Entanglement networks of 1,2-polybutadiene crosslinked in states of strain. IV. States of ease and stress–strain behavior

Linear 1,2-polybutadiene, glass transition temperature (T_g) ?18°C, is crosslinked at ?10°C, to ?20°C by γ irradiation while strained in simple extension, with extension, ratios (λ₀) from 1.2 to 2.7. After release, the sample retracts to a state of ease (λ_s) at room temperature. From equilibrium stress–strain measurements up to a stretch ratio relative to the state of ease (Λ) of 1.2, together with λ₀ and λ_s, the concentration of network strands terminated by trapped entanglements (νN) is calculated. For this purpose, a three-constant Mooney–Rivlin formulation is used, in which the entanglement network is described by Mooney–Rivlin coefficients C_1N and C_2N, whereas the crosslink networks is described by the coefficient C_1x only. The ratio ψ_N = C_2N/(C_1N + C_2N) is estimated from parallel studies of nonlinear stress relaxation of the uncrosslinked polymer, taking into account the thermal history before and during irradiation. For substantial degrees of crosslinking, i.e., for R_0′ = ν_x/ν_N > 0.4 (where ν_N is the concentration of network strands terminated by crosslinks), and for λ₀ < 1.8, C_2N agrees rather well with the value obtained from stress relaxation of the uncrosslinked polymer in the range of time scale where it is nearly independent of time (1.87 X 10⁵ pascals). The corresponding value of ν_N is 2.3 × 10^?4 moles/cm³, in good agreement with that obtained from viscoelastic measurements of the uncrosslinked polymer in the plateau zone (2.5 × 10^?4). However, for R_0′ ? 0.2, smaller values of C_2N and ν_N are obtained, indicating that for low degrees of crosslinking the entanglements are not completely trapped. Also, for higher values of λ₀, C_2N and ν_N turn out to be somewhat smaller. Similar, less extensive results were obtained previously on a 1,2-polybutadiene with somewhat higher vinyl content and a higher T_g. Crosslinked samples of both these polymers were subjected to equilibrium stress–strain measurements in simple elongation from the state of ease at higher strains up to Λ = 1.7. The results agreed closely with calculations from the three-constant Mooney–Rivlin theory.     

Automated and Continuous Production of Microstructured Metallic Plates via Cold Embossing

Many critical issues need to be addressed when microstructured reactors are manufactured in large unit volumes. The most crucial of these are cost, ease of production, and reliability. The lack of breakthrough manufacturing technology to provide high‐efficiency, low‐cost, high‐precision plates is a hindrance to the early market implementation of systems requiring metallic microstructured plates. This contribution focuses on the development and optimization of a combined embossing and bending tool for the quick and continuous manufacture of easily machined plates.     

Knowledge‐Based Conceptual Synthesis of Industrial‐Scale Downstream Processes for Biochemical Products

A generic, knowledge‐based guideline assisting downstream process synthesis for biochemical products is presented. It offers process designers a structured process design methodology supporting them in capturing potentially relevant information, which might be beyond their expertise. The guideline is based on heuristic knowledge which was collected, structured in a generic way, and clearly represented. The generation of alternative downstream routes as starting points for experiments, simulation, and cost calculation is hereby accelerated. The application of the guideline is demonstrated on the example of penicillin V downstream processing from fermentation broth.     

Gb3 Glycosphingolipids with Fluorescent Oligoene Fatty Acids: Synthesis and Phase Behavior in Model Membranes

Glycosphingolipids are involved in a number of physiological and pathophysiological processes, and they serve as receptors for a variety of bacterial toxins and viruses. To investigate their function in lipid membranes, fluorescently labeled glycosphingolipids are highly desirable. Herein, a synthetic route to access Gb₃ glycosphingolipids with fluorescently labeled fatty acids, consisting of pentaene and hexaene moieties either at the terminus or in the middle of the acyl chain, has been developed. The fluorescent properties of the Gb₃ derivatives were investigated in small unilamellar vesicles composed of a raft-like mixture. Phase-separated giant unilamellar vesicles (GUVs) allowed the quantification of the apparent partitioning coefficients of the Gb₃ compounds by means of confocal fluorescence laser scanning microscopy. The determined partition coefficients demonstrate that the Gb₃ derivatives are preferentially localized in the liquid-disordered (l_d) phase. To analyze whether the compounds behave like their physiological counterparts, Cy3-labeled (Cy: cyanine) Shiga toxin B subunits (STxB) were specifically bound to Gb₃-doped GUVs. However, the protein was favorably localized in the l_d phase, in contrast to results reported for STxB bound to naturally occurring Gb₃, which is discussed in terms of the packing density of the lipids in the liquid-ordered (l_o) phase.     

Autogenous shrinkage in high-performance cement paste: An evaluation of basic mechanisms

In this paper, various mechanisms suggested to cause autogenous shrinkage are presented. The mechanisms are evaluated from the point of view of their soundness and applicability to quantitative modeling of autogenous shrinkage. The capillary tension approach is advantageous, because it has a sound mechanical and thermodynamical basis. Furthermore, this mechanism is easily applicable in a numerical model when dealing with a continuously changing microstructure. In order to test the numerical model, autogenous deformation and internal relative humidity (RH) of a Portland cement paste were measured during the first week of hardening. The isothermal heat evolution was also recorded to monitor the progress of hydration and the elastic modulus in compression was measured. RH change, degree of hydration and elastic modulus were used as input data for the calculation of autogenous deformation based on the capillary tension approach. Because a part of the RH drop in the cement paste is due to dissolved salts in the pore solution, a method is suggested to separate this effect from self-desiccation and to calculate the actual stress in the pore fluid associated with menisci formation.     

