反应挤出法制备马来酸酐接枝聚乳酸

采用反应挤出方法制备了聚乳酸(PLA)与马来酸酐(MAH)的接枝共聚物,研究了工艺条件和配方对产物接枝率和熔体流动速率的影响。结果表明,聚乳酸的接枝反应主要依赖于大分子侧链自由基进行,过高的螺杆转速或过高的挤出反应温度会引发聚乳酸的降解反应,不利于产物接枝率的提高;在适宜的反应条件下(马来酸酐含量2%,DCP含量0.35%,温度180℃,螺杆转速100 r/min),可以方便制得马来酸酐接枝聚乳酸产物(接枝率≥0.45%);SEM观察显示,马来酸酐接枝聚乳酸有效改善了PLA/淀粉共混材料的相容性。     

马来酸酐改性木质素对聚乳酸/环氧大豆油性能的影响

制备了一种基于马来酸酐改性木质素(LM)、环氧大豆油(ESO)与聚乳酸(PLA)的全生物基复合材料(PLA/ESO/LM)。采用傅里叶变换红外光谱、核磁共振氢谱对LM进行测试与分析,确认马来酸酐改性木质素的结构;以差示扫描量热仪、热重分析仪、偏光显微镜等研究复合材料的热学性能及内部结构。结果表明,与PLA相比,PLA/ESO/LM复合材料冷结晶温度降低,结晶行为增强,结晶度提高;同时PLA/ESO/LM复合材料的初始热分解温度比PLA提高了35℃,表现出更高的热稳定性。通过优化复合材料的比例得出PLA/20ESO/0.5LM的复合材料具有最优的综合性能,拉伸强度为55 MPa,断裂伸长率提升到198%,约为PLA的20倍,PLA材料的综合性能得到极大提高。     

应力诱导引发马来酸酐官能化LLDPE的研究

采用提高双螺杆挤出机螺杆转速的应力诱导引发方法和添加引发剂与提高螺杆转速的复合引发方法,研究了线型低密度聚乙烯(LLDPE)与马来酸酐(MAH)的官能化反应;考察了官能化产物(LLDPE-g-MAH)对PET/铝箔复合薄膜T型粘合接头剥离强度的影响。结果表明:提高螺杆转速可抑制LLDPE在官能化过程中的交联副反应,制得具有较高接枝(嵌段)率、较好熔体流动速率和较低凝胶质量分数的官能化产物(Gd=0.30%~0.65%,MFR=1.0 g/10 min~4.7 g/10 min,凝胶质量分数≤0.4%),与单纯采用引发剂方法相比,高剪切应力诱导引发方法和复合引发方法所得官能化产物均可明显提高PET/铝箔复合薄膜T型粘合接头剥离强度。     

静电纺丝法制备PLA/CNCs纳米复合薄膜及其性能研究

采用静电纺丝法成功将纳米纤维素晶体(CNCs)植入聚乳酸(PLA)基体中,制备出网状结构的绿色纳米复合材料,并探讨了PLA/CNCs薄膜的微观形貌、结晶度、热学性能和机械性能随CNCs添加量的变化趋势。结果表明,随着CNCs添加量的增加,静电纺PLA/CNCs纳米复合材料薄膜珠状纤维减少,纤维直径增大;纳米复合纤维薄膜的结晶度提高了87.9%;纳米复合纤维薄膜的最大热解温度由369.36℃提升到380.02℃;纳米复合纤维的拉伸性能随CNCs添加量的增加而显著提高,CNCs添加量为11%(质量分数)时得到的最大拉伸力和拉伸强度最大分别为3.76N和4.58MPa,与纯PLA薄膜相比分别提高了289%和159%。     

基于MATLAB对PP/PLA复合材料薄膜均匀性评估方法

鉴于共混均匀性对复合材料各性能的重要影响,本研究基于MATLAB软件对聚丙烯(Polypropylene,PP)/聚乳酸(Polylactic Acid,PLA)复合材料薄膜共混后均匀性评判方法进行研究。首先对不同共混工艺下的PP/PLA复合材料薄膜电镜(SEM)图像进行单元离散划分,选取15组尺寸进行单元精度评估,确立出最优单元尺寸为500个单位。再对各单元内像素点进行灰度处理,去除相应杂质后,对各单元归一化处理,量化各单元间数值。根据Bar3与Surf函数绘制相应数值分布三维图像,并配合数值分析及箱形图分析法得出添加马来酸酐工艺的薄膜数值稳定性更高(R2=0.99152),在3个标准差内总体平均值为97.3%,且分布更趋近于正态分布。最终对比薄膜拉伸性能,拉伸强度与离散系数(CV)具有相同趋势,进一步验证了本方法的准确性。     

