Silane functionalization of perfluoroether oligomers for reaction management and morphology control of two‐phase epoxy networks

Mixtures of an epoxy resin, hardener, and acid functionalized perfluoroether oligomers will readily undergo phase separation during curing. However, the conditions to bring about the growth of nuclei into microscopic particles have hitherto been found only for systems cured with anhydrides. In the present study perfluoroether oligomers were functionalized by established procedures to introduce both carboxylic acid groups and alkoxysilane groups in sites within the chain extended segments. The presence of alkoxysilane groups together with the prereaction step with an excess epoxy resin, prior to the addition of the aromatic amine hardener, induced phase separation by a nucleation‐and‐growth mechanism. The dual functionality in the perfluoroether oligomer was even more beneficial when the alkoxysilane groups were hydrolyzed prior to the addition of the amine hardener. Under such circumstances the precipitation of the perfluoroether oligomer occurred quantitatively, as indicated by the complete absence of any plasticization effects in the epoxy matrix. From electron microscopy examinations, thermal analysis, and measurements of mechanical properties it was possible to deduce a plausible mechanism for the formation of the typical core‐shell aggregates within the precipitated particles for these systems, which could also be applied to other systems, such as those using carboxylic‐acid‐terminated butadiene acrylonitrile oligomers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1036–1049, 2005     

A resilience optimization approach for workforce-inventory control dynamics under uncertainty

The presence of uncertainties in manufacturing systems and supply chains can cause undesirable behavior. Failure to account for these in the design phase can further impair the capability of systems to respond to changes effectively. In this work, we consider a dynamic workforce-inventory control problem wherein inventory planning, production releases, and workforce hiring decisions need to be made. The objective is to develop planning rules to achieve important requirements related to dynamic transient behavior when system parameters are imprecisely known. To this end, we propose a resilience optimization model for the problem and develop a novel local search procedure that combines the strengths of recent developments in robust optimization technology and small signal stability analysis of dynamic systems. A numerical case study of the problem demonstrates significant improvements of the proposed solution in controlling fluctuations and high variability found in the system’s inventory, work-in-process, and workforce levels. Overall, the proposed model is shown to be computationally efficient and effective in hedging against model uncertainties.     

Partition coefficient of diglycerides in crystallization of palm oil

Crystallization of palm oil with and without solvent was carried out over a temperature range of 10–25°C. The yields of olein, the diglyceride contents, and compositions of the stearin and olein phases were determined by thin-layer and gas-liquid chromatography. The three major diglycerides, analyzed as C₃₂, C₃₄, and C₃₆, are mainly dipalmitoyl glycerol, palmitoyloleoyl glycerol, and dioleoyl glycerol. In crystallization without solvent, C₃₂ (PP) had a strong affinity for the stearin fraction and C₃₆ diglycerides concentrated in the olein phase. The partition coefficient of diglycerides between the olein and stearin phases was temperature-dependent and was influenced by the type of solvent used. Although solvent enhances the diglyceride partition into the olein phase, partitioning is more effective at low temperatures and with acetone as the solvent for fractionation.     

Effect of water on HDS of DBT over a dispersed Mo catalyst using in situ generated hydrogen

A novel process was developed for the bitumen emulsion upgrading, wherein emulsion breaking and upgrading occurred in the same reactor using H₂ generated in situ from the water in the emulsion via the water gas shift reaction (WGSR). In this study, dibenzothiophene (DBT) was chosen as a model compound to investigate the effect of water and in situ H₂ on hydrodesulfurization (HDS). All the experiments were performed in a 1-L autoclave reactor at temperatures between 300 and 380 °C using in situ H₂ and ex situ H₂ (externally supplied H₂) over a dispersed Mo catalyst formed from phosphomolybdic acid (PMA). At very low water content, water was found to promote the HDS reaction in the ex situ H₂ run probably because it facilitates the formation of more active dispersed MoS_x species. At higher water content, however, water inhibits every individual reaction in the reaction network in the HDS of DBT, blocking the hydrogenation pathway more than the hydrogenolysis pathway. The relative reactivity of the in situ and ex situ H₂ depends on the water content present in the reaction system. At an optimized mole ratio of H₂O:CO (1.35), higher HDS activity was observed in the in situ H₂ run compared to ex situ H₂ run, and particularly, the hydrogenation pathway was promoted in the in situ H₂ run.     

