环氧化改性天然橡胶／丁腈橡胶共混物研究

用电子扫描显微镜(SEM)、差示扫描量热计(DSC)、红外光谱、强力试验机等仪器,对环氧化改性天然橡胶/丁腈胶共混物的形态与性能进行研究,并与未改性的天然橡胶/丁腈胶共混物进行对比。结果表明,天然橡胶分子引入环氧化基团后极性增大,两组分分子间的相互作用力增强,共混物相容性得到明显的改善,从而具有较理想的形态,展现出较好的力学拉伸性能,可望达到使用的要求。     

天然橡胶/顺丁橡胶共混物相容性的分子模拟研究

天然橡胶（NR）具有优异的综合性能而广泛应用于各个领域,但较差的耐热、耐老化性能影响了NR制品的使用寿命。天然橡胶与顺丁橡胶（BR）共混可改善制品的拉伸强度、耐磨性、抗撕裂性能,提高制品的使用寿命和耐低温性能,二者共混常用于轮胎制造。NR与BR共混,二者的相容性对共混物的相结构和性能具有重要影响。本研究利用Material Studio软件构建模型,采用分子动力学（MD）和耗散粒子动力学（DPD）模拟方法在分子尺度和介观尺度上对室温下NR/BR共混的相容性进行探讨。通过MD模拟,确定了NR和BR在模拟过程的最小聚合度均为20;构建10/90、30/70、50/50、70/30、90/10的NR/BR共混物模型,并计算每个NR/BR共混模型的相互作用参数χ,发现在NR/BR共混体系中NR与BR分子间的相互作用参数χ_NR-BR始终比临界相互作用参数χ_C小;分析了不同质量比NR/BR共混物分子间的径向分布函数,发现NR与BR分子间的径向分布函数g_inter(r)始终高于NR与NR、BR与BR同种分子间的径向分布函数,表明共混物中不同种类分子间（NR与BR）的相互作用比同种类分子间（NR与NR、BR与BR）的相互作用要强;DPD模拟得到不同质量比NR/BR共混物的介观形貌,发现共混物分散相的相畴尺寸会随着分散相含量的增加而增加,但均未出现宏观相分离的情况。上述模拟结果表明,NR和BR在室温下以不同质量比混合时,始终表现出良好的相容性。为验证模拟结论是否准确,制备了NR/BR共混物试样,并采用动态热机械分析仪对样品进行测试,结果证实了NR/BR共混体系的混溶性。模拟结论与实验结果相匹配,证明分子模拟研究和预测共混物相容性是可行的,可为共混实验提供可靠的参考和指导。     

Effects of surface treatments on Mechanical properties of Continuous basalt fibre cords and their Adhesion with rubber matrix

To improve the mechanical properties and the adhesion to a natural rubber (NR)/styrene-butadiene rubber (SBR) matrix, continuous basalt fibre (CBF) cords with and without a silane coupling agent (3-aminopropyl)triethoxysilane (KH550) treatment were dipped into a typical resorcinol-formaldehyde-latex (RFL) system. The breaking force and elongation at break of the cords were tested using a universal testing machine. The adhesive properties were evaluated by both static mode and dynamic (fatigue) mode with H-shape cord-rubber samples. An elastomer testing system was employed to conduct the fatigue test, and the evolution of the adhesive properties between the CBF cord and the NR/SBR matrix was tracked. The interfacial fracture caused by H pull out and fatigue were both observed with a scanning electron microscope (SEM). The results of this investigation show that the RFL-dipping treatment can significantly improve the mechanical properties of the CBF cord and its adhesion to the NR/SBR matrix, and the pre-treatment of the CBF cord with KH550 can further improve the interfacial fatigue property.     