马来酸酐/丙烯酸丁酯双单体接枝聚丙烯

采用熔融法进行马来酸酐(MAH)和丙烯酸丁酯(BA)双单体接枝聚丙烯(PP)的研究。结果表明,在一定工艺条件下,仅添加一单体马来酸酐时,接枝率G在其加入量为4%(质量分数)时达到最大(0.65 mmol/g PP);马来酸酐添加量保持不变,接枝率随第二单体丙烯酸丁酯添加量增加而出现一极值(1.34 mmol/g PP),比一单体接枝聚丙烯的接枝率高出一倍,并高于文献值(0.36 mmol/g PP)。经红外光谱、热失重分析和差示扫描量热分析表明,马来酸酐、丙烯酸丁酯均与聚丙烯发生接枝反应,并且以短支链的形式连接在PP的主链上。     

聚丙烯/木粉复合材料的增容改性及其机理

为进一步改善聚丙烯(PP)/木纤维(WF)复合材料的力学性能,采用几种不同类型的马来酸酐接枝型相容剂对PP/WF复合材料进行增容改性,并通过红外光谱和扫描电镜,分析和研究其增容机理。结果表明,PP-g-MAH的改性效果最为明显,当其添加量为m(PP-g-MAH)/m(WF)=10/100时,PP/WF复合材料的拉伸强度提高40.9%,弯曲强度提高47.3%,弯曲模量提高35.3%。PP-g-MAH使PP与木粉产生良好的增容效果,木粉颗粒被PP包裹,材料抵抗外应力以及材料破坏由发生在两相界面变成发生在材料整体,从而有效提高了复合材料的力学性能。     

挤出机螺杆转速对马来酸酐官能化POE性能及增韧PA66效果的影响

采用在熔融挤出过程中添加引发剂与提高双螺杆挤出机螺杆转速的复合引发方法,研究了引发剂的含量、螺杆转速对马来酸酐官能化POE的接枝率、熔体流动速率和凝胶含量的影响。结果表明,提高双螺杆挤出机的螺杆转速可以较好地抑制POE在官能化过程中的交联副反应,控制制得具有较高接枝率(Gd=0.6%~0.92%)、较好熔体流动性(MI=0.4~4.0g/10min)和较低凝胶含量(≤0.3%)的官能化产物。复合引发所得官能化产物POE-g-MAH对PA66的增韧效果明显优于单纯采用引发剂引发所得产物。25%复合引发官能化POE产物可使PA66的缺口冲击强度由6.5kJ/m2提高至110kJ/m2。     

亚临界流体挤出制备木粉/聚丙烯复合材料

提出了一种通过亚临界流体辅助反应挤出制备木粉/聚丙烯(PP)复合材料的新型制备方法,其关键是在挤出过程中引入流体(乙醇和正丙醇),并使流体处于亚临界状态。同时,对木粉/PP复合材料进行了力学性能测试、FTIR和SEM观察。结果表明:在亚临界流体辅助反应挤出中,木粉发生了溶胀、液化等,有利于马来酸酐接枝聚丙烯渗入到木粉内部,其中酸酐基团与木粉中含有的大量羟基发生酯化反应增强,从而提高了木粉/PP复合材料的界面结合。在亚临界乙醇(190℃,(2.4±0.1)MPa,120r/min)作用下制备的木粉/PP复合材料的力学性能(拉伸强度、弯曲强度、弯曲模量和无缺口冲击强度)与无流体时制备的木粉/PP复合材料相比,其性能得到了一定的提高,它们分别达到了23.5 MPa、52.5 MPa、4.8GPa和5.9kJ·m~(-2)。     

