China PARTICUOLOGY

Multi-scale structures involved in emulsion and microsphere complex systems are presented and discussed. The stability and spatio-temporal structures of emulsions, as well as nano-structures formed on the surface of microspheres after polymerization, are affected by the molecular emulsifier/stabilizer structures and the adsorbed emulsifier/stabilizer nano-structures on the oil/water interface. The broad size distribution and variation of surface features of droplets are responsible for variations of the adsorbed emulsifier/stabilizer structures and the stability of the emulsions. On the other hand, preparation of a uniformly sized emulsion and employment of a combined emulsifier/stabilizer system can preserve the stability of the emulsions and microspheres. The above phenomena should be modeled by a multi-scale method, in order to maintain the stability of individual emulsion systems and realize the desired nano-structures of microspheres by choosing adequate emulsifier/stabilizer and experimental parameters.

The potentials of multi-scale design that combines both nanoscale and microscale mechanisms for biocatalysis involving multiple enzymes and cofactor(s) are examined. Performance of these complex systems depends on proper interactions among the enzymes and cofactor(s). In this work, nanoparticle-based multiple enzymes and tethered cofactor are designed to stimulate such interactions. Furthermore, the nanostructures are encapsulated in microcapsules with membranes possessing pores that are comparable to the size of nanoparticles. While the nanoparticles are the "motor" driving the complex reactions inside the capsules, the nano-sized pores of the microspheres allow efficient molecular diffusion for rapid reactant supply and product removal. The microcapsules can then be used in form of packed bed or suspension reactors for large-scale industrial operations. The multi-level design provides the mechanism for matching reaction and mass transfer rates, and for optimizing the volumetric productivity. This study showcases an interesting concept which entails interactions among nanostructured multiple enzymes and cofactor, the integration of complex nano-scale catalytic structures into micro-scale and then industrial process-scale systems for long-term continuous operations.

In this paper we review our work on self-assembly of the system, poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) block copolymers, which is a kind of macromolecular complex fluids. The control of self-assembly could be obtained by adding inorganic salts or aliphatic alcohols. By self-assembly of amphiphilic block copolymers, a microemulsion phase is formed, which could be applied in micelle extraction, such as hollow-fiber membrane micelle extraction, magnetic micelle extraction and immobilized micelle extraction.

Properties of materials are determined not only by their composition, but also by their structure. It is, therefore, of great significance to develop the ability of tailoring the structure of materials according to the requirements of intended applications. In this work a novel glutamic acid-assisted hydrothermal process was developed to synthesize apatite crystals with controllable morphologies. Varied morphologies from whisk broom, fibers, mushroom, prickly spheres, to dandelion were produced through modulating both the formation of a transitory phase and its transformation into the final phase.

The advent of flat-panel displays has opened the era of macroelectronics. Enthusiasm is gathering to develop macroelectronics as a platform for many technologies, ranging from paper-like displays to thin-film solar cells, technologies that aim to address the essential societal needs for easily accessible information, renewable energy, and sustainable environment. The widespread use of these large structures will depend on their ruggedness, portability and low cost, attributes that will come from new material choices and new manufacturing processes. For example, thin-film devices on thin polymer substrates lend themselves to roll-to-roll fabrication, and impart flexibility to the products. These large structures will have diverse architectures, hybrid materials, and small features; their mechanical behavior during manufacturing and use poses significant challenges to the creation of the new technologies. This paper describes on-going work in the emerging field of research — the mechanics of macroelectronics, with emphasis on the mechanical behavior at the scale of individual features, and over a long time.

Constructal approach is a recent concept allowing to generate and optimize multi-scale structures, in particular, branching structures, connecting a microscopic world to a macroscopic one, from an engineer's point of view. Branching morphologies are found in many types of natural phenomena, and may be associated to some kind of optimization, expressing the evolutionary adaptation of natural systems to their environment. In a sense, the constructal approach tries to imitate this morphogenesis while short-cutting the trial-and-error of nature.