改性碳酸钙对天然橡胶的补强效果

采用溶胀法、sEM和力学性能测定,研究了碳酸钙对天然橡胶的补强效果。结果表明,与未改性碳酸钙相比,改性碳酸钙与天然橡胶间具有较强的界面粘合作用 ,改性碳酸钙对天然橡胶具有较好的补强效果,硫化胶的力学性能得到明显的提高。     

4种复合粘合剂对天然橡胶制品力学性能的影响

研究了RE/A,RS/A,RS/RH,RE/RH,RH等粘合剂体系对天然橡胶硫化特性、物理机械性能、动态热力学性能的影响。结果表明:RS/RH,RE/RH,RH胶料的硫化速度明显较快,最大转矩和其硫化胶的拉伸强度、硬度及定伸应力都显著地高于对照(不加粘合剂),几种橡胶拉断伸长率均不同程度地小于对照,添加粘合剂的胶料其橡胶与织物附着强度远远大于对照,其中RE/RH胶料最大;对照和添加RE/A胶料的弹性模量(E’)、损耗模量(E″)和损耗因子(tanδ)明显最大,其次是RS/RH,RH/RE,RS/A,最低是RH胶料;对照和添加复合胶粘剂橡胶的玻璃化转变温度(Tg)分别为-53.5,-50.4,-54.6,-55.2,-55.8和-56.4℃;各胶料分子链段运动活化能(△H)按上述排列分别为150.6,268.6,163.5,151.6,148.7和113.4kJ/mol。      

环氧化天然胶／丁腈胶共混物硫化条件的研究

采用流变仪、差示扫描量热计、强力试验机等仪器,开展环氧化天然橡胶/丁腈橡胶共混物硫化条件的研究,包括配方的选择、制备工艺、贮存时间等方面,从而确定适宜的硫化条件与工艺,并据以制备出具有一定程度共硫化的硫化胶;与环氧化橡胶、丁腈橡胶、天然橡胶/丁腈胶共混物相比,环氧化橡胶/丁腈橡胶共混物在力学与耐油性能上均有所改善,因此可以在工业上应用。     

Physical properties of polymer composite: Natural rubber glove waste/polystyrene foam waste/cellulose

The polymer composite was prepared from the wastes of natural rubber glove (NRG) and polystyrene foam (PSF) blended with cellulose from sugar cane leaves via the laminate method. The NRG and PSF were firstly dispersed in toluene under continuous stirring. Then, maleic anhydride (MA) was added into the mixture. Effects of blend ratio and of MA content (0.5-15%, w/w) on physical properties of the polymer composite were investigated. The toluene resistance of the polymer blend was improved after adding MA and cellulose. The highest toluene resistance was achieved when using 12% cellulose. The chemical reactions of MA with polymer blend and with composite were confirmed by ATR-FTIR. The hardness of the polymer blend and composite increased as a function of PSF. In addition, their impact strength increased with increasing NRG and cellulose contents.     

共混型热塑天然橡胶研究 Ⅱ.组分及交联剂对结构与性能的影响

在前一研究工作基础上,我们采用差示量热计与力学—振动光谱等手段,进一步研究了不同橡胶组分对热塑天然橡胶(聚乙烯含量在30％以下)的结构与性能的影响。我们将溶胶—聚乙烯与凝胶—聚乙烯共混物进行了比较,结果证明,两者在结构与性能上的差异并不显著,但纯化胶—聚乙烯与未纯化胶—聚乙烯共混物之间,存在着明显的差异,证明非胶组分对共混物之间有影响。我们的结果还表明,交联剂DCP具有提高共混物宏观应力值及橡胶分子取向程度的作用。此外,本文还讨论了非胶组分及DCP对共混物电的聚乙烯结晶行为的影响。     

真空辅助酸凝固天然橡胶加工性能的研究

天然橡胶（NR）的性能与制胶工艺密切相关,其中凝固是制胶工艺的重要环节。本文采用真空辅助酸凝固天然橡胶,对比自然凝固天然橡胶和酸凝固天然橡胶,探讨了真空辅助酸凝固对天然橡胶门尼粘度、理化性能、物理机械性能以及加工性能的影响。研究表明,不同凝固方法得到的NR理化性能有一定的差异,自然凝固NR的氮含量>真空辅助酸凝固NR的氮含量>酸凝固NR的氮含量,真空辅助酸凝固NR的塑性初值（P₀）和塑性保持率（PRI）比自然凝固和酸凝固NR的P₀和PRI都高,其中真空辅助酸凝固NR的PRI为85%,而酸凝固NR的PRI为75.7%。真空辅助酸凝固NR的交联密度高于自然凝固NR和酸凝固NR。真空辅助酸凝固NR的拉伸强度、拉断伸长率均高于自然凝固NR和酸凝固NR的拉伸强度、拉断伸长率,3种NR的拉伸强度分别为21.06、19.35、17.60 MPa。RPA测试表明,真空辅助酸凝固NR的弹性模量（G'）<自然凝固NR的G'<酸凝固NR的G',损耗因子（tanδ）变化趋势恰好相反,即真空辅助酸凝固得到的胶样的加工性能最好,自然凝固胶样次之,酸凝固胶样最差。     

