SlideShare a Scribd company logo

Mesoscale modeling in chemical engineering Part I 1st Edition Li

P
pgicycw858

Mesoscale modeling in chemical engineering Part I 1st Edition Li Mesoscale modeling in chemical engineering Part I 1st Edition Li Mesoscale modeling in chemical engineering Part I 1st Edition Li

Education
1 of 57
Download to read offline
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
Mesoscale modeling in chemical engineering Part I 1st Edition Li download https://textbookfull.com/product/mesoscale-modeling-in-chemical- engineering-part-i-1st-edition-li/ Download full version ebook from https://textbookfull.com
We believe these products will be a great fit for you. Click the link to download now, or visit textbookfull.com to discover even more! Knowledge Science, Engineering and Management: 13th International Conference, KSEM 2020, Hangzhou, China, August 28–30, 2020, Proceedings, Part I Gang Li https://textbookfull.com/product/knowledge-science-engineering- and-management-13th-international-conference-ksem-2020-hangzhou- china-august-28-30-2020-proceedings-part-i-gang-li/ Scaling Chemical Processes Practical Guides in Chemical Engineering 1st Edition Jonathan Worstell https://textbookfull.com/product/scaling-chemical-processes- practical-guides-in-chemical-engineering-1st-edition-jonathan- worstell/ (SOLUTIONS) Chemical, Biochemical, and Engineering Thermodynamics (5th ed) 5th Edition Stanley I. Sandler https://textbookfull.com/product/solutions-chemical-biochemical- and-engineering-thermodynamics-5th-ed-5th-edition-stanley-i- sandler/ Reaction Engineering 1st Edition Shaofen Li https://textbookfull.com/product/reaction-engineering-1st- edition-shaofen-li/
Math Problem Book I Kin Y. Li (Kin-Yin Li) https://textbookfull.com/product/math-problem-book-i-kin-y-li- kin-yin-li/ Microgrid Technology and Engineering Application 1st Edition Li https://textbookfull.com/product/microgrid-technology-and- engineering-application-1st-edition-li/ Advanced Data Analysis & Modelling in Chemical Engineering 1st Edition Denis Constales https://textbookfull.com/product/advanced-data-analysis- modelling-in-chemical-engineering-1st-edition-denis-constales/ Modeling of Chemical Wear: Relevance to Practice 1st Edition A. Sethuramiah https://textbookfull.com/product/modeling-of-chemical-wear- relevance-to-practice-1st-edition-a-sethuramiah/ Chemical Reactor Design Mathematical Modeling and Applications Conesa https://textbookfull.com/product/chemical-reactor-design- mathematical-modeling-and-applications-conesa/
ADVANCES IN CHEMICAL ENGINEERING Editor-in-Chief GUY B. MARIN Department of Chemical Engineering, Ghent University, Ghent, Belgium Editorial Board DAVID H. WEST SABIC, Houston, TX JINGHAI LI Institute of Process Engineering, Chinese Academy of Sciences, Beijing, P.R. China SHANKAR NARASIMHAN Department of Chemical Engineering, Indian Institute of Technology, Chennai, India
Academic Press is an imprint of Elsevier 225 Wyman Street, Waltham, MA 02451, USA 525 B Street, Suite 1800, San Diego, CA 92101-4495, USA The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK 125 London Wall, London, EC2Y 5AS, UK First edition 2015 © 2015 Elsevier Inc. All Rights Reserved No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. ISBN: 978-0-12-801247-5 ISSN: 0065-2377 For information on all Academic Press publications visit our website at store.elsevier.com
CONTRIBUTORS Sergiy Antonyuk Chair of Particle Process Engineering, University of Kaiserslautern, Kaiserslautern, Germany Niels G. Deen Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands Maksym Dosta Institute of Solids Process Engineering and Particle Technology, Hamburg University of Technology, Hamburg, Germany Jieqing Gan Laboratory for Simulation and Modelling of Particulate Systems, Department of Chemical Engineering, Monash University, Clayton, Victoria, Australia Stefan Heinrich Institute of Solids Process Engineering and Particle Technology, Hamburg University of Technology, Hamburg, Germany Qinfu Hou Laboratory for Simulation and Modelling of Particulate Systems, Department of Chemical Engineering, Monash University, Clayton, Victoria, and Laboratory for Simulation and Modelling of Particulate Systems, School of Materials Science and Engineering, University of New South Wales, Sydney, New South Wales, Australia J.A.M. (Hans) Kuipers Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands Günter Leugering Institute of Applied Mathematics 2, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany Johan T. Padding Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands E.A.J.F. (Frank) Peters Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands Wolfgang Peukert Institute of Particle Technology (LFG), Friedrich-Alexander-Universität Erlangen- Nürnberg (FAU), Erlangen, Germany Lukas Pflug Institute of Applied Mathematics 2, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany ix
Doris Segets Institute of Particle Technology (LFG), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany Harry E.A. Van den Akker Bernal Institute and Department of Mechanical, Aeronautical and Biomedical Engineering, University of Limerick, Limerick, Ireland, and Department of Chemical Engineering, Delft University of Technology, Delft, The Netherlands Ning Yang Center for Mesoscience and State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, PR China Aibing Yu Laboratory for Simulation and Modelling of Particulate Systems, Department of Chemical Engineering, Monash University, Clayton, Victoria, Australia Zongyan Zhou Laboratory for Simulation and Modelling of Particulate Systems, Department of Chemical Engineering, Monash University, Clayton, Victoria, Australia x Contributors
PREFACE Opportunities and Challenges: Both at Mesoscales Evolution of chemical engineering science features increasing gener- ality of knowledge from “unit operations,” common for different industries, to “transport phenomena,” common in these operations, and is now at a transitional period with challenges in sustainable development and to its knowledge base. Designing materials, scaling-up reactors, and system opti- mization continue to be the main tasks for chemical engineers. However, upgraded knowledge and enabling technologies are needed to revolutionize R&D capability, which present challenges and opportunities to chemical engineering community. Opportunities are always obscured by challenges. Among many chal- lenges currently in chemical engineering, mesoscale phenomena at different levels of chemical engineering are recognized to be the most critical. At the material level, chemists and material scientists know molecular structures and properties of bulk materials very well, but they are still unable to manip- ulate the mesoscale structures in between. At the reactor level, chemical engineers have accumulated much knowledge on hydrodynamics, transport, and reaction behaviors of single particle and on global performance of reac- tors; however, what happen at the mesoscale between single particles and the whole reactor are still difficult to be formulated. These two mesoscales at different levels are believed to be essential not only for resolving the current global challenges but also for upgrading the knowledge base of chemical engineering science. Currently in chemical engineering, chemists and material scientists syn- thesize a variety of material structures every day, most of which, however, cannot be produced massively in industry due to the lack of understanding of the formation mechanisms of these structures and the difficulty in control- ling the microenvironment for their formation in reactors. In addition, scaling-up of reactors is still a big challenge for chemical engineers. Under- standing of mesoscale phenomena is critical to increase our capability in resolving these issues. In fundamental research, average approaches are widely used, such as computational fluid dynamics, which are however not sufficient enough in predictability. On the other hand, discrete approaches are blooming up, based on microscale mechanisms, which are unfortunately limited to xi
scalability in engineering applications. As a compromising strategy between these two, coarse-graining approaches received more and more attention, aiming at bridging the scales of continuum cells and the discrete moving elements, which still suffer from the lack of understanding of intrinsic mech- anisms at mesoscales. This is now a common challenge not only in chemical engineering. Gradually, people recognized that “meso” will be a big thing. Most importantly, there are many clues that a common principle for all mesoscale problems at different levels between elemental particles and the universe may exist, leading to exploration of a transdisciplinary science, mesoscience, though great efforts are needed to further clarify its rationale and importance. In responding to these new possibilities and challenges, Advances in Chemical Engineering published a thematic volume in 2011 with the title: “Charaterization of Flow, Particles and Interfaces,” aiming at showing the dynamic behaviors at mesoscales. These two volumes further this effort to analyze these mesoscale phenomena and processes with the title: “Mesoscale Modeling in Chemical Engineering” so as to stimulate wide dis- cussion and to promote transdisciplinarity between chemistry, material science, and chemical engineering, and even beyond. Volume I invited a few participants from the 4th International Conference on Multiscale Struc- tures and Systems with the theme of “Mesoscales: The key to multiscale problems,” and Volume II invited contributions from the major program on mesoscience of National Natural Science Foundation of China entitled “Mechanisms and manipulation at mesoscales in multi-phase reaction systems.” Although these contributions may be preliminary in addressing meso- scale problems, we hope these two volumes can play a role of “throwing out a minnow to catch a whale” and to stimulate thinking in the following questions: What are mesoscale phenomena? Why are they so important? How to relate mesoscale concepts to our research? And is it necessary or pos- sible to have a common science for all mesoscales? We would like to thank all authors for their contributions, and reviewers for their critical comments and suggestions. Help from Prof. Ning Yang and Dr. Xiaowei Wang are sincerely appreciated. JINGHAI LI AND GUY MARIN xii Preface
CHAPTER ONE Unified Design Strategies for Particulate Products Wolfgang Peukert*,1 , Doris Segets*, Lukas Pflug† , Günter Leugering†,1 *Institute of Particle Technology (LFG), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany † Institute of Applied Mathematics 2, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany 1 Corresponding authors: e-mail address: Wolfgang.Peukert@fau.de; Guenter.Leugering@fau.de Contents 1. Introduction 2 2. Hierarchical Products and Processes 6 3. Product Properties 12 4. Product Design 19 4.1 Particle Formation 19 4.2 Interactions 25 4.3 Structure Formation 30 4.4 Characterization Along the Process Chain 44 4.5 Multiscale Modeling and Simulation (MSS) 45 4.6 Integration of Particles into Devices 49 5. Processes and Properties by Design 52 5.1 Sensitivities of Parameter-Dependent Initial Value Problems 56 5.2 General Model-Based Optimal Control Setting 58 5.3 Examples of Optimization 60 6. Conclusions 70 Acknowledgements 71 References 71 Abstract Unit operations and product design are the two most important pillars of chemical engi- neering. Product design is the formation, formulation, handling, manufacturing, and characterization of complex multiphase products with specific properties and is thus at the core of mesoscale science and engineering. The applications define the required product properties which cover both classical fields of process technology in the chem- ical industry as well as new emerging fields of electronics, energy and environmental technologies, life sciences, materials science and engineering, nanotechnology, and photonic technologies highlighting the broad relevance of mesoscale science. Unifying principles of product design are proposed which are widely applicable to many Advances in Chemical Engineering, Volume 46 # 2015 Elsevier Inc. ISSN 0065-2377 All rights reserved. http://dx.doi.org/10.1016/bs.ache.2015.10.004 1
different kinds of products including solid, liquid, and even gaseous particles. Results from the Erlangen Cluster of Excellence “Engineering of Advanced Materials” show that the joint venture of chemical engineering with materials science in concert with the basic sciences opens new prospects for all involved disciplines. In particular, chemical and biochemical engineering expands through particle technologies also in physics- related fields of technology such as electronics, photonics, or 3D printing. Rigorous mathematical optimization methods based on predictive models for products, struc- tures, and processes catalyze new possibilities for true design of particulate products which is at the core of mesoscale science and technology. 1. INTRODUCTION In recent years, chemical engineering including particle science and technology has gone through major transitions. For most of the last century, process engineering was focused on unit operations, i.e., to understand and design certain process steps by general rules that should be as independent as possible of the processed chemicals and materials. This paradigm was very successful, for instance, in the petroleum industry, where very large pro- cesses for oil refineries were developed and optimized. Teaching concepts in chemical engineering were thus almost exclusively orientated toward thermal-, mechanical-, and chemical-based unit operations plus classical dis- ciplines including chemical thermodynamics, fluid mechanics, and transport processes for heat and mass. The unit operations approach for homogeneous systems that are mainly consisting of fluids today is mature with limited pros- pects for ground-breaking new developments. New momentum came by the advent of ionic liquids which opened new applications and put new emphasis on well-established lines such as characterization of fluid properties and their phase equilibria (Wasserscheid and Keim, 2000). The understanding and rigorous modeling and design of heterogeneous systems containing interfaces and, in particular, disperse particle systems are much less developed with many open fundamental and applied challenges. In general, disperse systems consist of solid, liquid, or gaseous particles in the form of dispersions, emulsions, or foams, respectively. After many years of extensive research, we have to admit that very few predictive models exist for unit operations where disperse systems are produced and processed. Good models exist for highly diluted systems where particle interactions can be neglected. Examples are deep bed filters (Baumgartner and L€ offler, 1986; Lee and Liu, 1982; Wang et al, 2007, 2008), cyclones (Mothes and L€ offler, 1988), or air classier mills (Toneva et al, 2011a, 2011b) operated 2 Wolfgang Peukert et al.
at low solid concentrations where the momentum transfer from the solid to the fluid phase can be neglected as first approximation. In most systems, which are operated at higher particle concentrations such as ball or stirred media mills (Kwade, 1999; Sommer et al, 2006), mixers (Portillo et al, 2008; Sommer, 1986; Vanarase et al, 2010), or granulators (Dhenge et al, 2012; Iveson et al, 2001; Rahmanian et al, 2011; Reynolds et al, 2005), the operational behavior cannot yet be predicted without free fitting param- eters. Although in recent years much progress has been made in the charac- terization and particularly in the modeling of dense fluid particle systems such as fluidized beds (Deen et al, 2007; Dosta et al, 2012; Fries et al, 2011; Wang et al, 2010), the key challenge is related to an overall cross-cutting topic: particles in contact, i.e., the mesoscale. In Germany, a nation-wide research program was dedicated to key questions in terms of contact mechanics, adhe- sion, fracture, and related applications (http:/ /www.piko.ovgu.de/). Unit operations involving particles are best described by a fundamental unit operation function which depends on the machine and the material function (see Section 4.5). The former describes the motion of particles in the unit operation depending on the applied operational parameters such as flow rates, velocities of moving parts, concentrations, and the fluid prop- erties. Within the unit operation, the particles react according to the applied stresses. This reaction is summarized by the material function involving all material properties such as particle density, Young’s modulus, or coefficients of restitution as a measure for the energy dissipation between the particles upon contact. We will later come back to this important and too often neglected question of particle properties. The two-phase or even multiphase flow at all concentrations in the various unit operations is subject to intensive research with still many open questions to be answered. In all these exam- ples, the key challenge is the mesoscale which is in the focus of this issue of Advances in Chemical Engineering and which will be addressed by the contri- butions of Hans Kuipers, Stefan Heinrich, and Aibing Yu. Since the nineties of the last century, the prevailing paradigm of unit operations has been complemented and partly replaced by a product- orientated approach (Cussler and Moggride, 2011; Hill, 2004; Kind, 1999). Now product properties are in the focus; product design strategies and the engineering of advanced materials are the results of this approach. The combination of the described developments in chemical engineer- ing together with materials science opens unseen perspectives for both dis- ciplines. Materials scientists are the experts in materials properties, a major challenge in modern chemical engineering. Advanced materials require 3 Unified Design Strategies for Particulate Products
sophisticated processes; thus chemical engineers come into play. Further- more, the strong link with basic science closes the observed transfer gap between visionary ideas and real-world applications. While design of novel materials, and in particular nanomaterials, starts from a fundamental physical and chemical understanding on the atomic and molecular levels, engineering of devices and systems requires length scales that range from micro- to meso- and macroscales. Thus, multiscales need to be covered. Advanced materials with properties tailored on the molecular and the mesoscales are expected to stimulate evolutionary advances and revolution- ary breakthroughs in emerging key-technology areas, such as information and communication as well as catalysis, energy, and transportation. Hence, the ability to design novel materials and processes will have a strong impact on assuring industrial competitiveness, economic growth, and better quality of life. In Fig. 1, the five most important incentives for product development are highlighted. These are resources including energy transformation and storage and their environmental impact, modern ways of transportation such as electric cars, and information technology with a manifold of electronic and photonic devices. Other aspects are related to improving and sustaining the quality of life, for instance, in developing countries without irreversible impact on our climate. Life sciences in the century of biology in general promise and require many future applications in bio-based economies and of course in food science and medicine. Progress in all these fields requires the development of new products that can only be realized if new materials Figure 1 Driving forces for new materials and processes. 4 Wolfgang Peukert et al.
are created together with innovative processes to produce them in an eco- nomical and sustainable way. Despite the quite different technology fields with their manifold prod- ucts, common underlying principles can be identified. They need to be implemented if new materials and processes shall be developed and put into operation. Key principles are the rigorous understanding and design of structure–property and process–structure functions. The latter strongly depend on analytical tools for materials and process characterization across all relevant length scales. In particular, multiscale modeling and simulation (MSS) are essential for the understanding and design of materials throughout their transient evolution in production processes. Of course, all these aspects rely on the application and advancement of fundamental knowledge from basic science, i.e., on biology, chemistry, mathematics, and physics. It is clear that product design is a highly inter- and transdisciplinary endeavor. At this point, it needs to be mentioned that the relevance of chemical engineering greatly expanded along with the product- and material-oriented paradigm. Today, chemical engineers are involved in such diverse fields as the development of biomaterials for tissue engineering, the design of the next generation of catalysts for water splitting, or the deposition of thin films in printable electronics or photovoltaics. An interesting and unresolved question in this respect is how to teach chemical engineers with such a wide spectrum of possible applications. This question is particularly pressing for particulate systems which expanded from the traditional mechanical powder processing approach to an extremely broad field of particle science and tech- nology involving gaseous, liquid, and solid particles of biological, chemical, or physical nature. Thereby sizes from below 1 nm up to meters are covered. In other words, the unifying principles beyond the classical unit operations in production and handling of disperse products, i.e., in mesoscale science and technology, need to be identified. These concepts should be reflected in any teaching curriculum to prepare young generations for challenges ahead. En route to answer these pressing questions, in this review, we focus on multiscale methods for the design of particulate products. We will highlight two main routes: from molecules to particles and from single particles to par- ticle ensembles in functional devices. Unifying principles of product design are proposed and examples will be given on how rigorous mathematical opti- mization can be implemented based on the predictive models for the design of particle properties and processes. Due to the very large field of applications only few selected examples can be presented. A comprehensive overview is 5 Unified Design Strategies for Particulate Products
neither intended nor possible due to space limitations. Many of the results and concepts in this review have been developed within the Erlangen Cluster of Excellence “Engineering of Advanced Materials—Hierarchical Structure Formation of Functional Devices” (www.eam.fau.de). 2. HIERARCHICAL PRODUCTS AND PROCESSES The hierarchical organization of matter at different length scales, from molecular to real-world macroscopic components, offers many degrees of freedom for creating materials with multifunctional properties. The proper- ties of an advanced material are related not just to the chemical nature of its atoms and molecules but also to their arrangement and distribution, includ- ing defects and imperfections. Similarly, the development of models to pre- dict material properties from the atomic to the macroscopic scale and the design of related novel processes are major topics on the agenda of mesoscale science and technology. The key challenge is how to bridge the gap between material design on a molecular level and the macroscopic engineering on the level of components and systems. This requires the development of adequate approaches that are able to cover an extended range of time and length scales in modeling and simulation, processing and manufacturing, as well as struc- ture, property, and process analyses. Figure 2 highlights these interconnec- tions for particulate products starting from different types of molecular and Figure 2 From building blocks to functional devices in an interdisciplinary environment. 6 Wolfgang Peukert et al.
particulate building blocks which are integrated into superstructures, here shown as printed thin films that are finally integrated into macroscopic devices (e.g., light-emitting devices or flexible solar panels). The involved disciplines and required skills comprise basic chemistry and physics, which are mostly active at the level of building blocks, chemical engineering fun- damentals, and formulation science and technology. Inks are designed, pre- pared and printed into superstructures under well-defined conditions in the lab and then transferred via process technologies to larger scales and to applications. The underlying fundamental hierarchy is exemplified in Fig. 3. The elec- tronic structure of atoms, molecules, and particles defines the molecular and particulate interactions between the objects and building blocks. Their rep- resentations are highlighted as cartoons on the right-hand side, showing on the level of building blocks the charge distribution of a nucleus that is formed during the crystallization (upper right), and the surface of a functionalized nanoparticle for printable electronics or photovoltaics. At the next level, those objects interact with each other in a continuous fluid phase until they are deposited as a thin film on a solid and maybe even flexible substrate. The film structure and the properties of the particles determine the macroscopic film properties in terms of, e.g., porosity, electrical, or thermal conductivity, their interaction with light or catalytic properties. Figure 3 Fundamental hierarchy from electronic and molecular structure to macro- scopic properties. 7 Unified Design Strategies for Particulate Products
Statistical thermodynamics already provide an excellent framework to describe and model equilibrium properties of molecular systems. Molecular interactions, summarized for instance in terms of a potential of mean force, determine correlation functions and all thermodynamic properties. The (pair) correlation function represents the material structure which can be determined by scattering experiments via the scattering function. All mac- roscopic properties of pure and mixed fluid systems can be derived by well- established multiphase thermodynamics. In contrast, a similar framework for particulate building blocks only partly exists and needs to be developed much further. Besides equilibrium properties, nonequilibrium effects are particularly important in most particulate systems and need to be included in a comprehensive and complete picture. We will come back to these aspects in Section 4. Advances in multiscale processing will provide enormous benefits for more reliable, energy-, and resource-efficient fabrication of high- performance multifunctional materials and for engineering of miniaturized devices and integrated systems. Producing complex devices from designed molecular and particulate structures requires local microscopic tailoring of structure and shape to be extended to the meso- and macroscopic levels of components and systems. This approach offers chemical engineers exten- sive new opportunities to tackle emerging fields outside the traditional domain of industrial chemistry (Pratsinis, 2010). As highlighted in Fig. 4, functional materials design and fabrication require both in-depth Figure 4 Structure–property and process–structure functions. 8 Wolfgang Peukert et al.
