Mixing of Racemic Poly(L-lactide)/Poly(D-lactide) Blend with Miscible Poly(D,L-lactide):Toward All Stereocomplex-type Polylactide with Strikingly Enhanced SC Crystallizability

Stereocomplex-type polylactide (SC-PLA) consisting of alternatively arranged poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) chains has gained a good reputation as a sustainable engineering plastic with outstanding heat resistance and durability,however its practical applications have been considerably hindered by the weak SC crystallizability.Current methods used to enhance the SC crystallizability are generally achieved at the expense of the precious bio-renewability and/or bio-degradability of PLAs.Herein,we demonstrate a feasible method to address these challenges by incorporating small amounts of poly(D,L-lactide) (PDLLA) into linear high-molecular-weight PLLA/PDLA blends.The results show that the incorporation of the atactic PDLLA leads to a significant enhancement in the SC crystallizability because its good miscibility with the isotactic PLAs makes it possible to greatly improve the chain mixing between PLLA and PDLA as an effective compatibilizer.Meanwhile,the melt stability (i.e.,the stability of PLLA/PDLA chain assemblies upon melting) could also be improved substantially.Very intriguingly,SC crystallites are predominantly formed with increasing content and molecular weight of PDLLA.More notably,exclusive SC crystallization can be obtained in the racemic blends with 20 wt％ PDLLA having weight-average molecular weight of above 1 ×10s g/mol,where the chain mixing level and intermolecular interactions between the PLA enantiomers could be strikingly enhanced.Overall,our work could not only open a promising horizon for the development of all SC-PLA-based engineering plastic with exceptional SC crystallizability but also give a fundamental insight into the crucial role of PDLLA in improving the SC crystallizability of PLLA/PDLA blends.     

Necking in non-isothermal high-speed spinning as a problem of sensitivity to external disturbances

Necking in non-isothermal high-speed melt spinning is treated as a problem of sensitivity to external disturbances at both ends of the spin-line. Necessary conditions for existence of necking are formulated in terms of the corresponding increments of velocities, forces, viscosities, etc. It is shown that necking may be present in the high-inertia range for a rather small viscosity variation. Small inertia effects require higher values of the radial viscosity gradients.     

Silanols cured by borates as lubricants in extrusion of LLDPE. Impact of elasticity of the lubricant on sliding friction

Addition of a viscoelastic material based on silanols cured by boron oxide was used to delay sharkskin and stick–slip instabilities in extrusion of linear low-density polyethylene (LLDPE). Delay of flow instabilities to rates of extrusion 25–35 times higher than without additive and about 40% less extrusion pressure at the same throughput are achieved by the use of this material as an additive (∼0.1%) to LLDPE or as a coating of the extrusion die. Mechanical properties of the lubricant were changed by small variations of composition to investigate the impact of elasticity on lubrication and sharkskin delay. Both lubrication and sharkskin delay were considerably improved when more elastic lubricants were used while the chemical composition of the lubricants was nearly the same. Filling the lubricants with powders of metal oxides or especially particulates having plate-like particles (kaolin, mica, BN) helped to delay the flow instabilities further to even higher throughputs. Together with experimental results, we present a tentative explanation for the importance of elasticity of polymer processing aids in the delay of sharkskin and the stabilization of slip. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Rheology/morphology/flow conditions relationships for polymethylmethacrylate/rubber blend

Viscoelastic behavior, phase morphology and flow conditions relationships in polymer/rubber blends have been investigated. The importance of such correlations is illustrated on polymethylmethacrylate (PMMA)/rubber blends subjected to different flow conditions both under small and large deformations. In small-amplitude oscillatory shear (the morphology does not change during the flow) the elastic modulus G of the concentrated blends shows a secondary plateau, G _p , in the low frequency region. This solid-like behavior appears for rubber particle contents beyond the percolation threshold concentration (15%). Morphological observations revealed that for concentrations higher than 15%, the particles are dispersed in a three-dimensional network-type structure.In capillary flow it was found that the network-type structure was destroyed and replaced by an alignment of particles in the flow direction. This morphological modification resulted in a decrease in both viscosity and post-extrusion swell of the blends. Morphological observations revealed that the ordered structure in the flow direction was concentrated only in the skin region of the extrudate, where the shear stress is higher than the secondary plateau, G _p . A simple kinetic mechanism is proposed to explain the observed morphology.Similarly, steady shear measurements performed in the cone-and-plate geometry revealed alignment of particles in the flow direction for shear stress values higher than G_p.Presented in part at the Symposium Recent Developments in Structured Continua Montréal (Canada) 26–28 May 1993 and at the 45th Canadian Chemical Engineering Conference, Quebec, October 15–18 (1995)     