Miscibility,Crystallization Behaviors and Toughening Mechanism of Poly(butylene terephthalate)/Thermoplastic Polyurethane Blends

Blends of poly(butylene terephthalate) (PBT)/thermoplastic polyurethane (TPU) were prepared by melt compounding. The miscibility, crystallization behaviors and toughening mechanism of the PBT/TPU blends were studied. Dynamic mechanical analysis results demonstrated that PBT was immiscible with TPU. Differential scanning calorimetry and wide angle X-ray diffraction results showed that the crystallinity of PBT decreased with increasing TPU content. Furthermore, blending with TPU did not modify the crystal structure of PBT. The small angle X-ray scattering results indicated that the crystal layer thickness decreased and the amorphous layer thickness increased with increasing TPU content, indicating that TPU mainly resided in the interlamellar region of PBT spherulites in the blends. An obvious improvement in toughness of PBT was achieved with addition of TPU. Neat PBT had elongation at break and impact strength of about 15 % and 2.9 kJ/m², respectively. However, the elongation at break and impact strength of the 70/30 PBT/TPU blend reached 410 % and 62.9 kJ/m², respectively. The morphology of the PBT/TPU blends after tensile and impact tests was investigated, and the corresponding toughening mechanism is discussed. It was found that the PBT showed obvious shear yielding in the blend during the tensile and impact tests, which induced dissipation of energy and, therefore, led to the improvement in toughness of the PBT/TPU blends.     

Nano-calcium carbonate reinforced polypropylene and propylene-ethylene copolymer nanocomposites: Tensile vs. impact behavior

Improvement of both the tensile and impact strength of the same polymeric material has always been a great challenge for the plastic industry. The study focuses on the effect of incorporation of calcium carbonate nanoparticles (0.3 wt% to 15 wt%) into three polypropylene (PP) based matrices viz. PP homopolymer, propylene-ethylene (PP-PE) copolymer and the blend of PP:PP-PE (30:70) to improve their impact behavior without hampering the tensile strength much. A loss in both the tensile and impact properties was observed in PP based nanocomposite. However, PP-PE based nanocomposites showed a significant improvement in impact strength (47 %) at 10 wt% loading with a loss of tensile strength by 22 %. To minimize this loss a blend of PP:PP-PE (30:70) was explored as a matrix. At 10 wt% loading, this matrix showed an improvement of 30 % in impact strength whereas the tensile loss was minimized to 10 %. Further, silane coupling agent which promoted good interfacial adhesion was used for best compositions. The variation of crystalline morphology of the nanocomposites with various formulations was analyzed using differential scanning calorimetry and X-ray diffraction.     

Effects of date palm leaf fiber on the thermal and tensile properties of recycled ternary polyolefin blend composites

This work investigated the effects of date palm leaf fiber (DPLF) content on the thermal and tensile properties; and morphology of compatibilized polyolefin ternary blend. Recycled polyolefin ternary blend consisting of low density polyethylene (RLDPE), high density polyethylene (RHDPE) and polypropylene (RPP) were fabricated at different parts per hundred resin (phr) of DPLF. Maleic anhydride grafted polyethylene (MAPE) was used as compatibilizer to enhance the adhesion between filler and polymer matrix. The composites were prepared using melt extrusion and tests samples were produced via injection molding process. Thermal conductivity results showed that as much as 11 % reduction in thermal conductivity was achieved with the incorporation of 30 phr DPLF. Highest tensile strength was observed with the incorporation of 10 phr DPLF. The elongation at break was reduced with the addition of DPLF due to impediment of chain mobility by the fillers. Initial degradation temperature increased with the addition of DPLF. Hence, it is concluded that DPLF can be used to develop green and thermally insulating composites. It is hoped that the present results will stimulate further studies on the thermally insulative materials based on natural fibers reinforced polymer composites for applications in the building industries.     