understanding of structure–property functions and rational design strategies which are directly linked to multiscale processing based on process–structure functions. Property functions, i.e., correlations between structure and related prop- erties, define the targets in any product design. These must be understood across all relevant levels, ranging from molecular, single particle, and particle ensembles to the final product. Very often, multifunctionality prevails, i.e., powders should be free flowing, easily dispersible in fluids and exhibit controlled defect states. The example in the upper left of Fig. 4 shows indium tin oxide nanopowders whose electronic defect states are related to their oxygen deficiency which controls their optical and electronic prop- erties. Thin films made of these powders are applied in opto-electronic devices such as displays. The thin film should be, e.g., transparent, smooth, and sufficiently strong and flexible to survive for instance its application on flexible substrates such as field effect transistors (FETs) as shown in the upper right of Fig. 4. The product properties evolve from multiscale process chains as highlighted in the lower part of Fig. 4. As an example, the particles are syn- thesized in phase A, say the gas phase or an organic solvent, and then they are transferred to an aqueous phase B where several formulation steps such as stabilization, surface functionalization, and adjustment of the suspension rheology may be included. Finally, a functional thin film is deposited in lab scale usually by spin- or dip coating, whereas in an industrial environ- ment the current development is targeted toward fast roll-to-roll processes. Depending on the type of product, the process chains including the involved unit operations may change of course. The process function (process–structure functions) as defined by Krekel and Polke relates the process parameters to the product property (Krekel and Polke, 1992): dispersity ¼ f processparameters,eductconcentrations ð Þ (1) Process parameters are the type of unit operations, their interconnection in the process, the process conditions under which the unit operations are operated (e.g., temperature, pressure, mass flow rates, etc.), and the materials that are processed. Structure–property as well as process–structure functions must be known in order to design optimal process variables and to achieve the desired goal, i.e., to produce well-defined, often multifunctional prod- uct properties. Usually, process chains (with or without recirculation loops) 9 Unified Design Strategies for Particulate Products
have to be developed during which both handling and end-use properties have to be optimized. While these developments of products and the related process chains have been done mostly empirical in the past, modern developments of pro- cess design make more and more use of computer-based methods including flow-sheeting software for design of the individual process steps as well as for the whole process. While such design tools are well developed for fluids, these are still in their infancy for solids processing. A larger coordinated pro- ject in Germany led to the development of SolidSim, a comparatively new flow-sheeting software tool for major unit operations including crystalliza- tion, agglomeration, comminution, gas–solid as well as solid-liquid separa- tion and transport (Hartge et al, 2006). The outcomes of these developments are now integrated in the Aspen software package. The next step along these lines is the development of dynamic models which can handle efficiently dis- tributed properties and time dependencies of individual unit operations and their interconnection within a whole production process. The required fun- damentals are currently developed within a nation-wide priority program in Germany and will be represented by a complex flow-sheet environment (http://www.dynsim-fp.de/spp-1679.html) (Dosta et al, 2014). However, these positive developments also show that predictive models for most unit operations are rare. The reasons for this deficiency are related to (i) poorly understood turbulent multiphase flows with mass and momentum exchange between the phases, in particular at high Re numbers, (ii) poorly understood particle–particle interactions, and (iii) the lack of reliable single particle and powder (particulate ensemble) properties. Mesoscale science and technology evolves from molecular systems and is key to the assembly of macroscopic products. Thus, the intermediate state of disperse systems must catalyze bet- ter and more efficient solutions to pressing technological challenges of the modern world. Molecular and nanoscale design, synthesis, and analysis of materials are becoming increasingly important for high-performance applications in emerging fields such as nanoelectronics, catalysis, and energy conversion. Molecules offer the opportunity of tailoring structure and function system- atically through modern concepts of synthetic (Negishi, 2011; Suzuki, 2011) and supramolecular chemistry (Steed and Atwood, 2009; Whitesides and Boncheva, 2002). Organic molecules are particularly versatile building blocks since they can combine stability with almost limitless structural and functional variation. Inorganic nanoparticles offer a number of addi- tional benefits, in particular high thermal stability. Individual molecules 10 Wolfgang Peukert et al.
(Lu and Lieber, 2007), hierarchically structured supramolecules (Schlundt et al, 2009), individual particles (Tenne, 2006), particle systems (Min et al, 2008; Pratsinis, 2010), and, last but not least, organic/inorganic hybrid structures (Gnichwitz et al, 2010) provide the key functionalities, for instance for devices (Lal et al, 2007) such as sensors, circuits, or photovoltaic cells. Research into fundamental processes such as charge transfer, mass transport, or interaction with light, into advanced materials, and into the for- mation of unprecedented structures and architectures for functional devices is of fundamental importance for many applications. The properties of multiphase components with microstructures modified on the molecular scale are governed by the interface structure and the chemical nature of the corresponding organic and inorganic components. Hence, understand- ing the structures of interfaces on the atomistic scale and their influence on materials processes and properties are key factors in manufacturing complex multiphase materials with optimized properties. A prominent example for the hierarchical organization of building blocks which is decisive for the later product properties is the case of mes- ocrystals. Mesocrystals are a relatively new class of crystals consisting of small buildings blocks which are self-assembled to larger units (C€ olfen and Antonietti, 2005; see Section 4.3). Both examples in Fig. 5 show ZnO mes- ocrystals. The mesocrystals in Fig. 5A consist of 5 nm ZnO quantum dots which are organized to quite uniform spherical single crystals of about 300 nm in diameter (Distaso et al, 2012). These show high UV-absorption and minimized light scattering in the region of visible light. The ZnO mesocrystals in Fig. 5B are also built from ZnO quantum dots which are then organized by multistep-oriented aggregation as rods, semi- and full ellipsoids (Klaumünzer et al, 2014). These particles show a high scattering intensity in the whole range of visible light. Particles are seldom sole as such, and they are usually integrated in prod- ucts. Paper, ceramics, and bread are just three well-known examples of everyday use. Advanced structural and functional materials consisting of par- ticles and powders are made to be integrated into all the functional devices mentioned in this overview. The implementation of nanotechnologies is still limited due to the difficulties in preserving the beautiful nanostructures and their excellent properties produced in the lab upon transferring them into industrial practice. We have to understand how hierarchical products evolve in multiscale processes. Important questions must be answered such as where does “quality” evolve in chemical processes and how can we con- trol electronic and structural defects of particles and particle systems across all 11 Unified Design Strategies for Particulate Products
length and time scales. Key to these questions is the in-depth understanding of particle properties. 3. PRODUCT PROPERTIES For particulate materials, the product properties depend on the chem- ical composition and on the dispersity of the material. The dispersity is char- acterized by the particle size distribution (PSD), the particles’ shape, their morphology in terms of internal structure (amorphous, crystalline, internal pore size distributions and their defects), and their interfacial properties. This relation was called by Rumpf already in the 1960s of the last century the “property function” (Rumpf, 1967). Control of the property function is the core of product engineering or product design. Productproperty ¼ f dispersity,chemicalcomposition ð Þ (2) Dispersity includes: • particle size and shape and their respective distribution, • particle morphology including defects, and • particle surface properties. Figure 5 Hierarchical structure of mesocrystals: (A) porous balls of ZnO quantum dots and (B) ellipsoids of ZnO nanorods and their formation mechanism. Panel (A): Distaso et al (2012). Panel (B): Klaumünzer et al (2014). Reproduced with permission from the Royal Society of Chemistry. 12 Wolfgang Peukert et al.
Thus, the property function relates the particulate structure (size, shape, morphology, and surface) to the product properties (structure–property– function). Examples of property functions are the taste of chocolate, the color of pigments, the strength of cements, or the bandgap of semiconductor nanoparticles. Particle ensembles in the form of agglomerates, thin films, or filter cakes are also included in this consideration. Modern products are often characterized by several properties which have to be achieved simulta- neously: transparent and scratch-resistant coatings, sun blockers which are transparent for visible light and UV-absorbing may serve as examples. Thus, a multifunctional product space evolves which must be created through design of the related structures using the respective process technology. Glotzer and coworkers proposed the following framework of evolving complexity for particles as shown in Fig. 6 (Glotzer and Solomon, 2007). By varying systematically geometric features such as size and shape and also surface coverage, patterns, branching, and chemical ordering, many different A Surface coverage (patchiness) Aspect ratio Faceting Pattern quantization Branching Chemical ordering Shape gradient Roughness B C D E F G H Figure 6 Overview of complexity generation of particles. Permission from Macmillan Publishers Ltd. Glotzer and Solomon (2007). Copyright 2007. 13 Unified Design Strategies for Particulate Products
types of particles can be envisioned for which the phase behavior will vary between ordered crystalline structures and disordered glassy structures. Dur- ing the last years, synthesis capabilities strongly improved. Therefore, it is within reach to realize at least some of those structures within the next years. In the following, examples for electronic, optical, and mechanical properties will be presented and related to dispersity in terms of size, shape, morphol- ogy, and surface. For the former, we will discuss possibilities for property optimization (Chapter 5), and the latter are most relevant for the question of particle–particle interactions in modeling approaches of particulate dense phase systems (Chapter 4). Many property functions in dependency of particle size are known. Today, PSDs can be measured reliably across all length scales from below 1 nm up to macroscopic sizes. In Fig. 7, we highlight a few examples of the size-dependent bandgap of semiconducting quantum dots which con- trols their electronic and optical properties. The latter strongly depend on the bandgap energy of the first excitonic transition: ZnO (Fig. 7A) and Figure 7 Bandgap of quantum dots: (A) ZnO (Viswanatha et al, 2004), (B) CIS (Akdas et al, 2015), and (C) PbSe (Segets et al, 2012b). EMA refers to the effective mass approx- imation originally established by Brus (1984) which usually fails for the accurate descrip- tion of the smallest particles. Panel (A): Reproduced from Viswanatha et al (2004) with permission of The Royal Society of Chemistry. Panel (B): Reproduced from Akdas et al. (2015) with permission of The Royal Society of Chemistry. Panel (C): Reprinted with permis- sion from Segets et al (2012b). Copyright 2012 American Chemical Society. 14 Wolfgang Peukert et al.
TiO2 are absorbing in the UV, CdS(e), CdTe, and CuInS2 (CIS, Fig. 7B) in the visible, whereas lead-based materials such as PbS(e) absorb in the NIR (Fig. 7C) (Akdas et al, 2015; Segets et al, 2012b; Viswanatha et al, 2004). In all cases, the bandgap ΔE widens due to the quantum size effect according to the following empiric equation: △E ¼ △Eg,bulk + xc a 1=b eV (3) where x is the particle diameter, ΔEg,bulk is the bandgap of the bulk material, and a (nm), b (), and c (nm) are material-dependent empiric parameters. Tailoring of the opto-electronic properties of these materials is thus directly linked to the control of their size. We will come back to this issue in Chapter 5. Only few examples of property functions as a function of particle shape are known. This lack is related to the difficulty of measuring size and shape simultaneously since at least two dimensions of the particle must be deter- mined in the process environment. The two most prominent examples with probably the best database are the drag force of nonspherical particles (Binder et al, 2009; Clift et al, 2005; Walter et al, 2015b; Yow et al, 2005) and the optical properties of metal nanoparticles. The latter are due to sur- face plasmon resonances which give rise to shape-dependent absorption peaks. For a long time, particle shape determination was restricted to tedious off-line imaging. Since a few years ago, particle shapes can be mea- sured (even inline) for particles larger than a few 10 μm in size by direct video-based shape analysis (Witt et al, 2013). For smaller particles, shape analysis is quite tedious because a statistical relevant number of particles (at least some 100) has to be measured by image analysis of deposited sam- ples using scanning electron microscopy (SEM), transmission electron microscopy (TEM), or atomic force microscopy (AFM). New possibilities for two-dimensional characterization come from the combination of sedimentation analysis with inline absorption spectrometry (Walter et al, 2014, 2015b). In brief, analytical (ultra-)centrifugation (AUC) allows the analysis of particles ranging from 1 nm when an ultracentrifuge is used up to a few 10 μm in size when a conventional centrifuge is used (Walter et al, 2015a). The sedimentation velocity depends on the size and shape of the particles. Figure 8A depicts as an example the frictional ratio of cylinders as a func- tion of their aspect ratio. This relationship for shape analysis of cylinders and platelets was recently demonstrated for graphene oxide monolayers (Walter et al, 2015b). The frictional ratio plotted on the y-axis is the drag force of the 15 Unified Design Strategies for Particulate Products
Figure 8 (A) Frictional ratio of sphero-cylinders (ratio of drag of cylinder and volume equivalent sphere) in dependence of their aspect ratio (Re≪1) and (B) absorption sed- imentation analysis of gold nanoparticles in an analytical ultracentrifuge. Panel (A): Reprinted with permission from Walter et al (2015b). Copyright 2015 Wiley. Panel (B): Reprinted with permission from Walter et al (2014). Copyright 2014 American Chemical Society. 16 Wolfgang Peukert et al.
cylinders related to the drag of volume equivalent spheres. During a sedi- mentation run, the separated particles can be analyzed with respect to their absorption properties. This is shown in Fig. 8B for gold nanorods. If the par- ticles are small enough to show strong diffusion (typically below 20 nm), simultaneous evaluation of sedimentation and diffusion can be used to obtain shape factors. In the next step, we discuss property functions in dependency of particle morphology. The term “morphology” includes amorphous and crystalline states, pore structures, and various defect structures of particles. Here, we give an example for mechanical particle properties. One of the grand chal- lenges in particle technology is how to characterize the contact mechanisms and contact forces between particles. Mechanical particle properties are the key parameters in discrete element models (DEMs) which have been devel- oped during the last decades and gradually reach “predictive power.” Mechanical particle properties are urgently needed to calibrate DEMs which despite their great progress still rely on global parameters such as spring con- stants or coefficients of restitution. The (nano-)mechanics of particles across all length scales down to the nanoscale are highly relevant in all situations where contact mechanics of particles must be considered, i.e., in dense par- ticle flows such as fluidization, transport, and particle storage (conveying, mixing, and silos), but also in agglomeration and granulation (adhesion), size reduction by comminution (fracture), and tribology. Particular interesting new fields are additive manufacturing and 3D printing. They “promise” a revolution in industrial manufacturing based on powder technologies where excellent flowability must be combined with dense packing structures. One key question in all these applications is how the particles react to the exter- nally applied stress. Briefly, this reaction can be elastic or inelastic. However, in many cases neither the elastic properties (Young’s modulus and Poisson ratio) are known nor the inelastic properties such as yield strength or visco- plastic properties which lead to internal defects (e.g., dislocations, twinning, and shear bands). Defect characterization inside particles requires high-end scattering or electron microscopy techniques (Vieweg et al, 2012). In recent years, more and more systematic studies are published focusing on mechanical properties of small particles (Fuchs et al, 2014; Meier et al, 2009b; Paul et al, 2015; Paulick et al, 2014; Romeis et al, 2014, 2015; Sanimi et al, 2005; Tomas, 2004; and references within). Mechanical elastic and inelastic particle properties have been measured systematically in a cus- tomized nanoindentation device installed within a SEM to simultaneously obtain force–displacement information and SEM images of deformed and 17 Unified Design Strategies for Particulate Products
broken particles (Romeis et al, 2012). Quantitative data of intrinsic particle properties (and their respective distributions) are derived with high statistical relevance from force–displacement curves of single oxide, metal, and poly- mer particles. These are related to internal structural properties of theparticles (Paul et al, 2014, 2015; Romeis et al, 2014). Figure 9 shows structure— property functions of “simple” amorphous St€ ober–Fink–Bohn (SFB) SiO2 particles (diameter 500 nm) (St€ ober et al, 1968) which were densified at various temperatures. Their internal structures including internal bond– network effects have been evaluated also by nuclear magnetic resonance (NMR) spectroscopy, Fourier-transformed infrared spectroscopy (FT-IR), and Raman spectroscopy. The as-synthesized sample (in a sol–gel process) did contain many hydroxyl and dangling bonds which gradually condensed with increasing temperature and are completely removed at 1000 °C. The last topic in this section concerns particulate surface properties. The importance of surface properties is known since a long time, e.g., in the field of colloid science. With the advent of nanotechnology, this issue is now very prominently on the agenda because of the high surface-to-volume ratio of small particles. Briefly, any technical realization of nanoparticulate products requires the careful control of interfaces (details are discussed in Section 4.2). However, since the surface roughness can influence the interaction forces by orders of magnitude, also the interactions of larger objects, for instance dur- ing adhesion and friction, are controlled by nanoscale effects (see the exam- ple on additive manufacturing in Section 4.6). Surface properties of particles are directly linked to their solubility in solvents, to their wetting properties, to their conductivity, and to their reactivity in catalysis just to mention a few of them. Conformal and nonconformal coatings on particles are used to tailor the interaction with light. The well-known and beautiful pearl luster effect pigments are based on diffraction effects such as titania-coated mica platelets. Figure 9 Distributions of (A) Young's Modulus, (B) hardness, and (C) yield pressure for 500 nm amorphous silica beads which were tempered at temperatures of 400, 800, and 1000 °C (U500S nontreated) (Romeis, 2015). Similar data have been used to predict the packing structure of silica particles as a function of size by a DEM simulation (Parteli et al, 2014). 18 Wolfgang Peukert et al.
Nevertheless, and as discussed in more detail in Section 4.2, it is very difficult to analyze the surfaces of small particles in detail with respect to structural (e.g., roughness, steps, and kinks) and chemical properties (e.g., chemical surface moieties of the particles, adsorbed or chemisorbed layers, and surface coverage). As an example how surfaces influence particle properties, we present the case of small nanoparticles for which the surface-to-volume ratio is quite large. The coordination number of molecules and atoms at the surface of nanoparticles is reduced relative to the bulk due to the curvature of the par- ticles. This gives rise to the enhanced solubility and vapor pressure of small particles in solution and in the gas phase, respectively. This is expressed by the well-known Kelvin equation. In a similar way, the sintering kinetics of small nanoparticles is enhanced. This effect is important during gas phase synthesis of particles where a balance of coagulation and sintering kinetics defines the morphology of the aggregates which is often expressed by a fractal dimen- sion. Coagulation without any sintering typically leads to a fractal dimension of around 1.8, whereas fast sintering leads to complete coalescence, i.e., to spheres with a fractal dimension of 3. The sintering kinetics (at least for amor- phous silica particles) is enhanced relative to bulk values below a critical size of about 100 nm (Kirchhof et al, 2012). In the context of mechanical prop- erties, we could recently show that the Young’s modulus of small metal and salt particles (Armstrong and Peukert, 2012; Miesbauer et al, 2003) is reduced due to this size or surface effect, respectively (see Fig. 10). 4. PRODUCT DESIGN Five unifying principles in product design can be identified. They will be discussed in the following under a generalized view: 1. Particle formation by top-down and bottom-up approaches. 2. Interactions between the building blocks. 3. Structure formation by self-organization and by transport. 4. Characterization along the process chain. 5. Multiscale modeling and simulation Finally, an outlook on the integration of particles into devices will be provided. 4.1 Particle Formation 4.1.1 Top-Down Approaches The most common size reduction processes, comminution, emulsification, and spraying, share several common features. Eggers and Villermaux discuss 19 Unified Design Strategies for Particulate Products
atomization of droplets from a unifying perspective (Eggers and Villermaux, 2008). Most importantly, size reduction occurs when sufficient external energy is supplied to the particles and made available to generate new sur- face. In case of solid particles, fracture is induced by stressing of the particles by impaction or compression. The transferred energy is stored in the parti- cles as elastic energy or dissipated by viscous and/or plastic deformation lead- ing to all sorts of structural defects. Fracture occurs when the elastically stored energy is released and sufficiently high to induce crack opening. In case of fluids, shear and more importantly elongational stresses act on the 0 0.6 0.7 0.8 0.9 1 1.1 6 7 8 9 10 11 12 13 A B 5 E/E bulk 10 15 20 Particle size (nm) 25 30 35 Bulk material Cu particles Au particles Fe particles Al particles Pt particles Ag particles 0 5 10 15 20 Particle size (nm) Avg. coordination number (a.u.) Bulk bcc Bulk fcc 25 30 35 Cu particles Au particles Fe particles Al particles Pt particles Ag particles Figure 10 (A) Average coordination number of six different metal nanoparticles and (B) their average Young's modulus E with respect to the value of the bulk as obtained from molecular statics simulations. Armstrong and Peukert (2012), with kind permission from Springer Science and Business Media. 20 Wolfgang Peukert et al.
fluid particles which in turn may be disintegrated into smaller droplets if the applied stresses are sufficiently high. Surprisingly and despite all differences between these top-down methods, the mean particles size x50 scales with the volume-specific energy input EV: x50 ¼ a EV ð Þb (4) where the parameters a and b depend on the unit operation and the type of particles (see Table 1). The minimal particle size which can be produced depends on the balance between the local stress energy and the energy required to increase the sur- face. In case of solid particles, cracks are initiated at internal particle defects due to local stress enhancement. The true grinding limit is reached when the particle cannot store anymore defects (Knieke et al, 2009). It has been shown for ZrO2 and SnO2 that this limit is reached at around 10 nm (Knieke et al, 2011). The width of the PSD depends on the spatial distribution of EV in the “reactor” volume, i.e., on the design of the mill, on the emulsifying device, or on the nozzle and the resulting multiphase flow and thus on the machine function. In summary, the slope of Eq. (4) varies in a band of the exponent b between 0.3 and 0.8 for different unit operations and materials. This indicates that unified scaling laws are valid which are based on fundamental similarities of particle formation in top-down processes. 4.1.2 Bottom-Up Methods Single particles are the building blocks of mesoscale science and technology including nanotechnology and many other fields of application as discussed Table 1 Value of Scaling Parameter b for size in Top-Down Processes Type of Unit Operation Value of Parameter b References Comminution in stirred media mills (varying sizes and operational parameters), limestone, and graphene oxide platelets 0.8 0.37 Becker et al (2001) Halbig et al (2016) Emulsification in colloid mill, homogenization, and ultrasound 0.3–0.8 Behrend et al (2000) and Schuchmann and Schubert (2001) Atomization in different spray nozzles 0.5–0.7 Walzel (1990) Ultrasound and graphene oxide platelets 0.48 Halbig et al (2016) 21 Unified Design Strategies for Particulate Products
