0.1mol), KI (0.1g) and toluene (5mL) at 40 ℃. Then, PS-CH2Cl beads (0.01mol, –CH2Cl),
prepared according to the previous report [14], in acetonitrile (15mL) was added to the formed
imidazole sodium salt solution, the reaction was carried out at 65 ℃ for 48 h. The PS-CH2-imidazole
product was filtered off and washed by soxhlet extraction using ethanol as solvent and dried under
vacuum. Second, PS-CH2-imidazole and equiv (relative to -imidazole) 1,3-propane sultone were
Advanced Materials Research Vol. 983 (2014) pp 20-25
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![added in anhydrous toluene and reacted at 75 ℃ for 14h. Then product named as the
PS-[SO3H-PMIM] was filtered off, washed with toluene and dried under vacuum. Last, dried
PS-[SO3H-PMIM] was soaked in dichloromethane at 0 ℃, and acidified with equiv concentrated
sulfuric acid or hydrochloric acid. The mixture were heated to 75 ℃ for 4h under stirring. The target
catalyst PS-[SO3H-PMIM][HSO4] or PS-[SO3H-PMIM][Cl] were collected by filtration, washed
with diethyl ether and dried under vacuum.
Scheme 1 Synthesis of PS-[SO3H-PMIM][HSO4] catalyst
Catalyst characterizations. IR spectroscopy was recorded using a Nicolet IS10 FTIR spectrometer.
TG/DSC studies were carried out using METTLER TOLEDO SDTA851e/DSC823e instrument.
Elemental analysis was determined by Vario MICRO EL. Average particle sizes and surface
morphologies were characterized by a SEM Leica S440i. GC spectra were recorded using Agilent
GC-6820 spectrometer. Acidic sites was confirmed by titration of PS-[SO3H-PMIM][HSO4] catalyst
with 2.08×10-2
M aq. NaOH, using phenolphthalein as indicator.
Catalyst for aromatics esterification reactions. PS-[SO3H-PMIM][HSO4] (0.95g), n-butyl alcohol
(96mmol), acetic acid (80mmol) and cyclohexane (8mL) were charged successively into a three-neck
flack with a water segregator, and stirred at 92℃ for length of time. The resultant mixture was cooled.
The catalyst was filtered off, washed with ethanol, and dried for the recycling experiments. The filtrate
was analyzed using GC.
Results and discussion
FT-IR. As shown in Fig.1, for PS-CH2Cl, the characteristic peaks of polystyrene exhibited the C–H
stretching vibration of aromatic ring at 3016 cm−1
, and C–H asymmetric and symmetric stretching
vibrations of methylene at 2920 cm−1
and 2855 cm−1
. The peaks at 1609 cm−1
and 1507 cm−1
were due
to the C–C skeleton vibration of aromatic ring of polystyrene. Moreover, a typical peak at 1265 cm−1
was attributed to stretching vibrations of the functional group –CH2Cl, and another peak at 672cm-1
was due to stretching vibrations of C-Cl[15]. The two typical peaks were practically omitted after
introduction of imidazole. Meanwhile, a peak assigned to the C=N stretching vibration of imidazole
ring at 1560 cm−1
appeared[16], which was indicated the imidazole anchored on the polystyrene by
covalent bond. In the IR spectrum of PS-[SO3-PMIM], several strong peaks, i.e. 1039 cm-1
, 1160 cm-1
and 1209 cm-1
, appeared which were attributed to the absorb of –SO3
-
. When PS-[SO3-PMIM] was
acidified with concentrated sulfuric acid, there were no obvious change in IR spectrum but two peaks,
1039 cm-1
and 1209 cm-1
became stronger, which were attributed to the S=O asymmetric and
symmetric stretching vibrations of –SO3– group.
Advanced Materials Research Vol. 983 21](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-35-320.jpg)
![Fig. 1 IR-spectra of PS-CH2Cl, PS-CH2-imidazole, PS-[SO3-PMIM] and PS-[SO3H-PMIM][HSO4].
Elements analysis of PS-CH2-imidazole and acidic sites of PS-[SO3H-PMIM][HSO4]. Table 1
showed the elemental analysis for PS-CH2-imidazole. It can be seen that the imidazole contents
increased with the increasing of VBC in feed composition of PS-CH2Cl. Acid sites of the
PS-[SO3H-PMIM][HSO4] catalyst was confirmed by acid base titration. The loading amounts of
[SO3H-PMIM][HSO4] in PS-[SO3H-PMIM][HSO4]1 and PS-[SO3H-PMIM][HSO4]2,
PS-[SO3H-PMIM][HSO4]3 were 2.22, 2.03 and 1.69mmol/g respectively.
Table 1 Elemental analysis of PS-CH2-imidazole
Sample VBC:St:DVB, vol% % C % H % N Imidazole, mmol/g
PS-CH2-imidazole1 98:0:2 73.88 6.84 12.77 4.56
PS-CH2-imidazole2 74:24:2 74.11 6.88 11.58 4.14
PS-CH2-imidazole3 49:49:2 77.50 7.09 9.24 3.30
“VBC:St:DVB, vol%”was the feed composition of PS-CH2Cl beads. “VBC, St and DVB” are the abbreviation of
“4-vinylbenzyl chloride, styrene and divinyl benzene” respectively.
SEM/TEM and TG-DSC. It can be seen that PS-CH2Cl (Fig. 2 A and C) was uniform globular in the
size of ~600 nm. After the introduction of [SO3H-PMIM][HSO4], the catalyst became big a little,
about ~700nm and the surface became smooth (Fig. 2 B and D), which is in accord with other report
[10].
Fig. 2 SEM and TEM of PS-CH2Cl (A and C)
and PS-[SO3H-PMIM][HSO4] (B and D).
Fig. 3 TG/DSC curves of PS-CH2Cl and
PS-[SO3H-PMIM][HSO4] catalyst.
TG/DSC analysis was carried out in N2 with heating rate of 10 ℃/min. As shown in Fig. 3, no
significant weight loss was observed from both PS-CH2Cl and PS-[SO3H-PMIM][HSO4] at
beginning. Above 120℃, weight loss was accelerated for both the two particles and weight loss speed
of PS-CH2Cl was quicker than that of PS-[SO3H-PMIM][HSO4]. There was a obvious weight loss
22 Advanced Materials and Engineering](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-36-320.jpg)
![from PS-CH2Cl nearby 150 ℃. Correspondingly, for the DSC curve of PS-CH2Cl, a small exothermic
peak appeared, however it didn’t appear in the DSC curve of PS-[SO3H-PMIM][HSO4]. The weight
loss and the exothermic peak of PS-CH2Cl were possibly ascribed to the water inside the porous
PS-CH2Cl particles. When the [SO3-PMIM] was immobilized onto PS-CH2Cl in organic solvent, the
water was droved and the holes were jammed. When the temperature further increased up to higher
than 300 ℃ for PS-CH2Cl and 410 ℃ for PS-[SO3H-PMIM][HSO4], weight loss accelerated heavily.
A possible reason is that their structures were destroyed or the chloromethyl groups and the
[SO3H-PMIM][HSO4] separated from PS. The residue weight of PS-[SO3H-PMIM][HSO4] and
PS-CH2Cl was about 56.5% and 27.2% at 450 ℃, respectively. These observations indicated that the
immobilization of [SO3H-PMIM][HSO4] onto polystyrene could improve the thermal stability of
PS-CH2Cl.
Catalytic reaction. The esterification of n-butyl alcohol with acetic acid is showed in Scheme 2.
Scheme 2 Esterification of n-butyl alcohol with acetic acid.
To evaluate the PS-[SO3H-PMIM][HSO4] catalyst described here, the catalytic activities of various
catalyst for the esterification reaction of n-butyl alcohol and acetic acid were examined under the
same reaction conditions (Table 2). Obviously, the yields of n-butyl acetate over
PS-[SO3H-PMIM][HSO4] (Table 2, entry1-3) were much higher than that over the support (Table 2,
entry 5) and no catalyst(Table 2, entry 6). This meant that the reaction hardly carried out without
catalyst and the support almost had no influence on the yield. It was worth noting that the
PS-[SO3-PMIM]1 had no influence on the reaction evidenced the scheme of the synthesis of
PS-[SO3H-PMIM][HSO4] catalyst at a certain extent. In addition, it easy to see that both the
PS-[SO3H-PMIM][HSO4] catalysts and PS-[SO3H-PMIM][Cl] (Table 2, entry 4) catalyst were
effective for the reaction of n-butyl alcohol and acetic acid although the catalytic activity of the latter
was far lower than that of the former. The reason was that both the two kinds of solid catalysts could
provide proton H+
, which could make the acetic acid protonated and then was attacked by
nucleophilic n-butyl alcohol to form n-Butyl acetate. Which analysis was based on the classical two
key steps esterfication [17-19]. Compared to PS-[SO3H-PMIM][HSO4] catalysts, there are two
groups, i.e. HSO4
-
anions and SO3
H- group, could supply proton H+
, the providing proton H+
ability
of PS-[SO3H-PMIM][Cl] is limited, which contributed lower catalytic capability.
It can be seen that all of the PS-[SO3H-PMIM][HSO4] catalysts exhibited high catalytic activity. The
yield of n-Butyl acetate increased with the increasing of [SO3H-PMIM][HSO4] content at same
reaction time, which was attributed to the gradually increasing amount of acid sites in the catalyst.
When using the PS-[SO3H-PMIM][HSO4]1 as catalyst, 98% yield was obtained at 92℃, within 1.5h,
which was better than the similar study reported by Xu[10].
Table 2 Result of n-Butyl acetate over various catalyst and reaction timea
Entry
Catalyst
Yield, %
0.75, hb
1.5, hb
3, hb
1 PS-[SO3H-PMIM][HSO4]1 94 98 98
2 PS-[SO3H-PMIM][HSO4]2 90 96 98
3 PS-[SO3H-PMIM][HSO4]3 90 93 98
4 PS-[SO3H-PMIM][Cl]1 57 68 74
5 PS-[SO3-PMIM]1 (or PS-CH2Cl1) 34 47 52
6 Blank 33 48 50
a
By quantitative GC based on crude product
b
Reaction time, h
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![Catalyst recycle study. The reusability of PS-[SO3H-PMIM][HSO4] catalyst was evaluated in
esterification of n-butyl alcohol with acetic acid catalyzed by PS-[SO3H-PMIM][HSO4]1. As shown
in Table 3, PS-[SO3H-PMIM][HSO4]1 still showed very high activity after third runs and the catalytic
activity decreased only 3% for 5 runs, which indicated that PS-[SO3H-PMIM][HSO4] catalyst was
efficient and reusable.
Table 3 The reusability of PS-[SO3H-PMIM][HSO4]1 for n-Butyl acetatea
Runs time 1 2 3 4 5
Yield, % 98 98 97 96 95
a
By quantitative GC based on crude product, reaction time 1.5h.
Conclusion
A series PS-[SO3H-PMIM][HSO4] catalysts were prepared by grafting [SO3H-PMIM][HSO4] onto
the highly chloromethylated polystyrene beads, and showed a better thermal stability than that of
PS-CH2Cl resins. These catalysts were efficiencies for esterification of n-butyl alcohol with acetic
acid. The yield of n-Butyl acetate generally increased with increasing of the [SO3H-PMIM][HSO4]
content. The best yield of 98% was obtained under 92℃ within 1.5h over PS-[SO3H-PMIM][HSO4]1
catalyst. The catalyst could be recovered by simple filtration, and the yield only decreased 3% after
reusing for 5 times. In conclusion, the PS-[SO3H-PMIM][HSO4] catalyst prepared in this paper was
an excellent recyclable catalyst for the synthesis of n-Butyl acetate, and it showed potential
application for carboxylic esters in industry.
This work was supported by the grant (No. 1281370046) from the Scientific Research Foundation for
the high-ranking talent of Jiangsu university.
References
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Concept for Homogeneous Hydroformylation Catalysis, J. Am. Chem. Soc. 124 (2002) 12932-12933.
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24 Advanced Materials and Engineering](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-38-320.jpg)
![[11] X.L. Li, Q. L. Ling, Z. L. Liu, et. al. Reusable and Efficient Polystryrene-supported Acidic Ionic
Liquid Catalyst for Mononitration of Aromatic Compounds, Bull. Korean Chem. Soc. 2012, 33(2012)
3373-3377.
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Catalyst for Mononitration of Toluene, Advanced Materials Research, 581-582(2012) 252-257.
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modified silica catalyst and applications in the hydrolysis of cellulose, Catal. Commun. 11 (2010)
1072-1075.
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Porous Polymer Nanospheres, Macromolecules 39 (2006) 5381-5384.
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acidic ionic liquids, Ind. Eng. Chem. Res. 46 (2007) 7955-7906.
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Advanced Materials Research Vol. 983 25](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-39-320.jpg)
![An exploration of factors affecting the preparation of
SiO2-coated α-Al2O3 pearlescent pigment
Nan Wu1,a
, Qinghua Chen1,b*
, Weiming Zhou2,c
, Meizhen Ke2,d
,
Qingrong Qian1,e*
, Zhanhui Yuan1,f
1
College of Environmental Science and Engineering, Fujian Normal University, Fuzhou, China
2
College of Materials Science and Engineering, Fujian Normal University, Fuzhou, China
a
270732913@qq.com, b
cqhuar@126.com, c
zhouweiming721@126.com, d
757412608@qq.com,
e
qrqian@fjnu.edu.cn, f
zhanhui.yuan@fzkuncai.com
Keywords: SiO2-coated α-Al2O3; pearlescent pigment; liquid phase deposition
Abstract: The SiO2-coated α-Al2O3 pearlescent pigment was prepared by liquid phase deposition
(LPD). The effects of concentration of sodium silicate solution, reaction temperature and pH value
of the aluminum oxide suspending liquid were systemically studied in this paper. The obtained
samples were characterized by scanning electron microscopy (SEM). The results showed that when the
process parameters are the concentration of sodium silicate solution of 0.1 mol/L, the reaction
temperature of 80 o
C and the pH value of 9.0, the high quality of SiO2-coated α-Al2O3 pearlescent
pigment could be obtained.
Introduction
Pearlescent pigment is one of the color effect materials which composed of a highly reflective
platelet-shaped substrate encapsulated with a low index of refraction material [1]. It is widely
applied in plastics, printing ink, cosmetic and ceramic materials due to its unique decorative optical
color effects and weather-resistance effects [2].
The common substrates of traditional pearlescent pigment were mica or synthetic mica [3]. The
defect of the mica or synthetic mica based pearlescent pigment are these: 1. the mica or synthetic
mica is difficult to delamination; 2. the pearlescent pigment made by mica or synthetic mica has a
poor dispersion.
α-Al2O3 based pearlescent pigment[4] is a newly emerging material which overcome the defect
of the mica or synthetic mica based pearlescent pigment. In this paper, the factors affecting the
preparation of SiO2-coated α-Al2O3 pearlescent pigment was studied in order to find a easy and fast
way of preparing the SiO2-coated α-Al2O3 pearlescent pigment.
Experimental
Raw materials and reagents. The platelet-shaped α-Al2O3 was supplied by Xiamen ZF Co., Ltd.
The morphology of α-Al2O3 was shown in Fig.1. The sodium hydroxide and sodium silicate were
provided by Tianjin Fuchen chemical reagents factory, both of them are analytical-reagent. And the
chemically-pure sulphuric acid was obtained from Fuzhou chemical engineering research institute.
Advanced Materials Research Vol. 983 (2014) pp 26-29
© (2014) Trans Tech Publications, Switzerland
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![Influence of the reaction temperature. Heating properly could promote the growth of SiO2
crystal particles as well as accelerate the hydrolysis of sodium silicate. With the increase of
temperature, the crystal particles that formed in the surface of α-Al2O3 would be larger and larger, as
shown from Fig.3-a to Fig.3-d. But when the temperature was too high, the crystal might also fail to
form, as shown in Fig.3-e. Therefore the optimum reaction temperature is 80 o
C.
Fig.3 The morphology of SiO2-coated α-Al2O3 prepared in different temperature (a: 75 o
C; b: 80
o
C; c: 85 o
C; d: 90 o
C; e: 95 o
C), all the sample above were prepared by 0.10 mol/L sodium silicate
solution, with the pH 9.0
Influence of the pH value. The pH value could affect both the hydrolysis and gelling of silicate.
The sodium silicate would hydrolyze rapidly at a low pH value, which might lead to self-nucleation
of silicate. We could learn from the pre-experiment that the hydrolysis rate of sodium silicate would
be appropriate when the pH value was 8.0~10.0. The relationship of gelling time with pH was
following N curve [5]. The pH 8.0~8.5 was nearly at the bottom of the N curve, at that range, the
gelling rate would be high, and the large grain of SiO2 would be formed before it deposited on the
surface of α-Al2O3, as shown in Fig.4-a and Fig.4-b. When the pH value was 9.0, the gelling rate
was moderate and close to the deposition rate, the SiO2 on the surface of α-Al2O3 would be
well-distributed, as shown in Fig.4-c. Therefore the optimum pH is 9.0.
28 Advanced Materials and Engineering](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-42-320.jpg)
![Fig.4 The morphology of SiO2-coated α-Al2O3 prepared in different pH (a: 8.0; b: 8.5; c: 9.0; d:
9.5; e: 10.0), all the sample above were prepared by 0.10 mol/L sodium silicate solution, in 80 o
C
Conclusions
The SiO2-coated α-Al2O3 pearlescent pigment was prepared by liquid phase deposition (LPD).
The result of SEM showed that when the process parameters are concentration of sodium silicate
solution of 0.1 mol/L, reaction temperature of 80 o
C and pH value of 9.0, the SiO2 on the surface of
α-Al2O3 would be dense, fine and well-distributed.
Acknowledgements
This work is supported by Program for the Fujian Provincial Science and Technology and the
Provincial Financial Department (2011H6005), and the Scientific Research Foundation for the
Returned Overseas Chinese Scholars, State Education Ministry (2011-1568).