Characterization of pre-gelatinized maize starch-zein blend films produced at alkaline pH

Biodegradable materials are considered as alternative to synthetic materials to alleviate the environmental burdens caused by petroleum based synthetic materials. Biopolymer blends have been extensively researched to improve the material properties of biopolymer-based materials for potential replacement of non-biodegradable materials. Compatible blends of pre-gelatinized maize starch (uncomplexed or complexed with stearic acid) and commercial zein in 0.1 M NaOH were used to produce the films. The effect of the ratio of uncomplexed starch, zein and starch complexed with stearic acid on the tensile, water vapour and oxygen barrier and thermal properties of the composite films were investigated. Blending zein with starch increased the tensile strength and reduced the tensile strain compared to starch films. Addition of starch complexed with stearic acid to the blend further increased the tensile strength and decreased the elongation at break. Both blending zein with starch and addition of starch complexed with stearic acid to the blend decreased the water vapour permeability, however, the oxygen permeability was increased compared to starch films. The starch-zein blend films had an endothermic temperature and thermal transition in between the uncomplexed maize starch and zein films suggesting possible compatibility at molecular level. The microstructure of the blend films also showed good miscibility of pre-gelatinized starch and commercial zein. In conclusion alkaline solvent (0.1 M NaOH) could produce compatible starch-zein blends that can produce films with improved tensile strength and water vapour permeability compared to starch films.     

Effects of nanoclay and short nylon fiber on morphology and mechanical properties of nanocomposites based on NR/SBR

Natural rubber and styrene butadiene rubber (NR/SBR) reinforced with both short nylon fibers and nanoclay (Cloisite 15A) nanocomposites were prepared in an internal and a two roll-mill mixer by a three-step mixing process. The effects of fiber loading and different loading of nanoclay (1, 3 and 5 wt. %) were studied on the microstructure and mechanical properties of the nanocomposites. The adhesion between the fiber and the matrix was improved by the addition of a dry bonding system consisting of resorcinol, hexamethylene tetramine and hydrated silica (HRH). This silicate clay layers was used in place of hydrated silica in a HRH bonding system for SBR/NR-short nylon fiber composite. Nanoclay was also used as a reinforcing filler in the matrix-short fiber hybrid composite. The cure and scorch times of the composites decreased while cure rate increased when the short fiber and nanoclay were added. The mechanical properties of the composites showed improvement in both longitudinal and transverse directions with increasing short fiber and nanoclay content. The structure of the nanocomposites was characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM). X-ray diffraction results of nanocomposites indicated that the interlayer distance of silicate layers increased. The mechanical properties of nanocomposites (tensile, hardness and tear strength) are examined and the outcome of these results is discussed in this paper.     

微波辐射凝固胶清橡胶性能的研究

将微波辐射应用于胶清橡胶的凝固,对比微波辐射凝固胶清橡胶(NR-s-m)与硫酸凝固胶清橡胶（NR-s-a）的性能差异。结果表明,理化性能方面,NR-s-m的灰分含量、杂质含量、挥发物含量以及氮含量较高,塑性初值、抗氧指数和门尼粘度也更高;力学性能方面,NR-s-m硫化胶拉伸强度、扯断伸长率、撕裂强度和硬度均比NR-s-a的高;硫化特性方面,NR-s-m比NR-s-a的硫化速度快,并随微波辐射功率的增大而加快。     

Compatibilization of poly(lactic acid)/polycarbonate blends by different coupling agents

In this study, PLA/PC blends were prepared in order to investigate the effects of the addition of PC loading level into PLA matrix on the mechanical properties of these blends. After that, PLA/PC (70/30), which has the lowest tensile strength value, was selected as a control sample for the compatibilization study. Commercial styrene-acrylic multi-functional-epoxide oligomeric agent (SAmfE), styrene maleic anhydride copolymer (SMA), tetrasilanol phenyl polyhedral oligomeric silsesquioxane (T-POSS) and glycidyl isooctyl-polyhedral oligomeric silsesquioxane (G-POSS) were used as compatibilizers for PLA/PC blends. The variation of mechanical, thermal, structural and morphological properties were examined by conducting tensile tests, dynamic mechanical analyses, differential scanning calorimetry, Fourier Transform IR and scanning electron microscope analyses. Tensile test results showed that the tensile strength and elongation at break values of the PLA/PC blend compatibilized with SAmfE were higher than those of the other blends. DSC analyses revealed that T_g and T_m values of the blends were not significantly affected by compatibilizer but, degree of crystallinity was found to be sensitive to compatibilizer type. DMA results showed that the best mechanical properties were obtained for the PLA/PC/SAmfE blend. When all of the results evaluated, it was found that the SAmfE is the most effective compatibilizer among the using compatibilizer types for PLA/PC blends.     