above. It is, however, beyond the scope of this review, to present a compre- hensive overview of particle synthesis and crystallization as several excellent books and review articles are available covering a broad range of materials. Therefore, we discuss here only a few guidelines for this important and very large field without claim to completeness. Bottom-up methods for particle synthesis in gas and liquid phase can be visualized by a unified scheme as highlighted in Fig. 11. In general, mass, momentum, and heat transfer processes coupled to chemical reactions pro- duce nucleating species. Their distribution in the reactor related to their equilibrium concentration/partial pressure (or activity/fugacity in a general sense) is defined as the supersaturation S. It is the thermodynamic driving force for the phase transition and thus for the formation of a new particle phase. Depending on the spatial and temporal distribution of S in the reac- tor, nuclei form with a size distribution q. Noteworthy, especially in the view of classical nucleation theory q strongly depends on S. For instance, a high supersaturation with narrow distribution in time and space would lead to small nuclei with narrow PSD since all particles “experience a similar history.” After nucleation, several processes may occur sequentially or in parallel. These are growth processes for further reduction of S, coagulation of the particles, their stabilization against coagulation, and finally ripening effects in the liquid phase or sintering in the gas phase. This quite general Figure 11 Principles of particle synthesis. Adapted from Peukert et al. (2003). Copyright 2003, with permission from Elsevier. 22 Wolfgang Peukert et al.
framework forms the basis of any modeling approach for particle formation dynamics including mixing, global reaction kinetics, nucleation, growth, agglomeration and stabilization and even ripening and sintering. Detailed reaction mechanisms of conversion of precursor molecules into stable and growing nuclei may be included in this general scheme which are, however, too seldom known. Their full elucidation requires coupling of quantum mechanical methods such as density functional theory (DFT) with molecular dynamics (MD) simulations (see, e.g., Menz et al, 2011; Milek and Zahn, 2014; Zheng et al, 2009). A key challenge in this field is how to tailor reac- tion networks so that a desired target phase does form. Particle formation processes can further be subdivided into transport- and reaction-controlled processes. Typically one assumes that the synthesis in the gas phase is not controlled by any mass transfer limitations, whereas mass transfer issues are very common in liquid phase synthesis. Prior dis- cussing mixing and reaction-controlled systems in more detail, it needs to be mentioned that perfect stabilization is assumed for the time being. Effects of coagulation would completely change the PSD. In transport or mixing controlled systems, the mixing intensity deter- mines the local concentration fields and thus the supersaturation as driving force (Schwarzer and Peukert, 2002). The energy dissipation in case of a stirred tank as well as in a continuous mixer such as a T- or Y-mixer is directly related to the volume-specific energy consumption. The mixing volume will follow similar scaling laws as already discussed in Chapter 3 for the top-down processes. Higher energy dissipation will lead to succes- sively smaller eddies in the fluid until the smallest eddy size (the Kolmogoroff length scale) is reached. Mixing is shifted from macro- to meso-mixing and finally to diffusion-controlled micromixing (Baldyga and Bourne, 1999; Bockhorn et al, 2010; Fox, 2003). The reactor design determines the resi- dence time of fluid particles and the local distribution of supersaturation. Both effects will control the width of the obtained PSD, or in other words, the width of the PSD is a measure of the mixing energy distribution. The full PSD can be modeled (at least for well-understood precipitation reactions such as the formation of BaSO4) without any free parameters by a combi- nation of direct numerical simulation for complete resolution of the fluid flow structures and an appropriate mixing model for mass transfer at subgrid level on the one hand that is combined with a population balance model, on the other hand (Gradl and Peukert, 2009; Gradl et al, 2006). In reaction-controlled systems, i.e., in systems where mixing is much faster than the chemical reactions leading to precursor formation, the 23 Unified Design Strategies for Particulate Products
Other documents randomly have different content
Lamb of God, Who takest away the sins of the world, Have mercy on us, O Lord! Holy Ghost, hear us, Holy Ghost, graciously hear us. V. Create a clean heart in us, O God. R. And renew a right spirit within us. Let Us Pray. Grant, O merciful Father, that Thy divine Spirit may enlighten, inflame, and cleanse our hearts; that He may penetrate us with His heavenly dew, and make us fruitful in good works. Through Jesus Christ Our Lord. Amen.
Hymns to the Holy Ghost. Veni, Creator Spiritus. Come, O Creator, Spirit blest, And in our souls take up Thy rest; Come with Thy grace and heavenly aid To fill the hearts which Thou hast made. Great Paraclete, to Thee we cry, O highest gift of God most high, O Fount of life, O Fire of love, And sweet anointing from above. [pg 359] Thou in thy sevenfold gifts art known; The finger of God's hand we own; The promise of the Father Thou, Who dost the tongue with pow'r endow. Our senses kindle from above, And make our hearts o'erflow with love; With patience firm and virtue high The weakness of our flesh supply. Drive far from us the foe we dread, And grant us Thy true peace instead; So shall we not, with Thee for guide, Turn from the path of life aside.
Oh, may Thy grace on us bestow The Father and the Son to know, And Thee through endless times confess'd Of both th' eternal Spirit blest. All glory, while the ages run, Be to the Father and the Son Who rose from death; the same to Thee, O Holy Ghost, eternally! Amen. Come, Holy Ghost. Come, Holy Ghost, send down those beams, Which sweetly flow in silent streams From Thy bright throne above. Come, Thou, the Father of the poor, Thou bounteous source of all our store; Come, fire our hearts with love. Come, Thou, of comforters the best, Come, Thou, the soul's delightful guest, The pilgrim's sweet relief. Thou art our rest in toil and sweat, Refreshment in excessive heat, And solace in our grief. O sacred Light, shoot home Thy darts, Oh, pierce the centre of these hearts, Whose faith aspires to Thee. [pg 360] Without Thy Godhead nothing can Have any price or worth in man; Nothing can harmless be.
Lord, wash our sinful stains away, Water from heaven our barren clay; Our wounds and bruises heal. To Thy sweet yoke our stiff necks bend, To inflame our cold hearts Thy fire send; Our wandering feet repel. Oh, grant Thy faithful, dearest Lord, Whose only hope is Thy sure word; The seven gifts of Thy Spirit. Grant us in life to obey Thy grace, Grant us in death to see Thy face; And endless joys inherit. Amen.
Act Of Oblation To The Holy Ghost. On my knees, before the great cloud of witnesses, I offer myself, soul and body, to Thee, eternal Spirit of God. I adore the brightness of Thy purity; the unerring keenness of Thy justice; and the might of Thy love. Thou art the strength and the light of my soul. In Thee I live and move and am. I desire never to grieve Thee by unfaithfulness to grace; and I pray with all my heart to be kept from the smallest sin against Thee. Make me faithful in every thought: and grant that I may always listen to Thy voice, and watch for Thy light, and follow Thy gracious inspirations. I cling to Thee, and give myself to Thee, and ask Thee by Thy compassion to watch over me in my weakness. Holding the pierced feet of Jesus, and looking at His five wounds and trusting to His precious blood, and adoring His opened side and stricken Heart, I implore Thee, adorable Spirit, helper of my infirmity, [pg 361] so to keep me in Thy grace that I may never sin against Thee with the sin which Thou canst not forgive. Give me grace, O Holy Ghost, Spirit of the Father and the Son, to say to Thee, always and everywhere, speak, Lord, for Thy servant heareth. Amen.
The Office of the Holy Ghost. At Matins. V. The grace of the Holy Ghost illuminate our senses and hearts. R. Amen. V. O Lord, open Thou my lips. R. And my mouth shall declare Thy praise. V. Incline unto my aid, O God. R. O Lord, make haste to help me. Glory be to the Father, and to the Son, and to the Holy Ghost. As it was in the beginning, is now, and ever shall be, world without end. Amen. Hymn. The Holy Ghost our souls invest With grace that does o'ershade the best Of Virgin maids, when from the spheres An angel came to greet her ears. The Word divine did flesh become, And fruitful made a virgin womb. Ant. Come, Holy Ghost, replenish the hearts of Thy faithful, and kindle in them the fire of Thy love. V. Send forth Thy Spirit, and they shall be created.
R. And Thou shalt renew the face of the earth. Prayer. We beseech Thee, O Lord, that the virtue of Thy Holy Spirit may be present within us, which may both purify our hearts, and defend us from all adversities; through Our Lord Jesus Christ, Thy Son, Who with Thee and the same Holy Ghost liveth and reigneth. Amen. [pg 362] At Prime. V. The grace of, etc. (as before). Hymn. Christ, born of Mary, that blest Maid, Was crucified, was dead, was laid Within a tomb, from whence He rose, And did His person soon disclose To His disciples, in whose sight He soar'd above the starry height. The anthem, verse, response, and prayer as before. At Tierce. V. The grace of, etc. (as before). Hymn. God sent from heaven the Holy Ghost Upon the day of Pentecost; He did the apostles' minds inspire, Inflaming them with tongues of fire. He would not have them orphans left, When of the sight of Christ bereft.
The anthem, verse, response, and prayer as before. At Sext. V. The grace of, etc. (as before). Hymn. With sevenfold grace God did enrich The apostles, then, by means of which They did both speak and understand The language of each distant land. To preach Christ's faith they then disperse Themselves throughout the universe. The anthem, verse, response, and prayer as before. At None. V. The grace of, etc. (as before). [pg 363] Hymn. The consoling Spirit He Entitled was true charity, The gift of God, a fire inflamed, The vivifying fountain named, A spiritual unction, sevenfold grace, A free gift of celestial race. The anthem, verse, response, and prayer as before. At Vespers. V. The grace of, etc. (as before). Hymn.
The right hand finger of Our Lord, His spiritual power to us afford A safe defence against all evil, That harm'd we be not by the devil. Protect us, nourish us, and bring Us under shelter of Thy wing. The anthem, verse, response, and prayer as before. At Compline. V. The grace of, etc. (as before). V. Convert us, O God Our Saviour: R. And avert Thy anger from us. V. Incline unto my aid, O God. R. O Lord, make haste to help me. Glory be to the Father, etc. Hymn. Vouchsafe, O holy Paraclete, To pour into our souls Thy light, And to direct us in our ways, That when to judgment God shall raise The sleeping world, He bid us stand Upon His right and saving hand. The anthem, verse, response, and prayer as before. [pg 364] Commendation. These hours canonical, to Thee, O Holy Ghost, addressed be, With piously devoted heart.
That to our souls Thou mayest impart Thy inspirations, and that we May live in heaven eternally. Amen.
Novena to the Holy Ghost. First Day: Fruits Of Charity And Joy. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—charity and joy. Our Father, Hail Mary. O most holy Spirit, the Paraclete, we adore Thee with all humility; and with the most lively affections of our hearts, we beseech Thee to assist us in this Thy novena, that we may rightly prepare ourselves to receive Thy heavenly gifts. We cannot, O divine Spirit, receive Thee without Thine own aid preventing us. Without Thee we cannot please Thee. Do Thou then, Who didst prepare the heart of Mary to receive the Word Incarnate, vouchsafe so to dispose our hearts that we may happily conceive the blessed flames of Thy love. Amen. O let us fall and worship Him, The love of Sire and Son, The consubstantial breath of God, The co-eternal One! [pg 365] Ah! see, how like the Incarnate Word, His blessed self He lowers
To dwell with us invisibly, And make His riches ours. Most loving Spirit! Mighty God! Sweet must Thy presence be, If loss of Jesus can be gain, So long as we have Thee! Come, Holy Spirit, fill the hearts of Thy faithful, and kindle in them the fire of Thy love. V. Send forth Thy spirit, and they shall be created. R. And Thou shalt renew the face of the earth. Burn, O Lord, with the fire of Thy Holy Spirit our reins and our hearts, that we may serve Thee with chaste bodies, and please Thee with clean hearts; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing of almighty God, the Father, Son, and Holy Ghost, descend upon us now, and abide with us always. Amen. Second Day: Fruits Of Peace And Patience. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—peace and patience. Our Father, Hail Mary. O sweetest and most dear Mother Mary, behold us at thy feet, and having kissed them a thousand times [pg 366] with the lips of our
hearts, we humbly implore of thee a favor more needful for us than all else in the world. Since thou art the spouse of the Holy Ghost, the dispenser of His treasures, and His sweet stewardess, since thou hast been enriched beyond all other creatures with His heavenly gifts, obtain for us, as thou didst obtain for the apostles, His coming into our hearts; and for this end obtain for us the grace to imitate, so far as in us lies, the examples of thy humility, thy purity, thy charity. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. O God, to Whom every heart is open and every will speaketh, and from Whom no secrets are hid, cleanse the thoughts of our hearts by the infusion of the Holy Ghost, that we may perfectly love Thee and worthily praise Thee; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Third Day: Fruits Of Benignity And Goodness. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—benignity and goodness. Our Father, Hail Mary. Most holy prince of the apostles, blessed St. Peter, behold us at thy feet, to implore thy aid in obtaining the Holy Spirit. We, indeed, have
been unfaithful [pg 367] to Our Redeemer, not three times only, as thou wert, but thousands and thousands of times; so that we could not hope that the spotless Dove would vouchsafe to descend into our poor souls, stained with so many sins; yet thine example, blessed apostle, gives us boldness. Thou didst weep bitterly, and with thy tears wert so cleaned as to receive all the gifts of the divine Paraclete. We too desire to bewail our sins with bitterest grief like thine, while we humbly implore thine intercession to obtain for us, first of all, cleanness of heart, and then the gift of the Holy Ghost, for which we yearn most earnestly. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. O God, Who hast taught the hearts of Thy faithful by the light of the Holy Spirit, grant us by the same Spirit to think the things that be right, and ever to rejoice in His consolations; through the same Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Fourth Day: Fruits Of Long-Suffering And Mildness. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—long-suffering and mildness. Our Father, Hail Mary.
O blessed and happy apostles of Our Lord, who in [pg 368] the upper room did receive the Holy Spirit with such fulness that thou wert sweetly inebriated with divine love, we congratulate thee with the most humble and lively affection, and contemplate thy graces with a holy envy. We beseech thee, by that love which thou dost bear the Holy Spirit, Who thus filled thee with His special benedictions, obtain for us efficacious aid rightly to practise that brotherly concord, that continual prayer, and that tender devotion to Mary, whereby we can obtain, even as thou didst obtain, the coming of the Holy Ghost. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. May the infusion of the Holy Spirit, O Lord, purify our hearts, and by the inward sprinkling of His gracious dew make them fertile in all good works; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Fifth Day: Fruits Of Faith And Modesty. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—faith and modesty. Our Father, Hail Mary.
O eternal Father, how shall we ever bless and praise Thee sufficiently, or thank Thy goodness as we ought? A thousand times blessed be Thine infinite [pg 369] charity, Thine infinite providence, and Thine infinite mercy, which moved Thee to repair our miseries, and to give unto us a gift wherein is contained all the good that proceedeth from Thee! Thou hast given us also the Holy Ghost, Who proceedeth from Thy will as Thine uncreated love. What can we seek for more? And what shall we give unto Thee for so great a gift? O Lord, vouchsafe, we beseech Thee, of Thy clemency to take for Thine own all our understanding, all our will, all ourselves, and that little for all eternity. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. We beseech Thee, O Lord, that the Paraclete, Who proceedeth from Thee, may enlighten our minds, and, according to the promise of Thy Son, may lead us into all truth; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Sixth Day: Fruits Of Continence And Chastity. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—continence and chastity. Our Father, Hail Mary.
Most holy, most divine Spirit, if there be any souls in the world more needful of Thine aid than others, it is surely ours, blinded by passions, chilled [pg 370] with obstinate lukewarmness, and defiled with a thousand imperfections. Come, then, O divine Spirit! come and enlighten us; kindle our fervor, and destroy in us all that is displeasing in Thy sight. The greater our miseries are, so much the more glorious will be Thy triumph over our perversity. Come and create in us new hearts, which shall have all for God, and nothing for the world. Create in us clean hearts, O God. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. Grant unto Thy Church, O merciful God, that she, being gathered together in the Holy Spirit, may be in no wise disturbed by the incursions of her enemies; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Seventh Day: Descent Of The Holy Ghost Upon Mary At The Annunciation. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary in honor of the descent of the Holy Ghost upon the ever-blessed Mother of God at the Annunciation. Our Father, Hail Mary.
Most divine Spirit, the Paraclete, we hardly dare to beseech Thee to come into our souls, knowing well how sinful and defiled they are. It seems an intolerable boldness to invite God—yea, no less a one [pg 371] than God!—to be a guest in a lodging so unclean. Yet Thou vouchsafest graciously to reassure us by that infinite goodness of Thine, whereby Thou dost dispose with Thy prevenient graces those hearts which Thou dost condescend to honor with Thy presence. O blessed Spirit, deign to come into us, and delay not Thy gracious coming, while we cease not calling upon Thee and beseeching Thee to console us with Thy long-expected coming. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. We beseech Thee of Thy goodness, O Lord, to pour into our minds the Holy Spirit, by Whose wisdom we were created, and by Whose providence we are ruled; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Eighth Day: Descent Of The Holy Ghost Upon Jesus At The Jordan. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary in honor of the descent of the Holy Ghost upon Jesus at the Jordan. Our Father, Hail Mary.
Most adorable Trinity, we venture with all humility and awe to approach the lofty throne of your exalted majesty; with our heads prostrated in the dust we adore you, and give you endless thanks for the immense blessings which you have bestowed on us [pg 372] miserable men. We thank Thee, O eternal Father, and Thee, O divine Son, for the gift which you have given us of the Holy Ghost; for in giving us this Love, Who proceedeth from you, you have given us your own selves. We thank Thee, O Holy Ghost, Who art at once the gift and the giver of all gifts, and we most earnestly beseech Thee to give us Thyself. No other gift but Thine own self can satisfy our souls, and having Thee alone we shall have all things. But what can we give Thee in exchange for so great benefits? O blessed Spirit, vouchsafe of Thy mercy to accept for all eternity all our thoughts, all our affections, and all ourselves. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. Grant, we beseech Thee, O Lord, that we may burn with that fire of the Holy Ghost which Our Lord Jesus Christ sent upon the earth, and which He desired to be vehemently enkindled; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Ninth Day: Transfiguration And Ascension Of Our Lord, And The Manifestations Of The Holy Ghost. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary in honor of the transfiguration and
ascension of our most dear Lord and Saviour Jesus Christ, and of the ineffable [pg 373] love of the Holy Ghost in all His manifestations to His creatures. Our Father, Hail Mary. Most holy Virgin and exalted Mother of God, who wast above all creatures disposed to receive the Holy Ghost, and who didst receive Him with greater fulness than all others; dispose, we beseech thee, by thy gracious aid, our cold hearts for the approaching solemnity of Pentecost. We fly to thee, most benignant Mother of sinners, that thou mayest obtain for us a lively contrition for our sins; so that although we cannot receive the Holy Ghost, as innocent, like thyself, yet may we receive Him as true penitents, together with those Gentile penitents who received Him in the upper room. Grant this, most holy Mother, not for our merits, for we have none, but out of thine own exceeding goodness, and that great love which thou bearest to the same blessed Spirit, Who hast chosen thee for His Spouse. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. Grant, we beseech Thee, almighty God, that the splendor of Thy brightness may shine upon us; and that the light of Thy light may, by the illumination of the Holy Spirit, confirm the hearts of those who by grace are regenerate; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing of almighty God, Father, Son, and Holy Ghost, descend upon us, and remain with us always. Amen.
[pg 374] September. The Immaculate Heart of Mary. This month is generally devoted to the consideration of the Heart of Mary and her Seven Dolors. Not only should we have a special devotion to the Sacred Heart of Jesus, but there are good reasons for us to have a devotion to the heart of Mary, so full of love for us, and to her dolors in connection with the redemption of mankind. Her life was full of sorrow, because she was actuated by the same sentiments as Our Lord in His desire to redeem us from the slavery of Satan. What heart, in fact, has ever been so intimately identified with that of Jesus as was Mary's? He died on the cross, and Mary stood beneath it, faithful to the end. Our Lord, in His thirty years' ministry, labored among the people, preaching and healing the sick, and Mary was certainly in perfect sympathy with Him in His great work. We are struck with the adorable goodness of His divine Heart, and for the same reason we are attracted to the heart of Mary. We will, then, during this month of September, pray to the heart of our beloved Mother, setting before our minds the goodness of that loving heart towards her children in this vale of tears. Let us love and honor these two hearts so intimately united; let us go to God
the Father through the Heart of Jesus: and to the divine Saviour through the heart of Mary. We can obtain all things from the Father and the Holy Ghost through the Heart of Jesus; and all things from the Son through the heart of His blessed Mother.
Considerations and Prayers for Every Day. First Day. Nowhere in the Old Testament, do we approach God more closely than in the book of Job, where we see the great prophet of God enduring so [pg 375] patiently the many sufferings that God has permitted; and nowhere do we recognize Him as the great Father good and kind to His children as in the same book. Job was a figure of Christ. There is something very holy in suffering endured in compliance to the will of God. To-day, then, we are to begin to think of Mary's sorrowful heart, and we will contemplate how the mysterious ways of Providence, the love of God, His mercy and kindness, inflicts chastisements on the Mother of His much loved Son. In the silence of the thirty years of Christ on earth, in the silence of the hours of agony on the cross, and in the silence of Mary underneath the cross, we will see the silence of a heart filled with sorrow, which God is imposing on His children for the good of mankind. The Church sets before our minds the seven sorrows of Mary, telling us the principal causes of her great grief in the life of Jesus. Prayer. O heart of Mary, I offer, I consecrate to thee my heart! Thou shalt be the object of my veneration, love and confidence; I will pay thee my devotions every day; I will celebrate thy feasts with joy; I will proclaim thy greatness and thy goodness without ceasing. I will neglect no means of obtaining for thee the honor and the homage which are due unto thee. I will bring all the thoughts and affections
Welcome to our website – the ideal destination for book lovers and knowledge seekers. With a mission to inspire endlessly, we offer a vast collection of books, ranging from classic literary works to specialized publications, self-development books, and children's literature. Each book is a new journey of discovery, expanding knowledge and enriching the soul of the reade Our website is not just a platform for buying books, but a bridge connecting readers to the timeless values of culture and wisdom. With an elegant, user-friendly interface and an intelligent search system, we are committed to providing a quick and convenient shopping experience. Additionally, our special promotions and home delivery services ensure that you save time and fully enjoy the joy of reading. Let us accompany you on the journey of exploring knowledge and personal growth! textbookfull.com