The corresponding authors are Qinghua Chen and Qingrong Qian.
References
[1] Curtis J. Zimmermann, James D. Christie, Vivian K. Doxey and Daniel Stevenson Fuller, U.S.
Patent 6,821,333. (2004)
[2] Deborah Cacace, Carolyn Lavallee, Michael T. Venturini, U.S. Patent 5,759,255. (1998)
[3] Frank J. Maile, Gerhard Pfaff, Peter Reynders, Effect pigments—past, present and future,
Progress in Organic Coatings. 54 (2005) 150-163.
[4] Jung Min Lee, Jeong Kwon Suh, Byung Ki Park, Dong Uk Choe, Gil Wan Chang, Kwang Su
Lim, Sung Yun Jo, Kwang Choong Kang, U.S. Patent 8,287,636. (2012)
[5] Cui Aili, Wang Tingjie, Jin Yong, Xiao Shuaigang, Ge Xudong, Mechanism and Structure
Analysis of TiO2 surface coated with SiO2 and Al2O3, Chemical journal of Chinese universities. 19
(1998) 1727-1729.
Advanced Materials Research Vol. 983 29](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-43-320.jpg)
![Assessment of Engineering Properties of Geosynthetics
with Seaming Methods
Han-Yong Jeon
Department of Applied Organic Materials Engineering, Inha University, Incheon, Korea(Rep.)
hyjeon@inha.ac.kr
Keywords: geosynthetics, seaming method, transmissivity, strength retention, chemical resistance,
seam strength, reduction factor
Abstract. 8 Geotextiles (; 4 woven and 4 nonwoven types), 4 geogrids and 2 geocomposites of
[nonwoven/fibers/nonwoven] structure were used as raw materials and the different seaming
methods were applied to compare the seam properties of 3 geosynthetics and transmissivity of
geocomposites. Tensile strength retentions of these geosynthetics were evaluated as the degree of
damage by chemical degradation. Woven geotextiles showed the higher seam strength in the order
(SSd-1 < SSd-2) > (SSa-1 < SSa-2) > geospacer without regard to the design strength. For
nonwoven geotextiles, the order of seam strength is geospacer > (SSa-1 < SSa-2). Geogrids showed
the higher seam strength in the order of band > geospacers but reduction factors were increased in
the order of band > geospacer without regard to the geogrid’s compositions. Finally, geocomposites
showed the higher seam strength in the order of geospacer > (SSa-1 < SSa-2) but showed the
transmissivity in the order of geospacer > (SSa-1 > SSa-2) without regard to the kinds of filled
fibers and weight of geocomposite.
Introduction
Geosynthetics have their seaming methods such as mechanical or chemical seaming techniques
due to their own structures, physical, chemical and thermal properties. Furthermore, the seam
strength of geosynthetics must be influenced by seaming methods and for reinforcement/protection
applications with geosynthetics, the seaming is typically the weak connection to applied load
transfer in the reinforcement/protection system [1]. For filtration or drainage applications, this
phenomena on geosynthetics could affect the vertical or horizontal hydraulic flow. Seaming can
have a significant impact on the performance of geosynthetic systems whether their intended
function is reinforcement/protection, separation or filtration and drainage. When reinforcement/
protection is the function, the seaming must be considered as a limiting strength factor and assessed
by the same performance standards as the reinforcement/protection geosynthetic only [2, 3, 4].
Besides this, the seaming of geosynthetics should be evaluated for durability limitations such as
installation damage, creep deformation, chemical and biological degradations etc. Seaming of
geotextiles by traditional sewing methods necessarily causes needle damage to fibers and yarns as
well as creating stress concentrations where the sewing threads reverse direction for their return
stroke. These effects are relatively small for light-weight geotextiles and the resulting seam strength
are generally quite high. For geogrids, the connection techniques require a high level of dimensional
Advanced Materials Research Vol. 983 (2014) pp 30-38
© (2014) Trans Tech Publications, Switzerland
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![stability within the geogrid structure to withstand the stress concentrations imposed by connection
techniques. Filtration or drainage performance of geocomposites could be also influenced by the
seam strength with different seaming methods. In this study, geotextiles - 4 woven and 4 nonwoven
types, 4 geogrids and 2 geocomposites of [nonwoven/fibers/nonwoven] structure were used as raw
materials and the different seaming methods were applied to compare the seam properties of 3
geosynthetics and transmissivities of geocomposites.
Experimental
Preparation of Samples and Seaming
8 Geotextiles(; 4 woven and 4 nonwoven types), 4 geogrids and 2 geocomposites of
[nonwoven/fibers/nonwoven] structure were used as raw materials. Geocomposites of 3-layer
structure which have the excellent drainage function under confined loading condition were
manufactured by needle punching method. Three different punching patterns were applied to
manufacture these geotextiles as , and punching pattern.
Assessments of Performance of Geosynthetics
Seaming methods that applied to geosynthetics were as following: (1) geotextiles - sewing methods :
flat seam(; SSa-1, -2), butterfly seam(; SSd-1, -2), geospacer, (2) geogrids - band and geospacer, (3)
geocomposites – flat seam(; SSa-1, -2) and geospacer. Table 1 shows the specifications and
seaming methods of these geosynthetics and Figure 1 shows the various seam types and geospacer.
Seam properties of geotextiles and geocomposites were examined by ASTM D 4884(; test method
for seam strength of sewn geotextiles) and those of geogrids were investigated through ASTM D
4884. Chemical resistance of geosynthetics were tested in the condition of pH 3 and 8, 25°C and
50°C during 360 days. These solutions were adopted to compare the chemical resistance by
considering the waste leachates. The degree of chemical resistance of geosynthetics were estimated
by comparing the tensile strength retention ratio after 360 days with ASTM D 5322. Especially for
geogrids, creep deformation tests were done to determine the reduction factor of geogrids to affect
the long-term performance by ASTM D 5262 and GRI GG 3(b). Transmissivities of geocomposites
were tested by ASTM D 4716. 2 types of geonet composites – GNC-1, -2 - having the same
thickness as smart geotextiles were used as comparison materials for drainage function and Figure 2
showed the cross sectional morphology of geocomposites and geonet composites.
Advanced Materials Research Vol. 983 31](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-45-320.jpg)
![Table 1. Specifications and seaming methods of geosynthetics
Geosynthetics Fibers
Design
Strength(kN/m)
Weight
(g/m2
)
Seaming
Methods
Geotextile
Woven
WGT-1
WGT-2
WGT-3
WGT-4
Polyester
50
100
150
200
Flat Seam,
Butterfly Seam,
Geospacer
Non-
woven
NWGT-1
NWGT-2
NWGT-3
NWGT-4
Polypropylene
712
1,024
1,532
2,156
Geogrid
GG-1
GG-2
GG-3
GG-4
High tenacity
Polyester
80
150
200
250
Band,
Geospacer
Geocomposite
[Nonwoven/Fibers*
/Nonwoven]
GC-1
GC-2
*Polypropylene
Waste Fiber
1,306
2,084
Flat Seam,
Geospacer
Fig 1. Schematic diagrams of various seam types and special geospacer
32 Advanced Materials and Engineering](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-46-320.jpg)
![Long-Term Design Strength of Geogrid by Creep Reduction Factor
From GRI Standard Test Method GG4, the allowable strength of geogrid could be written in the
following equation to be taken into consideration of the ultimate strength, reduction factors for
application of geogrids. The long-term design strength of geogrid should be used in the following
equation. The reference document can be found in the GRI Standard Test Method GG4(b)
“Determination of the Long-term Design Strength of Flexible Geogrids”.
]
1
[
bd
cd
cr
id
ultimate
design
RF
RF
RF
RF
T
T
×
×
×
×
×
×
×
×
×
×
×
×
=
=
=
= (1)
where, Tdesign = long-term design strength of geogrid
Tultimate = ultimate strength of geogrid
RFid = reduction factor for installation damage
RFcr = reduction factor for creep deformation
RFcd = reduction factor for chemical degradation
RFbd = reduction factor for biological degradation
Table 7 shows the longterm design strength of geogrids by the reduction factor of the above
mentioned conditions. We used the default values of each reduction factor to be written in the
reference, [1]. In here, reduction factors of the geospacer seam are smaller than those of the band
seam and this means geospacer seam is more effective than the band seam. Therefore, the long-term
design strength values of geospacer showed higher than those of the band seam.
Table 7. Long-Term design strength by reduction factor of geogrids with seam type.
Geogrid
Reduction Factor
Long-Term
Design Strength (KN/m)
Band Geospacer Band Geospacer
GG-1 2.4 2.0 33.3 40.0
GG-2 2.4 1.9 62.5 78.9
GG-3 2.4 1.8 83.3 111.1
GG-4 2.3 1.8 108.7 138.9
Transmissivities of Geocomposite
Table 8 shows the transmissivities of geocomposites by seam type. Geospacer seam showed higher
transmissivity than the flat seam(; SSa-1 SSa-2) without regard to the kinds of filled fibers and
weight of geocomposite. For the similar specification, geocomposites showed the better
transmissivities than the typical drainage materials, geonet composites.
GG-2 - - - - 90 91
GG-3 - - - - 90 91
GG-4 - - - - 91 92
GC-1 82 83 - - - 86
GC-2 82 84 - - - 86
Advanced Materials Research Vol. 983 37](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-51-320.jpg)
![Table 8. Transmissivities of geocomposites and geonet composites
Seam Type
Geogrid
SSa-1 SSa-2 Geospacer
GC-1 1.581 1.224 0.983
GC-2 1.218 1.057 0.915
GNC-1 - - 0.699
GNC-2 - - 0.485
Conclusion
Woven geotextiles showed the higher seam strength in the order of butterfly seam(; SSd-1 SSd-2)
flat seam(; SSa-1 SSa-2) geospacer without regard to the design strength. For nonwoven
geotextiles of 1,000g/m2~, the order of seam strength is geospacer flat seam(; SSa-1 SSa-2).
Geogrids showed the higher seam strength in the order of band geospacer but creep deformation
were increased in the order of band geospacer without regard to the design strength and geogrid’s
compositions. Geocomposites showed the higher seam strength in the order of geospacer flat
seam(; SSa-1 SSa-2) but showed the transmissivity in the order of geospacer flat seam(; SSa-1
SSa-2) without regard to the kinds of filled fibers and weight of geocomposite.
References
[1] R. M. Koerner, 1998, Designing with Geosynthetics, 4th Ed., Prentice-Hall, New Jersey, U.S.,
Chapter 4.
[2] R. D. Holtzs, B. R. Christopher and R. R. Berg, 1995, Geosynthetic Design and
Construction Guidelines, U.S. Dept. of Transportation Federal Highway
Administration, Publication No. FHWA HI-95-038, 27-105.
[3] FHWA, 1989, Geotextile Design Construction Guidelines, U.S. Dept. of Transportation
Federal Highway Administration, Publication No. FHWA HI-90-001, 24-46.
[4] Jewell R. A., 1996, Soil Reinforcement with Geotextiles, CIRLA Special Publication, Thomas
Telford, Westminster, Chapter 5.
38 Advanced Materials and Engineering](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-52-320.jpg)
![Comparative study of physico-chemical properties of pure Polyurethane
and Polyurethane based on Castor Oil
M. A. ALAA1, a*
, KAMAL YUSOH2, b
, S.F.HASANY3, c
1
Faculty of Chemical Natural Resources Engineering, University Malaysia Pahang, Malaysia
2
Department of Chemical Engineering, University of Technology, Baghdad, Iraq
Allavip63@yahoo.com, hjkamal@gmail.com, hasany_@live.co.uk
Keywords: PPG based PUs and Castor oil mixed PUs, In Situ polymerization, Physico- chemical
properties, comparison
Abstract.Petroleum based polyurethanes are contributing major portions in the world requirement.
To overcome the environmental issues and price adaptability, there is always a massive demand of
utilization of renewable resources for polyurethane synthesis with comparable physico-chemical
properties. Castor oil is the only major natural vegetable oil that contains a hydroxyl group (-OH)
and unsaturated double bonds (C=C) in its organic chain and therefore can be employed with or
without modification due to the excellent properties derived from the hydrophobic nature of
triglycerides. In this study, physico-chemical properties of high performance polyurethane
synthesized from Poly propylene glycol (PPG) in comparison with a combination of PPG and
Castor oil (a renewable source), by in situ polymerization technique has been studied. The
variations in properties of both types of polyurethanes are evaluated by Fourier Transform Infrared
Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and Thermogravimetric analysis
technique (TGA). Tensile strength properties were investigated by Film Tensile testing equipment.
Results indicated the presence of large -CH stretching in castor oil mixed polyurethane with a larger
oxidative thermal stability, over a pure PPG polyurethanes. Tensile properties were found almost
comparable in pure and mixed polymers, which signify the usage of mixed polymer in coming
future, to overcome the environmental and economical crisis in polyurethanes synthesis.
Introduction
Polyurethanes (PU) have been extensively used due to excellent physical properties (e.g.
low flexibility, high tensile strength, tear and abrasion resistance, solvent resistance, etc.) and high
versatility in chemical structures [1-2]. Polyurethane is generally synthesized from the isocyanate
reaction with polyol. Polypropylene glycol (PPG) is a polyol, is basically derived from the
petrochemical industry [3]. High rising costs of petrochemical feedstock’s and enhanced public
desire for environmentally friendly green products, utilization of renewable resources to
manufacture the rigid polyurethane is a work necessary at the present time [4-6].
Polyurethane based on polyols derived from different vegetable oils, like castor [7-8],
sunflower and rapeseed oils [9].Castor oil is one of the major natural vegetable oil that contains a
hydroxyl group and so it is widely used in many chemical industries, especially in the production of
polyurethanes [10]. Krushna Chandra Pradhan and P. L. Nayak investigated the synthesis of
polyurethane nanocomposites prepared from natural oil like castor oil using HMDI and organically
modified clay and covalently linked PU/n-HMDI composite, which was later collected successfully
by the electro spinning process [7]. D.J. dos Santos et al., study preparation ,diagnosis from castor
oil exhibited increasing of diisocyanate groups, in relation to polyol amount, has increasing of
Advanced Materials Research Vol. 983 (2014) pp 39-43
© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.983.39](https://image.slidesharecdn.com/2383070-250604232710-3719fb4b/85/Advanced-Materials-And-Engineering-Taufiq-Yap-Yun-Hin-53-320.jpg)
![diisocyanate groups, in relation to polyol amount, has increased the strength at rupture of the
obtained polymers and has decreased the polymers elongation, which has resulted into a modulus
increasing [11]. Anupama Kaushik et al., examines a series of 1,4-butane diol chain extended
polyurethane nanocomposites based on castor oil, and 4,40-diphenylmethane diisocyanate (MDI)
were synthesized with modified clay (Cloisite 30B) as filler [12].
1. Experimental
2.1 Materials
Commercial grade Castor oil was purchased from the local market. It was dehydrated at
80ºC in in a vacuum oven and characterized for hydroxyl value (148), acid value (2) and moisture
content (0.379%). Polypropylene glycol (PPG) (Mn=4000) was supplied by SIGMA- Aldrich
Company. Chain extender, 1, 4-butane diol was procured from Himedia, India. The toluene
diisocyanate (TDI), which were used as received, were supplied from SIGMA- Aldrich Company.
The catalyst used in this research is DABCO-33LV which is the mixture of triethylenediamine and
di (propylene glycol) and it was supplied by Air Products and Chemicals (United Kingdom).
2.2 Characterization Technique
Fourier transform infrared spectroscopy (FTIR) analysis of polyurethanes was done using A
Vector-22 FT-IR spectrometer (Nicolet 5DX FT-IR) with a resolution of 1 cm-1
from 4000 to 400
cm-1
. Thermal stability (TGA) of polyurethanes was carried out using a Universal V4.5A, TA
instruments under a nitrogen atmosphere. Scanning electron microscopy (SEM) was carried out on
a JEOL 6300F machine at an acceleration voltage of 5KV. Tensile testing of the nanocomposites
film was carried out on an instron model 4505 universal testing machine at 25ºC, with a load cell of
5 KN and following ASTM D 638. The crosshead speed was set to 2 mm/min. Samples were cut in
a dumbbell shape with an ASTM D 638 (type V).
3. Result and Discussion
3.1 FTIR Analysis
The micro-domain structures of the pure PU and castor oil based PU were analyzed by FTIR
as shown in Figure 1. A small broad band in the range 4000–3500 cm-1
, was observed in both
samples relating to the O-H stretching vibrations from either water or hydroxyl terminated
compounds, and N-H stretching vibrations from either urea or amine group [13-14]. The CH – CH3
peaks stretching are more prominent in castor oil based PU, then pure PU which may be due to
larger organic chain present in castor oil based PU. Peaks at 1727 cm-1
represents (C=O) non
bonded urethanes [12] which are likely to be present in larger number, in castor oil based PU
synthesis.