Determination of the elongational viscosity of polymer melts by melt spinning experiments. A comparison with different experimental techniques

In this work, melt spinning experiments were tentatively used for the determination of the elongational viscosity of polymer melts at different levels of tensile strain and strain rate. The materials examined were two high-density polyethylene grades for blow moulding with similar number-average molecular mass but different polydispersity index. The data from melt spinning tests were compared with transient extensional viscosity data obtained by uniform isothermal tensile tests, performed by means of an extensional rheometer, as well as with those produced by converging flow tests (Cogswell model). The results showed that for high strain and strain rate levels, the melt spinning experiments provide elongational viscosity data quite close to the transient extensional viscosity values obtained from the tensile tests.     

Numerical simulation of a two-phase melt spinning model

We consider a two-phase model of melt spinning including flow induced crystallization. Introducing slight modifications in the model we perform numerical simulations on it. We present comparison of our velocity profiles with the experimental profiles provided by the company Freudenberg & Co.     

Effects of phase explosion in pulsed laser deposition of nickel thin film and sub-micron droplets

Nickel (Ni) thin films were deposited on glass substrates in high vacuum and at room temperature with third-harmonic or 355-nm output from a nanosecond Nd:YAG laser. At low laser fluence of 1 J/cm², the deposition rate was about 0.0016 nm/shot which increased linearly until 4 J/cm². Above 4 J/cm², the onset of phase explosion in the ablation abruptly increased the optical emission intensity from laser-produced Ni plume as well as thin-film deposition rate by about 6×. The phase explosion also shifted the size distribution and number density of Ni droplets on its thin-film surface. On the other hand, the surface structures of the ablated Ni targets were compared between the scan-mode and the fixed-mode ablations, which may suggest that droplets observed on the thin-film surface were caused by direct laser-induced splashing of molten Ni rather than vapour-to-cluster condensation during the plume propagation.     

二乙醇胺改性聚乳酸的直接熔融聚合法合成及其表征

以乳酸(LA)、二乙醇胺(DEA)为原料,采用熔融聚合法直接合成了二乙醇胺改性聚乳酸,并用特性粘数、FT-IR、1H NMR、GPC、DSC、XRD等手段进行表征,探讨了催化剂种类和用量、熔融聚合反应时间、反应温度以及不同投料比、不同构型乳酸对聚合物合成的影响.在单体投料摩尔比n(DEA):n(L-LA)=1:200、160℃、70Pa、催化剂SnO用量0.7(wt)%、熔融聚合8h条件下,聚合物重均相对分子质量(Mw)可达8100.随着投料比中DEA的增加,产物特性粘数逐步降低,Mw逐渐减小,玻璃化温度(Tg)有降低的趋势.以L-LA聚合得到的聚合物的Mw、分散度(Mw/Mn)和结晶度均比由D,L-LA得到的产物的更高.因此,笔者认为,由于D,L-A与L-LA存在反应速率差异,因而二者有不同的反应历程.新合成方法有利于降低二乙醇胺改性聚乳酸作为药物缓释载体等生物医学材料的合成成本.     

Details of Structure Formation During the Induction Period of Spinodal-Type Polymer Crystallization

An unexpected type of primary crystal nucleation is described, involving spinodal decomposition (SD) type microphase separation due to the orientation fluctuations of rigid segments prior to crystal nucleation. This type of mechanism was found by the present authors about 10 years ago, and recently, it was theoretically revealed by Olmsted et al. to be one of three types of primary crystal nucleation: the well-known homogeneous crystal nucleation directly from the liquid–crystal coexistence domain, which occurs at higher temperatures above the binodal temperature T _b , crystal nucleation after binodal microphase separation between T _b and spinodal temperature T _s , and that after SD below T _s . The detailed experimental results for the spinodal-type crystal nucleation, especially the temperature dependence of characteristic wavelength in SD, are explained as well.