More Related Content

PDF
Thermochemical Process Engineering 1st Edition Kevin M Van Geem Eds
dradocrizza
 
PDF
Applications in Design and Simulation of Sustainable Chemical Processes 1st E...
fgnxnrag522
 
PDF
Life Cycle Sustainability Assessment for Decision-Making: Methodologies and C...
tphsssdib082
 
PDF
Applications in Design and Simulation of Sustainable Chemical Processes 1st E...
geurdssanter
 
PDF
Advanced Nanomaterials for Pollutant Sensing and Environmental Catalysis Qido...
chokcimc
 
PDF
Magnetic Skyrmions and Their Applications Giovanni Finocchio And Christos Pan...
caloincorte
 
PDF
Biofuels and Biorefining: Volume 2: Intensification Processes and Biorefineri...
rxouqaj255
 
PDF
Applications of Nanofluids in Chemical and Bio-medical Process Industry Shrir...
cwbjtmxvc7730
 
Thermochemical Process Engineering 1st Edition Kevin M Van Geem Eds
dradocrizza
 
Applications in Design and Simulation of Sustainable Chemical Processes 1st E...
fgnxnrag522
 
Life Cycle Sustainability Assessment for Decision-Making: Methodologies and C...
tphsssdib082
 
Applications in Design and Simulation of Sustainable Chemical Processes 1st E...
geurdssanter
 
Advanced Nanomaterials for Pollutant Sensing and Environmental Catalysis Qido...
chokcimc
 
Magnetic Skyrmions and Their Applications Giovanni Finocchio And Christos Pan...
caloincorte
 
Biofuels and Biorefining: Volume 2: Intensification Processes and Biorefineri...
rxouqaj255
 
Applications of Nanofluids in Chemical and Bio-medical Process Industry Shrir...
cwbjtmxvc7730
 

Similar to Mesoscale modeling in chemical engineering Part I 1st Edition Li (20)

PDF
Pem Water Electrolysis Volume 1 Dmitri Bessarabov And Pierre Millet
libukuhaquet
 
PDF
Life Cycle Sustainability Assessment for Decision-Making: Methodologies and C...
hoyotyrek
 
PDF
Nano-Optics: Fundamentals, Experimental Methods, and Applications (Micro and ...
awaraaudoux
 
PDF
Emerging Membrane Technology for Sustainable Water Treatment 1st Edition Hankins
sadowkaperzl
 
PDF
Biofuels And Biorefining Volume 2 Intensification Processes And Biorefineries...
zaivijmeai
 
PDF
Nanooptics Fundamentals Experimental Methods And Applications Micro And Nano ...
sebuhochax
 
PDF
Sustainable Nanoscale Engineering: From Materials Design to Chemical Processi...
itarulaljek
 
PDF
Emerging Membrane Technology for Sustainable Water Treatment 1st Edition Hank...
hixxigmcvc7083
 
PDF
Integrated Nano-Biomechanics 1st Edition Takami Yamaguchi (Editor)
nrcpaazeh127
 
PDF
Advanced Nanomaterials and Their Applications in Renewable Energy Tian-Hao Yan
ambekps535
 
PDF
Advanced Nanomaterials and Their Applications in Renewable Energy Tian-Hao Yan
ambekps535
 
PDF
Grandchallengesinchemicalengineering
Kiros Hagos
 
PDF
Product Engineering Molecular Structure And Properties James Wei
hejsandigbe92
 
PDF
Chemical Vapour Deposition (CVD): Advances, Technology and Applications 1st E...
gqdzhqn637
 
PDF
Integrated Nano-Biomechanics 1st Edition Takami Yamaguchi (Editor)
noicejaxenk7
 
PDF
Microwave wireless communications : from transistor to system level 1st Editi...
pdgxwetbxs6174
 
PDF
Chemometrics In Practical Applications Kurt Varmuza
pocomatyo86
 
PDF
Nanomaterial Interfaces in Biology Methods and Protocols 1st Edition Daniel F...
agywzcjox9017
 
PDF
Advanced Data Analysis & Modelling in Chemical Engineering 1st Edition Denis ...
yptobqmlti0509
 
PDF
Biotechnology For The Future 1st Edition Jens Nielsen
bkpbxsqqym1009
 
Pem Water Electrolysis Volume 1 Dmitri Bessarabov And Pierre Millet
libukuhaquet
 
Life Cycle Sustainability Assessment for Decision-Making: Methodologies and C...
hoyotyrek
 
Nano-Optics: Fundamentals, Experimental Methods, and Applications (Micro and ...
awaraaudoux
 
Emerging Membrane Technology for Sustainable Water Treatment 1st Edition Hankins
sadowkaperzl
 
Biofuels And Biorefining Volume 2 Intensification Processes And Biorefineries...
zaivijmeai
 
Nanooptics Fundamentals Experimental Methods And Applications Micro And Nano ...
sebuhochax
 
Sustainable Nanoscale Engineering: From Materials Design to Chemical Processi...
itarulaljek
 
Emerging Membrane Technology for Sustainable Water Treatment 1st Edition Hank...
hixxigmcvc7083
 
Integrated Nano-Biomechanics 1st Edition Takami Yamaguchi (Editor)
nrcpaazeh127
 
Advanced Nanomaterials and Their Applications in Renewable Energy Tian-Hao Yan
ambekps535
 
Advanced Nanomaterials and Their Applications in Renewable Energy Tian-Hao Yan
ambekps535
 
