Phase behavior,density, and crystallization of polyethylene in n‐pentane and in n‐pentane/CO2 at high pressures

The phase behavior and volumetric properties of polyethylene (PE) in solutions of n‐pentane and n‐pentane/CO₂ were studied in a temperature (T) range of 370–440 K at pressures up to 60 MPa. Measurements were conducted with a variable‐volume view‐cell system equipped with optical sensors to monitor the changes in the transmitted light intensity as the P or the T of the system was changed. Lower‐critical‐solution‐temperature‐type behavior was observed for all of the liquid–liquid (L–L) phase boundaries, which shifted to higher pressures in solutions containing CO₂. The solid–fluid (S–F) phase boundaries were investigated over a P range of 8–54 MPa and took place in a narrow T range, from 374 to 378 K in this P interval. The S–F phase boundary showed a unique feature in that the demixing temperatures showed both increasing and decreasing trends with P depending on the P range. This was observed in both the PE/n‐pentane and PE/n‐pentane/CO₂ mixtures. The density of these solutions were measured as a function of P at selected temperatures or as a function of T at selected pressures that corresponded to the paths followed in approaching the phase boundaries (S–F or L–L) starting from a homogeneous one‐phase condition. The data showed a smooth variation of the overall mixture density along these paths. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2201–2209, 2003     

石膏转化制硫酸钾结晶动力学及结晶添加剂研究

研究了浓氨介质中石膏与氯化钾直接转化制硫酸钾的结晶动力学及结晶添加剂的作用效果。结果表明 ,硫酸钾在氨介质中的成核速率与晶体生长速率、悬浮密度、搅拌速率存在如下关联式 :B0 =5 .64 13×10 8G3.32 0 8Mt0 .0 559np0 .2 92 8。加入异丙醇、OP乳化剂及十二烷基苯磺酸钠等添加剂 ,可使硫酸钾结晶产品纯度提高 ,晶体形态整齐均匀     

Clarification of a wheat straw‐derived medium with ion‐exchange resins for xylitol crystallization

BACKGROUND: Xylitol bioproduction from lignocellulosic residues comprises hydrolysis of the hemicellulose, detoxification of the hydrolysate, bioconversion of the xylose, and recovery of xylitol from the fermented hydrolysate. There are relatively few reports on xylitol recovery from fermented media. In the present study, ion‐exchange resins were used to clarify a fermented wheat straw hemicellulosic hydrolysate, which was then vacuum‐concentrated and submitted to cooling in the presence of ethanol for xylitol crystallization. RESULTS: Sequential adsorption into two anion‐exchange resins (A‐860S and A‐500PS) promoted considerable reductions in the content of soluble by‐products (up to 97.5%) and in medium coloration (99.5%). Vacuum concentration led to a dark‐colored viscous solution that inhibited xylitol crystallization. This inhibition could be overcome by mixing the concentrated medium with a commercial xylitol solution. Such a strategy led to xylitol crystals with up to 95.9% purity. The crystallization yield (43.5%) was close to that observed when using commercial xylitol solution (51.4%). CONCLUSION: The experimental data demonstrate the feasibility of using ion‐exchange resins followed by cooling in the presence of ethanol as a strategy to promote the fast recovery and purification of xylitol from hemicellulose‐derived fermentation media. Copyright © 2008 Society of Chemical Industry     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry     

Model Validation for Bridge-Road-Vehicle Dynamic Interaction System

The dynamic response of highway bridges subjected to moving truckloads has been observed to be dependent on (1) dynamic characteristics of the bridge; (2) truck configuration, speed, and lane position on the bridge; and (3) road surface roughness profile of the bridge and its approach. Historically, truckloads were measured to determine the load spectra for girder bridges. However, truckload measurements are either made for a short period of time [for example, weigh-in-motion (WIM) data] or are statistically biased (for example, weigh stations) and cost prohibitive. The objective of this paper is to present results of a 3D computer-based model for the simulation of multiple trucks on girder bridges. The model is based on the grillage approach and is applied to four steel girder bridges tested under normal truck traffic. Actual truckload data collected using a discrete bridge WIM system are used in the model. The data include axle loads, truck gross weight, axle configuration, and statistical data on multiple presence (side by side or following). The results are presented as a function of the static and dynamic stresses in each girder and compared with code provisions for dynamic load factor. The study provides an alternate method for the development of live-load models for bridge design and evaluation.     

