纤维素/NMMO·H_2O溶液体系流变性能的研究

利用 Brookfield DV-Ⅱ型粘度计对纤维素/NMMO·H2O 溶液体系的流变性能进行了研究,讨论了温度、纤维素浓度、浆粕聚合度及添加剂等对溶液粘度的影响。结果表明,纤维素/NMMO·H2O 溶液的流动活化能较低,因此其表观粘度随温度的变化不大;纤维素浓度和浆粕聚合度的增加都可使溶液粘度增大,但纤维素浓度对溶液粘度的影响更显著;抗氧化剂没食子酸丙酯(GPE)的加入减缓了加热时溶液粘度的下降,降低了纤维素的氧化降解;二甲亚砜(DMSO)的加入可有效地控制溶液粘度,改善溶液的加工性能。     

离子扩散型抗菌陶瓷中银离子的扩散

研究了离子扩散法制造抗菌陶瓷过程中Ag+在釉层中的扩散行为.用扫描电镜和电子探针分析了扩散过程中Ag的分布.用Fick定律分析扩散过程,提出用表层Ag+质量分数和表观扩散系数来描述实际的扩散过程.用余误差函数近似法确定扩散温度下不同成分釉层中Ag+的表观扩散系数.对于所研究的釉层,表观扩散系数为1.6×10-11～1.3×10-10 cm2/s.确定了上述2个参数与釉层成分、熔盐比例、扩散温度及扩散时间的关系.利用这些关系建立了优化制造条件的基础.     

Correlation between crystallization kinetics and melt phase behavior of crystalline-amorphous block copolymer/homopolymer blends

We show that the phase behavior of the strongly segregated blend consisting of a crystalline-amorphous diblock copolymer (C-b-A) and an amorphous homopolymer (h-A), which depends on the degree of wetting of A blocks by h-A, can be probed by the crystallization kinetics of the C block. A lamellae-forming poly(ethylene oxide)-block-polybutadiene (PEO-b-PB) was blended with PB homopolymers (h-PB) of different molecular weights to yield the blends exhibiting ‘wet brush’, ‘partially dry brush’, and ‘dry brush’ phase behavior in the melt state. The crystallization rate of the PEO blocks upon subsequent cooling, as manifested by the freezing (crystallization) temperature (T_f), was highly sensitive to the morphology and spatial connectivity of the microdomains governed by the degree of wetting of PB blocks. As the weight fraction of h-PB reached 0.48, for instance, T_f experienced an abrupt rise as the system entered from the wet-brush to the dry-brush regime, because the crystallization in the PEO cylindrical domains in the former required very large undercooling due to a homogeneous nucleation-controlled mechanism while the process could occur at the normal undercooling in the latter since PEO domains retained lamellar identity with extended spatial connectivity. Our results demonstrate that as long as the C block is present as the minor constituent the melt phase behavior of C-b-A/h-A blends can also be probed using a simple cooling experiment operated under differential scanning calorimetry (DSC).     

Determination of the predominant polymorphic form of mango (Mangifera indica) almond fat by differential scanning calorimetry and X‐ray diffraction

In this paper, some important properties, from the application point of view, of mango (Mangifera indica) almond fat var. Manila (MAF) were analyzed by differential scanning calorimetry and X‐ray diffraction techniques. The thermal profile, the solid fat content (SFC) and the predominant polymorphism of MAF samples, previously characterized chemically, were studied. The results showed that this fat, from one of the main residues of mango industrialization, had a relatively simple fusion/crystallization behavior. Stabilized samples showed a simple SFC profile with one marked slope between 35 and 40 °C. Different thermal histories demonstrated the existence of at least four polymorphs. The non‐stabilized samples corresponded predominantly to the formation of the crystalline &α form. The stabilized samples, tested under several time and temperature conditions, allowed the formation of two other polymorphs, which are both unstable forms and were formed during &α to β polymorphic transition. The X‐ray diffraction information confirmed the presence of the less and more stable MAF polymorphs, allowing us to conclude that MAF is a β‐stable fat, just as is cocoa butter.     