Grandchallengesinchemicalengineering
Kiros Hagos
 
Product Engineering Molecular Structure And Properties James Wei
hejsandigbe92
 
Chemical Vapour Deposition (CVD): Advances, Technology and Applications 1st E...
gqdzhqn637
 
Integrated Nano-Biomechanics 1st Edition Takami Yamaguchi (Editor)
noicejaxenk7
 
Microwave wireless communications : from transistor to system level 1st Editi...
pdgxwetbxs6174
 
Chemometrics In Practical Applications Kurt Varmuza
pocomatyo86
 
Nanomaterial Interfaces in Biology Methods and Protocols 1st Edition Daniel F...
agywzcjox9017
 
Advanced Data Analysis & Modelling in Chemical Engineering 1st Edition Denis ...
yptobqmlti0509
 
Biotechnology For The Future 1st Edition Jens Nielsen
bkpbxsqqym1009
 
Ad

Recently uploaded (20)

PPTX
CHAPTER IV. MAN AND BIOSPHERE AND ITS TOTALITY.pptx
greciamaycalambro
 
PDF
Trump Administration's workforce development strategy
Mebane Rash
 
PDF
International_Financial_Reporting_Standa.pdf
VrindaTayade1
 
PDF
FOISHS ANNUAL IMPLEMENTATION PLAN 2025.pdf
EllenJoyCaniya2
 
PPTX
Introduction to pro and eukaryotes and differences.pptx
AvaniKarumathil
 
PDF
Chinmaya Tiranga quiz Grand Finale.pdf
Nitin Suresh
 
PPTX
Virtual and Augmented Reality in Current Scenario
Shruti Dalela
 
PDF
FORM 1 BIOLOGY MIND MAPS and their schemes
arcade5
 
PPTX
ELIAS-SEZIURE AND EPilepsy semmioan session.pptx
eyoba2172
 
PPTX
History, Philosophy and sociology of education (1).pptx
tmdth1
 
PDF
Practical Manual AGRO-233 Principles and Practices of Natural Farming
MilindKhedekar2
 
PDF
David L Page_DCI Research Study Journey_how Methodology can inform one's prac...
David L Page
 
PPTX
A powerpoint presentation on the Revised K-10 Science Shaping Paper
JericEstaco2
 
PDF
Hazard Identification & Risk Assessment .pdf
estagiarioprotegesms
 
PDF
AI-driven educational solutions for real-life interventions in the Philippine...
EleniIlkou
 
PDF
advance database management system book.pdf
hinamannan364
 
PDF
My India Quiz Book_20210205121199924.pdf
AtandraDey2
 
PPTX
Onco Emergencies - Spinal cord compression Superior vena cava syndrome Febr...
Medpopz
 
PDF
IGGE1 Understanding the Self1234567891011
rhea22labucay
 
PDF
ChatGPT for Dummies - Pam Baker Ccesa007.pdf
Demetrio Ccesa Rayme
 
CHAPTER IV. MAN AND BIOSPHERE AND ITS TOTALITY.pptx
greciamaycalambro
 
Trump Administration's workforce development strategy
Mebane Rash
 
International_Financial_Reporting_Standa.pdf
VrindaTayade1
 
FOISHS ANNUAL IMPLEMENTATION PLAN 2025.pdf
EllenJoyCaniya2
 
Introduction to pro and eukaryotes and differences.pptx
AvaniKarumathil
 
Chinmaya Tiranga quiz Grand Finale.pdf
Nitin Suresh
 
Virtual and Augmented Reality in Current Scenario
Shruti Dalela
 
FORM 1 BIOLOGY MIND MAPS and their schemes
arcade5
 
ELIAS-SEZIURE AND EPilepsy semmioan session.pptx
eyoba2172
 
History, Philosophy and sociology of education (1).pptx
tmdth1
 
Practical Manual AGRO-233 Principles and Practices of Natural Farming
MilindKhedekar2
 
David L Page_DCI Research Study Journey_how Methodology can inform one's prac...
David L Page
 
A powerpoint presentation on the Revised K-10 Science Shaping Paper
JericEstaco2
 
Hazard Identification & Risk Assessment .pdf
estagiarioprotegesms
 
AI-driven educational solutions for real-life interventions in the Philippine...
EleniIlkou
 
advance database management system book.pdf
hinamannan364
 
My India Quiz Book_20210205121199924.pdf
AtandraDey2
 
Onco Emergencies - Spinal cord compression Superior vena cava syndrome Febr...
Medpopz
 