2.2 TGA Analysis
The result of the thermo gravimetric analysis (Figure 2) shows that thermal stability of pure
PU and castor oil PU based under identical conditions and a comparison of the weight losses
occurred. The thermal stability of these polymers is starting generally above 200 °C [15-16]. It is
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- 6. Advanced Materials and Engineering Edited by Taufiq Yap Yun Hin
- 7. Advanced Materials and Engineering Selected, peer reviewed papers from the Annual International Conference on Intelligent Materials and Nanomaterials (AIMN 14), April 18-19, 2014, Seoul, South Korea Edited by Taufiq Yap Yun Hin
- 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 983 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 In order to be organized as a leading annual international conference of IAMR for researchers, scientists to participate all over the world, Annual International Conference on Intelligent Materials and Nanomaterials (AIMN14) is successfully held on April 18-19, 2014 in Seoul, South Korea. AIMN14 serves as the important and influential platform for authors to publish manuscripts in excellent international proceedings and exchange new ideas face to face. AIMN14 is the unique conference with its strong organization team, dependable reputation and wide sponsors all around the world. All accepted papers of AIMN14 have been strictly selected for the quality and the relevance to the conference. We sincerely hope that the current selected papers provide a good overview of the research activities related to advanced materials and engineering. These new materials includes, intelligent materials, nanomaterials synthesis and properties, nano devices and system, nano materials, technologies for applications, materials/nanufacturing processes, etc. The volume of AIMN14 is expected to boast future research activities within the new actions, meetings and conferences and this volume is provided not only for the readers abroad overview of the latest research results on material science and related fields, but also for those who wish to have a valuable summary and reference in these fields. We would like to express our sincere appreciations to all the authors for their contributions to this volume. We are indebted to all the referees for their constructive comments on the papers. Many thanks are also warmly given to Trans Tech Publications, the distinguished publisher of AIMN14. All staffs of AIMN14 Organizing Committees from IAMR look forward to your continuous attention and support to this Annual International Conference in the future. AIMN14 Organizing Committees
- 10. Committees Honorary Chairs Prof. Vikas Tomar, Purdue University, USA Editorial Chairs Prof. Taufiq Yap Yun Hin, Universiti Pertanian Malaysia (UPM), Malaysia PC Co-Chairs Prof. Elias Saion, Universiti Pertanian Malaysia (UPM), Malaysia Prof. Razali Ismail, Universiti Teknologi Malaysia (UTM), Malaysia Prof. Jeonghoon Yoo, Yonsei University, South Korea Prof. Min Chen, Aalborg University, Denmark Dr. Xufeng Dong, Dalian University of Technology, China Prof. Mohd Sapuan Salit, Universiti Pertanian Malaysia (UPM), Malaysia Prof. Kurapati Srinivas, GMR institute of technology, India Prof. Jayabalan M, Biomaterials Subject Group of MRSI, India Prof. Avishai Yshai, Ben-Gurion University of the Negev, Israel Dr. Othman Inayatullah, Universiti Pertanian Malaysia (UPM), Malaysia Steering Committee Chairs Prof. Choi Changhwan, Hanyang University, South Korea Prof. Kun Zhao, China University of Petroleum (Beijing)
- 11. Table of Contents Preface and Committtess Chapter 1: Advanced Materials, Technologies and Applications Gangue as Flame Retardants for Flexible Poly(Vinyl Chloride) M. Gao, C.G. Song, D. Rong and Y.W. Ji 3 Novel Thermo Thickening Smart Gel with Interpenetrating Polymer and Surfactant Network J. Yang, Y.N. Zhou, Y.J. Lu, W.X. Cui, X.H. Qiu, B.S. Guan and Y.H. Ding 7 Smart and Robust Composite Tube Columns Frames for Offshore Sub-Structure Construction T.M.B. Albarody, Z.B. Mustaffa and M.S. Liew 11 The Research Process and Application Prospect of the Smart Piezoelectric Materials X.L. Fang, W.F. Zhang and H.X. Wang 16 Reusable and Efficient Polystryrene-Supported Acidic Ionic Liquid Catalyst for the Synthesis of n-Butyl Acetate Y.H. Cheng, B. Zhang, S.J. Dai, H.L. Tong and L.X. Li 20 An Exploration of Factors Affecting the Preparation of SiO2-Coated α-Al2O3 Pearlescent Pigment N. Wu, Q.H. Chen, W.M. Zhou, M.Z. Ke, Q.R. Qian and Z.H. Yuan 26 Assessment of Engineering Properties of Geosynthetics with Seaming Methods H.Y. Jeon 30 Comparative Study of Physico-Chemical Properties of Pure Polyurethane and Polyurethane Based on Castor Oil M.A. Alaa, K. Yusoh and S.F. Hasany 39 Temperature Effects and pH Value on Free Swell Behaviors of Bentonite Solutions H.Y. Jeon 44 The Thermal Properties of Unsaturated Polyester Resin Treated with Intumescent Flame Retardants M. Gao, D. Rong, C.G. Song and Y.W. Ji 52 Chapter 2: Nanomaterials and Nanotechnologies Microstructure of Gold Nano-Crystals from Nanometer to Micrometer Lengthscale in Gold Bulk Metallic Glass N. Boonchu, A. Lawan, K. Thipayarat, S. Pintasiri, W. Kanjanakijkasem, S. Kuimalee and B. Lohwongwatana 59 Nanotechnology and Earth Construction: The Mechanical Properties of Adobe Brick Stabilized by Laponite Nanoparticles F. Scalisi 63 On Optimal Planning for DNA Nanomechanical Robots V. Popov 67 Preparation of Nano Ni2P/TiO2-Al2O3 Catalyst and Catalytic Activity for Hydrodesulfurization H. Song, Z.D. Wang, Z.S. Jin, F. Li, H.Y. Wang and H.L. Song 71 Study on the Nanoemulsion Formulation of Piceatannol and In Vitro Release Y. Zhang, Y.F. Yu, Z.H. Shang, M. Du and C.F. Wang 75 The Green Preparation of Nano-Silver Particle by Reductive Polysaccharide M.S. Yang, X.P. Wen and L.K. Li 79 Hybrid Microstructures on Si Surface Formed by Nanosecond Pulse Laser for Broadband Antireflection L.T. Yang 84 Computer Aided Simulation and Prototype Experiment on Nanocoated Products J.Z. Li 90
- 12. b Advanced Materials and Engineering Influence of Injection Conditions on the Mechanical Property of MWCNTs/ PC Nanocomposites L.J. Wang, J.H. Qiu and E. Sakai 94 Nanomechanical Properties of Core-Shell Structured Ni@NiO Nanoparticles Reinforced Epoxy Nanocomposites H.Y. Wang, L. Yan, Y.J. Zhu, H. Song and J.H. Zhu 99 Chapter 3: Composites and Alloys Effect of Injection Conditions on the Electrical Conductivity of MWCNTs/PC Conductive Composites L.J. Wang, J.H. Qiu, E. Sakai and X.W. Wei 105 Influence of Casting Method and Heat Treatment for Corrosion Resistance of Magnesium Alloy AZ91D A. Dobkowska, B. Adamczyk-Cieślak, J. Zdunek, J. Mizera and K.J. Kurzydlowski 110 Low Temperature Oxidation Behaviors of CNTs/MoSi2 Composites H. Zhang, H.J. Wu, J. Lin, S.Y. Gu and L. Yu 116 Microsegregation Behavior of Single Crystal Superalloy Z.H. Yu and J.F. Qiang 121 Modeling the Correlation between Microstructure and Tensile Properties of Ti-17 Alloy Using Artificial Neural Network Z.Q. Jia and W.D. Zeng 127 One Step Fabrication of Core-Shell Structures in Immiscible Alloys for Thermal Energy Storage F.M. Xu, M.B. Fu, W. Dong, L. Zhao, D. Lu and Y. Tan 131 Surface Modification of Titanium Alloys Using Alumina Particles Blasting for Biomedical Applications S. Udomlertpreecha, P. Pavasant and B. Lohwongwatana 135 Technique Research on High Strength Low Alloy Structural Steel Used in Semi-Rigid Guardrail H.X. Yu, Z.W. Zhou and H.S. Zhang 141 The Effect of Co/Pd MgO Supported Catalyst Calcination Temperature on the Yield and Morphology of CNTs via Methane Decomposition G. Allaedini, S.M. Tasirin, J. Sahari and M.Z. Meor Talib 148 The Structure and Properties of NBR / Recycled Polytetrafluoroethylene (R-PTFE) Composites W.W. Chen, C.L. Cao, Y. Zhang, L.R. Xiao, Q.R. Qian and Q.H. Chen 152 Microstructure and Direct Measured Micro-Strain by TEM of Hot Iso-Static Pressed Alumina-Titanium Carbide (Al2O3-TiC) Composite S. Thumsoontorn, S. Kuimalee, B. Kuntalue, S. Pintasiri and B. Lohwongwatana 156 Characterization and Parametric Study of Multilayered IPMC Actuator M.F. Shaari and Z. Samad 161 A Novel Approach for Determining Critical Fracture Strain of a near Alpha Titanium Alloy during Hot Compression Deformation W.W. Peng, W.D. Zeng, Q.J. Wang and Y.C. Zhu 166 Thermal Behavior of Epoxy Resins Containing Manganese Compounds F.C. Wu, S. Tian and S. Liu 171 Thermal Degradation of Hemp Treated with Guanidine Dihydrogen Phosphate Y.J. Sun, Y.L. Yang and M. Gao 175 Improving Mechanical Properties of Poly-β-Hydroxybutyrate-co-β-Hydroxyvalerate by Blending with Natural Rubber and Epoxidized Natural Rubber M. Chutamas, S. Jackapon, J.K. Hyun and S. Klanarong 179 Chapter 4: Manufacturing Processes, Materials Forming and Machining
- 13. Advanced Materials Research Vol. 983 c Application of Calculus Equation in Solving Thermal Decomposition Kinetics Parameters of Flame Retardant Epoxy Resin C.Y. Sun, Y.L. Yang and M. Gao 185 Application of Calculus Equation in Solving Thermal Decomposition Kinetics Parameters of Flame Retardant Wood C.Y. Sun, Y.L. Yang and M. Gao 190 Dynamic Analysis of Stiffness Part for a Electromagnetic High Frequency Fatigue Testing Machine Y. Zheng, Y. Zhang and X.W. Fan 194 New Upgrade Solution to Highway Concrete Barrier M. Li and H.X. Yu 198 The Research of Demarcating the Laser Ranging Sensor by Least Squares Method Y. Zheng, Y. Zhang and X.W. Fan 204 A Fundamental Investigation on Ultrasonic Assisted Fixed Abrasive CMP (UF-CMP) of Silicon Wafer Y.B. Wu and L.J. Wang 208 Study on Slurry of SiC Crystal Substrate (0001) C Surface in CMP Based on Silica Sol (SiO2 Abrasive) Z.Q. Zhang, H.F. Cheng and J.X. Su 214 Thermal Stability of Cotton Cellulose Modified with Calcium Complexes Y.J. Sun, Y.L. Yang and M. Gao 218 UV-Radiation Curing Process of Cationic Epoxy Adhesive Materials W.L. Zhang, J.J. Chen, M.L. Tan, B. Li, L.Q. Ye, D.J. Fu, Q. Ma, X.W. Wang and D.S. Li 222 ABAQUS Based on Machining Simulation during Metal Milling Z. Dan and Z. Yan 226 Chapter 5: Power Systems, Energy and Environmental Engineering Design Study of Small Gas Cooled Fast Nuclear Power Plant for Synergetic Energy System with Renewable Energy by Employing Pump Storage Z. Suud 233 Electrochemical Performance of LiFePO4/C Prepared from Different Carbon Source A.F. Liu 238 Flow Field Analysis and Response Surface Research on the Rotor in Dry Powder Inhaler Z.C. Cao, H.Y. Li, S.H. Shi and E.L. Zhou 242 Gas Permeation Properties and Characterization of Polymer Based Carbon Membrane N. Sazali, W.N.W. Salleh, Z. Harun and A.F. Ismail 246 Measurement Principle of Glass Thermal Expansion Coefficient and Technology Application of DIL402PC Dilatometer Y.H. Sun, D.Q. Zhang, F. Wu and K. Sun 251 Methodology of Taguchi Optimization for Organic Rice Bran to Maximum Antioxidant Activity T.L. Su, S.W. Wang, H.H. Chien and C.J. Shen 257 Resolving National Energy Crisis through Energy Efficient Appliances: Use of Ground Water Heat Pump for Air Conditioning Systems A. Aizaz and N. Hafeez 261 Solar Hydrogen Production Research Status and Prospect D.Z. Wang, F.Z. Zhao and C.L. Zhu 265 Stability of a Class of Power System with Interval Parameters D. Xie, Z.H. Lu and W.J. Wang 270 The Design and Implementation of Optimal Scheduling in Hydro-Thermal-Wind System X.F. Tian 275 The Effect of Air Cold Plasma Treatment on UHMWPE Fiber Surface Modification X.X. Lin, X. Huang and Y.M. Wang 280 The Effects of the Total Number of Regions and Average Power Density on the Overall Performance of Modified CANDLE Burn-Up Scheme Based Gas Cooled Fast Reactors I. Rosidah, M. Afifah, Z. Suud, H. Sekimoto and A. Ferhat 284
- 14. d Advanced Materials and Engineering The Research of Marine Nuclear Power Two Loop Simulation Software Based on the Thermal System Analysis G.L. Zhang, X.D. Jin, Z. Zhao and Z.J. Shi 288 Transformer Impedance Determination for Power System Studies of Distribution Network integrated with Renewable Energy Resources J.H. Tang, M.Z. Che Wanik, A.M. Busrah and A.K.M. Hussin 292 Translational-Rotational Motion of Earth Artificial Satellite (EAS) in Hill's Gravity Field K. Astemessova, A. Bekov, M. Shinibaev and D. Ussipbekova 300 A Proposed Method of Photovoltaic Solar Array Configuration under Different Partial Shadow Conditions A.M. Humada, M. Hojabri, M.B. Mohamed, M.H. Bin Sulaiman and T.H. Dakheel 307 The Development of New Steel Backing Wood Landscape Guardrail Z.W. Zhou, C.H. Wang and M. Li 312 The Elimination of Pollution of Toxic Cadmium and Arsenic in Lead-Based Alloys of Lead- Acid Batteries in China X. Liu, J.C. Cai and Y.H. Shu 319 Thermal Stability and Smoke Suspension of Cotton Cellulose Modified with Magnesium Complexes F.C. Wu, C.Y. Chao and S. Tian 324 Phonon Interaction of Ultrasound Waves in Condensed Media S. Omarov, T. Begimov, M. Tukibayeva, K. Maylina and G. Bedelbaeva 328 Research on Internal Flow Field of Control Valve Outlet Blockage Fault Y.T. An, R.J. Ma and D. Zhao 338 Migration Study of Biodegradable Blends of Polylactic Acid and Epoxidized Natural Rubber T. Nampitch 342 Numerical Simulation of NOx Emission in Supercharged Boiler H.Y. Zhang, J. Zhao, L.B. Yang and Y.J. Li 347 Conceptual Design Study of Small 400 MWt Pb-Bi Cooled Modified Candle Burn-Up Based Long Life Fast Reactors Z. Suud and H. Sekimoto 353 Chapter 6: Applied Mechanics and Engineering Based on RFID Prefabricated Building Component Design and Monitoring System Research J. Wang 359 Design Optimization and Control Analysis of Mechanical Arm Equipped on Wheelchair G.B. Luo, C.C. Zeng and L.D. Zhu 363 In 16V265H Locomotive Diesel Engine Nozzle Flow Field Simulation Analysis S.H. Li, M.H. Li and X. Du 368 Mechanical Design to Adapt Changes to Existing Universal Test Bed Facility of Turbojet Engine for the Turbofan Engine F. Ahmed, A. Aizaz and Z. Mahmood 374 Simulation Analysis of Kinematics and Dynamics of 3-TPS Hybrid Robot J.S. Shi, S. Wang, L.D. Zhu, W.S. Wang and T.B. Yu 379 The Experiment Research on Storage Characteristic of PCM Storage Device by Spheres Piled Encapsulated for Vehicle Waste Heat T.S. Zhang, Q.Y. Wang, G.H. Wang, C. Gao and Q. Gao 383 The Phase Shift of Reflection and Refraction of SH-Wave at an Interface of Two Media A.L. Wang and F.P. Liu 388 The Research on Fault Diagnosis of Civil Aircraft Information Fusion Based on the Evidence Theory X. Peng 392 A Characteristic Seismic Study and Development of Earthquake Resistant Techniques in Existing Structures M. Yasuhide and H. Yashwanth 396
- 15. Advanced Materials Research Vol. 983 e Shock Response Analysis of Marine Gearbox W. Liu, T.J. Lin and Z.Y. He 400 Design on the Detection System of Stud Welding Dynamic Parameters B. Wang, X.X. Li and W.M. Zhang 404 Influence of Lateral Shift on Normal Moveout of SH-Wave A.L. Wang and F.P. Liu 408 Mixed Interface Stress Element-Finite Element Model with its Application Y.H. Sun, F. Wu, K. Sun and D.D. Li 412 Modeling of Mass-Spring-Damper System by Complex Stiffness Method S.G. Zhang and X.P. Dang 420 Study on Control Quality of Valve Outlet Blockage Fault Y.T. An, R.J. Ma and D. Zhao 424 Development of Digital Filter Software in Auto Safety Components Test C.J. Du, T.Q. Du and W. Liu 428 A New Type of Adjusting Coaxiality Structure Design B.R. Sun, Y. Zheng, Y. Zhang and X.W. Fan 436 Design of a PLC-Based Engineering Training Unit J.B. Han 440 Flexible Thermosetting Pipe Z.B. Mustaffa and T.M.B. Albarody 444
- 16. CHAPTER 1: Advanced Materials, Technologies and Applications
- 17. Gangue as Flame Retardants for Flexible Poly (Vinyl Chloride) 1 Ming Gao1,a , Chun-guang Song 1,b ,Dan Rong1,c ,Yu-wen Ji1,d 1 School of Environmental Engineering, North China University of Science and Technology, Box 206,Yanjiao Beijing 101601, China a gaoming@ncist.edu.cn, b 1114149912@qq.com, c 2235697702@qq.com, d 1633910613@qq.com Key words: Gangue, flame retardant, aluminum hydroxide ,PVC Abstract: Gangue as flame retardant was used to PVC, the mechanical properties and flame retardance of the samples were studied. The resultant data show that gangue little effect on the mechanical properties of the sample, especially tensile strength, yield stress, and 10% of gangue obtained good flame retardance. PVC treated with flame-retardants showed a high limiting oxygen index, char yield, which indicated that the flame retardance of the treated PVC was improved. Introduction PVC materials or products tend to have excellent fire performance. But to make it easy to process, semirigid and flexible PVC compound always contains a large volume of plasticizer such as DOP [di(2-ethylhexyl)phthalate], which can deteriorate the flame retardation and smoke suppression properties. When the PVC products contain 45 parts DOP, the limiting oxygen index (LOI) would decrease to about 24 and the PVC would thus become a high-flammability material. However, plasticized PVC products can still have good fire performance, particularly if additionally fire-retarded [1,2]. In recent years, the use of metal hydroxide flame retardant and smoke suppressant in PVC has been reported [3,4].These flame-retardants, e.g., Mg(OH)2, Al(OH)3 are required at high concentrations (40–60%) for imparting a good degree of flame retardancy. Because of the high loading it is essential that good degree of flame retardancy be obtained, but mechanical properties decrease obviously. Using coupling agents and synergists are good ways to solving this problem [5–7]. Many elements, such as alloys, organic substances and inorganic compounds including antimony, tin, zinc, copper, iron and molybdenum, have been used in the flame retardation and smoke suppression of PVC. Gangue contains many kinds of metal oxides, which may have the similar effective. The purpose of our present study is to study mechanical properties, flame retardant of the samples treated with combinations of Al(OH)3 and gangue. Experimental Materials PVC, S G Type 2, dioctyl phthalate (DOP); Tribasic lead sulfate, Dibasic lead phosphate, commercially available; Stearic acid, industrial grade; Mg(OH)2, industrial grade; Al(OH)3, ZX-131 type. Instrumentation LOI values were determined in accordance with ASTM D2863-70 by means of a General Model HC-1 LOI apparatus. The vertical burning test was conducted by a CZF-II horizontal and vertical burning tester (Jiang Ning Analysis Instrument Company, China). The mechanical properties were Advanced Materials Research Vol. 983 (2014) pp 3-6 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.983.3