MAH/GMA共接枝聚乳酸对木粉/PLA复合材料性能的影响

采用熔融接枝法分别制备马来酸酐接枝聚乳酸、甲基丙烯酸缩水甘油酯接枝聚乳酸和马来酸酐/甲基丙烯酸缩水甘油酯共接枝聚乳酸,并利用红外光谱对接枝共聚物进行结构表征。分别以三种接枝共聚物为相容剂,采用注塑成型制备了木粉/PLA复合材料。利用扫描电子显微镜(SEM)对复合材料的断面形貌进行微观分析,结果表明,加入不同接枝共聚物后木粉/PLA复合材料两相看不出明显相界面,界面相容性得到改善。对不同接枝共聚物制备的复合材料的力学性能、加工流动性能和动态流变性能测定的结果显示,加入MAH/GMA共接枝聚乳酸后的木粉/PLA复合材料和未添加相容剂的复合材料相比,拉伸强度和冲击强度分别提高了9.54%和7.23%,复合体系的平衡扭矩和剪切热提高,储能模量及复数黏度均增大。     

Effects of extruder parameters and silica on physico-mechanical and foaming properties of PP/wood-fiber composites

In this study, the effects of screw configuration, screw speed and silica content on the physico-mechanical and foaming properties of PP/wood-fiber (WF) composites were investigated. PP/WF composites were produced by the intermeshing co-rotating twin screw extruder. Microcellular closed cell PP/WF composite foams were prepared using pressure-quench batch process method. Firstly, an attempt has been made to determine the optimum conditions of extrusion that involve screw configurations and screw speed. The mechanical properties and morphology results showed that PP/WF composite prepared under the configuration C at screw speed of 150 rpm have higher mechanical properties, and narrower cell size distribution caused by uniform dispersion of wood fiber. And then, under the optimal processing conditions, the effect of silica content on the physico-mechanical properties of PP/WF composite, the final cell morphology as well as the relative density of the foamed PP/WF/Silica composites is studied.     

Chopped glass and recycled newspaper as reinforcement fibers in injection molded poly(lactic acid) (PLA) composites: A comparative study

Natural/bio-fibers are replacing synthetic reinforcements traditionally used for the preparation of the environmentally friendly composites. Composite materials are also replacing conventional materials in various fields due to their ease of processability. Chopped glass fiber- and recycled newspaper cellulose fiber (RNCF)- reinforced poly(lactic acid) (PLA) composites were processed using a full size twin-screw extruder and an injection molder. Additionally, a glass-reinforced polypropylene (PP) composite was compounded and molded, and compared to PLA/RNCF and PLA/glass fiber composites. The tensile and flexural moduli of RNCF- reinforced composites were significantly higher when compared to the virgin resin. The morphology, evaluated by scanning electron microscopy, indicated uniform dispersion of both fibers in the PLA matrix. The mechanical and thermo-physical properties of PLA/RNCF, PLA/glass and PP/glass fiber composite were studied and compared using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). DMA results confirmed that the storage and loss moduli of the PLA/RNCF composites increased with respect to the pure polymer, whereas the mechanical loss factor (tan delta) decreased. The results of the TGA experiments indicated that the addition of fibers increased the thermal stability of the biocomposites compared to neat PLA. The heat defection temperature of PLA/RNCF was found to be comparable to that of the glass fiber-reinforced PLA composites. Such studies are of great interest in the development of environmentally friendly composites from biodegradable polymers.     

The effect of silane treated- and untreated-talc on the mechanical and physico-mechanical properties of poly(lactic acid)/newspaper fibers/talc hybrid composites