真空制盐蒸发结晶器的设计与实践

真空蒸发制盐外热式强制逆循环轴向出料蒸发结晶器，经多个厂家生产应用实践证明是成功的，具有生命力的。这种新型结构，作为一项新技术新设备应加强研究，总结提高，推广应用。不断完善。文章从流体力学、结晶机理角度要求，到具体工程设计参数和材质选用。论述了该罐的特点。     

Dynamic vulcanisation of EPDM/PE-based thermoplastic vulcanisates studied along the extruder axis

Simple blending and dynamic vulcanisation of EPDM/PE blends using the resol/SnCl₂ system was studied in an extruder using a series of sampling devices. The melting of the PE pellets occurs just in front of and in the first kneading zone. Upon complete melting of the PE phase, the EPDM/PE blends reach very quickly their final morphology. Crosslinking of the EPDM phase to high levels occurs already when the PE phase is not yet fully molten. The higher the EPDM content, the higher the viscous dissipation, the higher the melt temperature and, consequently, the higher the crosslinking rate. For the EPDM/PE (50/50; w/w) TPV a transition from continuous via co-continuous to fully dispersed EPDM is observed, which is driven by crosslinking. Although the degree of crosslinking of the EPDM rubber is very high, this does not prevent phase inversion of the blend. The EPDM/PE interface is rather blurred, because PE crystalline lamellae are growing into the EPDM domains, probably because of the high compatibility between PE and EPDM (60 wt% of ethene). This study shows that dynamic vulcanisation in extruders proceeds quite differently from that in batch kneaders, where melting, mixing and crosslinking are separated in time. In extruders mass and heat transport, melting of the thermoplastic, morphology development (including dispersion and phase inversion), distribution and dissolution of (crosslinking) chemicals and crosslinking of the rubber do not occur as independent phenomena, but mutually and/or continuously interact.     

Prediction and quality control of the melt index during production of high-density polyethylene

In polyolefin processes the melt index (MI) is the most important control variable indicating product quality. Because of the difficulty in the on-line measurement of MI, a lot of MI estimation and correlation methods have been proposed. In this work a new dynamic MI estimation scheme is developed based on system identification techniques. The empirical MI estimation equation proposed in the present study is derived from the 1 ^st -order dynamic models. Effectiveness of the present estimation scheme was illustrated by numerical simulations based on plant operation data including grade change operations in high density polyethylene (HDPE) processes. From the comparisons with other estimation methods it was found that the proposed estimation scheme showed better performance in MI predictions. The virtual sensor model developed based on the estimation scheme was combined with the virtual on-line analyzer (VOA) to give a quality control system to be implemented in the actual HDPE plant. From the application of the present control system, significant reduction of transition time and the amount of off-spec during grade changes was achieved     

Phase behavior in liquid crystallization for diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components

Phase behavior in liquid crystallization was studied for a series of liquid crystalline (LC) diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components, poly(n-butyl acrylate) (PBA) and poly[11-(4′-cyanophenyl-4″-phenoxy)undecyl acrylate] (PLC), respectively, using a time-resolved small-angle X-ray scattering (SAXS) techniques, DSC and polarized optical microscopy (POM). The block copolymers used had three kinds of copolymer compositions, 44, 20 and 15 wt% of PLC compositions (BLC44, BLC20 and BLC15, respectively). BLC44 showed a smectic liquid crystalline structure. In the process of liquid crystallization for BLC44, the SAXS peak due to the microphase separation structure existing before liquid crystallization was changed continuously to be at a smaller angular side, and at almost the same time, a new peak appeared at a further smaller angular side and developed. The former peak disappeared with the development of liquid crystallization. The behavior of these SAXS peaks suggests that the microphase separation structure was changed discretely at the transition from isotropic to smectic and that two phases coexist in the early stage of the liquid crystallization. The coexistence of two peaks in the early stage of the liquid crystallization corresponded to the POM observation. In the isotropization process, coexistence of two phases was not observed. For BLC20 exhibiting a cylindrical structure in both isotropic and liquid crystalline states, the liquid crystalline structure was not smectic but probably nematic, and the spacing was changed continuously in liquid crystallization. No liquid crystallization was observed in SAXS, POM and DSC for BLC15. The orientation of smectic layers within lamellar domains was investigated using 2D-SAXS images. The smectic layer was aligned perpendicularly to the lamellar interface.