- 18. tested according to GB/T 1040.2-2006 standard with a LJ-5000 tensile testing machine (Chengde Experimental Factory). Preparation of Flame Retardant PVC Samples Formulation according to predetermined material (including PVC, three salts, salts of stearic acid, DOP, hydroxide, chloride, coal) are mixed in a mixer 3 to 5 minutes at 35 - 45 °C. Then the mixture was plastified on the two-roll mill at 165°C for 6-8 min, compressed at 180°C to form sheets of 100mm×10mm×3mm. The test specimens were cut from the molded sheets. Table 1 The composition of the samples Sample PVC (g) DOP (g) Tribasic lead sulfate (g) Dibasic lead phosphate (g) Stearic acid (g) Al(OH)3 (g) Gangue (g) Oxygen index (%) A 500.0 150.0 7.5 7.5 5.0 0.0 0.0 24.5 B 500.0 150.0 7.5 7.5 5.0 5 0.0 0.0 26.6 C 500.0 150.0 7.5 7.5 5.0 75.0 0.0 28.4 D 500.0 150.0 7.5 7.5 5.0 100.0 0.0 29.5 E 500.0 150.0 7.5 7.5 5.0 125.0 0.0 29.4 F 500.0 150.0 7.5 7.5 5.0 125.0 5.0 29.7 G 500.0 150.0 7.5 7.5 5.0 125.0 10.0 29.8 H 500.0 150.0 7.5 7.5 5.0 125.0 15.0 29.2 I 500.0 150.0 7.5 7.5 5.0 125.0 20.0 27.9 RESULTS AND DISCUSSION Flame retardancy of Al(OH)3 and gangue Al(OH)3 as one halogen-free, flame-retardant additives, inorganic acid, used in plastics and rubber industry, attracted widespread attention. From the oxygen index values in Table 1, the flexible PVC added Al(OH)3 has good flame retardancy, whose LOI increase from 24.5% to 29.4%. The flame-retardant effect of Al(OH)3 in soft PVC is mainly based on their dehydration endothermic effect, thus inhibiting soft PVC temperature from rising. When addition of Al(OH)3 reaches 100g, the best effect is obtained. To get better flame retardancy for PVC, gangue was added. The data were shown in Table 1, LOI of samples (F,G) increase with the addition of gangue. When more gangue was added, the LOI of samples decrease, 10g gangue is optimal. Gangue and Al (OH) 3 can be a good flame retardant for flexible PVC. Effect of Al(OH)3 and gangue on the Mechanical Properties Mechanical properties such as tensile strength, breaking strain, yield stress and tensile modulus of samples were measured, and shown in Figs.1-4. Fig.1 shows the effect of the gangue on tensile strain of samples (TS), which shows that the TS increase when the added gangue’s weight is less than 5g, when it is more than 5g and less than 10g, the TS decrease. When it is more than 10g and less than 15g, the TS second increase but slowly, while more than 15g, the TS decrease. Fig.2 shows the effect of the gangue on breaking strain of samples (BS). We can see that the BS increase when the added gangue’s weight is less than 7g, the BS start decreasing when the weight is more than 7g. Obviously, the highest value of BS is obtained when the gangue’s weight is 7g. 4 Advanced Materials and Engineering
- 19. 0 5 10 15 20 20 22 24 26 Tensile strength / MPa Gangue / g 0 5 10 15 20 300 400 500 600 Breaking strain / % Gangue / g Fig.1 Tensile strength of samples Fig.2 Breaking strain of samples 0 5 10 15 20 4.5 5.0 5.5 6.0 Yield stress / MPa Gangue / g 0 5 10 15 20 80 120 160 200 Tensile modulus / MPa Gangue / g Fig.3 Yield stress of samples Fig.4 Tensile modulus of samples Fig.3 shows the effect of the gangue on yield stress of samples (YS). When the added gangue’s weight is less than 5g, the YS keep increasing, then the YS decreases, sometimes it also has slightly increase, when the gangue’s weight is 5g, the YS has its highest value. Fig.4 shows the effect of the gangue on tensile modulus of samples (TM). The TM constantly increases. However, the TM is much greater in the range of 5-10g of gangue. Similar to other additives, the gangue can reduce some mechanical properties. This is because the interactions among the polymer molecules were decreased and the movement of the polymer chains was limited when the flame-retardants reached at 15g. Analysis of Char Yield Fig.5, 6 present the SEM photographs of the surface of char of the samples (sample A, sample G). From Figure 5, it can be observed that the char is very slight, loose and soft, which could not protect the underlying material from fire. Contrarily, Figure 6 shows that the char is compact, tough and hard though there are some holes on the surface. It is possible that the gangue could promote the formation of effective charring layer. The structure of the intumescent charring layer may increase the efficiency of the flame retardancy, act as heat insulation, and protect inner matrix materials. Advanced Materials Research Vol. 983 5
- 20. Fig.5 SEM photographs of sample A Fig.6 SEM photographs of sample G Conclusions 10g gangue and 100g Al (OH) 3 were added can obtain a good flame retardant for flexible PVC, whose LOI reached 29.8%. Gangue has little effect on the mechanical properties of the sample, especially tensile strength, yield stress. The flame-retardant effect of Al(OH)3 in soft PVC is mainly based on their dehydration endothermic effect, thus inhibiting soft PVC temperature from rising. Gangue could promote the formation of effective charring layer. The structure of the intumescent charring layer may increase the efficiency of the flame retardancy, act as heat insulation, and protect inner matrix materials. 1 Contract grant sponsor: Fundamental research funds for the Central Universities: 3142013102. References [1] Hirschler, M.M. (1998). Fire Performance of Poly (Vinyl Chloride) Updated and Recent Developments, Flame Retardants, 98: 103. [2] Hirschler, M.M. (1982). Recent Developments in Flame-Retardant Mechanisms, Development in Polymer Stabilisation, Vol. 5, p. 107, Applied Science Publ, London. [3] Tong, N. and Shaoyun, G. (2000). Flame-Retardant and Smoke-Suppression Properties of Zinc Borate and Aluminum Trihydrate-Filled Rigid PVC, J. Appl. Polym. Sci., 77: 3119. [4] Hornsby, P.R. and Watson. C.L. (1990). A Study of the Mechanism of Flame Retardance and Smoke Suppression in Polymers Filled with Magnesium Hydroxide, Polymer Degradation and Stability, 30: 73. [5] Jha, N.K., Misra, A.C. and Bajaj, P. (1984). Flame-Retardant Additives for Polypropylene, J. Macromol Sci., Rev. Macromol. Chem. Phys., C24: 1: 69. [6] Pearce, E.M. (1986). Flame Retardants for Polymer Systems, Pure & Appl. Chem., 58: 925. [7] Shigco, M., Takeshi, I. and Hitoshi, A. (1980). Fire-Retarding Polypropylene with Magnesium Hydroxide, J. Appl. Polym. Sci., 25: 415. 6 Advanced Materials and Engineering
- 21. Novel Thermo Thickening Smart Gel with Interpenetrating Polymer and Surfactant Network Jiang Yang1,2,a , Yining Zhou2 , Yongjun Lu1 , Weixiang Cui1 , Xiaohui Qiu1 , Baoshan Guan1 , Yunhong Ding1 1 Research Institute of Petroleum Exploration & Development-Langfang, PetroChina, Hebei, China 2 Department of Petroleum Engineering, Xi’an Petroleum University, Xi’an, Shaanxi, China a Corresponding author email: jyang98@126.com Keywords: Thermo gel, Surfactant, Polymer, Wormlike Micelle Abstract A novel smart gel based on interpenetrating network of anionic polymer and surfactant was investigated. A supramolecular assembly structured gel is formed by associating polymer side chain with wormlike micelle of surfactant. The physical interaction of val der vaal and hydrogen bonding force between surfactant and polymer gives a strong viscoelastic gel at evaluated temperature. The viscoelastic properties and gel structure were characterized by dynamic rheometer and cryo-TEM. The polymer and VES complex gel is highly elastic, which elastic moduli G’ is higher than loss moduli G’’ at low angular frequency, 0.1 rad/s, in high temperature. The total concentration of surfactant and polymer is low which is economically to use in industries. Introduction The smart intelligent materials which properties can be controlled by environmental changes are much interested research areas around the world. The environmental change can be electrical, magnetic, light, thermal and pH etc. Among these materials, the polymer could be designed from molecular structure and form smart materials in response different environmental changes [1-4]. The small molecules such as surfactant can also form different aggregates which respond to environmental changes [5-8]. The microstructure changes can induce major changes in the macroscopic properties such as viscoelasticity and solid-liquid transition. The intelligent materials have been used in pharmaceutical [9], automobile [10], drag reduction [11] and oil industry [12,13] etc. Thermo thickening gel is interested for application in oil and pharmaceutical industries, where fluid has lower viscosity at low temperature and form gel at higher temperature. In oil and gas stimulation operation, fluid is preferred to have low viscosity at low temperature for easy of pumping with low friction pressure, and form viscoelastic gel to suspend proppant particles at high temperature at reservoir. For example, sodium erucate as surfactant can transform from fluid to elastic gel at high temperature above its Kraft temperature [7]. Polymer and surfactant could have synergistic interaction at certain condition. For examples, associating polymer can interact with spherical micelle and formed the network [14]. We hereby study a new class of surfactant with wormlike micelle structure in combination of associating polymer. The new system forms viscoelastic fluid at broader range of concentration and forms stronger gel at higher temperature. The complex gel can be used in oil and gas stimulation. Advanced Materials Research Vol. 983 (2014) pp 7-10 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.983.7
- 22. Experiment Materials Amphoteric surfactant with C18 chain length and hydrophobically modified polyacrylamide polymer with anionic group (AP) were made by our lab. Anionic surfactant, sodium lauryl sulfate, was received from Sinopharm Chemcial Co, China. Conventional polyacrylamide with anionic group (CP) was obtained from Beijing Henju Co. Water was deionized. Methods Rheological properties were measured by a Haake Mars II Rheometer Pressured Cell. Dynamic properties were measured by cone and plate geometry on rheometer. Cryo-transimission electron microscopy (Cryo-TEM) observation of surfactant solution was carried out in a controlled-environment vitrification system. Samples were prepared at 25 °C and 100% RH on a Quantifoil holey carbon grid (Electron Microscopy Sciences). The grid was quenched rapidly in liquid ethane at -180 °C and then transferred to liquid nitrogen (-196 °C) for storage. Imageing of the samples was performed using JEM2010 cryo-microscope with a Gatan 626 cryoholder. The acceleration voltage was 200 keV, and the working temperature was kept below - 170 °C. Digital images were recorded using a charge-coupled device camera (Gatan 832). Results and Discussions The surfactant studied is a mixture of amphoteric and anionic surfactant (MS) similar to system studied previously [6]. The surfactant system showed viscoelastic behavior itself above certain concentration which forms entangled wormlike micelle structure. The viscosity of surfactant and polymer with variation of temperature is shown in Fig. 1. It can be seen that viscosity of fluid with single surfactant or polymer all decreases as temperature increases. The viscosity in mixture of conventional polymer (CP) and surfactant (MS) also decreases with increasing temperature. However, the viscosity in mixture of hydrophobically modified polymer (AP) and surfactant (MS) increases with increasing temperature. The overall concentration of mixed AP and MS is also higher than their individual combined. Hence, there is positive synergism interaction between these two materials at increasing temperature. It can be seen that viscosity starts to increase above 50 °C. This behavior could be due to the increase of solubility of longer chain surfactant at higher temperature. The complex fluid formed between associating polymer (AP) and surfactant (MS) is a highly elastic gel as shown in Table 1, which the storage modulus, G’, is larger than loss modulus, G’’ at frequency 0.1-100 rad/s. At further higher temperature above 80 °C, formation of branches along the micelles leading to a multionconnected rather than an entangled network. Branch junction points increase the number of possible configurations, enabling percolation, and the formation of extended micellar networks, which leads to a multiconnected rather than an entangled network of cylindrical micelles. Hence the visocosity decreases for branched worm-like micelles. The driving force for this increased viscosity in mixed polymer and surfactant system is due to physical crosslinking of polymer and surfactant through intermolecular val der vaal interaction of hydrophobic side chain in associating polymer and surfactant micelle. In addition, hydrogen bonding between the polymer hydrophilic and surfactant head group could also reinforce their interaction and crosslinking. The interpenetrating network of wormlike micelle from surfactant and hydrophobic modified polymer is graphically shown in Fig. 2a. 8 Advanced Materials and Engineering
- 23. 0 20 40 60 80 100 20 30 40 50 60 70 80 90 Temperature (C) Viscosity (mPa.s, 100 1/s) 1% MS Surfactant 0.15% AP Polymer 1% MS+0.15%AP 0.15% CP Polymer 1% MS+0.15% CP Figure 1. Viscosity versus temperature for polymer, surfactant and their mixture. Table 1. Storage modulus (G’) and loss modulus (G’’) versus angular frequency for 1% mixed surfactant (MS) and 0.15% associating polymer (AP) at 70 °C. Augular Frequency [rad/s] 0.10 0.40 1.58 6.31 25.10 100.00 G’ [Pa] 5.45 6.36 7.78 9.37 11.20 11.90 G’’ [Pa] 1.37 1.48 1.69 2.10 2.80 4.16 The presence of wormlike micelle structure in surfactant studied is directly confirmed by Cyro- TEM observation as shown in Fig. 2b. It can be seen that threadlike structure with about 10nm in diameter and >1 µm in length exists. The wormlike micelles entangle with each other as well as polymer gives highly elastic gel. (a) (b) Figure 2. (a) Illustrated crosslink model of wormlike micelle and associating polymer. (b) Cryo- TEM micrographs of wormlike micelle in mixed ampheteric and anionic surfactant (1%, wt) at 25 °C. Advanced Materials Research Vol. 983 9
- 24. Conclusions A novel smart gel based on interpenetrating network of anionic polymer and surfactants was formed through physical crosslink. The val der vaal and hydrogen bonding interaction between wormlike micelle and polymer network gives strong viscoelastic gel. The gel strength is stronger at evaluated temperature. The smart gel is useful as stimulation fluids in oil and gas industry, hydraulic fluid, household and personal care products. Acknowledgement The authors acknowledgement the supports from the National Hi-Tech Development (863) Plan Project (2013AA064801) and National Natural Science Foundation of China (Grant No 51174163). References [1] J. Zhang, R.D.K. Misra, Magnetic drug-targeting carrier encapsulated with thermosensitive smart polymer: Core–shell nanoparticle carrier and drug release response, Acta Biomaterialia, 3 (2007) 838-850. [2] G. Filipcsei, I. Csetneki, A. Szilágyi, M. Zrínyi, Magnetic field-responsive smart polymer composites, Advances in Polymer Science, 206(2007)137-189. [3] M. S. Yavuz, Y. Cheng, J. Chen et al, Gold nanocages covered by smart polymers for controlled release with near-infrared light, Nature Materials, 8 (2009)935-939. [4] K. Al-Tahami, J. Singh, Smart polymer based delivery systems for peptides and proteins, Recent Patents on Drug Delivery & Formulation, 1(2007) 65-71. [5] J. Yang, Cur. Viscoelastic wormlike micelles and their applications, Opin. Colloid Interface Sci., 7(2002) 276-281. [6] J. Yang, Z. Yang, Y. Lu et al, Rheological properties of zwitterionic wormlike micelle in presence of solvents and cosurfactant at high temperature， J. Dispersion Sci. Tech. 34 (2013) 1124-1129. [7] Y. Zhang, Y. Han, Z. Chu, S. He, J. Zhang, Y. Feng, Thermally induced structural transitions from fluids to hydrogels with pH-switchable anionic wormlike micelles, J. Col. Interf Sci, 394 (2013) 319–328. [8] R. Kumar , A. M. Ketner, S. R. Raghavan, Nonaqueous photorheological fluids based on light- responsive reverse wormlike micelles, Langmuir, 26 (2010) 5405–5411. [9] A.S. Hoffman, “Intelligent” polymers in medicine and biotechnology, Macromolecular Symposia, 98 (1995) 645–664. [10] A.G. Olabi, A. Grunwald, Design and application of magneto-rheological fluid, Materials & Design, 28(2007) 2658-2664. [11] Y. Qi, J.L. Zakin, Chemical and rheological characterization of drag-reducing cationic surfactant systems, Ind. Eng. Chem. Res., 41(2002) 6326-6336. [12] L. Li, H.A.Nasr-El-Din, K.E. Cawiezel. Rheological properties of a new class of viscoelastic surfactant, SPE Prod. Oper, 25(2010) 355-366. [13] Y.J. Lu, B. Fang, D. Y. Fang et al, Viscoelastic surfactant micelle systems and their rheological properties, Oilfield Chemistry, 20(2003)291-294. [14] N. Gaillard, A.Thomas, C. Favero, Novel associative acrylamide-based polymers for proppant transport in hydraulic fracturing fluids, SPE International Symposium on Oilfield Chemistry, SPE- 164072, 8-10 April, The Woodlands, Texas, 2013. 10 Advanced Materials and Engineering
