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41.
The effect of specific β‐nucleation on morphology and mechanical behavior of isotactic polypropylene
The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002 相似文献
42.
Starlike macromers were prepared from hydroxypropyl organosolv lignin by reaction with propylene oxide, and they were analyzed by a combination of conventional analysis techniques. The average number of arms per macromer was controlled by partial capping with an alkoxy group; and the average length of arms by the degree of chain extension with propylene oxide. Analysis methods included treatment with hydriodic acid followed by gas chromatographic separation of alkyl iodides (HI/GC), UV spectroscopy, H-NMR spectroscopy, and thermal analysis. The results were consistent with a hypothetical pentameric model structure having between two and six radiating arms, each with a length of between 1 and 4 propylene oxide units. The UV method was best qualified to determine degree of chain extension, while HI/GC was best suited for analyzing average number of arms per macromer fragment. The synthesis and analysis of starlike macromers from lignin is viewed as an important stepping stone for the formulation of lignin-based engineering plastics and multiphase materials. 相似文献
43.
A series of polyurethane (PU) films was prepared from chain-extended hydroxypropyl lignins (CEHPL). In appearance, these films ranged from brittle and dark brown to rubbery and bronze. The thermal, mechanical, and network properties of these PUs were investigated by DMTA and DSC analysis. All films exhibited single Tg's which varied between ?53° and 101°C, depending on lignin content. From swelling experiments, molecular weight between crosslinks (M c) was determined and found to vary over 2.5 orders of magnitude. The M c's were related to the change in Tg that accompanied network formation. Stress–strain experiments showed a variation in Young's modulus between 7 and 1300 MPa. Most of the variation in material properties was related to lignin content and to a lesser extent to diisocyanate type, hexamethylene diisocyanate, or toluene diisocyanate. The source of the CEHPL had no effect on the observed properties. From these results it was concluded that the properties of PUs can be controlled and engineered for a wide variety of practical uses. 相似文献
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Elastomer materials are used in a wide application range and subjected to different loading from which failure of the material results. Because this failure is caused by initiation and propagation of cracks, the application of fracture mechanics methods for the assessment of the material is obvious. A short summary of the methods of technical fracture mechanics including possibilities of determination of crack resistance curves is given. Vulcanizates on the basis of SBR 1500 with various sulfur and carbon black contents were investigated. For describing the crack initiation and crack propagation behavior, several fracture mechanics examination methods were applied. Tear‐analyzer results were used to assess the crack propagation behavior under fatigue‐like loading conditions. Furthermore, for the characterization of the crack resistance of the materials under impact‐like loading conditions, instrumented tensile‐impact tests were performed. To obtain information about the initiation and propagation of a stable crack, quasi‐static fracture mechanics tests were applied. The results of the several tests are discussed in dependence on sulfur and carbon black contents. We found a non‐monotonous behavior of the toughness as a function of carbon black loading. An explanation is given in connection with a percolation‐like transition in filler morphology on larger length scales.
46.
Wolfgang Knoll Mieko Matsuzawa Andreas Offenhäusser Jürgen Rühe 《Israel journal of chemistry》1996,36(4):357-369
Various strategies are described for the bio-functionalization of solid substrates by design of interfacial architectures. The first approach is based on the self-assembly process of long-chain thiol molecules from solution to a (noble) metal surface. If some of these building blocks carry a binding site (ligand) for proteins (receptors, antibodies, etc.) the metal surface can be tailored for maximum specific binding while simultaneously minimizing nonspecific adsorption. The second concept is based on polymers that are covalently attached to (oxide) surfaces. The preparation of these (end-) grafted functional polymers involves either the binding of preformed macromolecules to corresponding sites at the surface of the support or the recently introduced “grafting-from” method, by which an initiator molecule is first covalently bound to the surface and then activated — either by heat or light — in the presence of suitable monomer units such that a polymer chain grows from the solid/solution interface. Finally, the functionalization of patterned surfaces by peptide chains that mimic the binding domains of cell adhesion proteins is summarized. It is demonstrated that not only the selective adhesion of neuronal cells can then be controlled, but also their development with the outgrowth of dendrites and axons. 相似文献
47.
A theoretical approach to the kinetics of the thermal decomposition of molten thermoplastic polyurethane elastomers, under conditions of thermoplastic processing, is described. On the basis of these considerations, the thermal decomposition in different instruments (melt index analyser and measuring extruder) can be described quantitatively and the various results can be compared. As a result, identical conditions of decomposition of the melt can be defined accurately, thus opening up the possibility of combining experimental values from different instruments. The fundamental kinetic equation obtained for the kinetics of the thermal decomposition of thermoplastic polyurethanes describes the decomposition reaction and the reverse reaction (formation reaction) – which is dependent on the system of measurement and processing – as a function of the molar mass (end‐group concentration) of the original product, determined from the velocity constants for the decomposition reaction and back reaction. The consideration of the limiting value for t → ∞ is in agreement with the equilibrium constant. Consequently, the development of physical characteristic functions of thermoplastic polyurethane elastomers – independent of the system of measurement – is possible.
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50.
Vasudev P. Saraf Wolfgang G. Glasser Garth L. Wilkes James E. McGrath 《应用聚合物科学杂志》1985,30(5):2207-2224
Hydroxypropyl lignin-based thermosetting polyurethanes were synthesized with excess hexamethylene diisocyanate (HDI) and tolylene diisocyanate (TDI) by solution casting. Four polyethylene glycols (PEG) of molecular weight 400, 600, 1000, and 4000 were mixed with lignin polyol to incorporate different proportions of soft segment into the network prior to crosslinking. Neither thermal nor mechanical and limited small angle x-ray scattering (SAXS) analysis provided distinct evidence for phase separation and microstructure formation. The study examines the effect of the soft segment in relation to chain length and weight contribution on the thermal and mechanical properties of the final networks. A significant sensitivity of glass transition temperature (Tg), of swelling in DMF, and of the mechanical properties to soft segment content was observed. Some of this sensitivity must, however, be attributed to differences in crosslink density since the polyol to diisocyanate weight ratio was kept constant throughout the synthesis series. The magnitude of the change of the different properties was found to be influenced by both glycol content and glycol molecular weight. The Tg of the network decreased from 105°C to as low as 38°C (HDI), and from 158°C to 70°C (TDI), with incorporation of up to 17.8% glycol, and it was greater with lower molecular weight glycols than with higher ones at any weight fraction. Swelling in DMF increased as expected with soft segment content. Mechanical properties were affected most if HDI and lower molecular weight glycols were used. The uniformity in structure, reduction in brittleness, and considerable improvement in mechanical properties with inclusion of minor PEG contents indicates that lignin-based network polyurethanes can be synthesized with controllable performance characteristics. 相似文献