CO2‐assisted polymer processing: A new alternative for intractable polymers

CO₂‐assisted polymer processing is proposed as an alternative route for intractable and high molecular weight polymers based on the plasticization effects of CO₂ and its direct effect on the melting behavior of semicrystalline polymers. A modified processing system was used to process a variety of polymers in the presence of high‐pressure CO₂. The system includes an extruder that was modified to allow for high pressures created by the injection of CO₂. The new design includes a modified feed section that allows a given mass of polymer to interact with CO₂ before and during the extrusion process. The inherent shear mixing and the presence of CO₂ allow for a specific control over the extrudate morphology. Results suggest that this alternative design provides a new and easy route to melt process high melt viscosity polymers of commercial importance, such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), and syndiotactic polystyrene (s‐PS). The increased processability of these systems in CO₂ is related to the plasticization effect of CO₂ that was quantified through a depression in the glass‐transition temperature according to the Chow model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1501–1511, 2004     

Carbonization and liquid crystal (mesophase) development. 14. Co-carbonization of coals with A240 Ashland petroleum pitch: effects of conditions of carbonization upon optical textures of resultant cokes

This study examines the effect of pitch concentration, rate of heating, soak temperature and time of soak upon the optical texture of cokes prepared from the co-carbonizations of a coal (Oxcroft-Clowne, NCB Rank 802) and three vitrains of NCB Rank 204, 801, 902 with Ashland A240 petroleum pitch. Using the coal (Rank 802) with 10 wt % and 25 wt % additions of pitch caused progressive penetration of the pitch into the coal with a resultant development of a mozaic anisotropy in the coke to replace partially the original coke isotropy. With 50 wt % addition of pitch almost all of the coal particles, 600 to 1100 μm in size, were modified during carbonization. Some pitch coke was formed. For the coal and three vitrains with increasing rates of co-carbonization from 0.5–10 K min^?1 to 1200 K, using 25 wt % of A240 pitch, resultant cokes showed progressively increased extents of modification. For the two vitrains (Rank 801, 902) soaking at temperatures of 650–690 K caused a decrease in the extent of modification of isotropic coke when compared with the coke of HTT 1200 K. Evidently fast heating rates create the conditions of fluidity necessary for the pitch to modify the coal leading to growth of mesophase and anisotropic coke.     

Estimation of impact forces during multi-point collisions involving small deformations

Multibody System Dynamics - Collision between hard objects causes abrupt changes in the velocities of the system, which are characterized by very large contact forces over very small time...     

Hot isostatic pressed pyrochlore glass-ceramics: Revealing structure insides at the reaction interface

As potential waste forms for immobilizing actinide-rich radioactive wastes, Eu₂Ti₂O₇ (Eu as a surrogate for minor actinides) pyrochlore glass-ceramics were fabricated via hot isostatic pressing (HIPing) at 1200°C. The structure and microstructure at the reaction interface between the glass-ceramic waste form and the stainless steel (SS) canister under HIPing conditions were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and synchrotron single crystal X-ray diffraction (SC-XRD). The interactions at the reaction interface led to the formations of a ~10-µm-thick Cr₂O₃ layer as the oxidation front of the SS and a layer of a mixed oxide phase (Eu_1.25SiCr_0.8Ti_1.2O_7.5) on the glass-ceramic side of the reaction interface. The crystal structure of such a unique mixed oxide phase was revealed indubitably with a combination of synchrotron SC-XRD and TEM assisted with a focused ion beam (FIB) SEM system. The improved structural understanding of the reaction interface will help to support the utilization of HIPing as a versatile hot consolidation process for the treatment of radioactive wastes.     

Simple approach for the plasma treatment of polymeric membranes and investigation of the aging effect

The modification of the surface characteristics after treatment with plasma in polymeric materials, such as the aging phenomenon, calls the attention of research in the area of nonthermal plasma technology. In this work, a direct treatment with dielectric-barrier discharge plasma was used on the surfaces of ultrafiltration membranes. The measurements of the contact angle with water, attenuated total reflectance accessory, zeta potential, atomic force microscopy and scanning electron microscopy-MEV were performed on the surfaces to verify changes after plasma treatment and to understand the occurrence and timing of the plasma aging effect. In the analysis of the membrane performance, hydraulic permeation and protein retention tests were performed. The results showed an improvement in wettability and hydrophilic properties in the post-treated membranes. The study of reversibility/aging of the post-plasma surface is important for research that deals with the modification of polymeric membranes. Changes in surface morphology, topography and wettability of the membranes were observed up to seven days after treatment, with a tendency to return to the initial characteristics of the membranes.     