- 25. Smart and Robust Composite Tube Columns Frames for Offshore Sub- Structure Construction Thar M. Badri Albarodya, *, Zahiraniza Bt Mustaffab and Mohd Shahir Liewc Civil Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia a t.albarody@ymail.com, b zahiraniza@petronas.com.my, c shahir_liew@petronas.com.my Keywords: Offshore Structure; Steel-encased Composite; Nano-Hyprid Composite; FGM; Laminated Shell theory. Abstract. Offshore industry has been welcoming to composite material for its saliences. Features such as corrosion and temperature resistance, construction cost reduction, and superb fatigue performance are some of the reasons for this choice. Steel tube-encased composite is an appropriate found composite replacement for traditional offshore construction. Regardless of all its advantages, they suffer from the interfacing problem between composite and steel layers; however, magnetostrictive nanofillers are proposed to increase the integration between the layers. Therefore, current effort is discussed the vibrational behavior of the proposed robust steel tube column as well as the actuation characteristics of the magnetostrictive nanofillers in encased composite. The result reveals that, the steel tube-encased composite columns exhibit greater stiffness in compare with traditional steel tube. Furthermore, magnetostrictive nanofillers have shown higher actuation capability of vibration at seismic mode. Introduction Composites have found extensive applications in the oil & gas industry since last two decades. Significant advances have been made in the areas of composite pipe work and fluid handling [1, 2]. The high cost to replace steel elements in retrofit applications and increased longevity in new construction are driving the use of composites, which withstand severe conditions as experienced in offshore environment [3, 4]. In the offshore oil and gas industry, the cost of manufacturing and erecting oil rigs could be reduced significantly if heavy metal column could be replaced with lighter ones made of composites. Composite column also could be used for: 1. Replace steel components to eliminate corrosion 2. Exhibit excellent fatigue performance, good resistance to temperature extremes and wear, especially in offshore industrial sectors. 3. Build lighter structures to increase platform performance. 4. Improved combat survivability. 5. Produce complex structural parts at reduced cost, especially in quantity 6. The tailorability of composites to suit specific applications has been one of its greater advantages such as imparting low thermal conductivity, low coefficient of thermal expansion, high axial strength and stiffness etc. Therefore, offshore engineering center in Universiti Teknologi PETRONAS (OECU) has shifted attention to the development of composite structures of carbon and/or glasses fiber reinforced epoxy and steel for offshore jacket sub-structure construction with the aim of becoming a medium-scale contractor with leading-edge technology. Steel Tube-Encased Composite (STEC) column is developed essentially as weldable tubular structural element expected to be good replacement of traditionally steel tubes in offshore industrial facilities constructions. However, still the interfacing problem between composite and steel layers in STEC represent a challenge to be work out. Advanced Materials Research Vol. 983 (2014) pp 11-15 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.983.11
- 26. Therefore, a Nano-Hyprid-functionally graded composite (NHFG) proposed to increase the integration between the layers and grading the structural properties across tube thickness using magnetic nanoparticles as fillers. Furthermore, such functional composites could utilize the magnetostrictive properties to actuate the vibration inside the composite tubes. Several models have been found in the literature dealt with functional composite [5, 6]. Some of them could specialize to demonstrate the vibrational behavior of multilayered and functionally graded magnetostrictive composite. Albarody, et.al., [5] derived the exact solution for linearly constitutive properties, simply supported, functional composite shell subjected to static and dynamic loadings. The authors were investigated and analyzed the effects of the material properties, lay-ups of the constituent layers, and shell parameters under the free vibration behavior. In this paper, a STEC columns filled with magnetic nanoparticles is modeled and the vibrational characteristic is discussed. Also, some of NHFG composite are examined. Theoretical Formulation Based on Hamilton's variational principle linked with Gibbs free energy functions, the steel tube- encased composite model is casted according to the first-order shear deformation shell theory. The exact solution is derived for linearly magnetostrictive constitutive properties, simply supported, and thick shell having rectangular plane-form. Expressed in the (meter–kilogram–second) system of units, the generation procedure of thick composite shell model, written in curvilinear coordinates and provides the much-needed materials in state of the smart or adaptive materials are as follows; 1. Constitutive Relations: In a system gather mechanical, magnetic, and thermal influences, the constitutive relations are expressed formally as: S = ς , ε – κ χ – λ τ , (1) 2. Kinematic Relations: According to the FOSD shell theory, the following representation of the 3D displacement and magnetic potentials is postulated: u(α, β, ζ, t) = u (α, β, t) + ζψ (α, β, t), v(α, β, ζ, t) = v (α, β, t) + ζψ (α, β, t), w(α, β, ζ, t) = w (α, β, t), and ϑ(α, β, ζ, t) = − ϑ (α, β, t) + ζϑ (α, β, t) , (2) where uo, vo, and wo are referred to as the mid-surface displacement functions, and ψα and ψβ are the midsurface rotation functions of the shell, and ϑ is the magnetic potential function. The strains at any point in the shell can be written in terms of mid-surface strains and curvature changes as: ε = (ε + ζε ), ε = ε + ζε , ε = ε + ζ ψ R ⁄ , ε = ε + ζε , ε = ε + ζε , ε = ε + ζ ψ R ⁄ . (3) However, the mid-surface strains as well as the curvature and twist changes are extended by Codazzi-Gauss geometric relations, as [6]. The distributions of magnetic fields at any point in the composite shell are assumed as: χ = (χ + ζχ ), χ = χ + ζχ . (4) and the magnetic field changes are χ = − , χ = − , χ = − , χ = − . (5) 3. Kinetic Relations: The elastic, electric, and magnetic force and moment resultants are obtained by integrating the constitutive relations (1) over the shell thickness as below: 12 Advanced Materials and Engineering
- 27. N , M = (1, ζ) S γ dζ + N , M , (6) where γ = (1 + ζ R ⁄ ), the subscripts n denote either of α, β or αβ, and h is the shell thickness. In order to gain a numerical stability and pursue a possible integration of Eq. (6) in absence of thermal forces, the term (1 + ζ R ⁄ ) should be expanded in a geometric series as in [7, 8]. 4. Variational Principle: The variational energy method via the Hamiltonian axiom has been used by [9, 10] for coupling of the energy phenomena and to derive a consistent set of equations of motion coupled with the free charge equation. In summary, the total energy of a shell element can be defined as: δ (K − P) dt = 0, (7) where P is the total potential energy induced in the system given by: P = ∭ ς , ε – κ χ – λ τ dV − ∬ t S , G , + W S , G , , (8) where Q(S , G , T) is the thermodynamic potential. t S , G , and W(S , G ) are the tractions and the work done by body force, and magnetic charge, respectively. The kinetic energy is given as: K = ∬ (u + v + w ) + ζ ψ + ψ + 2ζ u ψ + v ψ − γ γ ABdζdA. (9) The traction is t(S , G ) = S δu + S δv + S δw + G δϑ + G δϑ (10) and the external work is W(S , G ) = F u + F v + F w + C ψ + C ψ − F ϑ + C ϑ , (11) where F , F , and F are the distributed forces in α, β and ζ directions, respectively, while C and C are the distributed couples about the middle surface of the shell. F and C are the distributed forces and couples due to the magnetic charge. Hence, the temperature, τ is a known function of position and enter the formulation only through the constitutive equations. Substituting Eqs. (1, 10, and 11) into Eq. (8) and equating the resulting equation with Eq. (9), yields after expanding the terms: δ ∬ ̅ (u + v + w ) + ̅ ψ + ψ +I̅ u ψ + v ψ ABdAdt– ∭ (ς ε − κ χ − λ τδε) dVdt + ∬ S δu + S δv + S δw + G δϑ + G δϑ ABdAdt + ∬ F u + F v + F w + C ψ + C ψ − F ϑ − C ϑ ABdAdt = 0. (12) Replacing the constitutive terms in Eq. (12) by the kinetic relations (6), then integrating the displacement gradients by parts to obtain only the virtual displacements, we can set the coefficients of δuo, δvo, δwo, δψα, δψβ, δϑ0 and δϑ1 to zero, individually. The equations of motion and the charge equilibrium equation for isothermal case are BN + AN + N – N + Q + Q + ABF = AB I̅ + I̅ , Advanced Materials Research Vol. 983 13
- 28. AN + BN + N – N + Q + Q + ABF = AB I̅ + I̅ , – AB + + + BQ + AQ + ABF = AB I̅ , BM + AM + M – M – ABQ + P + ABC = AB I̅ + I̅ AM + BM + M – M – ABQ + P + ABC = AB I̅ + I̅ . (13) here I̅ , I̅ , and I̅ are the inertia terms defined as: I̅ = I + I R + R R R + I R R , , , I , I , I , I , I = I (1, ζ, ζ , ζ , ζ , ζ )dζ, where Ik is the mass density of the kth layer of the shell per unit mid-surface area. Eqs. (13) can be written in a matrix form as K + ∂ ∂t ⁄ M ∆ = F − F , where K and M are stiffness and mass matrices, respectively, and F is the thermal forces. Thus, the forced method will apply satisfying SS boundary conditions and admit specially-orthotropic rectangular laminates, to determine the governing equations that satisfied everywhere in the domain of the shell. Thus far, the accurate treatment of thermal, magnetic and elastic energies that are taken into account in this smart composite shell that encased a steel tube column, expect yields rather sophisticated equations interlink the magnetic inductions and stress resultants. Parametric Analysis As deepwater structures for the future developments are expected to be floating structures. Structural systems that can adapt to the environment automatically offer new vistas for designers and lead to novel efficient developments. An offshore structure that form from the proposed steel tube-encased composite is defined smart due to the actuation capability of the magnetostrictive materials that integrated into structural. The challenging part of the offshore structural adaption is that the structure is subjected to highly uncertain environmental forces. Thus, the effects of the material properties, and lay-ups of the constituent layers of the encased composite and the steel tube parameters on the vibration behavior are required to be dissected. In Fig. 1, a CoFe2O4 Nano particle material is scrutinized and the mechanical properties of the encased shell are found to be varied in a very orderly manner across the tube thickness. The STEC tubes that encased with shell made of composite filled with CoFe2O4 appear with higher stiffness as compared to traditional steel tube and exhibit possible actuations when a magnetic field propagate along the tube. 14 Advanced Materials and Engineering
- 29. Fig 1. The transvers stresses and magnetic induction across the composite tube thickness, at unity load. GRFE properties are (E1/ E2=15, G12/ E2=0.5, G13/ E2=0.5, υ12=0.3, a/b=1, a/h=10, and the lamination scheme is (0/09)S), while CoFe2O4 properties and the grading material properties model can be found in [5]. Conclusions The evolutionary process of development of adaptive steel tube-encased composite for tubular constructions has opened up new vistas for the several interdisciplinary applications. The benefits of these composite tubes are expected to be enormous. The concept of a structure with capability of automatically responding to the environment by change in the self-configuration, or by changing the interface with the environment is one which offers the potential of extremely attractive advantages in the design, development and operation of offshore structures. The STEC columns comprising magnetostrictive materials have been modeled and scrutinized. The present model may serve as a reference in developing a prototype of STEC columns for further experimentations. Acknowledgment Authors would like to acknowledge Universiti Teknologi PETRONAS for sponsoring this work. References [1] Z. Mustaffa, M. B. Taufiq, T. M. Badri, Applied Mechanics and Materials 353, 3316 (2013). [2] T. M. Badri, M. Zahiraniza, M. B. Taufiq, Applied Mechanics and Materials 376, 181 (2013). [3] Z. Mustaffa, M. B. Taufiq, T. M. Badri, Applied Mechanics and Materials 353, 3280 (2013). [4] T. M. Badri, M. Zahiraniza, M. Badri Taufiq, Applied Mechanics and Materials 376, 185 (2013). [5] T. M. B. Albarody, H. H. Al-Kayiem, in Shell Structures: Theory and Application. (CRC Press, Taylor & Francis, ISBN: 978-1-138-00082-7, London, 2013), vol. 3, pp. 49. [6] T. M. B. Albarody, H. H. Al-Kayiem, M. B. Taufiq, The Theory of Functional and Adaptive Shell Structures. Mschmoeltz, Ed., (LAP LAMBERT Academic Publishing GmbH & Co., ISBN: 978-3-8465-2175-5, Saarbrücken, Germany., 2013), pp. 212 Pages. [7] Leissa A.W., Chang J., Compos. Struct. 35, 53 (1996). [8] T. M. Badri, H. H. Al-Kayiem, Asian Journal of Scientific Research 6, 236 (2013). [9] Y. Bao, University of Kentucky (1996). [10]T. M. Badri, H. H. Al-Kayiem, Journal of Applied Sciences 12, 2541 (2012). -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0 x 10 -7 -0.15 -0.1 -0.05 0 0.05 0.1 0.15 0.2 Thickness of Shell in (mm) Magnetic Induction -200 0 200 400 600 800 1000 1200 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 Thickness of Shell in (mm) Transvers Stress Mpa GRFE NHFC Steel Tube Advanced Materials Research Vol. 983 15
- 30. The research process and application prospect of the smart piezoelectric materials Xiaoliang Fang1, a , Weifang Zhang1, b , Hongxun Wang 1, c 1 BeiHang University, School of Reliability and Systems Engineering, Science & Technology Laboratory on Reliability & Environment Engineering, XueYuan Road No.37,HaiDian District, Beijing, China. a bit20092110@live.cn, b 08590@buaa.edu.cn, c wanghongxun1990@163.com Keywords: Smart piezoelectric materials; Preparation process; Application status and prospects Abstract: Piezoelectric material which can be used as both sensor and drive is an important kind of smart material. Studies on piezoelectric materials are now the research focus and hotspots of smart materials which have achieved fruitful results. This article describes the working principle of smart piezoelectric materials, provides an overview of the preparation progresses and application status, based on which the research and development trends are discussed. 1. Introduction The performance requirement of the smart materials is that the perceptions, drive and information processing should be integrated in one system, which is similar to biological materials that have intellectual properties [1]. Smart materials system can get the outside world information by its own perception, make judgment and processing, emit instruction, and then adjust own state and structure to adapt to the changes in the extemal environment. Consequently, the smart materials system fulfill various special functions, such as self-detection, self-diagnosis, self-regulation, self-adaptive and self-repair, which are similar to biological system [2]. The smart materials are based on the function materials which can be divided into two categories according to their different roles playing at work. These can be made into various types of sensors are known perception materials, which are used to sense the signal of stimulation and changes from the outside or internal, such as stress, heat, light and electricity etc. The common perception materials include photosensitive materials, heat-sensitive materials, moisture-sensitive materials, acoustic emission material, inductor material, shape memory materials, magnetostrictive materials, piezoelectric materials etc. These can be made into drivers are known as actuating materials, which can change the shape, size, location, stiffness and structure of their own according to the changes of temperature, electric field and magnetic field etc. The common actuating materials include shape-memory materials, electrostrictive materials, electrorheological fluids, magnetostrictive material, magnetorheological fluid and piezoelectric materials [2, 3, 4]. With the progress of the research of the smart materials, the piezoelectric materials which can be made into both driver and sensor drive more and more attention. Piezoelectric materials are able to achieve mutual transformation between mechanical energy and electric energy. Transforming the changes of the outside pressure into appropriate electric signal, piezoelectric materials fulfill the function of being a sensor, meanwhile piezoelectric materials meet the requirement of being a driver while transforming the electric signal of the excitation source into corresponding mechanical signal, such as the vibration signal and deformation signal [5, 6, 7]. With the rapid development of the materials science, microelectronics and computer technology, the piezoelectric materials show broad prospect of application which catches the interests of the global scientists. Based on the background above, the working principle of smart piezoelectric materials are described; an overview of the preparation progresses and application status are provided and the research and development trends are discussed in this article [5.8]. Advanced Materials Research Vol. 983 (2014) pp 16-19 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.983.16