The basic ideas underlying the constructal concept and methodology are illustrated here by the examples of fluid distribution to a multi-channel reactor, and of the design of a porous material and system for gas adsorption and storage. In usual constructal theory, a tree branching is postulated for the channels or flow-paths or conductors, usually a dichotomic tree (every branch is divided into two "daughters"). The objective function of the optimization is built from the resistances to mass or heat transport, expressed here as "characteristic transport times", and the geometric result is expressed as a shape factor of a domain. The optimized shape expresses the compromise between the mass or heat transport characteristics at adjacent scales. Under suitable assumptions, simple analytical scaling laws are found, which relate the geometric and transport properties of different scales.

Some challenging geometric problems may arise when applying the constructal approach to practical situations where strong geometric constraints exist. The search for analytical solutions imposes simplifying assumptions which may be at fault, calling for less constraining approaches, for example making only weak assumptions on the branching structure. Some of these challenges are brought forward along this text.

Protein expression in E. coli often results in the formation of a kind of protein aggregate called inclusion body. Conversion of the inactive protein aggregate into biologically active protein is a key step in production of recombinant products. Conventional dilution refolding technique suffers from disadvantages of low recovery and low concentration. Various chromatographic refolding techniques have been developed over the last few years. These include size-exclusion chromatography, ion exchange chromatography, hydrophobic interaction chromatography and different affinity chromatography. A successful strategy is the use of gradient elution in column control which provides a gentle and gradual change of the solution environment for the macromolecule to refold at nano-scale. The gradient refolding at column scale could minimize misfolding and aggregation which are induced by sudden change of the solution in conventional refolding operation.

In this mini-review, the complexity of protein fractionation using ultrafiltration is discussed. The coupling of the system hydrodynamics, boundary layer transport, membrane permeation, electrostatic and hydrophobic interactions and its effects on protein transmission and membrane selectivity are analysed. Although ultrafiltration is promising for larger scale protein purification and also with outstanding advantages both technically and economically, much needs to be done to derive the general guidance for membrane selection, process design and system operation. With fine tuning of operational and physiochemical conditions, the process can be greatly improved in terms of process productivity and protein purity. A coupled multi-scale approach might provide a way forward to analyse this complex system and improve the confidence in applying such a promising technology and predictability of the outcome.

More and more biomolecules are being produced by the biotechnology industry for applications ranging from medicine and food to engineering materials. Liquid chromatography plays a center-stage role in a typical downstream process producing biomolecules such as recombinant proteins. Rigid gigaporous media are porous particles possessing large transecting through-pores with a pore-to-particle diameter ratio of d_pore/d_particle > 0.01. They allow convective flow in the large through-pores, while the smaller diffusion-pores (typically several hundred angstroms in size) supply the needed surface areas. Because of the transecting gigapores, a portion of the mobile phase flows through the pores in addition to fluid flow in the interstitial spaces between the particles in a packed-bed column. This considerably lowers the operating column pressure drop. This lower pressure drop makes axial-direction scale-up of chromatographic columns possible to avoid pancake columns that invariably degrade separation resolution. The large gigapores also make the binding sites on the diffusion pore surfaces more accessible, thus increasing the loading capacity of large protein molecules that can be hindered sterically if only diffusion pores are present. This work discusses the development of rigid gigaporous media and their potential impact on the design of multi-stage downstream process from the angle of multi-scale analysis.

This paper analyses three popular methods simulating granular flow at different time and length scales: discrete element method (DEM), averaging method and viscous, elastic-plastic continuum model. The theoretical models of these methods and their applications to hopper flows are discussed. It is shown that DEM is an effective method to study the fundamentals of granular flow at a particle or microscopic scale. By use of the continuum approach, granular flow can also be described at a continuum or macroscopic scale. Macroscopic quantities such as velocity and stress can be obtained by use of such computational method as FEM. However, this approach depends on the constitutive relationship of materials and ignores the effect of microscopic structure of granular flow. The combined approach of DEM and averaging method can overcome this problem. The approach takes into account the discrete nature of granular materials and does not require any global assumption and thus allows a better understanding of the fundamental mechanisms of granular flow. However, it is difficult to adapt this approach to process modelling because of the limited number of particles which can be handled with the present computational capacity, and the difficulty in handling non-spherical particles. Further work is needed to develop an appropriate approach to overcome these problems.

