A unique grain-boundary structure evolution was observed in two MgO-doped silicon nitride specimens (Norton, NC-132) that were tested in ultra-long flexure stress rupture experiments with an applied stress of 266 MPa and fractured at 14 941 and 17 376 h. Transmission electron microscopy showed that, although the starting material had a secondary glass phase both at multi-grain junctions and along grain boundaries, the tested specimens contained no residual glass phase. Concurrent with the elimination of the secondary glass phase, a continuous network of cracked grain boundaries was observed after long-term flexure testing consistent with the concept of elastic creep. It is, therefore, concluded that at ultra-long annealing times, this material is affected by creep deformation via microcrack nucleation and growth due to the depletion of the amorphous siliceous grain-boundary phase, which is seen as a truly transient, fugitive secondary phase. 相似文献
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.
Experimental values and calculated curves for the thermal decomposition of PUR‐Et in a melt index analyser. 相似文献
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
Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA-DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only. 相似文献
Described is a reaction sequence for the total synthesis of lyso platelet activating factor (lysoPAF; 1-O-alkyl-sn-glycero-3-phosphocholine) and its enantiomer. The procedure is versatile and yields optically pure isomers of defined chain
length. The synthesis is equally suited for the preparation of lysoPAF analogues and its enantiomers with unsaturation in
the long aliphatic chain. First,rac-1(3)-O-alkylglycerol is prepared by alkylation ofrac-isopropylideneglycerol with alkyl methanesulfonate followed by acid-catalyzed removal of the ketal group. The primary hydroxy
group of alkylglycerol is then protected by tritylation, the secondary hydroxy group is acylated, and the protective trityl
group is removed under mild acidic conditions with boric acid on silicic acid, essentially without acyl migration. Condensation
of the diradylglycerol with bromoethyl dichlorophosphate in diethyl ether, hydrolysis of the resulting chloride, and nucleophilic
displacement of the bromine with trimethylamine givesrac-1-O-alkyl-2-acylglycero-3-phosphocholine in good overall yield. The racemic alkylacylglycerophosphocholine is finally treated
with snake venom phospholipase A2 (Ophiophagus hannah) which affords 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) of natural configuration in optically pure form. The “unnatural” 3-O-alkyl-2-O-acyl-sn-glycerol-1-phosphocholine enantiomer, which is not susceptible to phospholipase A2 cleavage, gives 3-O-alkyl-sn-glycero-1-phosphocholine upon deacylation with methanolic sodium hydroxide. Homogeneity and structure of the intermediates
and final products were ascertained by carbon-13 nuclear magnetic resonance spectroscopy on monomeric solutions. 相似文献
Due to the growing energy requirements, the proportion of external thermal insulation composite systems (ETICS) installed has increased significantly during the past 50 years. Due to the longevity of these systems, ETICS waste is currently accumulating. Owing to the complex construction as well as a multitude of differently installed materials and substances of the past generations, there are many uncertainties and problems with the clean and low-pollutant processing of such systems. In the frame of this work, the ETICS were processed and sorted before being screened for ingredients or pollutants as well as for the purity of the recovered material fractions. 相似文献