This paper evaluates the effect of the addition of silane treated- and untreated- talc as the fillers on the mechanical and physico-mechanical properties of poly(lactic acid) (PLA)/recycled newspaper cellulose fibers (RNCF)/talc hybrid composites. For this purpose, 10 wt% of a talc with and without silane treatment were incorporated into PLA/RNCF (60 wt%/30 wt%) composites that were processed by a micro-compounding and molding system. PLA is utilized is a bio-based polymer that made from dextrose, a derivative of corn. Talc is also a natural product. The RNCF and talc hybrid reinforcements of PLA polymer matrix were targeted to design and engineer bio-based composites of balanced properties with added advantages of cost benefits besides the eco-friendliness of all the components in the composites. In this work, the flexural and impact properties of PLA/RNCF composites improved significantly with the addition of 10 wt% talc. The flexural and impact strength of these hybrid composites were found to be significantly higher than that made from either PLA/RNCF. The hybrid composites showed improved properties such as flexural strength of 132 MPa and flexural modulus of 15.3 GPa, while the unhybridized PLA/RNCF based composites exhibited flexural strength and modulus values of 77 MPa and 6.7 GPa, respectively. The DMA storage modulus and the loss modulus of the PLA/RNCF hybrid composites were found to increase, whereas the mechanical loss factor (tan delta) was found to decrease. The storage modulus increased with the addition of talc, because the talc generated a stiffer interface in the polymer matrix. Differential scanning calorimetry (DSC) thermograms of neat PLA and of the hybrid composites showed nearly the similar glass transition temperatures and melting temperatures. Scanning electron microscopy (SEM) micrographs of the fracture surface of Notched Izod impact specimen of 10 wt% talc filled PLA/RNCF composite showed well filler particle dispersion in the matrix and no large aggregates are present. The comparison data of mechanical properties among samples filled with silane-treated- and untreated- talc fillers showed that the hybrid composites filled with silane treated talc displayed the better mechanical prosperities relative to the other hybrid composites. Talc-filled RNCF-reinforced polypropylene (PP) hybrid composites were also made in the same way that of PLA hybrid composites for a comparison. The PLA hybrid bio-based composites showed much improvement in mechanical properties as compared to PP-based hybrid counterparts. This suggests that these PLA hybrid bio-based composites have a potential to replace glass fibers in many applications that do not require very high load bearing capabilities and these recycled newspaper cellulose fibers could be a good candidate reinforcement fiber of high performance hybrid biocomposites.     

MAH改性方法对淀粉/聚乳酸界面相容性的影响

以玉米淀粉和聚乳酸(PLA)为原料,马来酸酐(MAH)为改性剂,通过熔融挤出法制备淀粉/PLA复合材料。研究了MAH分别作为增容剂和淀粉酯化剂这两种改性方法对淀粉/PLA相容性的影响,并对复合材料的熔融加工性能、力学性能和耐水性能进行了测试。X射线衍射(XRD)、扫描电子显微镜(SEM)和热重分析(TGA)结果都证明,MAH与原淀粉先进行干法酯化改性再与PLA复配制得酯化淀粉/PLA复合材料,比MAH作为增容剂直接添加制得原淀粉/MAH/PLA复合材料具有更好的界面相容性。受界面相容性提高程度的影响,酯化淀粉/PLA复合材料的熔融加工性能、拉伸强度、弯曲强度、断裂伸长率和耐水性能都优于原淀粉/MAH/PLA复合材料。     

A hybrid twin screw extrusion/electrospinning method to process nanoparticle-incorporated electrospun nanofibres

A new hybrid methodology that fully integrates the processing capabilities of the twin screw extrusion process (conveying solids, melting, dispersive and distributive mixing, pressurization, temperature profiling, devolatilization) with electrospinning is described. The hybrid process is especially suited to the dispersion of nanoparticles into polymeric binders and the generation of nanoparticle-incorporated fibres and nanofibres. The new technology base is demonstrated with the dispersion of β-tricalcium phosphate (β-TCP) nanoparticles into poly(ε-caprolactone) (PCL) to generate biodegradable non-woven meshes that can be targeted as scaffolds for tissue engineering applications. The new hybrid method yielded fibre diameters in the range of 200-2000?nm for both PCL and β-TCP/PCL (35% by weight) composite scaffolds. The degree of crystallinity of polycaprolactone meshes could be manipulated in the 35.1-41% range, using the voltage strength as a parameter. The electrospinning process, integrated with dispersive kneading disc elements, facilitated the decrease of the cluster sizes and allowed the continuous compounding of the nanoparticles into the biodegradable polymer prior to electrospinning. Thermogravimetric analysis (TGA) of the non-woven meshes validated the continuous incorporation of 35 ± 1.5% (by weight) β-TCP nanoparticles for a targeted concentration of 35%. Uniaxial tensile testing of the meshes with and without the nanoparticles indicated that the ultimate tensile strength at break of the meshes increased from 0.47 ± 0.04 to 0.79 ± 0.08?MPa upon the incorporation of the β-TCP nanoparticles. This demonstration study suggests that the new technology base is particularly suitable for the concomitant dispersion and electrospinning of nanoparticles in the generation of myriad types of functional nanofibres.     