Prediction of particle transport in enclosed environment is crucial to the welfare of its occupants. The prediction requires not only a reliable particle model but also an accurate flow model. This paper introduces two categories of flow models — Reynolds Averaged Navier-Stokes equation modeling (RANS modeling) and Large Eddy Simulation (LES); as well as two popular particle models — Lagrangian and Eulerian methods. The computed distributions of air velocity, air temperature, and tracer-gas concentration in a ventilated room by the RANS modeling and LES agreed reasonably with the experimental data from the literature. The two flow models gave similar prediction accuracy. Both the Lagrangian and Eulerian methods were applied to predict particle transport in a room. Again, the computed results were in reasonable agreement with the experimental data obtained in an environmental chamber. The performance of the two methods was nearly identical. Finally the flow and particle models were applied to study particle dispersion in a Boeing 767 cabin and in a small building with six rooms. The computed results look plausible.

A computational fluid dynamic model is established for a coking process analysis of a coke oven using PHOENICS CFD package. The model simultaneously calculates the transient composition, temperatures of the gas and the solid phases, velocity of the gas phase and porosity and density of the semi-coke phase. Numerical simulation is illustrated in predicting the evolution of volatile gases, gas flow paths, profiles of density, porosity of the coke oven charge, profiles of temperatures of the coke oven gas and the semi-coke bed. On the basis of above modeling, the flow of coke oven gas (COG) blown from the bottom of the coke oven into the porous semi-coke bed is simulated to reveal whether or not and when the blown COG can uniformly flow through the porous semi-coke bed for the purpose of desulfurizing the semi-coke by recycling the COG. The simulation results show that the blown COG can uniformly flow through the semi-coke bed only after the temperature at the center of the semi-coke bed has risen to above 900 °C.

Mesoporous silica was prepared using tetrathoxysilane (TEOS), cetadecyltrimethylammonium bromide (CTAB), aqueous ammonia, acetone and water as silica source, template agent, precipitator and solvent respectively. Stearic acid and polyvinylpyrrolidone (PVP) were employed as additional templates to tailor the pore size in the resultant porous silica. BET, SAXRD and SEM analyses were used to characterize the surface area, pore size, pore structure, pore regularity and morphology of the sample. BET measurement results showed that PVP could increase the surface area but diminish the pore size while stearic acid could decrease the surface area but enlarge the pore size. SAXRD analysis indicated that more additional template introduction gave rise to less order-structured products. All these various results could be attributed to the differently modified CTAB micelles involving stearic acid and PVP addition.

Catalyst and catalytic process technology has been an ever-growing field that involves chemical engineering, chemistry, and material science. A number of excellent review articles and books have been published on the subject. In this work, the author reviews the evolution and development of catalyst products with multi-scale methodology. The catalyst technologies are classified into three levels, macro-scale (reactor size), mini- and micro-scale (catalyst unit), and nano-scale (catalyst intrinsic structures). Innovation at different scales requires different sets of expertise, method, and knowledge. Specific examples of significant impact to practical application are used to illustrate technology development at each scale. The multi-scale analysis enables clear delineation of technology components and their relationship for a catalyst product and catalytic process. Manipulation of catalyst structures at nano-scale to increase intrinsic activity and/or selectivity is considered of large potential for future catalyst product development. Recent research results on Cu-CeO₂ and Au-CeO₂ composite catalysts for air pollution control and hydrogen production are used to show how novel catalytic properties can be discovered by unique combination of different but common materials at the nano-scale.

Electrostatic charges are generated by particle-wall, particle-particle and particle-gas contacts in gas-solids transport lines and fluidized bed reactors. High particle charge densities can lead to particle agglomeration, particle segregation, fouling of reactor walls and internals, leading to undesirable by-product and premature shut-down of processing equipment. In this paper, the charge generation, dissipation and segregation mechanisms are examined based on literature data and recent experimental findings in our laboratory. The particle-wall contact charging is found to be the dominant charge generation mechanism for gas-solids pneumatic transport lines, while bipolar charging due to intimate particle-particle contact is believed to be the dominant charge generation mechanism in gas fluidized beds. Such a bipolar charging mechanism is also supported by the segregation patterns of charged particles in fluidized beds in which highly charged particles tend to concentrate in the bubble wake and drift region behind rising bubbles.