IGGE1 Understanding the Self1234567891011
rhea22labucay
 
ChatGPT for Dummies - Pam Baker Ccesa007.pdf
Demetrio Ccesa Rayme
 
Ad

Mesoscale modeling in chemical engineering Part I 1st Edition Li

  • 1. Mesoscale modeling in chemical engineering Part I 1st Edition Li download https://textbookfull.com/product/mesoscale-modeling-in-chemical- engineering-part-i-1st-edition-li/ Download full version ebook from https://textbookfull.com
  • 2. We believe these products will be a great fit for you. Click the link to download now, or visit textbookfull.com to discover even more! Knowledge Science, Engineering and Management: 13th International Conference, KSEM 2020, Hangzhou, China, August 28–30, 2020, Proceedings, Part I Gang Li https://textbookfull.com/product/knowledge-science-engineering- and-management-13th-international-conference-ksem-2020-hangzhou- china-august-28-30-2020-proceedings-part-i-gang-li/ Scaling Chemical Processes Practical Guides in Chemical Engineering 1st Edition Jonathan Worstell https://textbookfull.com/product/scaling-chemical-processes- practical-guides-in-chemical-engineering-1st-edition-jonathan- worstell/ (SOLUTIONS) Chemical, Biochemical, and Engineering Thermodynamics (5th ed) 5th Edition Stanley I. Sandler https://textbookfull.com/product/solutions-chemical-biochemical- and-engineering-thermodynamics-5th-ed-5th-edition-stanley-i- sandler/ Reaction Engineering 1st Edition Shaofen Li https://textbookfull.com/product/reaction-engineering-1st- edition-shaofen-li/
  • 3. Math Problem Book I Kin Y. Li (Kin-Yin Li) https://textbookfull.com/product/math-problem-book-i-kin-y-li- kin-yin-li/ Microgrid Technology and Engineering Application 1st Edition Li https://textbookfull.com/product/microgrid-technology-and- engineering-application-1st-edition-li/ Advanced Data Analysis & Modelling in Chemical Engineering 1st Edition Denis Constales https://textbookfull.com/product/advanced-data-analysis- modelling-in-chemical-engineering-1st-edition-denis-constales/ Modeling of Chemical Wear: Relevance to Practice 1st Edition A. Sethuramiah https://textbookfull.com/product/modeling-of-chemical-wear- relevance-to-practice-1st-edition-a-sethuramiah/ Chemical Reactor Design Mathematical Modeling and Applications Conesa https://textbookfull.com/product/chemical-reactor-design- mathematical-modeling-and-applications-conesa/
  • 4. ADVANCES IN CHEMICAL ENGINEERING Editor-in-Chief GUY B. MARIN Department of Chemical Engineering, Ghent University, Ghent, Belgium Editorial Board DAVID H. WEST SABIC, Houston, TX JINGHAI LI Institute of Process Engineering, Chinese Academy of Sciences, Beijing, P.R. China SHANKAR NARASIMHAN Department of Chemical Engineering, Indian Institute of Technology, Chennai, India
  • 5. Academic Press is an imprint of Elsevier 225 Wyman Street, Waltham, MA 02451, USA 525 B Street, Suite 1800, San Diego, CA 92101-4495, USA The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK 125 London Wall, London, EC2Y 5AS, UK First edition 2015 © 2015 Elsevier Inc. All Rights Reserved No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. ISBN: 978-0-12-801247-5 ISSN: 0065-2377 For information on all Academic Press publications visit our website at store.elsevier.com
  • 6. CONTRIBUTORS Sergiy Antonyuk Chair of Particle Process Engineering, University of Kaiserslautern, Kaiserslautern, Germany Niels G. Deen Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands Maksym Dosta Institute of Solids Process Engineering and Particle Technology, Hamburg University of Technology, Hamburg, Germany Jieqing Gan Laboratory for Simulation and Modelling of Particulate Systems, Department of Chemical Engineering, Monash University, Clayton, Victoria, Australia Stefan Heinrich Institute of Solids Process Engineering and Particle Technology, Hamburg University of Technology, Hamburg, Germany Qinfu Hou Laboratory for Simulation and Modelling of Particulate Systems, Department of Chemical Engineering, Monash University, Clayton, Victoria, and Laboratory for Simulation and Modelling of Particulate Systems, School of Materials Science and Engineering, University of New South Wales, Sydney, New South Wales, Australia J.A.M. (Hans) Kuipers Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands Günter Leugering Institute of Applied Mathematics 2, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany Johan T. Padding Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands E.A.J.F. (Frank) Peters Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands Wolfgang Peukert Institute of Particle Technology (LFG), Friedrich-Alexander-Universität Erlangen- Nürnberg (FAU), Erlangen, Germany Lukas Pflug Institute of Applied Mathematics 2, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany ix
  • 7. Doris Segets Institute of Particle Technology (LFG), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany Harry E.A. Van den Akker Bernal Institute and Department of Mechanical, Aeronautical and Biomedical Engineering, University of Limerick, Limerick, Ireland, and Department of Chemical Engineering, Delft University of Technology, Delft, The Netherlands Ning Yang Center for Mesoscience and State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, PR China Aibing Yu Laboratory for Simulation and Modelling of Particulate Systems, Department of Chemical Engineering, Monash University, Clayton, Victoria, Australia Zongyan Zhou Laboratory for Simulation and Modelling of Particulate Systems, Department of Chemical Engineering, Monash University, Clayton, Victoria, Australia x Contributors
  • 8. PREFACE Opportunities and Challenges: Both at Mesoscales Evolution of chemical engineering science features increasing gener- ality of knowledge from “unit operations,” common for different industries, to “transport phenomena,” common in these operations, and is now at a transitional period with challenges in sustainable development and to its knowledge base. Designing materials, scaling-up reactors, and system opti- mization continue to be the main tasks for chemical engineers. However, upgraded knowledge and enabling technologies are needed to revolutionize R&D capability, which present challenges and opportunities to chemical engineering community. Opportunities are always obscured by challenges. Among many chal- lenges currently in chemical engineering, mesoscale phenomena at different levels of chemical engineering are recognized to be the most critical. At the material level, chemists and material scientists know molecular structures and properties of bulk materials very well, but they are still unable to manip- ulate the mesoscale structures in between. At the reactor level, chemical engineers have accumulated much knowledge on hydrodynamics, transport, and reaction behaviors of single particle and on global performance of reac- tors; however, what happen at the mesoscale between single particles and the whole reactor are still difficult to be formulated. These two mesoscales at different levels are believed to be essential not only for resolving the current global challenges but also for upgrading the knowledge base of chemical engineering science. Currently in chemical engineering, chemists and material scientists syn- thesize a variety of material structures every day, most of which, however, cannot be produced massively in industry due to the lack of understanding of the formation mechanisms of these structures and the difficulty in control- ling the microenvironment for their formation in reactors. In addition, scaling-up of reactors is still a big challenge for chemical engineers. Under- standing of mesoscale phenomena is critical to increase our capability in resolving these issues. In fundamental research, average approaches are widely used, such as computational fluid dynamics, which are however not sufficient enough in predictability. On the other hand, discrete approaches are blooming up, based on microscale mechanisms, which are unfortunately limited to xi
  • 9. scalability in engineering applications. As a compromising strategy between these two, coarse-graining approaches received more and more attention, aiming at bridging the scales of continuum cells and the discrete moving elements, which still suffer from the lack of understanding of intrinsic mech- anisms at mesoscales. This is now a common challenge not only in chemical engineering. Gradually, people recognized that “meso” will be a big thing. Most importantly, there are many clues that a common principle for all mesoscale problems at different levels between elemental particles and the universe may exist, leading to exploration of a transdisciplinary science, mesoscience, though great efforts are needed to further clarify its rationale and importance. In responding to these new possibilities and challenges, Advances in Chemical Engineering published a thematic volume in 2011 with the title: “Charaterization of Flow, Particles and Interfaces,” aiming at showing the dynamic behaviors at mesoscales. These two volumes further this effort to analyze these mesoscale phenomena and processes with the title: “Mesoscale Modeling in Chemical Engineering” so as to stimulate wide dis- cussion and to promote transdisciplinarity between chemistry, material science, and chemical engineering, and even beyond. Volume I invited a few participants from the 4th International Conference on Multiscale Struc- tures and Systems with the theme of “Mesoscales: The key to multiscale problems,” and Volume II invited contributions from the major program on mesoscience of National Natural Science Foundation of China entitled “Mechanisms and manipulation at mesoscales in multi-phase reaction systems.” Although these contributions may be preliminary in addressing meso- scale problems, we hope these two volumes can play a role of “throwing out a minnow to catch a whale” and to stimulate thinking in the following questions: What are mesoscale phenomena? Why are they so important? How to relate mesoscale concepts to our research? And is it necessary or pos- sible to have a common science for all mesoscales? We would like to thank all authors for their contributions, and reviewers for their critical comments and suggestions. Help from Prof. Ning Yang and Dr. Xiaowei Wang are sincerely appreciated. JINGHAI LI AND GUY MARIN xii Preface
  • 10. CHAPTER ONE Unified Design Strategies for Particulate Products Wolfgang Peukert*,1 , Doris Segets*, Lukas Pflug† , Günter Leugering†,1 *Institute of Particle Technology (LFG), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany † Institute of Applied Mathematics 2, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany 1 Corresponding authors: e-mail address: Wolfgang.Peukert@fau.de; Guenter.Leugering@fau.de Contents 1. Introduction 2 2. Hierarchical Products and Processes 6 3. Product Properties 12 4. Product Design 19 4.1 Particle Formation 19 4.2 Interactions 25 4.3 Structure Formation 30 4.4 Characterization Along the Process Chain 44 4.5 Multiscale Modeling and Simulation (MSS) 45 4.6 Integration of Particles into Devices 49 5. Processes and Properties by Design 52 5.1 Sensitivities of Parameter-Dependent Initial Value Problems 56 5.2 General Model-Based Optimal Control Setting 58 5.3 Examples of Optimization 60 6. Conclusions 70 Acknowledgements 71 References 71 Abstract Unit operations and product design are the two most important pillars of chemical engi- neering. Product design is the formation, formulation, handling, manufacturing, and characterization of complex multiphase products with specific properties and is thus at the core of mesoscale science and engineering. The applications define the required product properties which cover both classical fields of process technology in the chem- ical industry as well as new emerging fields of electronics, energy and environmental technologies, life sciences, materials science and engineering, nanotechnology, and photonic technologies highlighting the broad relevance of mesoscale science. Unifying principles of product design are proposed which are widely applicable to many Advances in Chemical Engineering, Volume 46 # 2015 Elsevier Inc. ISSN 0065-2377 All rights reserved. http://dx.doi.org/10.1016/bs.ache.2015.10.004 1
  • 11. different kinds of products including solid, liquid, and even gaseous particles. Results from the Erlangen Cluster of Excellence “Engineering of Advanced Materials” show that the joint venture of chemical engineering with materials science in concert with the basic sciences opens new prospects for all involved disciplines. In particular, chemical and biochemical engineering expands through particle technologies also in physics- related fields of technology such as electronics, photonics, or 3D printing. Rigorous mathematical optimization methods based on predictive models for products, struc- tures, and processes catalyze new possibilities for true design of particulate products which is at the core of mesoscale science and technology. 1. INTRODUCTION In recent years, chemical engineering including particle science and technology has gone through major transitions. For most of the last century, process engineering was focused on unit operations, i.e., to understand and design certain process steps by general rules that should be as independent as possible of the processed chemicals and materials. This paradigm was very successful, for instance, in the petroleum industry, where very large pro- cesses for oil refineries were developed and optimized. Teaching concepts in chemical engineering were thus almost exclusively orientated toward thermal-, mechanical-, and chemical-based unit operations plus classical dis- ciplines including chemical thermodynamics, fluid mechanics, and transport processes for heat and mass. The unit operations approach for homogeneous systems that are mainly consisting of fluids today is mature with limited pros- pects for ground-breaking new developments. New momentum came by the advent of ionic liquids which opened new applications and put new emphasis on well-established lines such as characterization of fluid properties and their phase equilibria (Wasserscheid and Keim, 2000). The understanding and rigorous modeling and design of heterogeneous systems containing interfaces and, in particular, disperse particle systems are much less developed with many open fundamental and applied challenges. In general, disperse systems consist of solid, liquid, or gaseous particles in the form of dispersions, emulsions, or foams, respectively. After many years of extensive research, we have to admit that very few predictive models exist for unit operations where disperse systems are produced and processed. Good models exist for highly diluted systems where particle interactions can be neglected. Examples are deep bed filters (Baumgartner and L€ offler, 1986; Lee and Liu, 1982; Wang et al, 2007, 2008), cyclones (Mothes and L€ offler, 1988), or air classier mills (Toneva et al, 2011a, 2011b) operated 2 Wolfgang Peukert et al.
  • 12. at low solid concentrations where the momentum transfer from the solid to the fluid phase can be neglected as first approximation. In most systems, which are operated at higher particle concentrations such as ball or stirred media mills (Kwade, 1999; Sommer et al, 2006), mixers (Portillo et al, 2008; Sommer, 1986; Vanarase et al, 2010), or granulators (Dhenge et al, 2012; Iveson et al, 2001; Rahmanian et al, 2011; Reynolds et al, 2005), the operational behavior cannot yet be predicted without free fitting param- eters. Although in recent years much progress has been made in the charac- terization and particularly in the modeling of dense fluid particle systems such as fluidized beds (Deen et al, 2007; Dosta et al, 2012; Fries et al, 2011; Wang et al, 2010), the key challenge is related to an overall cross-cutting topic: particles in contact, i.e., the mesoscale. In Germany, a nation-wide research program was dedicated to key questions in terms of contact mechanics, adhe- sion, fracture, and related applications (http:/ /www.piko.ovgu.de/). Unit operations involving particles are best described by a fundamental unit operation function which depends on the machine and the material function (see Section 4.5). The former describes the motion of particles in the unit operation depending on the applied operational parameters such as flow rates, velocities of moving parts, concentrations, and the fluid prop- erties. Within the unit operation, the particles react according to the applied stresses. This reaction is summarized by the material function involving all material properties such as particle density, Young’s modulus, or coefficients of restitution as a measure for the energy dissipation between the particles upon contact. We will later come back to this important and too often neglected question of particle properties. The two-phase or even multiphase flow at all concentrations in the various unit operations is subject to intensive research with still many open questions to be answered. In all these exam- ples, the key challenge is the mesoscale which is in the focus of this issue of Advances in Chemical Engineering and which will be addressed by the contri- butions of Hans Kuipers, Stefan Heinrich, and Aibing Yu. Since the nineties of the last century, the prevailing paradigm of unit operations has been complemented and partly replaced by a product- orientated approach (Cussler and Moggride, 2011; Hill, 2004; Kind, 1999). Now product properties are in the focus; product design strategies and the engineering of advanced materials are the results of this approach. The combination of the described developments in chemical engineer- ing together with materials science opens unseen perspectives for both dis- ciplines. Materials scientists are the experts in materials properties, a major challenge in modern chemical engineering. Advanced materials require 3 Unified Design Strategies for Particulate Products
  • 13. sophisticated processes; thus chemical engineers come into play. Further- more, the strong link with basic science closes the observed transfer gap between visionary ideas and real-world applications. While design of novel materials, and in particular nanomaterials, starts from a fundamental physical and chemical understanding on the atomic and molecular levels, engineering of devices and systems requires length scales that range from micro- to meso- and macroscales. Thus, multiscales need to be covered. Advanced materials with properties tailored on the molecular and the mesoscales are expected to stimulate evolutionary advances and revolution- ary breakthroughs in emerging key-technology areas, such as information and communication as well as catalysis, energy, and transportation. Hence, the ability to design novel materials and processes will have a strong impact on assuring industrial competitiveness, economic growth, and better quality of life. In Fig. 1, the five most important incentives for product development are highlighted. These are resources including energy transformation and storage and their environmental impact, modern ways of transportation such as electric cars, and information technology with a manifold of electronic and photonic devices. Other aspects are related to improving and sustaining the quality of life, for instance, in developing countries without irreversible impact on our climate. Life sciences in the century of biology in general promise and require many future applications in bio-based economies and of course in food science and medicine. Progress in all these fields requires the development of new products that can only be realized if new materials Figure 1 Driving forces for new materials and processes. 4 Wolfgang Peukert et al.
  • 14. are created together with innovative processes to produce them in an eco- nomical and sustainable way. Despite the quite different technology fields with their manifold prod- ucts, common underlying principles can be identified. They need to be implemented if new materials and processes shall be developed and put into operation. Key principles are the rigorous understanding and design of structure–property and process–structure functions. The latter strongly depend on analytical tools for materials and process characterization across all relevant length scales. In particular, multiscale modeling and simulation (MSS) are essential for the understanding and design of materials throughout their transient evolution in production processes. Of course, all these aspects rely on the application and advancement of fundamental knowledge from basic science, i.e., on biology, chemistry, mathematics, and physics. It is clear that product design is a highly inter- and transdisciplinary endeavor. At this point, it needs to be mentioned that the relevance of chemical engineering greatly expanded along with the product- and material-oriented paradigm. Today, chemical engineers are involved in such diverse fields as the development of biomaterials for tissue engineering, the design of the next generation of catalysts for water splitting, or the deposition of thin films in printable electronics or photovoltaics. An interesting and unresolved question in this respect is how to teach chemical engineers with such a wide spectrum of possible applications. This question is particularly pressing for particulate systems which expanded from the traditional mechanical powder processing approach to an extremely broad field of particle science and tech- nology involving gaseous, liquid, and solid particles of biological, chemical, or physical nature. Thereby sizes from below 1 nm up to meters are covered. In other words, the unifying principles beyond the classical unit operations in production and handling of disperse products, i.e., in mesoscale science and technology, need to be identified. These concepts should be reflected in any teaching curriculum to prepare young generations for challenges ahead. En route to answer these pressing questions, in this review, we focus on multiscale methods for the design of particulate products. We will highlight two main routes: from molecules to particles and from single particles to par- ticle ensembles in functional devices. Unifying principles of product design are proposed and examples will be given on how rigorous mathematical opti- mization can be implemented based on the predictive models for the design of particle properties and processes. Due to the very large field of applications only few selected examples can be presented. A comprehensive overview is 5 Unified Design Strategies for Particulate Products
  • 15. neither intended nor possible due to space limitations. Many of the results and concepts in this review have been developed within the Erlangen Cluster of Excellence “Engineering of Advanced Materials—Hierarchical Structure Formation of Functional Devices” (www.eam.fau.de). 2. HIERARCHICAL PRODUCTS AND PROCESSES The hierarchical organization of matter at different length scales, from molecular to real-world macroscopic components, offers many degrees of freedom for creating materials with multifunctional properties. The proper- ties of an advanced material are related not just to the chemical nature of its atoms and molecules but also to their arrangement and distribution, includ- ing defects and imperfections. Similarly, the development of models to pre- dict material properties from the atomic to the macroscopic scale and the design of related novel processes are major topics on the agenda of mesoscale science and technology. The key challenge is how to bridge the gap between material design on a molecular level and the macroscopic engineering on the level of components and systems. This requires the development of adequate approaches that are able to cover an extended range of time and length scales in modeling and simulation, processing and manufacturing, as well as struc- ture, property, and process analyses. Figure 2 highlights these interconnec- tions for particulate products starting from different types of molecular and Figure 2 From building blocks to functional devices in an interdisciplinary environment. 6 Wolfgang Peukert et al.
  • 16. particulate building blocks which are integrated into superstructures, here shown as printed thin films that are finally integrated into macroscopic devices (e.g., light-emitting devices or flexible solar panels). The involved disciplines and required skills comprise basic chemistry and physics, which are mostly active at the level of building blocks, chemical engineering fun- damentals, and formulation science and technology. Inks are designed, pre- pared and printed into superstructures under well-defined conditions in the lab and then transferred via process technologies to larger scales and to applications. The underlying fundamental hierarchy is exemplified in Fig. 3. The elec- tronic structure of atoms, molecules, and particles defines the molecular and particulate interactions between the objects and building blocks. Their rep- resentations are highlighted as cartoons on the right-hand side, showing on the level of building blocks the charge distribution of a nucleus that is formed during the crystallization (upper right), and the surface of a functionalized nanoparticle for printable electronics or photovoltaics. At the next level, those objects interact with each other in a continuous fluid phase until they are deposited as a thin film on a solid and maybe even flexible substrate. The film structure and the properties of the particles determine the macroscopic film properties in terms of, e.g., porosity, electrical, or thermal conductivity, their interaction with light or catalytic properties. Figure 3 Fundamental hierarchy from electronic and molecular structure to macro- scopic properties. 7 Unified Design Strategies for Particulate Products
  • 17. Statistical thermodynamics already provide an excellent framework to describe and model equilibrium properties of molecular systems. Molecular interactions, summarized for instance in terms of a potential of mean force, determine correlation functions and all thermodynamic properties. The (pair) correlation function represents the material structure which can be determined by scattering experiments via the scattering function. All mac- roscopic properties of pure and mixed fluid systems can be derived by well- established multiphase thermodynamics. In contrast, a similar framework for particulate building blocks only partly exists and needs to be developed much further. Besides equilibrium properties, nonequilibrium effects are particularly important in most particulate systems and need to be included in a comprehensive and complete picture. We will come back to these aspects in Section 4. Advances in multiscale processing will provide enormous benefits for more reliable, energy-, and resource-efficient fabrication of high- performance multifunctional materials and for engineering of miniaturized devices and integrated systems. Producing complex devices from designed molecular and particulate structures requires local microscopic tailoring of structure and shape to be extended to the meso- and macroscopic levels of components and systems. This approach offers chemical engineers exten- sive new opportunities to tackle emerging fields outside the traditional domain of industrial chemistry (Pratsinis, 2010). As highlighted in Fig. 4, functional materials design and fabrication require both in-depth Figure 4 Structure–property and process–structure functions. 8 Wolfgang Peukert et al.