- 31. 2. Working principle of the smart piezoelectric materials The working principle of the smart piezoelectric materials is based on piezoelectric effect. The piezoelectric effect is that when there is a deformation of the materials by external forces, positive and negative electric charges will arise in the relative two surfaces of the material due to an internal polarization at the same time. There are direct piezoelectric effect when mechanical energy is transformed into electrical energy and inverse piezoelectric effect electrical energy is transformed into mechanical energy [3, 5]. 3. New preparation technology of the smart piezoelectric materials 3.1 The piezoelectric coatings prepared by plasma spraying method W Haessler et al. investigated the structure and piezoelectric properties of the PZT coatings prepared by plasma spraying method. They found out that the heat treatment and polarization process after spraying have a significant effect on the piezoelectric properties of the PZT coatings [9]. Songlin Gu, Guolu Li et al. fabricated PZT coatings on the surface of 45 steel by supersonic plasma spraying method. The research results showed that the PZT coatings with a typical layered structure had dense microstructure, of which the surface was flat and the air hole rate was 1.6%. The PZT coating was well bonded to the substrate, which met the requirement of application at actual work [10]. 3.2 Piezoelectric ceramic materials prepared by sol-gel method Piezoelectric ceramic materials fabricated by sol-gel method have high purity, well-distributed chemical constituents and low temperature of reaction compared with these prepared by the traditional solid state reaction. Minglei Zhao et al. prepared Na0.5Bi0.5TiO3 ceramic by sol-gel method. The piezoelectric constant d33=173×10-12 pC/N increased by 40% compared with that fabricated by traditional method. Meanwhile the piezoelectric ceramic in this study had small coercive field and large residual polarization [11]. Y. D. Hou et al. investigated the fabrication of (Na0.8K0.2)0.5Bi0.5TiO3 (NKBT) prepared by sol-gel –hydrothermal method and its densification. The analysis of the morphology and structure showed that NKBT nanowire with pure perovskite structure could be prepared by sol-gel-hydrothermal method with the synthetic temperature of 160 ºC, of which the diameter was 50-80nm, and the length was 1.5-2.0µm. The theoretical density of the flake made of NKBT nanowire was more than 98% [12]. 3.3 Fabrication of piezoelectric composites Lei Dai, Shan Hu et al. prepared PZN-PZT/PVDF piezoelectric composite material by solid phase sintering combined with solution blending method, and investigated the properties of the materials. The results revealed that the generation of pyrochlore phase could be restrained by appropriately excessive Pb, but too much Pb would reduce the degree of crystallization of the main crystal phase and the piezoelectric properties of the piezoelectric composite material [13]. 4. Application prospect of the smart piezoelectric materials 4.1 Application in structural health monitoring Due to chemical corrosion, stress effect, tiny impact and influence and other factors, local damage and micro-cracks may appear on the surface of the structure of large aircraft, nuclear Advanced Materials Research Vol. 983 17
- 32. reactors, bridges, and large pipes. On the structure of local damage, especially micro - cracks on the surface of monitoring it is a very important part of structural health monitoring system to monitor the local damage and micro-cracks on the surface of the vital structure [14]. A damage detection method based on an innovative 2D phased sensor array made of piezoelectric paint is proposed for in situ damage detection of a thin isotropic panel using guided Lamb waves. In this study, a 2D phased sensor array with a spiral configuration is fabricated using a piezoelectric composite patch and used for detecting damages in an aluminum panel. Steered array responses are generated from the raw sensor signals using a directional filtering algorithm based on phased array signal processing. To enhance the proposed analysis technique, empirical mode decomposition (EMD) and a Hilbert–Huang transform (HHT) are applied. A new damage detection algorithm including threshold setting and damage index (DI) calculation is developed and implemented for detecting damages in the form of holes and a simulated crack. The characteristic damage indices consistently increase as damage size grows [15]. 4.2 Application in energy converter In order to optimize the deformation and brittleness of the piezoelectric materials, the Langley research center of the NASA fabricated a new kind of smart piezoelectric macro fiber composite (MFC). Tungpimoluryt K, Hatti N et.al designed an energy collection device based on MFC materials. The main structure of the device is cantilever structure with the MFC fixed on the surface of the cantilever. When sinusoidal excitation is applied, capacitor of the energy collection device is used to collect the electric current generated by MFC, so that the function of collecting energy is fulfilled. The study results showed that this device can produce up to 45. 6v voltage [16]. 4.3 Application in adaptive wing Based on the inverse piezoelectric effect, Paradies et al. designed and made an active control wing model of which the wingspan was 500mm.The key parts of the model were seven set of MFC modules. The wings would be controlled to auto-deform while the MFC parts were applied with voltage. The study results showed that the deformation value of the wing end was 4.3mm when the voltage applied was 1.5kV [17]. 5. Research prospect of the smart piezoelectric materials In this paper, new fabrication methods and application of the smart piezoelectric materials are introduced. Although the smart piezoelectric materials have been used in many fields owing to the big driving force and fast response speed, it should be noted that the effects to decrease the brittleness and improve the deformation degree of the smart piezoelectric materials are still needed. The key focus of the study of smart piezoelectric materials are to compound the structures and increase the serviceability. As the synthesis and integration of various materials and high technology, the research of smart piezoelectric materials is bound to have a good and broad prospects. References [1] Y. Liu, K. Gall, M.L. Dunn: Mech. of Mater. Vol.36 (2004), p.929. [2] C. Lin, F. Chen, L. Yuan, G.Z. Liang: FRP/Compo. Vol. 2 (2012), p. 74. [3] X.M. Zhang: FRP/Compo. Vol. 6 (2013), p. 57. [4] J.H. Xie, W.G. Zhang, D.K. Liang: Mater. Review. Vol. 20 (2006), p. 6. [5] C. He, W.G. Chen: Jour. Fun. Mater. Vol. S1 (2010), p. 11. 18 Advanced Materials and Engineering
- 33. [6] S.R. Platt, S. Farritor, H. Haider: IEEE/ ASME Transactions on Techtronic. Vol. 10 (2005), p. 240. [7] Y.X. Bian, C.H. Yang: Piezoelectrics & Acoustooptics, Vol. 33 (2011), p. 612. [8] H. Takahashi, Y. Numamoto et al: Appl. Phys. Vol. 47 (2008), p. 8468. [9] W. Haessler et al: Mater. Lett. Vol. 24 (1995), p. 387. [10] S.L. Gu, G.L. Li et al: Mater. Sci. Eng. Powder Metall. Vol. 18 (2013), p. 560. [11] M.L. Zhao et al: Acta. Phys. Sin. Vol. 52 (2003), p. 229. [12] Y. D. Hou et al: J Am Ceram Soc. Vol. 90 (2007), p. 1738. [13] L. Dai, S. Hu et al: CHN Ceram. Vol. 43 (2007), p. 47. [14] F. Zhang et al: Chinese Journal Sensors and Actuators. Vol. 18 (2005), p. 215. [15] B. Yoo, A.S. Purekar, Y. Zhang: Smart Mater. Struct. Vol. 19 (2010), p. 17 [16] K. Tungpimoluryt et al: IEEE International Symposium on Applications of Ferroelectrics, 2011. [17] R. Paradies, P. Ciresa: Smart Mater. Struct. Vol. 18 (2009), p. 1. Advanced Materials Research Vol. 983 19
- 34. Reusable and efficient polystryrene-supported acidic ionic liquid catalyst for the synthesis of n-butyl acetate Yuhe Cheng a , Biao Zhang b , Shangjiang Dai c , Hanlin Tong d , Lixia Li e * 1 School of environment and safety engineering, Jiangsu University, Zhenjiang 212013, PR China a chengyuhe@126.com, b 851974763@qq.com, c 584119471@qq.com, d tonghanlin1@163.com, e *qingpipa@163.com Keywords: Polystyrene-supported acidic ionic liquid. Esterification. n-Butyl acetate. Abstract. A series of polystyrene-supported 1-(propyl-3-sulfonate)-3-methy-imidazolium hydrosulfate acidic ionic liquid (PS-[SO3H-PMIM][HSO4]) catalysts with different [SO3H-PMIM] [HSO4] contents were prepared and tested for esterification of n-butyl alcohol with acetic acid. It was found that the reactivity of the catalyst increased with increasing [SO3H-PMIM][HSO4] content, and best yield of n-Butyl acetate of 98% was obtained using PS-[SO3H-PMIM][HSO4]1 within 1.5h. The catalytic activity of this catalyst decreased slightly after fifth using. Introduction Caboxylic esters is a important intermediates. Traditionally, they were synthesized by Fischer esterification of carboxylic acids and alcohols under the catalyst of hydrochloric acid or sulfuric acid [1]. Although much success has been achieved with these inorganic liquid-phase acids, some problems still remain, for example, tedious purification procedure of the product, needing of a lot of inorganic acids, corrosion of equipments[2,3]. Various novel catalysts have therefore been explored in order to avoid these insufficient. Since the end of last century, with more and more recognition of room temperature ionic liquids (TSILs), there are growing interests in using ionic liquids as solvents or catalysts for esterification [4,5], but high costs and unendurable viscosities limited their further applications [6]. In recent years, some researches were reported about supported acidic ionic liquid catalyst for organic reactions [7-9]. These researches showed that the supported ionic liquid catalysts had many advantages over their unsupported counterparts, such as separation, reusability, and the ability to provide practical conveniences in a continuous system. Recently, Xu[10] reported a new approach of synthesis of PS-supported acidic ionic liquid (PS-CH2-[SO3H-pIM][HSO4]) catalyst and its catalytic performance for Fischer esterification. In the previous work, we supported a imidazole type Brønsted-acidic TSILs, 1-(propyl-3-sulfonate)-3-methy-imidazolium hydrosulfate acidic ionic liquid ([SO3H-PMIM][HSO4]), onto three kind of chloromethylated polystyrene beads prepared in lab to prepare a series of PS-[SO3H-PMIM][HSO4] catalysts, and studied their catalytic capability in nitration of aromatic compounds [11, 12]. As part of our continuing interests, here, we tested for esterification of n-butyl alcohol with acetic acid. The catalysts were characterized by FT-IR, SEM/TEM, elements analysis, TG/DSC and acid base titration. Experimental Catalyst preparation. Scheme 1 showed the synthetic process of PS-[SO3H-PMIM][HSO4] [10, 13]. First, sodium methylate (0.1mol) in methanol (10mL) was added dropwise into the mixture of imidazole (0.1mol), KI (0.1g) and toluene (5mL) at 40 ℃. Then, PS-CH2Cl beads (0.01mol, –CH2Cl), prepared according to the previous report [14], in acetonitrile (15mL) was added to the formed imidazole sodium salt solution, the reaction was carried out at 65 ℃ for 48 h. The PS-CH2-imidazole product was filtered off and washed by soxhlet extraction using ethanol as solvent and dried under vacuum. Second, PS-CH2-imidazole and equiv (relative to -imidazole) 1,3-propane sultone were Advanced Materials Research Vol. 983 (2014) pp 20-25 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.983.20
- 35. added in anhydrous toluene and reacted at 75 ℃ for 14h. Then product named as the PS-[SO3H-PMIM] was filtered off, washed with toluene and dried under vacuum. Last, dried PS-[SO3H-PMIM] was soaked in dichloromethane at 0 ℃, and acidified with equiv concentrated sulfuric acid or hydrochloric acid. The mixture were heated to 75 ℃ for 4h under stirring. The target catalyst PS-[SO3H-PMIM][HSO4] or PS-[SO3H-PMIM][Cl] were collected by filtration, washed with diethyl ether and dried under vacuum. Scheme 1 Synthesis of PS-[SO3H-PMIM][HSO4] catalyst Catalyst characterizations. IR spectroscopy was recorded using a Nicolet IS10 FTIR spectrometer. TG/DSC studies were carried out using METTLER TOLEDO SDTA851e/DSC823e instrument. Elemental analysis was determined by Vario MICRO EL. Average particle sizes and surface morphologies were characterized by a SEM Leica S440i. GC spectra were recorded using Agilent GC-6820 spectrometer. Acidic sites was confirmed by titration of PS-[SO3H-PMIM][HSO4] catalyst with 2.08×10-2 M aq. NaOH, using phenolphthalein as indicator. Catalyst for aromatics esterification reactions. PS-[SO3H-PMIM][HSO4] (0.95g), n-butyl alcohol (96mmol), acetic acid (80mmol) and cyclohexane (8mL) were charged successively into a three-neck flack with a water segregator, and stirred at 92℃ for length of time. The resultant mixture was cooled. The catalyst was filtered off, washed with ethanol, and dried for the recycling experiments. The filtrate was analyzed using GC. Results and discussion FT-IR. As shown in Fig.1, for PS-CH2Cl, the characteristic peaks of polystyrene exhibited the C–H stretching vibration of aromatic ring at 3016 cm−1 , and C–H asymmetric and symmetric stretching vibrations of methylene at 2920 cm−1 and 2855 cm−1 . The peaks at 1609 cm−1 and 1507 cm−1 were due to the C–C skeleton vibration of aromatic ring of polystyrene. Moreover, a typical peak at 1265 cm−1 was attributed to stretching vibrations of the functional group –CH2Cl, and another peak at 672cm-1 was due to stretching vibrations of C-Cl[15]. The two typical peaks were practically omitted after introduction of imidazole. Meanwhile, a peak assigned to the C=N stretching vibration of imidazole ring at 1560 cm−1 appeared[16], which was indicated the imidazole anchored on the polystyrene by covalent bond. In the IR spectrum of PS-[SO3-PMIM], several strong peaks, i.e. 1039 cm-1 , 1160 cm-1 and 1209 cm-1 , appeared which were attributed to the absorb of –SO3 - . When PS-[SO3-PMIM] was acidified with concentrated sulfuric acid, there were no obvious change in IR spectrum but two peaks, 1039 cm-1 and 1209 cm-1 became stronger, which were attributed to the S=O asymmetric and symmetric stretching vibrations of –SO3– group. Advanced Materials Research Vol. 983 21
- 36. Fig. 1 IR-spectra of PS-CH2Cl, PS-CH2-imidazole, PS-[SO3-PMIM] and PS-[SO3H-PMIM][HSO4]. Elements analysis of PS-CH2-imidazole and acidic sites of PS-[SO3H-PMIM][HSO4]. Table 1 showed the elemental analysis for PS-CH2-imidazole. It can be seen that the imidazole contents increased with the increasing of VBC in feed composition of PS-CH2Cl. Acid sites of the PS-[SO3H-PMIM][HSO4] catalyst was confirmed by acid base titration. The loading amounts of [SO3H-PMIM][HSO4] in PS-[SO3H-PMIM][HSO4]1 and PS-[SO3H-PMIM][HSO4]2, PS-[SO3H-PMIM][HSO4]3 were 2.22, 2.03 and 1.69mmol/g respectively. Table 1 Elemental analysis of PS-CH2-imidazole Sample VBC:St:DVB, vol% % C % H % N Imidazole, mmol/g PS-CH2-imidazole1 98:0:2 73.88 6.84 12.77 4.56 PS-CH2-imidazole2 74:24:2 74.11 6.88 11.58 4.14 PS-CH2-imidazole3 49:49:2 77.50 7.09 9.24 3.30 “VBC:St:DVB, vol%”was the feed composition of PS-CH2Cl beads. “VBC, St and DVB” are the abbreviation of “4-vinylbenzyl chloride, styrene and divinyl benzene” respectively. SEM/TEM and TG-DSC. It can be seen that PS-CH2Cl (Fig. 2 A and C) was uniform globular in the size of ~600 nm. After the introduction of [SO3H-PMIM][HSO4], the catalyst became big a little, about ~700nm and the surface became smooth (Fig. 2 B and D), which is in accord with other report [10]. Fig. 2 SEM and TEM of PS-CH2Cl (A and C) and PS-[SO3H-PMIM][HSO4] (B and D). Fig. 3 TG/DSC curves of PS-CH2Cl and PS-[SO3H-PMIM][HSO4] catalyst. TG/DSC analysis was carried out in N2 with heating rate of 10 ℃/min. As shown in Fig. 3, no significant weight loss was observed from both PS-CH2Cl and PS-[SO3H-PMIM][HSO4] at beginning. Above 120℃, weight loss was accelerated for both the two particles and weight loss speed of PS-CH2Cl was quicker than that of PS-[SO3H-PMIM][HSO4]. There was a obvious weight loss 22 Advanced Materials and Engineering