PE-g-MAH/PP/高岭土复合材料的制备与性能

目的以PE,PP为原料,接枝马来酸酐(MAH)后,与高岭土经双螺杆挤出机熔融共混挤出,制备PE-g-MAH/PP/高岭土复合材料。方法采用电子万能试验机分析复合材料的拉伸性能;采用电子悬臂冲击实验机分析材料的缺口冲击强度;采用水平垂直燃烧仪测试分析复合材料的阻燃性;采用红外光谱仪分析复合材料的化学结构。结果含MAH质量分数为5%的PE与PP按质量比1∶1混合后,加入15%的高岭土,制备的PE-g-MAH/PP/高岭土复合材料拉伸强度、缺口冲击强度和断裂伸长率均为最佳,分别为10.925 MPa,40.6 k J/m2,89.5%;复合材料的阻燃性与高岭土加入量呈先快速增大后慢速降低趋势,加入量为15%时阻燃性最好;复合材料各组分间实现了化学键合。结论适量的高岭土提升了PE/PP复合材料的阻燃性,而MAH的加入改善了PE,PP和高岭土间的相容性。     

A simplified fabrication process for biofiber-reinforced polymer composites for automotive interior trim applications

A simplified process was developed for fabricating natural bio-based fiber-reinforced polymer composites for applications such as automotive interior trim substrates. Biofiber (Kraft pulp fiber) and four types of thermoplastic polymers (PP, two PP/PE polymer blends, and PLA) were first wet-formed into fiber/polymer mats and the mats were made into composites using a match-mold thermoforming process. The effects of void content on the composite tensile and flexural properties were investigated. Impact resistance and heat deflection temperature were tested and acoustic absorption coefficients of the composites were evaluated as well. Two types of prototype panels (2-D and 3-D) containing biofiber/polymer composite substrates with a bonded synthetic leather decorative surface were successfully made using this process. Biofiber/PP composites had comparable performance to the commercially available non-wood natural fiber/PP composite counterparts for the properties investigated in this study at the same density level (0.8 g/cm³).     

基于离散元法的双组份复合涂料搅拌螺杆参数优化

为了提高双组份复合涂料的混合均匀度，对搅拌螺杆的参数进行优化。以混合销钉式搅拌螺杆为对象，建立其三维模型后导入EDEM软件，然后基于离散元法对双组份复合涂料在该搅拌螺杆中的搅拌过程进行仿真分析，研究了螺杆的转速、螺距和长径比对混合均匀度的影响。最后通过单轴压缩实验对螺杆参数优化后的搅拌效果进行了对比验证。结果表明：螺杆转速、螺距和长径比分别通过改变颗粒抛撒程度、螺旋叶片间隙和螺杆长度来影响复合涂料的混合均匀度；稳定出料后，螺杆转速为200 r/min、螺距为80 mm、长径比为5.57∶1时的搅拌效果最佳；实验验证了利用优化后搅拌螺杆搅拌时复合涂料的力学性能优于手工搅拌时的。研究结果可为自动化搅拌螺杆的结构设计和参数优化提供理论依据。     

Characterization of thermoplastic natural fibre composites made from woven hybrid yarn prepregs with different weave pattern

This paper focuses on the effect of weave structure on mechanical behaviour and moisture absorption of the PLA/hemp woven fabric composites made by compression moulding. The unidirectional woven fabric prepregs were made from PLA (warp) and PLA/hemp wrapped-spun hybrid yarn (weft) with two different weave patterns; 8-harness satin and basket. Unidirectional composites with 30 mass% hemp content were fabricated from these prepregs, and compared to winded PLA/hemp hybrid yarn laminates with same composition. The composite from the satin fabric had significantly lowest porosities and best mechanical properties compared to the composite made from the winded hybrid yarn and basket fabric. The tensile, flexural, and impact strength were 88 MPa, 113.64 MPa, and 24.24 kJ/m², respectively. The effect of weave pattern on water absorption is significant. Although the composite from hybrid yarn laminate has larger water absorption than that of the pure PLA, it exhibits lower moisture absorption than both weaves.