Autogenous deformation and RH-change in perspective

Autogenous deformation and change of the relative humidity (RH-change) have been described and registered for a century. However, it is only within the last decade that these phenomena have received appreciable attention. The reason for this is that autogenous deformation and autogenous RH-change are phenomena of special importance within high-strength (high-performance) concrete technology, and a significant utilisation of these concretes did not take place until the early 1980s. In the present paper an historical overview of autogenous deformation and RH-change is given. In addition, due to the present status of this research field both terminology and measuring techniques are described in detail. Finally, some expectations for future research in this field are given.     

Layered silicate nanocomposites based on various high‐functionality epoxy resins. Part II: The influence of an organoclay on the rheological behavior of epoxy prepolymers

The effect of an organically surface modified layered silicate on the viscosity of various epoxy resins of different structures and different functionalities was investigated. Steady and dynamic shear viscosities of the epoxy resins containing 0–10 Wt% of the organoclay were determined using parallel plate rheology. Viscosity results were compared with those achieved through addition of a commonly used micronsized CaCO₃ filler. It was found that changes in viscosities due to the different fillers were of the same order, since the layered silicate was only dispersed on a micron‐sized scale in the monomer (prior to reaction), as indicated by X‐ray diffraction measurements. Flow activation energies at a low frequency were determined and did not show any significant changes due to the addition of organoclay or CaCO₃. Comparison between dynamic and steady shear experiments showed good agreement for low layered silicate concentrations below 7.5 wt%, i.e. the Cox‐Merz rule can be applied. Deviations from the Cox‐Merz rule appeared at and above 10 wt%, although such deviations were only slightly above experimental error. Most resin organoclay blends were well predicted by the Power Law model, only concentrations of 10 wt% and above requiring the Herschel‐Buckley (yield stress) model to achieve better fits. Wide‐angle X‐ray measurements have shown that the epoxy resin swells the layered silicate with an increase in the interlayer distance of approximately 15 Å, and that the rheology behavior is due to the lateral, micron‐size of these swollen tactoids.     

熔盐电解精炼提纯金属硅(英文)

对熔盐电解质中硅的沉积过程进行电化学研究。在 973~223K,在硅氯化物熔盐中采用电解精炼提纯金属硅。结果表明,液态硅铜合金阳极有利于 CaCl2-NaCl-CaO-Si 熔盐体系的电解精炼。ICP-AES 分析结果显示,通过电解精炼可有效去除原料中大量的钛、铝、铁等金属杂质,硅中的硼和磷含量分别由 36×106和 25×106降低至 4.6×10 6和 2.8×10 6,电解能耗约为 9.3 kW·h/kg。     

3D Simulation of Nano-Imprint Lithography

A proof of concept study of the feasibility of fully three-dimensional (3D) time-dependent simulation of nano-imprint lithography of polymer melt, where the polymer is treated as a structured liquid, has been presented. Considering the flow physics of the polymer as a structured liquid, we have followed the line initiated by de Gennes, using a Molecular Stress Function model of the Doi and Edwards type. We have used a 3D Lagrangian Galerkin finite element methods implemented on a parallel computer architecture. In a Lagrangian techniques, the node point follows the particle movement, allowing for the movement of free surfaces or interfaces. We have extended the method to handle the dynamic movement of the contact line between the polymer melt and stamp during mold filling.     

In Vivo Analysis of the Biocompatibility and Bone Healing Capacity of a Novel Bone Grafting Material Combined with Hyaluronic Acid

The present in vivo study analyses both the inflammatory tissue reactions and the bone healing capacity of a newly developed bone substitute material (BSM) based on xenogeneic bone substitute granules combined with hyaluronate (HY) as a water-binding molecule. The results of the hyaluronate containing bone substitute material (BSM) were compared to a control xenogeneic BSM of the same chemical composition and a sham operation group up to 16 weeks post implantationem. A major focus of the study was to analyze the residual hyaluronate and its effects on the material-dependent healing behavior and the inflammatory tissue responses. The study included 63 male Wistar rats using the calvaria implantation model for 2, 8, and 16 weeks post implantationem. Established and Good Laboratory Practice (GLP)-conforming histological, histopathological, and histomorphometrical analysis methods were conducted. The results showed that the new hyaluronate containing BSM was gradually integrated within newly formed bone up to the end of the study that ended in a condition of complete bone defect healing. Thereby, no differences to the healing capacity of the control BSM were found. However, the bone formation in both groups was continuously significantly higher compared to the sham operation group. Additionally, no differences in the (inflammatory) tissue response that was analyzed via qualitative and (semi-) quantitative methods were found. Interestingly, no differences were found between the numbers of pro- and anti-inflammatory macrophages between the three study groups over the entire course of the study. No signs of the HY as a water-binding part of the BSM were histologically detectable at any of the study time points, altogether the results of the present study show that HY allows for an optimal material-associated bone tissue healing comparable to the control xenogeneic BSM. The added HY seems to be degraded within a very short time period of less than 2 weeks so that the remaining BSM granules allow for a gradual osteoconductive bone regeneration. Additionally, no differences between the inflammatory tissue reactions in both material groups and the sham operation group were found. Thus, the new hyaluronate containing xenogeneic BSM and also the control BSM have been shown to be fully biocompatible without any differences regarding bone regeneration.