- 37. from PS-CH2Cl nearby 150 ℃. Correspondingly, for the DSC curve of PS-CH2Cl, a small exothermic peak appeared, however it didn’t appear in the DSC curve of PS-[SO3H-PMIM][HSO4]. The weight loss and the exothermic peak of PS-CH2Cl were possibly ascribed to the water inside the porous PS-CH2Cl particles. When the [SO3-PMIM] was immobilized onto PS-CH2Cl in organic solvent, the water was droved and the holes were jammed. When the temperature further increased up to higher than 300 ℃ for PS-CH2Cl and 410 ℃ for PS-[SO3H-PMIM][HSO4], weight loss accelerated heavily. A possible reason is that their structures were destroyed or the chloromethyl groups and the [SO3H-PMIM][HSO4] separated from PS. The residue weight of PS-[SO3H-PMIM][HSO4] and PS-CH2Cl was about 56.5% and 27.2% at 450 ℃, respectively. These observations indicated that the immobilization of [SO3H-PMIM][HSO4] onto polystyrene could improve the thermal stability of PS-CH2Cl. Catalytic reaction. The esterification of n-butyl alcohol with acetic acid is showed in Scheme 2. Scheme 2 Esterification of n-butyl alcohol with acetic acid. To evaluate the PS-[SO3H-PMIM][HSO4] catalyst described here, the catalytic activities of various catalyst for the esterification reaction of n-butyl alcohol and acetic acid were examined under the same reaction conditions (Table 2). Obviously, the yields of n-butyl acetate over PS-[SO3H-PMIM][HSO4] (Table 2, entry1-3) were much higher than that over the support (Table 2, entry 5) and no catalyst(Table 2, entry 6). This meant that the reaction hardly carried out without catalyst and the support almost had no influence on the yield. It was worth noting that the PS-[SO3-PMIM]1 had no influence on the reaction evidenced the scheme of the synthesis of PS-[SO3H-PMIM][HSO4] catalyst at a certain extent. In addition, it easy to see that both the PS-[SO3H-PMIM][HSO4] catalysts and PS-[SO3H-PMIM][Cl] (Table 2, entry 4) catalyst were effective for the reaction of n-butyl alcohol and acetic acid although the catalytic activity of the latter was far lower than that of the former. The reason was that both the two kinds of solid catalysts could provide proton H+ , which could make the acetic acid protonated and then was attacked by nucleophilic n-butyl alcohol to form n-Butyl acetate. Which analysis was based on the classical two key steps esterfication [17-19]. Compared to PS-[SO3H-PMIM][HSO4] catalysts, there are two groups, i.e. HSO4 - anions and SO3 H- group, could supply proton H+ , the providing proton H+ ability of PS-[SO3H-PMIM][Cl] is limited, which contributed lower catalytic capability. It can be seen that all of the PS-[SO3H-PMIM][HSO4] catalysts exhibited high catalytic activity. The yield of n-Butyl acetate increased with the increasing of [SO3H-PMIM][HSO4] content at same reaction time, which was attributed to the gradually increasing amount of acid sites in the catalyst. When using the PS-[SO3H-PMIM][HSO4]1 as catalyst, 98% yield was obtained at 92℃, within 1.5h, which was better than the similar study reported by Xu[10]. Table 2 Result of n-Butyl acetate over various catalyst and reaction timea Entry Catalyst Yield, % 0.75, hb 1.5, hb 3, hb 1 PS-[SO3H-PMIM][HSO4]1 94 98 98 2 PS-[SO3H-PMIM][HSO4]2 90 96 98 3 PS-[SO3H-PMIM][HSO4]3 90 93 98 4 PS-[SO3H-PMIM][Cl]1 57 68 74 5 PS-[SO3-PMIM]1 (or PS-CH2Cl1) 34 47 52 6 Blank 33 48 50 a By quantitative GC based on crude product b Reaction time, h Advanced Materials Research Vol. 983 23
- 38. Catalyst recycle study. The reusability of PS-[SO3H-PMIM][HSO4] catalyst was evaluated in esterification of n-butyl alcohol with acetic acid catalyzed by PS-[SO3H-PMIM][HSO4]1. As shown in Table 3, PS-[SO3H-PMIM][HSO4]1 still showed very high activity after third runs and the catalytic activity decreased only 3% for 5 runs, which indicated that PS-[SO3H-PMIM][HSO4] catalyst was efficient and reusable. Table 3 The reusability of PS-[SO3H-PMIM][HSO4]1 for n-Butyl acetatea Runs time 1 2 3 4 5 Yield, % 98 98 97 96 95 a By quantitative GC based on crude product, reaction time 1.5h. Conclusion A series PS-[SO3H-PMIM][HSO4] catalysts were prepared by grafting [SO3H-PMIM][HSO4] onto the highly chloromethylated polystyrene beads, and showed a better thermal stability than that of PS-CH2Cl resins. These catalysts were efficiencies for esterification of n-butyl alcohol with acetic acid. The yield of n-Butyl acetate generally increased with increasing of the [SO3H-PMIM][HSO4] content. The best yield of 98% was obtained under 92℃ within 1.5h over PS-[SO3H-PMIM][HSO4]1 catalyst. The catalyst could be recovered by simple filtration, and the yield only decreased 3% after reusing for 5 times. In conclusion, the PS-[SO3H-PMIM][HSO4] catalyst prepared in this paper was an excellent recyclable catalyst for the synthesis of n-Butyl acetate, and it showed potential application for carboxylic esters in industry. This work was supported by the grant (No. 1281370046) from the Scientific Research Foundation for the high-ranking talent of Jiangsu university. References [1] S. Kaewta, L. Edgar, G.G. James, Solid bronsted acid catalysis in the gas-phase esterification of acetic acid, Ind. Eng. Chem. Res. 46 (2007) 7050–7056. [2] X.Z. Li, W.J. Eli, A green approach for the synthesis of long chain aliphatic acid esters at room temperature, J. Mol. Catal. A: Chem. 279 (2008) 159–164. [3] V.R. Vamsi, V.R. Modukuri, A. Ratnamala, et. al. A Simple, Efficient, Green, Cost Effective and Chemoselective Process for the Esterification of Carboxylic Acids, Org. Process Res. Dev. 13 (2009) 769-773. [4] J.F. Dubreuil, K. Bourahla, M. Rahmouni, et. al. Catalysed esterifications in room temperature ionic liquids with acidic counteranion as recyclable reaction media, Catal. Commun. 3 (2002) 185-190. [5] T. Joseph, S. Sahoo, S.B. Halligudi, Brönsted acidic ionic liquids: A green, efficient and reusable catalyst system and reaction medium for Fischer esterification, J. Mol. Catal. A: Chem. 234 (2005) 107-110. [6] P.M. Christian, A.C. Raymond, C.D. Nicholas, et. al. Supported Ionic Liquid Catalysis − A New Concept for Homogeneous Hydroformylation Catalysis, J. Am. Chem. Soc. 124 (2002) 12932-12933. [7] C. DeCastro, E. Sauvage, M.H. Valkenberg, et. al. Immobilised Ionic Liquids as Lewis Acid Catalysts for the Alkylation of Aromatic Compounds with Dodecene, J. Catal. 196 (2000) 86-94. [8] H.L. Shim, S. Udayakumar, J.I. Yu, et.al. Synthesis of cyclic carbonate from allyl glycidyl ether and carbon dioxide using ionic liquid-functionalized amorphous silica, Catal. Today 148 (2009) 350-354. [9] D.W. Kim, D.J. Hong, K.S. Jang, et. al. Structural modification of polymer-supported ionic liquids as catalysts for nucleophilic substitution reactions including fluorination, Adv. Synth. Catal. 348 (2006) 1719-1727. [10] Z.J. Xu, H. Wan, J.M. Miao, et. al. Reusable and efficient polystyrene-supported acidic ionic liquid catalyst for esterifications, J. Mol. Catal. A: Chem 332 (2010) 152-157. 24 Advanced Materials and Engineering
- 39. [11] X.L. Li, Q. L. Ling, Z. L. Liu, et. al. Reusable and Efficient Polystryrene-supported Acidic Ionic Liquid Catalyst for Mononitration of Aromatic Compounds, Bull. Korean Chem. Soc. 2012, 33(2012) 3373-3377. [12] L.X. Li, Q.L. Ling, X.D. Xing, et. al. Reusable and Efficient PS-supported Acidic Ionic Liquid Catalyst for Mononitration of Toluene, Advanced Materials Research, 581-582(2012) 252-257. [13] A.S. Amarasekara, O.S. Owereh, Synthesis of a sulfonic acid functionalized acidic ionic liquid modified silica catalyst and applications in the hydrolysis of cellulose, Catal. Commun. 11 (2010) 1072-1075. [14] F.S. Macintyre, D.C. Sherrington, L. Tetley, Synthesis of Ultrahigh Surface Area Monodisperse Porous Polymer Nanospheres, Macromolecules 39 (2006) 5381-5384. [15] Q. Wu, H. Chen, M.H. Han, et. al. Transesterification of Cottonseed oil catalyzed by bronsted acidic ionic liquids, Ind. Eng. Chem. Res. 46 (2007) 7955-7906. [16] M.J. Earl, S. Haas, C.B. Carl, et. al. Catalystic nitration of aromatics by ionic liquid, CN1469859A, 2004. [17] F. Xu, H.Y. Chen, H.B. Zhang, et. al. Protophilic amide ionic liquid assisted esterification and catalysis mechanism, J. Mol. Catal. A: Chem. 307 (2009) 9-12. [18] S.R. Kirumakki, N. Nagaraju, S. Narayanan, A comparative esterification of benzyl alcohol with acetic acid over zeolites Hβ, HY and HZSM5, Appl. Catal. A 273 (2004) 1-9. [19] J.Z. Gui, H.Y. Ban, X.H. Cong, et.al. Selective alkylation of phenol with tert-butyl alcohol catalyzed by Brönsted acidic imidazolium salts, J. Mol. Catal. A: Chem. 225 (2005) 27-31. Advanced Materials Research Vol. 983 25
- 40. An exploration of factors affecting the preparation of SiO2-coated α-Al2O3 pearlescent pigment Nan Wu1,a , Qinghua Chen1,b* , Weiming Zhou2,c , Meizhen Ke2,d , Qingrong Qian1,e* , Zhanhui Yuan1,f 1 College of Environmental Science and Engineering, Fujian Normal University, Fuzhou, China 2 College of Materials Science and Engineering, Fujian Normal University, Fuzhou, China a 270732913@qq.com, b cqhuar@126.com, c zhouweiming721@126.com, d 757412608@qq.com, e qrqian@fjnu.edu.cn, f zhanhui.yuan@fzkuncai.com Keywords: SiO2-coated α-Al2O3; pearlescent pigment; liquid phase deposition Abstract: The SiO2-coated α-Al2O3 pearlescent pigment was prepared by liquid phase deposition (LPD). The effects of concentration of sodium silicate solution, reaction temperature and pH value of the aluminum oxide suspending liquid were systemically studied in this paper. The obtained samples were characterized by scanning electron microscopy (SEM). The results showed that when the process parameters are the concentration of sodium silicate solution of 0.1 mol/L, the reaction temperature of 80 o C and the pH value of 9.0, the high quality of SiO2-coated α-Al2O3 pearlescent pigment could be obtained. Introduction Pearlescent pigment is one of the color effect materials which composed of a highly reflective platelet-shaped substrate encapsulated with a low index of refraction material [1]. It is widely applied in plastics, printing ink, cosmetic and ceramic materials due to its unique decorative optical color effects and weather-resistance effects [2]. The common substrates of traditional pearlescent pigment were mica or synthetic mica [3]. The defect of the mica or synthetic mica based pearlescent pigment are these: 1. the mica or synthetic mica is difficult to delamination; 2. the pearlescent pigment made by mica or synthetic mica has a poor dispersion. α-Al2O3 based pearlescent pigment[4] is a newly emerging material which overcome the defect of the mica or synthetic mica based pearlescent pigment. In this paper, the factors affecting the preparation of SiO2-coated α-Al2O3 pearlescent pigment was studied in order to find a easy and fast way of preparing the SiO2-coated α-Al2O3 pearlescent pigment. Experimental Raw materials and reagents. The platelet-shaped α-Al2O3 was supplied by Xiamen ZF Co., Ltd. The morphology of α-Al2O3 was shown in Fig.1. The sodium hydroxide and sodium silicate were provided by Tianjin Fuchen chemical reagents factory, both of them are analytical-reagent. And the chemically-pure sulphuric acid was obtained from Fuzhou chemical engineering research institute. Advanced Materials Research Vol. 983 (2014) pp 26-29 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.983.26
- 41. Fig.1 The morphology of α-Al2O3 (a:×500; b:×10000) Preparation process. Measured 25 g α-Al2O3 and added it to 100 mL distilled water as the reaction mother liquor. The suspending liquid was heated and stirred in certain temperature. The pH value was adjusted by sodium hydroxide. Then injected Na2SiO3 dropwisely (about 0.75 mL/min) into the suspending liquid and added H2SO4 (0.1 mol/L) at the same time to kept the pH value constant (The H2SO4 was added by ProMinent Dulcometer D1Cb, a pH controller). After that, the product was filtered and washed for several time to move the free SiO2. In the end, the precipitate was dried at 102 o C for 12 h. Characterizations. The morphologies of SiO2-coated α-Al2O3 were tested by the scanning electron microscope (JSM 7500F). Results and discussion Influence of concentration of sodium silicate solution. Elevated the concentration of sodium silicate solution could accelerate the hydrolysis of sodium silicate, so the H2SiO3.nH2O would generate massly and rapidly. The crystal particles would be small, because they didn’t have enough time to grow up, as shown in Fig.2-b and Fig.2-c. But if the generation rate of H2SiO3.nH2O was far faster than its deposition rate, the H2SiO3.nH2O would be more likely to formed free SiO2 or large grain of SiO2 on the surface of α-Al2O3, as shown in Fig.2-d. Therefore the optimum concentration is 0.10 mol/L. Fig.2 The morphology of SiO2-coated α-Al2O3 prepared by different concentration of sodium silicate solution (a: 0.05 mol/L ; b: 0.10 mol/L; c: 0.15 mol/L; d: 0.20 mol/L; e: 0.25 mol/L), all the sample above were prepared in 80 o C, with the pH 9.0 Advanced Materials Research Vol. 983 27
- 42. Influence of the reaction temperature. Heating properly could promote the growth of SiO2 crystal particles as well as accelerate the hydrolysis of sodium silicate. With the increase of temperature, the crystal particles that formed in the surface of α-Al2O3 would be larger and larger, as shown from Fig.3-a to Fig.3-d. But when the temperature was too high, the crystal might also fail to form, as shown in Fig.3-e. Therefore the optimum reaction temperature is 80 o C. Fig.3 The morphology of SiO2-coated α-Al2O3 prepared in different temperature (a: 75 o C; b: 80 o C; c: 85 o C; d: 90 o C; e: 95 o C), all the sample above were prepared by 0.10 mol/L sodium silicate solution, with the pH 9.0 Influence of the pH value. The pH value could affect both the hydrolysis and gelling of silicate. The sodium silicate would hydrolyze rapidly at a low pH value, which might lead to self-nucleation of silicate. We could learn from the pre-experiment that the hydrolysis rate of sodium silicate would be appropriate when the pH value was 8.0~10.0. The relationship of gelling time with pH was following N curve [5]. The pH 8.0~8.5 was nearly at the bottom of the N curve, at that range, the gelling rate would be high, and the large grain of SiO2 would be formed before it deposited on the surface of α-Al2O3, as shown in Fig.4-a and Fig.4-b. When the pH value was 9.0, the gelling rate was moderate and close to the deposition rate, the SiO2 on the surface of α-Al2O3 would be well-distributed, as shown in Fig.4-c. Therefore the optimum pH is 9.0. 28 Advanced Materials and Engineering
- 43. Fig.4 The morphology of SiO2-coated α-Al2O3 prepared in different pH (a: 8.0; b: 8.5; c: 9.0; d: 9.5; e: 10.0), all the sample above were prepared by 0.10 mol/L sodium silicate solution, in 80 o C Conclusions The SiO2-coated α-Al2O3 pearlescent pigment was prepared by liquid phase deposition (LPD). The result of SEM showed that when the process parameters are concentration of sodium silicate solution of 0.1 mol/L, reaction temperature of 80 o C and pH value of 9.0, the SiO2 on the surface of α-Al2O3 would be dense, fine and well-distributed. Acknowledgements This work is supported by Program for the Fujian Provincial Science and Technology and the Provincial Financial Department (2011H6005), and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (2011-1568). The corresponding authors are Qinghua Chen and Qingrong Qian. References [1] Curtis J. Zimmermann, James D. Christie, Vivian K. Doxey and Daniel Stevenson Fuller, U.S. Patent 6,821,333. (2004) [2] Deborah Cacace, Carolyn Lavallee, Michael T. Venturini, U.S. Patent 5,759,255. (1998) [3] Frank J. Maile, Gerhard Pfaff, Peter Reynders, Effect pigments—past, present and future, Progress in Organic Coatings. 54 (2005) 150-163. [4] Jung Min Lee, Jeong Kwon Suh, Byung Ki Park, Dong Uk Choe, Gil Wan Chang, Kwang Su Lim, Sung Yun Jo, Kwang Choong Kang, U.S. Patent 8,287,636. (2012) [5] Cui Aili, Wang Tingjie, Jin Yong, Xiao Shuaigang, Ge Xudong, Mechanism and Structure Analysis of TiO2 surface coated with SiO2 and Al2O3, Chemical journal of Chinese universities. 19 (1998) 1727-1729. Advanced Materials Research Vol. 983 29
- 44. Assessment of Engineering Properties of Geosynthetics with Seaming Methods Han-Yong Jeon Department of Applied Organic Materials Engineering, Inha University, Incheon, Korea(Rep.) hyjeon@inha.ac.kr Keywords: geosynthetics, seaming method, transmissivity, strength retention, chemical resistance, seam strength, reduction factor Abstract. 8 Geotextiles (; 4 woven and 4 nonwoven types), 4 geogrids and 2 geocomposites of [nonwoven/fibers/nonwoven] structure were used as raw materials and the different seaming methods were applied to compare the seam properties of 3 geosynthetics and transmissivity of geocomposites. Tensile strength retentions of these geosynthetics were evaluated as the degree of damage by chemical degradation. Woven geotextiles showed the higher seam strength in the order (SSd-1 < SSd-2) > (SSa-1 < SSa-2) > geospacer without regard to the design strength. For nonwoven geotextiles, the order of seam strength is geospacer > (SSa-1 < SSa-2). Geogrids showed the higher seam strength in the order of band > geospacers but reduction factors were increased in the order of band > geospacer without regard to the geogrid’s compositions. Finally, geocomposites showed the higher seam strength in the order of geospacer > (SSa-1 < SSa-2) but showed the transmissivity in the order of geospacer > (SSa-1 > SSa-2) without regard to the kinds of filled fibers and weight of geocomposite. Introduction Geosynthetics have their seaming methods such as mechanical or chemical seaming techniques due to their own structures, physical, chemical and thermal properties. Furthermore, the seam strength of geosynthetics must be influenced by seaming methods and for reinforcement/protection applications with geosynthetics, the seaming is typically the weak connection to applied load transfer in the reinforcement/protection system [1]. For filtration or drainage applications, this phenomena on geosynthetics could affect the vertical or horizontal hydraulic flow. Seaming can have a significant impact on the performance of geosynthetic systems whether their intended function is reinforcement/protection, separation or filtration and drainage. When reinforcement/ protection is the function, the seaming must be considered as a limiting strength factor and assessed by the same performance standards as the reinforcement/protection geosynthetic only [2, 3, 4]. Besides this, the seaming of geosynthetics should be evaluated for durability limitations such as installation damage, creep deformation, chemical and biological degradations etc. Seaming of geotextiles by traditional sewing methods necessarily causes needle damage to fibers and yarns as well as creating stress concentrations where the sewing threads reverse direction for their return stroke. These effects are relatively small for light-weight geotextiles and the resulting seam strength are generally quite high. For geogrids, the connection techniques require a high level of dimensional Advanced Materials Research Vol. 983 (2014) pp 30-38 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.983.30