  • 18. understanding of structure–property functions and rational design strategies which are directly linked to multiscale processing based on process–structure functions. Property functions, i.e., correlations between structure and related prop- erties, define the targets in any product design. These must be understood across all relevant levels, ranging from molecular, single particle, and particle ensembles to the final product. Very often, multifunctionality prevails, i.e., powders should be free flowing, easily dispersible in fluids and exhibit controlled defect states. The example in the upper left of Fig. 4 shows indium tin oxide nanopowders whose electronic defect states are related to their oxygen deficiency which controls their optical and electronic prop- erties. Thin films made of these powders are applied in opto-electronic devices such as displays. The thin film should be, e.g., transparent, smooth, and sufficiently strong and flexible to survive for instance its application on flexible substrates such as field effect transistors (FETs) as shown in the upper right of Fig. 4. The product properties evolve from multiscale process chains as highlighted in the lower part of Fig. 4. As an example, the particles are syn- thesized in phase A, say the gas phase or an organic solvent, and then they are transferred to an aqueous phase B where several formulation steps such as stabilization, surface functionalization, and adjustment of the suspension rheology may be included. Finally, a functional thin film is deposited in lab scale usually by spin- or dip coating, whereas in an industrial environ- ment the current development is targeted toward fast roll-to-roll processes. Depending on the type of product, the process chains including the involved unit operations may change of course. The process function (process–structure functions) as defined by Krekel and Polke relates the process parameters to the product property (Krekel and Polke, 1992): dispersity ¼ f processparameters,eductconcentrations ð Þ (1) Process parameters are the type of unit operations, their interconnection in the process, the process conditions under which the unit operations are operated (e.g., temperature, pressure, mass flow rates, etc.), and the materials that are processed. Structure–property as well as process–structure functions must be known in order to design optimal process variables and to achieve the desired goal, i.e., to produce well-defined, often multifunctional prod- uct properties. Usually, process chains (with or without recirculation loops) 9 Unified Design Strategies for Particulate Products
  • 19. have to be developed during which both handling and end-use properties have to be optimized. While these developments of products and the related process chains have been done mostly empirical in the past, modern developments of pro- cess design make more and more use of computer-based methods including flow-sheeting software for design of the individual process steps as well as for the whole process. While such design tools are well developed for fluids, these are still in their infancy for solids processing. A larger coordinated pro- ject in Germany led to the development of SolidSim, a comparatively new flow-sheeting software tool for major unit operations including crystalliza- tion, agglomeration, comminution, gas–solid as well as solid-liquid separa- tion and transport (Hartge et al, 2006). The outcomes of these developments are now integrated in the Aspen software package. The next step along these lines is the development of dynamic models which can handle efficiently dis- tributed properties and time dependencies of individual unit operations and their interconnection within a whole production process. The required fun- damentals are currently developed within a nation-wide priority program in Germany and will be represented by a complex flow-sheet environment (http://www.dynsim-fp.de/spp-1679.html) (Dosta et al, 2014). However, these positive developments also show that predictive models for most unit operations are rare. The reasons for this deficiency are related to (i) poorly understood turbulent multiphase flows with mass and momentum exchange between the phases, in particular at high Re numbers, (ii) poorly understood particle–particle interactions, and (iii) the lack of reliable single particle and powder (particulate ensemble) properties. Mesoscale science and technology evolves from molecular systems and is key to the assembly of macroscopic products. Thus, the intermediate state of disperse systems must catalyze bet- ter and more efficient solutions to pressing technological challenges of the modern world. Molecular and nanoscale design, synthesis, and analysis of materials are becoming increasingly important for high-performance applications in emerging fields such as nanoelectronics, catalysis, and energy conversion. Molecules offer the opportunity of tailoring structure and function system- atically through modern concepts of synthetic (Negishi, 2011; Suzuki, 2011) and supramolecular chemistry (Steed and Atwood, 2009; Whitesides and Boncheva, 2002). Organic molecules are particularly versatile building blocks since they can combine stability with almost limitless structural and functional variation. Inorganic nanoparticles offer a number of addi- tional benefits, in particular high thermal stability. Individual molecules 10 Wolfgang Peukert et al.
  • 20. (Lu and Lieber, 2007), hierarchically structured supramolecules (Schlundt et al, 2009), individual particles (Tenne, 2006), particle systems (Min et al, 2008; Pratsinis, 2010), and, last but not least, organic/inorganic hybrid structures (Gnichwitz et al, 2010) provide the key functionalities, for instance for devices (Lal et al, 2007) such as sensors, circuits, or photovoltaic cells. Research into fundamental processes such as charge transfer, mass transport, or interaction with light, into advanced materials, and into the for- mation of unprecedented structures and architectures for functional devices is of fundamental importance for many applications. The properties of multiphase components with microstructures modified on the molecular scale are governed by the interface structure and the chemical nature of the corresponding organic and inorganic components. Hence, understand- ing the structures of interfaces on the atomistic scale and their influence on materials processes and properties are key factors in manufacturing complex multiphase materials with optimized properties. A prominent example for the hierarchical organization of building blocks which is decisive for the later product properties is the case of mes- ocrystals. Mesocrystals are a relatively new class of crystals consisting of small buildings blocks which are self-assembled to larger units (C€ olfen and Antonietti, 2005; see Section 4.3). Both examples in Fig. 5 show ZnO mes- ocrystals. The mesocrystals in Fig. 5A consist of 5 nm ZnO quantum dots which are organized to quite uniform spherical single crystals of about 300 nm in diameter (Distaso et al, 2012). These show high UV-absorption and minimized light scattering in the region of visible light. The ZnO mesocrystals in Fig. 5B are also built from ZnO quantum dots which are then organized by multistep-oriented aggregation as rods, semi- and full ellipsoids (Klaumünzer et al, 2014). These particles show a high scattering intensity in the whole range of visible light. Particles are seldom sole as such, and they are usually integrated in prod- ucts. Paper, ceramics, and bread are just three well-known examples of everyday use. Advanced structural and functional materials consisting of par- ticles and powders are made to be integrated into all the functional devices mentioned in this overview. The implementation of nanotechnologies is still limited due to the difficulties in preserving the beautiful nanostructures and their excellent properties produced in the lab upon transferring them into industrial practice. We have to understand how hierarchical products evolve in multiscale processes. Important questions must be answered such as where does “quality” evolve in chemical processes and how can we con- trol electronic and structural defects of particles and particle systems across all 11 Unified Design Strategies for Particulate Products
  • 21. length and time scales. Key to these questions is the in-depth understanding of particle properties. 3. PRODUCT PROPERTIES For particulate materials, the product properties depend on the chem- ical composition and on the dispersity of the material. The dispersity is char- acterized by the particle size distribution (PSD), the particles’ shape, their morphology in terms of internal structure (amorphous, crystalline, internal pore size distributions and their defects), and their interfacial properties. This relation was called by Rumpf already in the 1960s of the last century the “property function” (Rumpf, 1967). Control of the property function is the core of product engineering or product design. Productproperty ¼ f dispersity,chemicalcomposition ð Þ (2) Dispersity includes: • particle size and shape and their respective distribution, • particle morphology including defects, and • particle surface properties. Figure 5 Hierarchical structure of mesocrystals: (A) porous balls of ZnO quantum dots and (B) ellipsoids of ZnO nanorods and their formation mechanism. Panel (A): Distaso et al (2012). Panel (B): Klaumünzer et al (2014). Reproduced with permission from the Royal Society of Chemistry. 12 Wolfgang Peukert et al.
  • 22. Thus, the property function relates the particulate structure (size, shape, morphology, and surface) to the product properties (structure–property– function). Examples of property functions are the taste of chocolate, the color of pigments, the strength of cements, or the bandgap of semiconductor nanoparticles. Particle ensembles in the form of agglomerates, thin films, or filter cakes are also included in this consideration. Modern products are often characterized by several properties which have to be achieved simulta- neously: transparent and scratch-resistant coatings, sun blockers which are transparent for visible light and UV-absorbing may serve as examples. Thus, a multifunctional product space evolves which must be created through design of the related structures using the respective process technology. Glotzer and coworkers proposed the following framework of evolving complexity for particles as shown in Fig. 6 (Glotzer and Solomon, 2007). By varying systematically geometric features such as size and shape and also surface coverage, patterns, branching, and chemical ordering, many different A Surface coverage (patchiness) Aspect ratio Faceting Pattern quantization Branching Chemical ordering Shape gradient Roughness B C D E F G H Figure 6 Overview of complexity generation of particles. Permission from Macmillan Publishers Ltd. Glotzer and Solomon (2007). Copyright 2007. 13 Unified Design Strategies for Particulate Products
  • 23. types of particles can be envisioned for which the phase behavior will vary between ordered crystalline structures and disordered glassy structures. Dur- ing the last years, synthesis capabilities strongly improved. Therefore, it is within reach to realize at least some of those structures within the next years. In the following, examples for electronic, optical, and mechanical properties will be presented and related to dispersity in terms of size, shape, morphol- ogy, and surface. For the former, we will discuss possibilities for property optimization (Chapter 5), and the latter are most relevant for the question of particle–particle interactions in modeling approaches of particulate dense phase systems (Chapter 4). Many property functions in dependency of particle size are known. Today, PSDs can be measured reliably across all length scales from below 1 nm up to macroscopic sizes. In Fig. 7, we highlight a few examples of the size-dependent bandgap of semiconducting quantum dots which con- trols their electronic and optical properties. The latter strongly depend on the bandgap energy of the first excitonic transition: ZnO (Fig. 7A) and Figure 7 Bandgap of quantum dots: (A) ZnO (Viswanatha et al, 2004), (B) CIS (Akdas et al, 2015), and (C) PbSe (Segets et al, 2012b). EMA refers to the effective mass approx- imation originally established by Brus (1984) which usually fails for the accurate descrip- tion of the smallest particles. Panel (A): Reproduced from Viswanatha et al (2004) with permission of The Royal Society of Chemistry. Panel (B): Reproduced from Akdas et al. (2015) with permission of The Royal Society of Chemistry. Panel (C): Reprinted with permis- sion from Segets et al (2012b). Copyright 2012 American Chemical Society. 14 Wolfgang Peukert et al.
  • 24. TiO2 are absorbing in the UV, CdS(e), CdTe, and CuInS2 (CIS, Fig. 7B) in the visible, whereas lead-based materials such as PbS(e) absorb in the NIR (Fig. 7C) (Akdas et al, 2015; Segets et al, 2012b; Viswanatha et al, 2004). In all cases, the bandgap ΔE widens due to the quantum size effect according to the following empiric equation: △E ¼ △Eg,bulk + xc a 1=b eV (3) where x is the particle diameter, ΔEg,bulk is the bandgap of the bulk material, and a (nm), b (), and c (nm) are material-dependent empiric parameters. Tailoring of the opto-electronic properties of these materials is thus directly linked to the control of their size. We will come back to this issue in Chapter 5. Only few examples of property functions as a function of particle shape are known. This lack is related to the difficulty of measuring size and shape simultaneously since at least two dimensions of the particle must be deter- mined in the process environment. The two most prominent examples with probably the best database are the drag force of nonspherical particles (Binder et al, 2009; Clift et al, 2005; Walter et al, 2015b; Yow et al, 2005) and the optical properties of metal nanoparticles. The latter are due to sur- face plasmon resonances which give rise to shape-dependent absorption peaks. For a long time, particle shape determination was restricted to tedious off-line imaging. Since a few years ago, particle shapes can be mea- sured (even inline) for particles larger than a few 10 μm in size by direct video-based shape analysis (Witt et al, 2013). For smaller particles, shape analysis is quite tedious because a statistical relevant number of particles (at least some 100) has to be measured by image analysis of deposited sam- ples using scanning electron microscopy (SEM), transmission electron microscopy (TEM), or atomic force microscopy (AFM). New possibilities for two-dimensional characterization come from the combination of sedimentation analysis with inline absorption spectrometry (Walter et al, 2014, 2015b). In brief, analytical (ultra-)centrifugation (AUC) allows the analysis of particles ranging from 1 nm when an ultracentrifuge is used up to a few 10 μm in size when a conventional centrifuge is used (Walter et al, 2015a). The sedimentation velocity depends on the size and shape of the particles. Figure 8A depicts as an example the frictional ratio of cylinders as a func- tion of their aspect ratio. This relationship for shape analysis of cylinders and platelets was recently demonstrated for graphene oxide monolayers (Walter et al, 2015b). The frictional ratio plotted on the y-axis is the drag force of the 15 Unified Design Strategies for Particulate Products
  • 25. Figure 8 (A) Frictional ratio of sphero-cylinders (ratio of drag of cylinder and volume equivalent sphere) in dependence of their aspect ratio (Re≪1) and (B) absorption sed- imentation analysis of gold nanoparticles in an analytical ultracentrifuge. Panel (A): Reprinted with permission from Walter et al (2015b). Copyright 2015 Wiley. Panel (B): Reprinted with permission from Walter et al (2014). Copyright 2014 American Chemical Society. 16 Wolfgang Peukert et al.
  • 26. cylinders related to the drag of volume equivalent spheres. During a sedi- mentation run, the separated particles can be analyzed with respect to their absorption properties. This is shown in Fig. 8B for gold nanorods. If the par- ticles are small enough to show strong diffusion (typically below 20 nm), simultaneous evaluation of sedimentation and diffusion can be used to obtain shape factors. In the next step, we discuss property functions in dependency of particle morphology. The term “morphology” includes amorphous and crystalline states, pore structures, and various defect structures of particles. Here, we give an example for mechanical particle properties. One of the grand chal- lenges in particle technology is how to characterize the contact mechanisms and contact forces between particles. Mechanical particle properties are the key parameters in discrete element models (DEMs) which have been devel- oped during the last decades and gradually reach “predictive power.” Mechanical particle properties are urgently needed to calibrate DEMs which despite their great progress still rely on global parameters such as spring con- stants or coefficients of restitution. The (nano-)mechanics of particles across all length scales down to the nanoscale are highly relevant in all situations where contact mechanics of particles must be considered, i.e., in dense par- ticle flows such as fluidization, transport, and particle storage (conveying, mixing, and silos), but also in agglomeration and granulation (adhesion), size reduction by comminution (fracture), and tribology. Particular interesting new fields are additive manufacturing and 3D printing. They “promise” a revolution in industrial manufacturing based on powder technologies where excellent flowability must be combined with dense packing structures. One key question in all these applications is how the particles react to the exter- nally applied stress. Briefly, this reaction can be elastic or inelastic. However, in many cases neither the elastic properties (Young’s modulus and Poisson ratio) are known nor the inelastic properties such as yield strength or visco- plastic properties which lead to internal defects (e.g., dislocations, twinning, and shear bands). Defect characterization inside particles requires high-end scattering or electron microscopy techniques (Vieweg et al, 2012). In recent years, more and more systematic studies are published focusing on mechanical properties of small particles (Fuchs et al, 2014; Meier et al, 2009b; Paul et al, 2015; Paulick et al, 2014; Romeis et al, 2014, 2015; Sanimi et al, 2005; Tomas, 2004; and references within). Mechanical elastic and inelastic particle properties have been measured systematically in a cus- tomized nanoindentation device installed within a SEM to simultaneously obtain force–displacement information and SEM images of deformed and 17 Unified Design Strategies for Particulate Products
  • 27. broken particles (Romeis et al, 2012). Quantitative data of intrinsic particle properties (and their respective distributions) are derived with high statistical relevance from force–displacement curves of single oxide, metal, and poly- mer particles. These are related to internal structural properties of theparticles (Paul et al, 2014, 2015; Romeis et al, 2014). Figure 9 shows structure— property functions of “simple” amorphous St€ ober–Fink–Bohn (SFB) SiO2 particles (diameter 500 nm) (St€ ober et al, 1968) which were densified at various temperatures. Their internal structures including internal bond– network effects have been evaluated also by nuclear magnetic resonance (NMR) spectroscopy, Fourier-transformed infrared spectroscopy (FT-IR), and Raman spectroscopy. The as-synthesized sample (in a sol–gel process) did contain many hydroxyl and dangling bonds which gradually condensed with increasing temperature and are completely removed at 1000 °C. The last topic in this section concerns particulate surface properties. The importance of surface properties is known since a long time, e.g., in the field of colloid science. With the advent of nanotechnology, this issue is now very prominently on the agenda because of the high surface-to-volume ratio of small particles. Briefly, any technical realization of nanoparticulate products requires the careful control of interfaces (details are discussed in Section 4.2). However, since the surface roughness can influence the interaction forces by orders of magnitude, also the interactions of larger objects, for instance dur- ing adhesion and friction, are controlled by nanoscale effects (see the exam- ple on additive manufacturing in Section 4.6). Surface properties of particles are directly linked to their solubility in solvents, to their wetting properties, to their conductivity, and to their reactivity in catalysis just to mention a few of them. Conformal and nonconformal coatings on particles are used to tailor the interaction with light. The well-known and beautiful pearl luster effect pigments are based on diffraction effects such as titania-coated mica platelets. Figure 9 Distributions of (A) Young's Modulus, (B) hardness, and (C) yield pressure for 500 nm amorphous silica beads which were tempered at temperatures of 400, 800, and 1000 °C (U500S nontreated) (Romeis, 2015). Similar data have been used to predict the packing structure of silica particles as a function of size by a DEM simulation (Parteli et al, 2014). 18 Wolfgang Peukert et al.
  • 28. Nevertheless, and as discussed in more detail in Section 4.2, it is very difficult to analyze the surfaces of small particles in detail with respect to structural (e.g., roughness, steps, and kinks) and chemical properties (e.g., chemical surface moieties of the particles, adsorbed or chemisorbed layers, and surface coverage). As an example how surfaces influence particle properties, we present the case of small nanoparticles for which the surface-to-volume ratio is quite large. The coordination number of molecules and atoms at the surface of nanoparticles is reduced relative to the bulk due to the curvature of the par- ticles. This gives rise to the enhanced solubility and vapor pressure of small particles in solution and in the gas phase, respectively. This is expressed by the well-known Kelvin equation. In a similar way, the sintering kinetics of small nanoparticles is enhanced. This effect is important during gas phase synthesis of particles where a balance of coagulation and sintering kinetics defines the morphology of the aggregates which is often expressed by a fractal dimen- sion. Coagulation without any sintering typically leads to a fractal dimension of around 1.8, whereas fast sintering leads to complete coalescence, i.e., to spheres with a fractal dimension of 3. The sintering kinetics (at least for amor- phous silica particles) is enhanced relative to bulk values below a critical size of about 100 nm (Kirchhof et al, 2012). In the context of mechanical prop- erties, we could recently show that the Young’s modulus of small metal and salt particles (Armstrong and Peukert, 2012; Miesbauer et al, 2003) is reduced due to this size or surface effect, respectively (see Fig. 10). 4. PRODUCT DESIGN Five unifying principles in product design can be identified. They will be discussed in the following under a generalized view: 1. Particle formation by top-down and bottom-up approaches. 2. Interactions between the building blocks. 3. Structure formation by self-organization and by transport. 4. Characterization along the process chain. 5. Multiscale modeling and simulation Finally, an outlook on the integration of particles into devices will be provided. 4.1 Particle Formation 4.1.1 Top-Down Approaches The most common size reduction processes, comminution, emulsification, and spraying, share several common features. Eggers and Villermaux discuss 19 Unified Design Strategies for Particulate Products
  • 29. atomization of droplets from a unifying perspective (Eggers and Villermaux, 2008). Most importantly, size reduction occurs when sufficient external energy is supplied to the particles and made available to generate new sur- face. In case of solid particles, fracture is induced by stressing of the particles by impaction or compression. The transferred energy is stored in the parti- cles as elastic energy or dissipated by viscous and/or plastic deformation lead- ing to all sorts of structural defects. Fracture occurs when the elastically stored energy is released and sufficiently high to induce crack opening. In case of fluids, shear and more importantly elongational stresses act on the 0 0.6 0.7 0.8 0.9 1 1.1 6 7 8 9 10 11 12 13 A B 5 E/E bulk 10 15 20 Particle size (nm) 25 30 35 Bulk material Cu particles Au particles Fe particles Al particles Pt particles Ag particles 0 5 10 15 20 Particle size (nm) Avg. coordination number (a.u.) Bulk bcc Bulk fcc 25 30 35 Cu particles Au particles Fe particles Al particles Pt particles Ag particles Figure 10 (A) Average coordination number of six different metal nanoparticles and (B) their average Young's modulus E with respect to the value of the bulk as obtained from molecular statics simulations. Armstrong and Peukert (2012), with kind permission from Springer Science and Business Media. 20 Wolfgang Peukert et al.
  • 30. fluid particles which in turn may be disintegrated into smaller droplets if the applied stresses are sufficiently high. Surprisingly and despite all differences between these top-down methods, the mean particles size x50 scales with the volume-specific energy input EV: x50 ¼ a EV ð Þb (4) where the parameters a and b depend on the unit operation and the type of particles (see Table 1). The minimal particle size which can be produced depends on the balance between the local stress energy and the energy required to increase the sur- face. In case of solid particles, cracks are initiated at internal particle defects due to local stress enhancement. The true grinding limit is reached when the particle cannot store anymore defects (Knieke et al, 2009). It has been shown for ZrO2 and SnO2 that this limit is reached at around 10 nm (Knieke et al, 2011). The width of the PSD depends on the spatial distribution of EV in the “reactor” volume, i.e., on the design of the mill, on the emulsifying device, or on the nozzle and the resulting multiphase flow and thus on the machine function. In summary, the slope of Eq. (4) varies in a band of the exponent b between 0.3 and 0.8 for different unit operations and materials. This indicates that unified scaling laws are valid which are based on fundamental similarities of particle formation in top-down processes. 4.1.2 Bottom-Up Methods Single particles are the building blocks of mesoscale science and technology including nanotechnology and many other fields of application as discussed Table 1 Value of Scaling Parameter b for size in Top-Down Processes Type of Unit Operation Value of Parameter b References Comminution in stirred media mills (varying sizes and operational parameters), limestone, and graphene oxide platelets 0.8 0.37 Becker et al (2001) Halbig et al (2016) Emulsification in colloid mill, homogenization, and ultrasound 0.3–0.8 Behrend et al (2000) and Schuchmann and Schubert (2001) Atomization in different spray nozzles 0.5–0.7 Walzel (1990) Ultrasound and graphene oxide platelets 0.48 Halbig et al (2016) 21 Unified Design Strategies for Particulate Products
