ZnS bubble clusters with onion-like structures

Following recent studies which showed that the most stable structures for (ZnS)(n) clusters (n= 10-47) are the so-called "bubble clusters", in which all the atoms are three-coordinated, we have used simulated annealing techniques to find the most stable structure for a larger cluster, (ZnS)(60). We find an onion-like structure, with one small cluster enclosed inside a bigger one. The inner cluster has the structure of a sodalite cage. Bonding between the inner and the outer clusters creates a network of four-coordinated atoms.     

Strain-induced crystallization in elongated polyisobutylene elastomers

Elastomeric networks were prepared from a sample of polyisobutylene having 2 mol% isoprene units as unsaturated sites for free-radical crosslinking. Four samples having different degrees of crosslinking were obtained by peroxide thermolysis, and were then studied with regard to their thermoelastic properties in elongation. Each network strip was elongated at 338 K to ensure that it was completely amorphous, and then held at this constant length. The temperature was then slowly decreased at intervals, and the equilibrium value of the elastic force recorded for each temperature. The temperatures at which crystallization was observed from changes in the stress-temperature dependence were taken to be approximate melting points. The temperature range over which crystallization occurred was found to narrow considerably with increase in elongation. It was found that at lower elongations, the nominal melting points increased gradually with increase in elongation, while at higher elongations, their dependence on elongation became linear and more pronounced. The dependence of the melting points on the molecular weights between crosslinks and on strain were documented, and then compared with relevant theory. For each degree of crosslinking, estimated degrees of crystallinity were found to increase substantially and linearly with increase in elongation.     

Strain-induced fibrillation of glassy polymers

Literature data on structural rearrangements taking place in amorphous glassy polymers upon their plastic deformation are analyzed. This deformation is shown to be primarily accompanied by polymer self-dispersion into fibrillar aggregates composed of oriented macromolecules with a diameter of 1—10 nm. The above structural rearrangements proceed independently of the deformation mode of polymers (cold drawing, crazing, or shear banding of polymers under the conditions of uniaxial drawing or uniaxial compression). Principal characteristics of the formed fibrils and the conditions providing their development are considered. Information on the properties of the fibrillated glassy polymers is presented, and the pathways of their possible practical application are highlighted.     

Strain-induced post-curing of acrylate networks

The mechanical properties and network structure of photocurable polymers are strongly dependent on processing conditions. Here it is reported that highly crosslinked acrylate systems undergo unexpected additional post-curing during DMTA measurements, resulting in an increase in glass-transition temperature (T_g). A detailed study of the conditions under which this increase in T_g takes place unequivocally shows that a small (0.1%) oscillatory strain applied above T_g is responsible for additional cross-linking reactions. The effect of strain-induced post-curing is confirmed by applying post-curing treatments under oscillatory shear strain in rheological tests. Different acrylate systems were characterized and the results show that the strain induced post-curing depends on the network structure of the polymer. In polymer networks with an initial high crosslink density the effect is pronounced while in polymers with an initial lower crosslink density no shift in T_g is observed.     

Strain-induced reversal of charge transfer in contact electrification

We have contact! Material strain can have a dominating effect on contact electrification. When a deflated (relaxed) balloon is rubbed against teflon, the teflon surface charges positively, but when the same balloon is inflated (strained), the teflon surface charges negatively. This result illustrates that material strain can control contact electrification and alter the driving force of some (yet unknown) charge-transfer species.     

Strain-induced director reorientation in nematic liquid single crystal elastomers

The strain-induced director reorientation process in nematic liquid single crystal elastomers is investigated for the case of an arbitrary angle between the original director and the external stress axis. If the mechanical stress is applied perpendicular to the original director axis, the reorientation process sets in at a threshold strain. The mesogens are realigning ‘clockwise’ or ‘counter-clockwise’ towards the axis of external stress, simultaniously the monodomain structure is distorted and a periodic pattern formation is observed. If the mechanical stress is applied obliquely with respect to the original director axis, a uniform director reorientation is obtained with retention of the monodomain structure. No threshold strain is observed for this process. The existence of a threshold strain in the case of a perpendicular arrangement of the director to the external stress axis can be understood as a consequence of the distortion of the monodomain structure.     

Strain-induced crystallization of swollen,crosslinked polyethylene

The kinetics of strain-induced crystallization of swollen polyethylene networks have been measured using dynamometry coupled with optical birefringence. Fibers were prepared by gel-spinning ultrahigh-molecular-weight polyethylene followed by crosslinking in dicumyl peroxide and swelling in xylene. Retractive force on crystallization was monitored at various temperatures and draw ratios. Fiber visualization was achieved using optical illumination coupled with video recording and digital analysis of the in situ transformation. Avrami plots of the transformation data showed good linear fits for low draw ratios in the range α < 1.2 and moderate undercoolings (60 < T_c < 70°C). Time exponents of unity were found, indicating a one-dimensional, heterogeneous growth mechanism whose temperature dependence could be described by a formalism similar to that recently used for flow-induced growth.     

Strain-induced regioselectivities in reactions of benzyne possessing a fused four-membered ring

[reaction: see text] A fused four-membered ring has a powerful directing ability in effecting the regioselective reactions of benzyne with ketene silyl acetal, nucleophile, and alpha-alkoxyfuran.     