Fabrication and characterization of dense Chitosan/polyvinyl-alcohol/poly-lactic-acid blend membranes

Dense membranes of Chitosan (CS)/Poly(vinyl alcohol) (PVA)/Poly(lactic acid) (PLA) blend were successfully fabricated using casting technique. The mechanical properties, moisture regain and water vapor permeability of polymer blend membranes were estimated by tensile test, moisture regain rate and dish method test respectively. The microstructures, morphology, chemical composition and thermal properties were also characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) respectively. Results indicated that there were interactions and good compatibility among CS, PLA and PVA. And the blend membranes have good breaking elongation and slightly decreased breaking strength, and show best moisture regain at the case of CS60 (the content of CS in the blends is 60 %). They also have excellent porous structure, which is beneficial to their air permeability and may also contribute to cell regeneration. With the adding of PVA content, the melting peaks of blend membranes reduce and gradually close to that of PVA, demonstrating that the regularity of CS molecular chain may be destroyed and hydrogen bonds of macromolecules in polymers were newly formed. As a result, solution blending of the three polymers could complement their disadvantages and significantly improve the membrane performance of a single polymer, thus promote the mechanical and biological properties of blend membrane.     

纳米TiO_2/天然橡胶复合材料的抗菌性研究

采用溶胶凝胶法,以钛酸四丁酯掺杂金属Ag制备纳米二氧化钛(Ag-TiO2)水溶胶,并与天然胶乳湿法共混制备得到纳米TiO2/天然橡胶复合材料。紫外可见光谱表明,金属Ag能提高TiO2的光催化性能;透射电子显微镜观察到TiO2颗粒粒径为50nm左右,并且均匀的吸附在胶粒表面。研究此复合材料的抗菌性能结果表明,其具有良好的抗细菌和抗霉菌效果,对大肠杆菌的抗菌率达到90%以上,特别是硫化过后的纳米TiO2/天然橡胶复合材料的抗细菌率更达98.5%。     

Preparation and characterization of bacterial cellulose/hydroxypropyl chitosan blend as-spun fibers

In the work, N-methylmorpholine-N-oxide monohydrate (NMMO·H₂O) was used as a solvent to solve bacterial cellulose (BC) and hydroxypropyl chitosan (HPCS) together, and regenerated bacterial cellulose (RBC)/HPCS blend as-spun fibers were prepared by blending BC with HPCS via wet-spinning in the Lyocell process. Structure and properties of the blend as-spun fibers were characterized by different techniques, together with the antibacterial activity of the blend as-spun fibers against Staphylococcus aureus. Results revealed that HPCS was mixed with BC very well. The blend as-spun fibers showed a rough and folded surface morphology and an interior pore structure on the cross-section. Compared with pure RBC as-spun fibers, the blend as-spun fibers had lower degree of crystallinity and thermal stability. Although extension at break of the blend as-spun fibers was lower than the pure RBC as-spun fibers, their tensile strength and modulus had been enhanced obviously. The blend as-spun fibers were also found to exhibit excellent antibacterial activities against S. aureus.     

Antimicrobial fibers based on chitosan and polyvinyl-alcohol

A series of antimicrobial fibers with different weight ratio of chitosan (CS) and polyvinyl alcohol (PVA) were fabricated via a primarily industrialized trail of wet-spinning method, and the morphology and structure of the resulting fibers were studied with the aid of scanning electron micrography (SEM), infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The CP60 blend fiber (60 % chitosan content) was confirmed as the best optimal sample among the blend fibers owing to strong intermolecular hydrogen bonds between PVA and chitosan and showed the maximum mechanical, antistatic, moisture absorption/desorption properties. The CP60 also exhibited good antimicrobial effects against Escherichia coli and Staphylococcus aureus as the chitosan fiber and could be recommended as the alternative material for the wound dressing and the food packing.