  • 31. above. It is, however, beyond the scope of this review, to present a compre- hensive overview of particle synthesis and crystallization as several excellent books and review articles are available covering a broad range of materials. Therefore, we discuss here only a few guidelines for this important and very large field without claim to completeness. Bottom-up methods for particle synthesis in gas and liquid phase can be visualized by a unified scheme as highlighted in Fig. 11. In general, mass, momentum, and heat transfer processes coupled to chemical reactions pro- duce nucleating species. Their distribution in the reactor related to their equilibrium concentration/partial pressure (or activity/fugacity in a general sense) is defined as the supersaturation S. It is the thermodynamic driving force for the phase transition and thus for the formation of a new particle phase. Depending on the spatial and temporal distribution of S in the reac- tor, nuclei form with a size distribution q. Noteworthy, especially in the view of classical nucleation theory q strongly depends on S. For instance, a high supersaturation with narrow distribution in time and space would lead to small nuclei with narrow PSD since all particles “experience a similar history.” After nucleation, several processes may occur sequentially or in parallel. These are growth processes for further reduction of S, coagulation of the particles, their stabilization against coagulation, and finally ripening effects in the liquid phase or sintering in the gas phase. This quite general Figure 11 Principles of particle synthesis. Adapted from Peukert et al. (2003). Copyright 2003, with permission from Elsevier. 22 Wolfgang Peukert et al.
  • 32. framework forms the basis of any modeling approach for particle formation dynamics including mixing, global reaction kinetics, nucleation, growth, agglomeration and stabilization and even ripening and sintering. Detailed reaction mechanisms of conversion of precursor molecules into stable and growing nuclei may be included in this general scheme which are, however, too seldom known. Their full elucidation requires coupling of quantum mechanical methods such as density functional theory (DFT) with molecular dynamics (MD) simulations (see, e.g., Menz et al, 2011; Milek and Zahn, 2014; Zheng et al, 2009). A key challenge in this field is how to tailor reac- tion networks so that a desired target phase does form. Particle formation processes can further be subdivided into transport- and reaction-controlled processes. Typically one assumes that the synthesis in the gas phase is not controlled by any mass transfer limitations, whereas mass transfer issues are very common in liquid phase synthesis. Prior dis- cussing mixing and reaction-controlled systems in more detail, it needs to be mentioned that perfect stabilization is assumed for the time being. Effects of coagulation would completely change the PSD. In transport or mixing controlled systems, the mixing intensity deter- mines the local concentration fields and thus the supersaturation as driving force (Schwarzer and Peukert, 2002). The energy dissipation in case of a stirred tank as well as in a continuous mixer such as a T- or Y-mixer is directly related to the volume-specific energy consumption. The mixing volume will follow similar scaling laws as already discussed in Chapter 3 for the top-down processes. Higher energy dissipation will lead to succes- sively smaller eddies in the fluid until the smallest eddy size (the Kolmogoroff length scale) is reached. Mixing is shifted from macro- to meso-mixing and finally to diffusion-controlled micromixing (Baldyga and Bourne, 1999; Bockhorn et al, 2010; Fox, 2003). The reactor design determines the resi- dence time of fluid particles and the local distribution of supersaturation. Both effects will control the width of the obtained PSD, or in other words, the width of the PSD is a measure of the mixing energy distribution. The full PSD can be modeled (at least for well-understood precipitation reactions such as the formation of BaSO4) without any free parameters by a combi- nation of direct numerical simulation for complete resolution of the fluid flow structures and an appropriate mixing model for mass transfer at subgrid level on the one hand that is combined with a population balance model, on the other hand (Gradl and Peukert, 2009; Gradl et al, 2006). In reaction-controlled systems, i.e., in systems where mixing is much faster than the chemical reactions leading to precursor formation, the 23 Unified Design Strategies for Particulate Products
  • 33. Other documents randomly have different content
  • 34. Lamb of God, Who takest away the sins of the world, Have mercy on us, O Lord! Holy Ghost, hear us, Holy Ghost, graciously hear us. V. Create a clean heart in us, O God. R. And renew a right spirit within us. Let Us Pray. Grant, O merciful Father, that Thy divine Spirit may enlighten, inflame, and cleanse our hearts; that He may penetrate us with His heavenly dew, and make us fruitful in good works. Through Jesus Christ Our Lord. Amen.
  • 35. Hymns to the Holy Ghost. Veni, Creator Spiritus. Come, O Creator, Spirit blest, And in our souls take up Thy rest; Come with Thy grace and heavenly aid To fill the hearts which Thou hast made. Great Paraclete, to Thee we cry, O highest gift of God most high, O Fount of life, O Fire of love, And sweet anointing from above. [pg 359] Thou in thy sevenfold gifts art known; The finger of God's hand we own; The promise of the Father Thou, Who dost the tongue with pow'r endow. Our senses kindle from above, And make our hearts o'erflow with love; With patience firm and virtue high The weakness of our flesh supply. Drive far from us the foe we dread, And grant us Thy true peace instead; So shall we not, with Thee for guide, Turn from the path of life aside.
  • 36. Oh, may Thy grace on us bestow The Father and the Son to know, And Thee through endless times confess'd Of both th' eternal Spirit blest. All glory, while the ages run, Be to the Father and the Son Who rose from death; the same to Thee, O Holy Ghost, eternally! Amen. Come, Holy Ghost. Come, Holy Ghost, send down those beams, Which sweetly flow in silent streams From Thy bright throne above. Come, Thou, the Father of the poor, Thou bounteous source of all our store; Come, fire our hearts with love. Come, Thou, of comforters the best, Come, Thou, the soul's delightful guest, The pilgrim's sweet relief. Thou art our rest in toil and sweat, Refreshment in excessive heat, And solace in our grief. O sacred Light, shoot home Thy darts, Oh, pierce the centre of these hearts, Whose faith aspires to Thee. [pg 360] Without Thy Godhead nothing can Have any price or worth in man; Nothing can harmless be.
  • 37. Lord, wash our sinful stains away, Water from heaven our barren clay; Our wounds and bruises heal. To Thy sweet yoke our stiff necks bend, To inflame our cold hearts Thy fire send; Our wandering feet repel. Oh, grant Thy faithful, dearest Lord, Whose only hope is Thy sure word; The seven gifts of Thy Spirit. Grant us in life to obey Thy grace, Grant us in death to see Thy face; And endless joys inherit. Amen.
  • 38. Act Of Oblation To The Holy Ghost. On my knees, before the great cloud of witnesses, I offer myself, soul and body, to Thee, eternal Spirit of God. I adore the brightness of Thy purity; the unerring keenness of Thy justice; and the might of Thy love. Thou art the strength and the light of my soul. In Thee I live and move and am. I desire never to grieve Thee by unfaithfulness to grace; and I pray with all my heart to be kept from the smallest sin against Thee. Make me faithful in every thought: and grant that I may always listen to Thy voice, and watch for Thy light, and follow Thy gracious inspirations. I cling to Thee, and give myself to Thee, and ask Thee by Thy compassion to watch over me in my weakness. Holding the pierced feet of Jesus, and looking at His five wounds and trusting to His precious blood, and adoring His opened side and stricken Heart, I implore Thee, adorable Spirit, helper of my infirmity, [pg 361] so to keep me in Thy grace that I may never sin against Thee with the sin which Thou canst not forgive. Give me grace, O Holy Ghost, Spirit of the Father and the Son, to say to Thee, always and everywhere, speak, Lord, for Thy servant heareth. Amen.
  • 39. The Office of the Holy Ghost. At Matins. V. The grace of the Holy Ghost illuminate our senses and hearts. R. Amen. V. O Lord, open Thou my lips. R. And my mouth shall declare Thy praise. V. Incline unto my aid, O God. R. O Lord, make haste to help me. Glory be to the Father, and to the Son, and to the Holy Ghost. As it was in the beginning, is now, and ever shall be, world without end. Amen. Hymn. The Holy Ghost our souls invest With grace that does o'ershade the best Of Virgin maids, when from the spheres An angel came to greet her ears. The Word divine did flesh become, And fruitful made a virgin womb. Ant. Come, Holy Ghost, replenish the hearts of Thy faithful, and kindle in them the fire of Thy love. V. Send forth Thy Spirit, and they shall be created.
  • 40. R. And Thou shalt renew the face of the earth. Prayer. We beseech Thee, O Lord, that the virtue of Thy Holy Spirit may be present within us, which may both purify our hearts, and defend us from all adversities; through Our Lord Jesus Christ, Thy Son, Who with Thee and the same Holy Ghost liveth and reigneth. Amen. [pg 362] At Prime. V. The grace of, etc. (as before). Hymn. Christ, born of Mary, that blest Maid, Was crucified, was dead, was laid Within a tomb, from whence He rose, And did His person soon disclose To His disciples, in whose sight He soar'd above the starry height. The anthem, verse, response, and prayer as before. At Tierce. V. The grace of, etc. (as before). Hymn. God sent from heaven the Holy Ghost Upon the day of Pentecost; He did the apostles' minds inspire, Inflaming them with tongues of fire. He would not have them orphans left, When of the sight of Christ bereft.
  • 41. The anthem, verse, response, and prayer as before. At Sext. V. The grace of, etc. (as before). Hymn. With sevenfold grace God did enrich The apostles, then, by means of which They did both speak and understand The language of each distant land. To preach Christ's faith they then disperse Themselves throughout the universe. The anthem, verse, response, and prayer as before. At None. V. The grace of, etc. (as before). [pg 363] Hymn. The consoling Spirit He Entitled was true charity, The gift of God, a fire inflamed, The vivifying fountain named, A spiritual unction, sevenfold grace, A free gift of celestial race. The anthem, verse, response, and prayer as before. At Vespers. V. The grace of, etc. (as before). Hymn.
  • 42. The right hand finger of Our Lord, His spiritual power to us afford A safe defence against all evil, That harm'd we be not by the devil. Protect us, nourish us, and bring Us under shelter of Thy wing. The anthem, verse, response, and prayer as before. At Compline. V. The grace of, etc. (as before). V. Convert us, O God Our Saviour: R. And avert Thy anger from us. V. Incline unto my aid, O God. R. O Lord, make haste to help me. Glory be to the Father, etc. Hymn. Vouchsafe, O holy Paraclete, To pour into our souls Thy light, And to direct us in our ways, That when to judgment God shall raise The sleeping world, He bid us stand Upon His right and saving hand. The anthem, verse, response, and prayer as before. [pg 364] Commendation. These hours canonical, to Thee, O Holy Ghost, addressed be, With piously devoted heart.
  • 43. That to our souls Thou mayest impart Thy inspirations, and that we May live in heaven eternally. Amen.
  • 44. Novena to the Holy Ghost. First Day: Fruits Of Charity And Joy. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—charity and joy. Our Father, Hail Mary. O most holy Spirit, the Paraclete, we adore Thee with all humility; and with the most lively affections of our hearts, we beseech Thee to assist us in this Thy novena, that we may rightly prepare ourselves to receive Thy heavenly gifts. We cannot, O divine Spirit, receive Thee without Thine own aid preventing us. Without Thee we cannot please Thee. Do Thou then, Who didst prepare the heart of Mary to receive the Word Incarnate, vouchsafe so to dispose our hearts that we may happily conceive the blessed flames of Thy love. Amen. O let us fall and worship Him, The love of Sire and Son, The consubstantial breath of God, The co-eternal One! [pg 365] Ah! see, how like the Incarnate Word, His blessed self He lowers
  • 45. To dwell with us invisibly, And make His riches ours. Most loving Spirit! Mighty God! Sweet must Thy presence be, If loss of Jesus can be gain, So long as we have Thee! Come, Holy Spirit, fill the hearts of Thy faithful, and kindle in them the fire of Thy love. V. Send forth Thy spirit, and they shall be created. R. And Thou shalt renew the face of the earth. Burn, O Lord, with the fire of Thy Holy Spirit our reins and our hearts, that we may serve Thee with chaste bodies, and please Thee with clean hearts; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing of almighty God, the Father, Son, and Holy Ghost, descend upon us now, and abide with us always. Amen. Second Day: Fruits Of Peace And Patience. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—peace and patience. Our Father, Hail Mary. O sweetest and most dear Mother Mary, behold us at thy feet, and having kissed them a thousand times [pg 366] with the lips of our
  • 46. hearts, we humbly implore of thee a favor more needful for us than all else in the world. Since thou art the spouse of the Holy Ghost, the dispenser of His treasures, and His sweet stewardess, since thou hast been enriched beyond all other creatures with His heavenly gifts, obtain for us, as thou didst obtain for the apostles, His coming into our hearts; and for this end obtain for us the grace to imitate, so far as in us lies, the examples of thy humility, thy purity, thy charity. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. O God, to Whom every heart is open and every will speaketh, and from Whom no secrets are hid, cleanse the thoughts of our hearts by the infusion of the Holy Ghost, that we may perfectly love Thee and worthily praise Thee; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Third Day: Fruits Of Benignity And Goodness. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—benignity and goodness. Our Father, Hail Mary. Most holy prince of the apostles, blessed St. Peter, behold us at thy feet, to implore thy aid in obtaining the Holy Spirit. We, indeed, have
  • 47. been unfaithful [pg 367] to Our Redeemer, not three times only, as thou wert, but thousands and thousands of times; so that we could not hope that the spotless Dove would vouchsafe to descend into our poor souls, stained with so many sins; yet thine example, blessed apostle, gives us boldness. Thou didst weep bitterly, and with thy tears wert so cleaned as to receive all the gifts of the divine Paraclete. We too desire to bewail our sins with bitterest grief like thine, while we humbly implore thine intercession to obtain for us, first of all, cleanness of heart, and then the gift of the Holy Ghost, for which we yearn most earnestly. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. O God, Who hast taught the hearts of Thy faithful by the light of the Holy Spirit, grant us by the same Spirit to think the things that be right, and ever to rejoice in His consolations; through the same Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Fourth Day: Fruits Of Long-Suffering And Mildness. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—long-suffering and mildness. Our Father, Hail Mary.
  • 48. O blessed and happy apostles of Our Lord, who in [pg 368] the upper room did receive the Holy Spirit with such fulness that thou wert sweetly inebriated with divine love, we congratulate thee with the most humble and lively affection, and contemplate thy graces with a holy envy. We beseech thee, by that love which thou dost bear the Holy Spirit, Who thus filled thee with His special benedictions, obtain for us efficacious aid rightly to practise that brotherly concord, that continual prayer, and that tender devotion to Mary, whereby we can obtain, even as thou didst obtain, the coming of the Holy Ghost. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. May the infusion of the Holy Spirit, O Lord, purify our hearts, and by the inward sprinkling of His gracious dew make them fertile in all good works; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Fifth Day: Fruits Of Faith And Modesty. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—faith and modesty. Our Father, Hail Mary.
  • 49. O eternal Father, how shall we ever bless and praise Thee sufficiently, or thank Thy goodness as we ought? A thousand times blessed be Thine infinite [pg 369] charity, Thine infinite providence, and Thine infinite mercy, which moved Thee to repair our miseries, and to give unto us a gift wherein is contained all the good that proceedeth from Thee! Thou hast given us also the Holy Ghost, Who proceedeth from Thy will as Thine uncreated love. What can we seek for more? And what shall we give unto Thee for so great a gift? O Lord, vouchsafe, we beseech Thee, of Thy clemency to take for Thine own all our understanding, all our will, all ourselves, and that little for all eternity. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. We beseech Thee, O Lord, that the Paraclete, Who proceedeth from Thee, may enlighten our minds, and, according to the promise of Thy Son, may lead us into all truth; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Sixth Day: Fruits Of Continence And Chastity. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary, to obtain, by the merits of Jesus ascended, the fruits of the Holy Ghost—continence and chastity. Our Father, Hail Mary.
  • 50. Most holy, most divine Spirit, if there be any souls in the world more needful of Thine aid than others, it is surely ours, blinded by passions, chilled [pg 370] with obstinate lukewarmness, and defiled with a thousand imperfections. Come, then, O divine Spirit! come and enlighten us; kindle our fervor, and destroy in us all that is displeasing in Thy sight. The greater our miseries are, so much the more glorious will be Thy triumph over our perversity. Come and create in us new hearts, which shall have all for God, and nothing for the world. Create in us clean hearts, O God. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. Grant unto Thy Church, O merciful God, that she, being gathered together in the Holy Spirit, may be in no wise disturbed by the incursions of her enemies; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Seventh Day: Descent Of The Holy Ghost Upon Mary At The Annunciation. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary in honor of the descent of the Holy Ghost upon the ever-blessed Mother of God at the Annunciation. Our Father, Hail Mary.
  • 51. Most divine Spirit, the Paraclete, we hardly dare to beseech Thee to come into our souls, knowing well how sinful and defiled they are. It seems an intolerable boldness to invite God—yea, no less a one [pg 371] than God!—to be a guest in a lodging so unclean. Yet Thou vouchsafest graciously to reassure us by that infinite goodness of Thine, whereby Thou dost dispose with Thy prevenient graces those hearts which Thou dost condescend to honor with Thy presence. O blessed Spirit, deign to come into us, and delay not Thy gracious coming, while we cease not calling upon Thee and beseeching Thee to console us with Thy long-expected coming. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. We beseech Thee of Thy goodness, O Lord, to pour into our minds the Holy Spirit, by Whose wisdom we were created, and by Whose providence we are ruled; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Eighth Day: Descent Of The Holy Ghost Upon Jesus At The Jordan. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary in honor of the descent of the Holy Ghost upon Jesus at the Jordan. Our Father, Hail Mary.
  • 52. Most adorable Trinity, we venture with all humility and awe to approach the lofty throne of your exalted majesty; with our heads prostrated in the dust we adore you, and give you endless thanks for the immense blessings which you have bestowed on us [pg 372] miserable men. We thank Thee, O eternal Father, and Thee, O divine Son, for the gift which you have given us of the Holy Ghost; for in giving us this Love, Who proceedeth from you, you have given us your own selves. We thank Thee, O Holy Ghost, Who art at once the gift and the giver of all gifts, and we most earnestly beseech Thee to give us Thyself. No other gift but Thine own self can satisfy our souls, and having Thee alone we shall have all things. But what can we give Thee in exchange for so great benefits? O blessed Spirit, vouchsafe of Thy mercy to accept for all eternity all our thoughts, all our affections, and all ourselves. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. Grant, we beseech Thee, O Lord, that we may burn with that fire of the Holy Ghost which Our Lord Jesus Christ sent upon the earth, and which He desired to be vehemently enkindled; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing, etc. Ninth Day: Transfiguration And Ascension Of Our Lord, And The Manifestations Of The Holy Ghost. Veni Creator. Let us prostrate ourselves before the majesty of the most Holy Trinity, and uniting our dispositions with those of our blessed Lady and the holy apostles in the upper room at Jerusalem, let us say one Our Father and one Hail Mary in honor of the transfiguration and
  • 53. ascension of our most dear Lord and Saviour Jesus Christ, and of the ineffable [pg 373] love of the Holy Ghost in all His manifestations to His creatures. Our Father, Hail Mary. Most holy Virgin and exalted Mother of God, who wast above all creatures disposed to receive the Holy Ghost, and who didst receive Him with greater fulness than all others; dispose, we beseech thee, by thy gracious aid, our cold hearts for the approaching solemnity of Pentecost. We fly to thee, most benignant Mother of sinners, that thou mayest obtain for us a lively contrition for our sins; so that although we cannot receive the Holy Ghost, as innocent, like thyself, yet may we receive Him as true penitents, together with those Gentile penitents who received Him in the upper room. Grant this, most holy Mother, not for our merits, for we have none, but out of thine own exceeding goodness, and that great love which thou bearest to the same blessed Spirit, Who hast chosen thee for His Spouse. Amen. O let us fall and worship Him, etc. Come, Holy Spirit, etc. V. and R. Send forth Thy Spirit, etc. Grant, we beseech Thee, almighty God, that the splendor of Thy brightness may shine upon us; and that the light of Thy light may, by the illumination of the Holy Spirit, confirm the hearts of those who by grace are regenerate; through Our Lord Jesus Christ. In the unity of the same. Amen. May the blessing of almighty God, Father, Son, and Holy Ghost, descend upon us, and remain with us always. Amen.
  • 54. [pg 374] September. The Immaculate Heart of Mary. This month is generally devoted to the consideration of the Heart of Mary and her Seven Dolors. Not only should we have a special devotion to the Sacred Heart of Jesus, but there are good reasons for us to have a devotion to the heart of Mary, so full of love for us, and to her dolors in connection with the redemption of mankind. Her life was full of sorrow, because she was actuated by the same sentiments as Our Lord in His desire to redeem us from the slavery of Satan. What heart, in fact, has ever been so intimately identified with that of Jesus as was Mary's? He died on the cross, and Mary stood beneath it, faithful to the end. Our Lord, in His thirty years' ministry, labored among the people, preaching and healing the sick, and Mary was certainly in perfect sympathy with Him in His great work. We are struck with the adorable goodness of His divine Heart, and for the same reason we are attracted to the heart of Mary. We will, then, during this month of September, pray to the heart of our beloved Mother, setting before our minds the goodness of that loving heart towards her children in this vale of tears. Let us love and honor these two hearts so intimately united; let us go to God
  • 55. the Father through the Heart of Jesus: and to the divine Saviour through the heart of Mary. We can obtain all things from the Father and the Holy Ghost through the Heart of Jesus; and all things from the Son through the heart of His blessed Mother.
  • 56. Considerations and Prayers for Every Day. First Day. Nowhere in the Old Testament, do we approach God more closely than in the book of Job, where we see the great prophet of God enduring so [pg 375] patiently the many sufferings that God has permitted; and nowhere do we recognize Him as the great Father good and kind to His children as in the same book. Job was a figure of Christ. There is something very holy in suffering endured in compliance to the will of God. To-day, then, we are to begin to think of Mary's sorrowful heart, and we will contemplate how the mysterious ways of Providence, the love of God, His mercy and kindness, inflicts chastisements on the Mother of His much loved Son. In the silence of the thirty years of Christ on earth, in the silence of the hours of agony on the cross, and in the silence of Mary underneath the cross, we will see the silence of a heart filled with sorrow, which God is imposing on His children for the good of mankind. The Church sets before our minds the seven sorrows of Mary, telling us the principal causes of her great grief in the life of Jesus. Prayer. O heart of Mary, I offer, I consecrate to thee my heart! Thou shalt be the object of my veneration, love and confidence; I will pay thee my devotions every day; I will celebrate thy feasts with joy; I will proclaim thy greatness and thy goodness without ceasing. I will neglect no means of obtaining for thee the honor and the homage which are due unto thee. I will bring all the thoughts and affections
  • 57. Welcome to our website – the ideal destination for book lovers and knowledge seekers. With a mission to inspire endlessly, we offer a vast collection of books, ranging from classic literary works to specialized publications, self-development books, and children's literature. Each book is a new journey of discovery, expanding knowledge and enriching the soul of the reade Our website is not just a platform for buying books, but a bridge connecting readers to the timeless values of culture and wisdom. With an elegant, user-friendly interface and an intelligent search system, we are committed to providing a quick and convenient shopping experience. Additionally, our special promotions and home delivery services ensure that you save time and fully enjoy the joy of reading. Let us accompany you on the journey of exploring knowledge and personal growth! textbookfull.com