New polymer synthesis. XXX. Synthesis and thermal behavior of new organometallic polyketones and copolyketones based on diferrocenylidenecycloheptanone

A new interesting category of organometallic polyketones and copolyketones was synthesized via Friedel–Crafts reactions through the polymerization of 2,7‐bis[(2‐ferrocenyl)methylene] cycloheptanone ( II ) with different diacid chlorides. The model compound was synthesized by reacting monomer II with benzoyl chloride and characterized by ¹H‐NMR, IR, and elemental analyses. The polyketones and copolyketones were insoluble in most organic solvents but easily soluble in concentrated H₂SO₄. The thermal properties of these polyketones and copolyketones were evaluated and correlated to their structural units by TGA and DTG measurements and had inherent viscosity of 0.32–0.65 dI g^?1. Moreover, the electrical conductivity of polyketone Va and copolyketone VI was investigated above the temperature range (300–500 K) and followed an Arrhenius equation with activation energy 2.09 eV. Also, the morphological properties of selected example of polyketones were detected by scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2394–2401, 2005     

A Unified Model for the Mixing of Non‐Newtonian Fluids in the Laminar,Transition, and Turbulent Region

Summary: Non‐Newtonian fluid behavior has significant influence on quantities in chemical engineering like power input, mixing time, heat transfer etc. In the laminar flow region, the concept of effective viscosity by Metzner and Otto is well established. In the transition region between laminar and turbulent flow, the existing concepts use three and even more empirical parameters to determine the specific power input. Here, a unified and general but simple approach is introduced to calculate the power input for shear thinning fluids over the whole flow region using just one empirical parameter. The Metzner‐Otto relation is obtained as a limiting case for the laminar region. The empirical parameter of the new approach is related to the Metzner‐Otto constant. The concept is validated for eight different stirrer systems. Mixing time and maximum shear rate and heat transfer can also be calculated using this approach. The new concept presented should also be applicable for other apparatuses, e.g., static mixers.

Comparison of experimental data and a curve calculated according to the new method (solid line).     

The Influence of Cooling Rate on the Specific Volume of Isotactic Poly(propylene) at Elevated Pressures

Summary: We used a custom designed dilatometer to measure quantitatively the time evolution of the specific volume of (semi‐crystalline) polymers for an unusual combined wide range of cooling rates and elevated pressures, covering processing conditions. For an isotactic poly(propylene), applying the Schneider rate equations for quiescent crystallization, experimental results are compared to numerical predictions. Average cooling rates imposed during crystallization of the material vary from 0.1 to 35 °C · s^?1 while pressures range from 20 to 60 MPa. The results show the well‐known profound influence of pressure and cooling rate on the specific volume. An increasing cooling rate shifts the crystallization temperature T_c towards lower temperatures, increases the final specific volume, and the transition due to crystallization is more gradual and widespread. For the highest cooling rate applied, the shift in T_c is as much as 30 °C, while the final specific volume increases up to 1.4%. Increasing pressure has an opposite effect on the shift in T_c, while the final specific volume, after pressure release, also increases. Finally, a comparison of numerical predictions with experimental data shows that the crystallization temperature T_c is consistently predicted too low, and that the predictions at high cooling rate are sensitive to (small) variations in model parameters.

Influence of cooling rate on the specific volume of iPP.     

Cover Picture: Macromol. Mater. Eng. 8/2005

Summary: Poly(butylene succinate‐co‐adipate) (PBSA) and organically modified montmorillonite (OMMT) nanocomposites of three different compositions were prepared by melt‐extrusion in a batch mixer. The structure of the nanocomposites was studied using X‐ray diffraction (XRD) and transmission electron microscopy (TEM) that revealed a coexistence of exfoliated and intercalated silicate layers dispersed in the PBSA matrix, regardless of the silicate loading. The degree of crystallinity of PBSA decreases with the addition of OMMT platelets. Dynamic mechanical analysis revealed remarkable increase in flexural storage modulus when compared with that of neat PBSA. Tensile property measurements exhibit substantial increase in stiffness with simultaneous increase in elongation at break of nanocomposites as compared to that of neat PBSA. The effect of clay loading on the melt‐state linear viscoelastic behavior of mixed intercalated/exfoliated nanocomposites was also investigated.

Elongation at break of compression molded annealed samples of neat PBSA and various PBSACNs.     

Diffusional behavior of multi-arm star polymers by H pulsed field gradient spin-echo NMR method

The diffusional behavior of multi-arm star-shaped p(tBMA) was investigated in a concentration range from dilute to semidilute region with ¹H pulsed field gradient spin-echo NMR (PFGSE-NMR). An 142-arm star-shaped p(tBMA) showed two diffusional mode, which reflected the coexistence of liquid ordering phase and liquid phase near the ordering transition. On the other hand, for star-shaped p(tBMA) with 55 arms showed a single diffusional relaxation in all concentration ranges during observation time. In the semidilute region, the relationship between the diffusion coefficient against the polymer concentration was affected strongly not only the arm number but also liquid ordering structure.