- 45. stability within the geogrid structure to withstand the stress concentrations imposed by connection techniques. Filtration or drainage performance of geocomposites could be also influenced by the seam strength with different seaming methods. In this study, geotextiles - 4 woven and 4 nonwoven types, 4 geogrids and 2 geocomposites of [nonwoven/fibers/nonwoven] structure were used as raw materials and the different seaming methods were applied to compare the seam properties of 3 geosynthetics and transmissivities of geocomposites. Experimental Preparation of Samples and Seaming 8 Geotextiles(; 4 woven and 4 nonwoven types), 4 geogrids and 2 geocomposites of [nonwoven/fibers/nonwoven] structure were used as raw materials. Geocomposites of 3-layer structure which have the excellent drainage function under confined loading condition were manufactured by needle punching method. Three different punching patterns were applied to manufacture these geotextiles as , and punching pattern. Assessments of Performance of Geosynthetics Seaming methods that applied to geosynthetics were as following: (1) geotextiles - sewing methods : flat seam(; SSa-1, -2), butterfly seam(; SSd-1, -2), geospacer, (2) geogrids - band and geospacer, (3) geocomposites – flat seam(; SSa-1, -2) and geospacer. Table 1 shows the specifications and seaming methods of these geosynthetics and Figure 1 shows the various seam types and geospacer. Seam properties of geotextiles and geocomposites were examined by ASTM D 4884(; test method for seam strength of sewn geotextiles) and those of geogrids were investigated through ASTM D 4884. Chemical resistance of geosynthetics were tested in the condition of pH 3 and 8, 25°C and 50°C during 360 days. These solutions were adopted to compare the chemical resistance by considering the waste leachates. The degree of chemical resistance of geosynthetics were estimated by comparing the tensile strength retention ratio after 360 days with ASTM D 5322. Especially for geogrids, creep deformation tests were done to determine the reduction factor of geogrids to affect the long-term performance by ASTM D 5262 and GRI GG 3(b). Transmissivities of geocomposites were tested by ASTM D 4716. 2 types of geonet composites – GNC-1, -2 - having the same thickness as smart geotextiles were used as comparison materials for drainage function and Figure 2 showed the cross sectional morphology of geocomposites and geonet composites. Advanced Materials Research Vol. 983 31
- 46. Table 1. Specifications and seaming methods of geosynthetics Geosynthetics Fibers Design Strength(kN/m) Weight (g/m2 ) Seaming Methods Geotextile Woven WGT-1 WGT-2 WGT-3 WGT-4 Polyester 50 100 150 200 Flat Seam, Butterfly Seam, Geospacer Non- woven NWGT-1 NWGT-2 NWGT-3 NWGT-4 Polypropylene 712 1,024 1,532 2,156 Geogrid GG-1 GG-2 GG-3 GG-4 High tenacity Polyester 80 150 200 250 Band, Geospacer Geocomposite [Nonwoven/Fibers* /Nonwoven] GC-1 GC-2 *Polypropylene Waste Fiber 1,306 2,084 Flat Seam, Geospacer Fig 1. Schematic diagrams of various seam types and special geospacer 32 Advanced Materials and Engineering
- 47. (a) Smart geotextiles (b) Geonet composite Fig 2. Photographs of cross section areas of geosynthetics Result and Discussion Seamed geosynthetics by geospacers Fig. 2 shows the seamed geosynthetics, e.g., nonwoven geotextile, geogrid and geocomposite by the geospacer. In this Figure, it was seen that this seaming method has no problem to be used in the bonded area instead of the overlapping the geosynthetics, especially the thick geotextiles which have the weight more than 1,000g/m2. (a) Nonwoven geotextile (b) Geogrid (c) Geocomposite Fig 3. Photographs of seamed geosynthetics by geospacer Seam Strength Table 2 shows the seam strength of the seamed geosynthetics with the seam type. For woven geotextiles, the butterfly seam(SSd-1 and SSd-2) shows the excellent seam strength than the flat seam(SSa-1 and SSa-2) but the geospacer seam shows the lower seam strength than the flat and butterfly seams. From this, it was seen that the geospacer seam is not optimum for the woven geotrextiles. For nonwoven geotextiles, the geospacer seam shows the excellent seam strength than the flat and butterfly seams with the increase of weight. It is thought that geospacer makes more Advanced Materials Research Vol. 983 33
- 48. compact seam than the flat and butterfly seams for thicker nonwoven geotextiles. For geogrids and geocomposites, the geospacer seam shows the excellent seam strength than the band seam without regard to the design strength and geogrid’s composition. Table 2. Seam strength of geosynthetics with seam type Chemical Resistance The degree of chemical resistance of geosynthetics in the acidic and alkaline solutions were represented in Table 3~6. Nonwoven geotextiles showed the excellent chemical resistance than the woven geotextiles. The tensile strength retentions of woven geotextiles was decreased with high pH value and temperature. This is the typical phenomena of polyester fibers which were unstable against the high pH value and temperature. However, the geospacer seam showed the excellent chemical resistance for all geosynthetics. For geogrids, chemical resistance is not dependent on the seam type and the design strength. Geocomposites showed the same tendency of chemical resistance as the nonwoven geotextiles but smaller change than nonwoven geotextiles. Table 3. Tensile strength retention of geosynthetics with seam type at pH 3, 25°C Seam Type Geosynthetics SSa-1 SSa-2 SSd-1 SSd-2 Band Geospacer WGT-1 116 120 127 134 - 86 WGT-2 118 123 134 138 - 92 WGT-3 121 127 138 143 - 101 WGT-4 124 131 141 148 - 118 NWGT-1 78 85 - - - 92 NWGT-2 80 87 - - - 98 NWGT-3 81 89 - - - 106 NWGT-4 83 92 - - - 113 GG-1 - - - - 66 76 GG-2 - - - - 68 84 GG-3 - - - - 72 78 GG-4 - - - - 76 86 GC-1 64 78 - - - 154 GC-2 81 94 - - - 158 Seam type Geosynthetics SSa-1 SSa-2 SSd-1 SSd-2 Band Geospacer WGT-1 82 84 84 86 - 86 WGT-2 84 85 86 87 - 86 WGT-3 84 85 86 88 - 87 WGT-4 85 86 86 88 - 88 NWGT-1 78 80 - - - 83 NWGT-2 80 83 - - - 85 NWGT-3 82 83 - - - 87 34 Advanced Materials and Engineering
- 49. Table 4. Tensile strength retention of geosynthetics with seam type at pH 3, 50°C NWGT-4 83 85 - - - 88 GG-1 - - - - 92 92 GG-2 - - - - 92 92 GG-3 - - - - 92 92 GG-4 - - - - 92 92 GC-1 84 86 - - - 88 GC-2 84 86 - - 88 Seam type Geosynthetics SSa-1 SSa-2 SSd-1 SSd-2 Band Geospacer WGT-1 80 82 83 85 - 85 WGT-2 82 83 84 86 - 85 WGT-3 82 84 85 86 - 86 WGT-4 82 84 84 87 - 86 NWGT-1 78 80 - - - 83 NWGT-2 81 82 - - - 84 NWGT-3 82 82 - - - 86 NWGT-4 82 84 - - - 86 GG-1 - - - - 92 92 GG-2 - - - - 92 93 GG-3 - - - - 93 92 GG-4 - - - - 92 92 GC-1 83 86 - - - 88 GC-2 84 86 - - 88 Advanced Materials Research Vol. 983 35
- 50. Table 5. Tensile strength retention of geosynthetics with seam type at pH 8, 25°C Table 6. Tensile strength retention of geosynthetics with seam type at pH 8, 50°C Seam type Geosynthetics SSa-1 SSa-2 SSd-1 SSd-2 Band Geospacer WGT-1 74 76 78 80 - 82 WGT-2 76 76 78 82 - 82 WGT-3 76 78 80 82 - 83 WGT-4 78 79 80 83 - 83 NWGT-1 78 80 - - - 82 NWGT-2 80 81 - - - 83 NWGT-3 80 81 - - - 83 NWGT-4 82 83 - - - 84 GG-1 - - - - 91 92 GG-2 - - - - 91 92 GG-3 - - - - 91 93 GG-4 - - - - 92 92 GC-1 82 84 - - - 86 GC-2 82 85 - - 86 Seam type Geosynthetics SSa-1 SSa-2 SSd-1 SSd-2 Band Geospacer WGT-1 74 75 78 81 - 78 WGT-2 76 75 78 82 - 78 WGT-3 76 77 80 83 - 80 WGT-4 78 78 80 84 - 80 NWGT-1 74 78 - - - 81 NWGT-2 75 80 - - - 82 NWGT-3 77 80 - - - 82 NWGT-4 78 81 - - - 83 GG-1 - - - - 91 91 36 Advanced Materials and Engineering
- 51. Long-Term Design Strength of Geogrid by Creep Reduction Factor From GRI Standard Test Method GG4, the allowable strength of geogrid could be written in the following equation to be taken into consideration of the ultimate strength, reduction factors for application of geogrids. The long-term design strength of geogrid should be used in the following equation. The reference document can be found in the GRI Standard Test Method GG4(b) “Determination of the Long-term Design Strength of Flexible Geogrids”. ] 1 [ bd cd cr id ultimate design RF RF RF RF T T × × × × × × × × × × × × = = = = (1) where, Tdesign = long-term design strength of geogrid Tultimate = ultimate strength of geogrid RFid = reduction factor for installation damage RFcr = reduction factor for creep deformation RFcd = reduction factor for chemical degradation RFbd = reduction factor for biological degradation Table 7 shows the longterm design strength of geogrids by the reduction factor of the above mentioned conditions. We used the default values of each reduction factor to be written in the reference, [1]. In here, reduction factors of the geospacer seam are smaller than those of the band seam and this means geospacer seam is more effective than the band seam. Therefore, the long-term design strength values of geospacer showed higher than those of the band seam. Table 7. Long-Term design strength by reduction factor of geogrids with seam type. Geogrid Reduction Factor Long-Term Design Strength (KN/m) Band Geospacer Band Geospacer GG-1 2.4 2.0 33.3 40.0 GG-2 2.4 1.9 62.5 78.9 GG-3 2.4 1.8 83.3 111.1 GG-4 2.3 1.8 108.7 138.9 Transmissivities of Geocomposite Table 8 shows the transmissivities of geocomposites by seam type. Geospacer seam showed higher transmissivity than the flat seam(; SSa-1 SSa-2) without regard to the kinds of filled fibers and weight of geocomposite. For the similar specification, geocomposites showed the better transmissivities than the typical drainage materials, geonet composites. GG-2 - - - - 90 91 GG-3 - - - - 90 91 GG-4 - - - - 91 92 GC-1 82 83 - - - 86 GC-2 82 84 - - - 86 Advanced Materials Research Vol. 983 37
- 52. Table 8. Transmissivities of geocomposites and geonet composites Seam Type Geogrid SSa-1 SSa-2 Geospacer GC-1 1.581 1.224 0.983 GC-2 1.218 1.057 0.915 GNC-1 - - 0.699 GNC-2 - - 0.485 Conclusion Woven geotextiles showed the higher seam strength in the order of butterfly seam(; SSd-1 SSd-2) flat seam(; SSa-1 SSa-2) geospacer without regard to the design strength. For nonwoven geotextiles of 1,000g/m2~, the order of seam strength is geospacer flat seam(; SSa-1 SSa-2). Geogrids showed the higher seam strength in the order of band geospacer but creep deformation were increased in the order of band geospacer without regard to the design strength and geogrid’s compositions. Geocomposites showed the higher seam strength in the order of geospacer flat seam(; SSa-1 SSa-2) but showed the transmissivity in the order of geospacer flat seam(; SSa-1 SSa-2) without regard to the kinds of filled fibers and weight of geocomposite. References [1] R. M. Koerner, 1998, Designing with Geosynthetics, 4th Ed., Prentice-Hall, New Jersey, U.S., Chapter 4. [2] R. D. Holtzs, B. R. Christopher and R. R. Berg, 1995, Geosynthetic Design and Construction Guidelines, U.S. Dept. of Transportation Federal Highway Administration, Publication No. FHWA HI-95-038, 27-105. [3] FHWA, 1989, Geotextile Design Construction Guidelines, U.S. Dept. of Transportation Federal Highway Administration, Publication No. FHWA HI-90-001, 24-46. [4] Jewell R. A., 1996, Soil Reinforcement with Geotextiles, CIRLA Special Publication, Thomas Telford, Westminster, Chapter 5. 38 Advanced Materials and Engineering
- 53. Comparative study of physico-chemical properties of pure Polyurethane and Polyurethane based on Castor Oil M. A. ALAA1, a* , KAMAL YUSOH2, b , S.F.HASANY3, c 1 Faculty of Chemical Natural Resources Engineering, University Malaysia Pahang, Malaysia 2 Department of Chemical Engineering, University of Technology, Baghdad, Iraq Allavip63@yahoo.com, hjkamal@gmail.com, hasany_@live.co.uk Keywords: PPG based PUs and Castor oil mixed PUs, In Situ polymerization, Physico- chemical properties, comparison Abstract.Petroleum based polyurethanes are contributing major portions in the world requirement. To overcome the environmental issues and price adaptability, there is always a massive demand of utilization of renewable resources for polyurethane synthesis with comparable physico-chemical properties. Castor oil is the only major natural vegetable oil that contains a hydroxyl group (-OH) and unsaturated double bonds (C=C) in its organic chain and therefore can be employed with or without modification due to the excellent properties derived from the hydrophobic nature of triglycerides. In this study, physico-chemical properties of high performance polyurethane synthesized from Poly propylene glycol (PPG) in comparison with a combination of PPG and Castor oil (a renewable source), by in situ polymerization technique has been studied. The variations in properties of both types of polyurethanes are evaluated by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and Thermogravimetric analysis technique (TGA). Tensile strength properties were investigated by Film Tensile testing equipment. Results indicated the presence of large -CH stretching in castor oil mixed polyurethane with a larger oxidative thermal stability, over a pure PPG polyurethanes. Tensile properties were found almost comparable in pure and mixed polymers, which signify the usage of mixed polymer in coming future, to overcome the environmental and economical crisis in polyurethanes synthesis. Introduction Polyurethanes (PU) have been extensively used due to excellent physical properties (e.g. low flexibility, high tensile strength, tear and abrasion resistance, solvent resistance, etc.) and high versatility in chemical structures [1-2]. Polyurethane is generally synthesized from the isocyanate reaction with polyol. Polypropylene glycol (PPG) is a polyol, is basically derived from the petrochemical industry [3]. High rising costs of petrochemical feedstock’s and enhanced public desire for environmentally friendly green products, utilization of renewable resources to manufacture the rigid polyurethane is a work necessary at the present time [4-6]. Polyurethane based on polyols derived from different vegetable oils, like castor [7-8], sunflower and rapeseed oils [9].Castor oil is one of the major natural vegetable oil that contains a hydroxyl group and so it is widely used in many chemical industries, especially in the production of polyurethanes [10]. Krushna Chandra Pradhan and P. L. Nayak investigated the synthesis of polyurethane nanocomposites prepared from natural oil like castor oil using HMDI and organically modified clay and covalently linked PU/n-HMDI composite, which was later collected successfully by the electro spinning process [7]. D.J. dos Santos et al., study preparation ,diagnosis from castor oil exhibited increasing of diisocyanate groups, in relation to polyol amount, has increasing of Advanced Materials Research Vol. 983 (2014) pp 39-43 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.983.39
- 54. diisocyanate groups, in relation to polyol amount, has increased the strength at rupture of the obtained polymers and has decreased the polymers elongation, which has resulted into a modulus increasing [11]. Anupama Kaushik et al., examines a series of 1,4-butane diol chain extended polyurethane nanocomposites based on castor oil, and 4,40-diphenylmethane diisocyanate (MDI) were synthesized with modified clay (Cloisite 30B) as filler [12]. 1. Experimental 2.1 Materials Commercial grade Castor oil was purchased from the local market. It was dehydrated at 80ºC in in a vacuum oven and characterized for hydroxyl value (148), acid value (2) and moisture content (0.379%). Polypropylene glycol (PPG) (Mn=4000) was supplied by SIGMA- Aldrich Company. Chain extender, 1, 4-butane diol was procured from Himedia, India. The toluene diisocyanate (TDI), which were used as received, were supplied from SIGMA- Aldrich Company. The catalyst used in this research is DABCO-33LV which is the mixture of triethylenediamine and di (propylene glycol) and it was supplied by Air Products and Chemicals (United Kingdom). 2.2 Characterization Technique Fourier transform infrared spectroscopy (FTIR) analysis of polyurethanes was done using A Vector-22 FT-IR spectrometer (Nicolet 5DX FT-IR) with a resolution of 1 cm-1 from 4000 to 400 cm-1 . Thermal stability (TGA) of polyurethanes was carried out using a Universal V4.5A, TA instruments under a nitrogen atmosphere. Scanning electron microscopy (SEM) was carried out on a JEOL 6300F machine at an acceleration voltage of 5KV. Tensile testing of the nanocomposites film was carried out on an instron model 4505 universal testing machine at 25ºC, with a load cell of 5 KN and following ASTM D 638. The crosshead speed was set to 2 mm/min. Samples were cut in a dumbbell shape with an ASTM D 638 (type V). 3. Result and Discussion 3.1 FTIR Analysis The micro-domain structures of the pure PU and castor oil based PU were analyzed by FTIR as shown in Figure 1. A small broad band in the range 4000–3500 cm-1 , was observed in both samples relating to the O-H stretching vibrations from either water or hydroxyl terminated compounds, and N-H stretching vibrations from either urea or amine group [13-14]. The CH – CH3 peaks stretching are more prominent in castor oil based PU, then pure PU which may be due to larger organic chain present in castor oil based PU. Peaks at 1727 cm-1 represents (C=O) non bonded urethanes [12] which are likely to be present in larger number, in castor oil based PU synthesis. 2.2 TGA Analysis The result of the thermo gravimetric analysis (Figure 2) shows that thermal stability of pure PU and castor oil PU based under identical conditions and a comparison of the weight losses occurred. The thermal stability of these polymers is starting generally above 200 °C [15-16]. It is 40 Advanced Materials and Engineering
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