长碳链聚酰胺及其共聚物的拉伸诱导结晶

长碳链聚酰胺(LCPA)作为聚酰胺的特殊品种,较长的亚甲基链和极性酰胺基团使其兼具聚烯烃和聚酰胺的双重特性.在加工或使用过程中,拉伸诱导结晶现象对长碳链聚酰胺及其共聚物的强度和弹性行为具有重要影响,深入认识其在外场下的微观结构响应对该材料的设计及制备具有重要意义.围绕拉伸诱导结晶作用,该专论主要基于本团队2010年以来在长碳链聚酰胺及其共聚物的拉伸诱导结晶工作,并综述了国内外的相关研究,涉及拉伸诱导结晶现象、拉伸诱导结晶的影响因素、拉伸诱导结晶与力学性能的构效关系及拉伸诱导结晶的表征方法等方面.     

快压法制备非晶聚醚醚酮的应变诱导结晶行为

利用快速增压和淬火2种方法分别制备了非晶聚醚醚酮(PEEK), 并利用二维广角X射线衍射(WAXD)研究了2种非晶样品在不同拉伸温度(T_d)和不同应变速率(v)条件下的结晶行为. 结果表明, 在相同拉伸温度及应变速率条件下, 快压样品的临界结晶应变明显低于淬火样品; 随着拉伸温度和应变速率的升高, 2种样品的临界结晶应变均逐渐降低; 在相同应变条件下, 拉伸温度对PEEK材料结晶度的影响很大, 而应变速率对其影响较小.     

Turbulence intensity in bubble columns

A parameter for the intensity of turbulent flow in bubble columns, a characteristic turbulent kinematic viscosity, is discussed. A simple model for cha     

Plastic yielding of partially crystalline polymers

Measurements are described of characteristic stress-strain properties in tension for several representative partially crystalline polymers prepared by cooling from the melt. Striking differences were found in the natural draw ratio, ranging from 2x to 11x. They are interpreted in terms of a simple molecular model of the yielding process in which polymer chains, folded to different degrees in the crystallites, are pulled taut. Values of yield and draw stress were found to be of the same order as the free energy U_m of melting, suggesting that yielding and drawing take place by stress-induced disruption of crystallites, analogous to melting. The mechanical work of drawing was similar to, but generally larger than, that required for melting, ranging from U_m to about 4U_m. The difference is attributed to strain energy of drawn material and possible recrystallization during drawing.     

Critical bubble radius in solvent sublation

The complex compound of dithizone-Co(Ⅱ) was separated and concentrated from the aqueous phase to n-octanol by solvent sublation.From the analysis of the coalescence behavior of bubbles on water-organic interface,the conception of critical bubble radius was proposed,and the value of the critical bubble radius in the water-octanol system was obtained:1.196×10~(-3)m.The simulation of the mathematical model using CBR and experimental data is completed with perfect results,and the simulation of the mathematical model using CBR is very different with the classic one.The analytical results proved that the critical bubble radius should be adequately considered in mathematical model of solvent sublation.     

A ruthenium catalyst yielding crosslinked polyethylene

A ruthenium phosphane aryl sulfonate was found to be an efficient catalyst for the polymerization of ethene. Surprisingly, the resulting polyethylene is crosslinked.     

Work of Fracture and Strain-induced Cold Crystallization Behavior of Amorphous Copolyester Sheets

The toughness of amorphous copolyester sheets was assessed by the essential work of fracture (EWF) concept. While the yielding-related work of fracture terms did not change significantly, the necking-related parameters strongly decreased with decreasing entanglement density of the copolyesters having different amounts of cyclohexylenedimethylene (CHDM) units in their backbones. Furthermore, copolyesters with high CHDM content and thus less entanglement density showed full recovery of the necked region beyond the glass transition temperature, i.e. the ‘plastic’ zone in the related specimens formed by cold drawing and not by true plastic deformation. By contrast, the copolyester with negligible amount of CHDM did not show this shape recovery. Modulated differential scanning calorimetry (MDSC) revealed that the necking in the latter system was accompanied by strain-induced crystallization. The superior work hardening in the necking stage of the respective poly(ethylene terephthalate) (PET) specimens can thus be ascribed to stretching of the entanglement network with superimposed crystallization. This revised version was published online in August 2006 with corrections to the Cover Date.     

Strain-induced substitutional lability in a Ru(II) complex of a hypodentate polypyridine ligand

The ruthenium(II) complex of heptadentate N,N,N',N'-tetrakis(2-pyridylmethyl)-2,6-bis(aminomethyl)pyridine (tpap) was isolated as the hexafluorophosphate complex Ru(tpap)(PF6)2. The crystal structure has been determined for the triflate salt Ru(tpap)(CF3SO3)2.2H2O, which crystallizes in the monoclinic space group P2(1)/n. The structure was refined to a final R value of 0.0549 for 5894 observed reflections. The heptadentate ligand coordinates with six nitrogens, i.e. with two tertiary nitrogens and four pyridine nitrogens, one of the pyridines remaining un-coordinated. The resulting structure is significantly distorted from octahedral geometry with an equatorial Nsp3-Ru-Npyridine angle of 120 degrees. The consequence of the above steric strain is a labilization of the system and fluxional behaviour involving exchange between equatorially coordinated and non-coordinated pyridines has been observed by 1H NMR for Ru(tpap)(PF6)2 in d6-acetone solution. The activation parameters of DeltaG(not equal to 298) = 53 kJ mol(-1), DeltaH(not equal) = 56 +/- 1 kJ mol(-1) and DeltaS(not equal) = -10 +/- 3 J mol(-1) K(-1) were determined on the basis of NMR experiments. In addition electronic structure calculations applying density functional theory (DFT) have been performed in order to identify a transition state and to estimate the activation barrier. On the basis of NMR and DFT results the mechanism of isoexchange involving a hepta-coordinated intermediate has been proposed.