Analysis of epoxidized natural rubber. A comparative study of d.s.c., n.m.r., elemental analysis and direct titration methods

A comparative analysis of epoxidized natural rubber samples by ¹H and ¹³C n.m.r., titrimetric, elemental and d.s.c. techniques has been made. Whereas the titrimetric method is only applicable at low epoxy contents (< 15 mol%) both n.m.r. methods give reasonable precision over the compositional range of 20–75 mol%. Elemental analysis appears less reliable. D.s.c. analysis through measurement of T_g provides the highest precision of measurement but requires independent calibration by one or more of the primary methods. The epoxy content may also be related to the polymer density.     

A study of the kinetics of nucleation in a palm oil melt

Nucleation from a supercooled melt of palm oil was studied by optical microscopy and differential scanning calorimetry (DSC). Despite being a multicomponent system, palm oil exhibits a rather simple cooling thermogram with its high- and low-T exotherms exclusively related to the “hard” and “soft” components of the oil. As the “hard” components are being removed, the position of the high-T peak shifts down toward the low-T peak with diminishing peak intensity, while the position of the latter remains virtually unchanged. At 288°K, nucleation in a palm oil melt is instantaneous. Its induction time-temperature curve shows an abrupt discontinuity at 297°K, which demarcates the occurrence of one polymorph from another. Nucleation data fit very well into the Fisher-Turnbull equation. Its larger activation free energy of nucleation is accompanied by lowering of the melting point and an increase in the crystal/melt interfacial free energy as compared to palm stearin. The slow rate of nucleation in palm oil is attributed to intermolecular interaction between its “hard” and “soft” components. Partly presented at the 1989 PORIM International Palm Oil Development Conference, September 5–9, Kuala Lumpur, Malaysia.     

Optimization-based cosmetic formulation: Integration of mechanistic model,surrogate model,and heuristics

Multiple functional and hard-to-quantify sensorial product attributes that can be satisfied by a large number of cosmetic ingredients are required in the design of cosmetics. To overcome this problem, a new optimization-based approach for expediting cosmetic formulation is presented. It exploits the use of a hierarchy of models in an iterative manner to refine the search for creating the highest-quality cosmetic product. First, a systematic procedure is proposed for optimization problem formulation, where the cosmetic formulation problem is defined, design variables are specified, and a set of models for sensorial perception and desired product properties are identified. Then, a solution strategy that involves iterative model adoption and two numerical techniques (i.e., generalized disjunctive programming reformulation and model substitution) is applied to improve the efficiency of solving the optimization problem and to find better solutions. The applicability of the proposed procedure and solution strategy is illustrated with a perfume formulation example.     

Influence of process parameters on the deposition footprint in plasma-spray coating

This paper presents an investigation of the influence of plasma spray process conditions on the in-flight particle behavior and their cumulative deposition to form a coating on the substrate. Three-dimensional computational fluid dynamics (CFD) analyses were performed to model the in-flight particle behavior in the plasma-spray process and their deposition on the substrate. The plasma spray was modeled as a jet issuing from the torch nozzle through the electrical heating of the arc gas. In the model, particles were injected into the plasma jet where they acquired heat and momentum from the plasma, some got melted and droplets were formed. By means of a droplet splatting model, the particle in-flight data generated by the CFD analyses were further processed to build up an imaginary three-dimensional deposition profile on a flat stationary substrate. It is found that the powder carrier gas flow rate influences the particle distribution on the substrate by imparting an injection momentum to the particles that were directed radially into the plasma jet in a direction perpendicular to the plasma jet. The larger sized particles will acquire higher injection momentum compared with the smaller sized particles. This causes particle distribution at the substrate surface that is elliptical in shape with the major axis of ellipse parallel to the particle injection port axis as illustrated in Fig. 1. Larger particles tend to congregate at the lower part of the ellipse, due to their greater momentum. The distribution of particle size, temperature, velocity, and count distribution at the substrate was analyzed. Further, based on the size and the computed particle temperature, velocity histories, and the impact sites on the substrate, the data were processed to build up a deposition profile with the Pasandideh-Fard model. The shapes of deposition profiles were found to be strongly driven by the segregation effect.     

形变诱发马氏体对1Cr18Ni9Ti不锈钢应力腐蚀破裂的影响

通过低温(-70℃)拉伸方法,制备出具有不同马氏体(铁磁相)含量的1Cr18Ni9Ti(AISI321)奥氏体不锈钢试件。采用恒载荷法对双边缺口试样进行应力腐蚀试验,测定了不同马氏体含量的试样在氯化物介质中应力腐蚀破裂(SCC)的归一化门槛值。用SEM观察断口形貌。结果表明:当铁磁相含量小于5%时,材料的SCC敏感性随含量增加而减小;在5～15%范围内,SCC敏感性不断增加;在15～24%区域中,材料的SCC敏感性迅速下降;超过24%,SCC敏感性又有所上升。