Upcycling by grafting onto semi-crystalline polymers using supercritical CO2

The creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer in supercritical CO₂ is demonstrated herein. The graft copolymer is synthesized by free radical polymerization of a vinyl monomer within the semi-crystalline polymer below its melt temperature. Such conditions afford selective grafting on the amorphous regions (block “B”) while leaving the crystalline domains (block “A”) unmodified. Accordingly, unique A-B, A-B-A, A-B-A-B-A, and so forth. block structures are formed. In this work, styrene is polymerized within polyamide 6, polyethylene terephthalate, and isotactic polypropylene. Purification of these material is performed to remove the un-grafted homopolymer, allowing for determination of the graft yield, the portion of polymer which covalently bonds to the semi-crystalline matrix. Grafting yields achieved in polyamide 6, polyethylene terephthalate, and isotactic polypropylene were 98%, 59%, and 15%, respectively. Property enhancements were observed upon further characterization of polystyrene-polyamide 6 copolymers, including high glass transition temperatures, the ability to be remelted, and tunable grafting molecular weight. Additionally, hydrophobicity is controlled by varying polystyrene composition. The remarkable range of accessed properties demonstrates this as a potential route to upcycling plastics.     

ZnO／Ag纳米复合材料光催化性能研究

通过XRD、TEM测试研究了自制ZnO／Ag纳米复合材料的结构和形貌，通过UV检测确定了以该纳米复合材料为光催化剂，在不同条件下对甲基橙的光催化降解率。结果表明：与空气煅烧相比，真空煅烧所得纳米复合材料的光催化降解效果更好，且光催化降解率随纳米复合材料用量增加而增大：甲基橙溶液的pH在5左右时，光催化降解率最高：H2O2浓度为0．9g／L时，光催化降解率可达100％。     

Impact of transient chemistry on the corrosion potential of a steam turbine disc steel

The adoption of two-shifting in coal-fired power generation (switching from on-load to off-load conditions on a daily basis and off-load for the weekend) results in regular cycling of the solution chemistry of the condensed steam on the turbine discs. A first stage investigation has been made of the effect of such chemistry cycling on the corrosion potential of the disc steel. The corrosion potential is typically about +0.05 V (SCE) in off-load chemistry (aerated pure water) and below −0.6 V (SCE) in on-load chemistry (deaerated solution containing chloride or chloride and sulphate anions). The critical observation was the sluggish response of the corrosion potential upon restoration of deaerated on-load conditions with the implication of a likely increase in pit and stress corrosion crack development.     

Numerical modeling of high-temperature corrosion processes

Numerical modeling of the diffusional transport associated with high-temperature corrosion processes is reviewed. These corrosion processes include external scale formation and internal subscale formation during oxidation, coating degradation by oxidation and substrate interdiffusion, carburization, sulfidation and nitridation. The studies that are reviewed cover such complexities as concentration-dependent diffusivities, cross-term effects in ternary alloys, and internal precipitation where several compounds of the same element may form (e.g., carbides of Cr) or several compounds exist simultaneously (e.g., carbides containing varying amounts of Ni, Cr, Fe or Mo). In addition, the studies involve a variety of boundary conditions that vary with time and temperature. Finite-difference (F-D) techniques have been applied almost exclusively to model either the solute or corrodant transport in each of these studies. Hence, the paper first reviews the use of F-D techniques to develop solutions to the diffusion equations with various boundary conditions appropriate to high-temperature corrosion processes. The bulk of the paper then reviews various F-D modeling studies of diffusional transport associated with high-temperature corrosion.     

工艺参数对合成ZnO／Ag纳米复合抗菌剂产率的影响

通过正交实验，研究了反应温度、反应时间、反应物配比对ZnO／Ag纳米复合抗菌剂合成产率的影响规律。获得了高产率合成ZnO／Ag纳米复合抗菌剂的优选工艺条件：反应温度为10～25℃，ZnSO4与NH4HCO3的摩尔比为1：2-2．5，ZnSO4与NH4HCO3的反应时间为2．5～3h，AgNO3与NH4HCO3的摩尔比为1：1．5～2，反应时间为0．5h，ZnO／Ag的产率超过98％。XRD、TEM和SAED结果表明：ZnO／Ag纳米复合抗菌剂为具有纤锌矿结构的ZnO和立方结构的Ag组成。粒径为15～25nm，分散性较好。