Unidirectional hemp and flax EP‐ and PP‐composites: Influence of defined fiber treatments

In some technical areas, mainly in the automotive industry, glass fiber reinforced polymers are intended to be replaced by natural fiber reinforced polymer systems. Therefore, higher requirements will be imposed to the physical fiber properties, fiber‐matrix adhesion, and the quality assurance. To improve the properties of epoxy resins (EP) and polypropylene (PP) composites, flax and hemp fibers were modified by mercerization and MAH‐PP coupling agent was used for preparing the PP composites. The effects of different mercerization parameters such as concentration of alkali (NaOH), temperature, and duration time along with tensile stress applied to the fibers on the structure and properties of hemp fibers were studied and judged via the cellulose I–II lattice conversion. It was observed that the mechanical properties of the fibers can be controlled in a broad range by using appropriate mercerization parameters. Unidirectional EP composites were manufactured by the filament winding technique; at the PP matrix material, a combination with a film‐stacking technique was used. The influence of mercerization parameters on the properties of EP composites was studied with hemp yarn as an example. Different macromechanical effects are shown at hemp‐ and flax‐PP model composites with mercerized, MAH‐PP‐treated, or MAH‐PP‐treated mercerized yarns. The composites' properties were verified by tensile and flexural tests. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2150–2156, 2004     

ABS/PP合金材料的研制

利用Brabender挤出机和密炼机分别制备了熔融接枝物PP g MAH,研究了ABS／PP、ABS／PP g MAH、ABS／PP／PP g MAH三种共混物的性能,且作了对比。实验结果表明:PP g MAH的加入,能在一定程度上改善共混物的冲击性能、加工流动性能和耐热性能。     

PA／PP—g—MAH／PP共混物的界面和形态研究

用小角X光衍射和偏光显微镜等方法研究了具有相容区的PA101／PP-g-MAH/PP熔融共混物的界面和结晶开态，PA101和PP－g-MAH在熔融共混过程中生成新的基团，在相间存有界面，体系中两相的结晶形态均匀，共混物的拉伸屈服强度随着界面层厚度的增大而提高。     

Melt grafting of maleic anhydride onto polypropylene with 1‐decene as a second monomer

The influence of 1‐decene as the second monomer on the melt‐grafting behavior of maleic anhydride (MAH) onto polypropylene (PP) was studied with differential scanning calorimetry and Fourier transform infrared spectroscopy. We found that the value of the grafting degree increased from 0.68% for pure MAH‐g‐PP to 1.43% for the system with a 1‐decene/MAH molar ratio of 0.3, whereas the maximum value with styrene (St) as the second monomer was 0.98% under an St/MAH molar ratio of 1.0. Compared with the contribution of St/MAH‐g‐PP to the peeling strength between the PP and polyamide (PA) layer for a PP/PA laminated film, the introduction of 1‐decene/MAH‐g‐PP increased the peeling strength from 180 g/15 mm to 250 g/15 mm. 1‐Decene inhibited the chain scission behavior of PP. 1‐Decene reacted with MAH to form a 1‐decene/MAH copolymer or the Alder‐ene reaction product before the two monomers grafted onto PP. The grafting of the reactive product onto PP greatly improved the grafting degree of MAH. What is more, because of the similar chemical structures of 1‐decene and PP, the affinity of 1‐decene with PP was higher than that of St. Compared with St, the introduction of less 1‐decene led to a higher grafting degree and higher peeling strength. Therefore, we concluded that 1‐decene was more effective for improving the grafting degree of MAH onto PP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polypropylene–clay blends compatibilized with MAH‐g‐POE

A series of new Polypropylene (PP)–clay blends, containing 5 wt % clay, were prepared by melt compounding with maleic anhydride grafted poly(ethylene‐co‐octene) (MAH‐g‐POE) as the compatibilizer by varying its content from 0 to 20 wt %. The effect of MAH‐g‐POE on the PP–clay miscibility was examined by X‐ray diffraction (XRD), scanning electronic microscope (SEM) observation, differential scanning calorimeter (DSC) analysis, dynamic mechanical thermal analysis (DMTA), and rheological testing in sequence. The results showed that the addition of MAH‐g‐POE could improve the dispersion of clay layers in PP matrix and promoted the interaction between PP molecules and clay layers. At 10 wt % MAH‐g‐POE, the PP–clay blend exhibited a highest value of Tc,onset and Tg as well as a biggest melt storage modulus (G′), indicating the greatest PP–clay interaction. On the other hand, improved toughness and stiffness coexisted in blends with 5–10 wt % loading of MAH‐g‐POE. In view of SEM and DMTA observations, MAH‐g‐POE was well miscible with the PP matrix, even with the concentration up to 20 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2558–2564, 2006     

PP-g-(MAH/VAc)接枝物对PP/PA6体系的增容作用

通过扫描电镜、差示扫描量热仪和力学性能测试等方法研究了聚丙烯接枝马来酸配和酷酸乙烯酷(PP-g-MAH/VAc)对聚丙烯康酸胺6(80/20}共混体系的增容效果。结果表明,PP-g-(MAH/DAc)用于PP/PA6共混体系,分散相PA6的微区尺寸可以减小到5μm以下,相应地提高了共混物的断裂伸长率、拉伸强度和冲击强度。使用接枝率为5.3%的PP-g-(MAH/VAc)作为相容剂,当用量为8%时,体系的拉伸强度为60.88MPa,断裂伸长率为558%,冲击强度为5.28KJ/㎡.DSC分析表明,PP/PA6共混体系各组分相互促进成核,结晶度降低。FTIR结果表明,PP-g-(MAH/VAc)中的MAH上的酸配基团与PA6中的酸胺键发生了化学反应从而改善了体系的相容性。     

Flax fibre physical structure and its effect on composite properties: Impact strength and thermo-mechanical properties

Earlier investigations by the authors showed that the tensile modulus of flax fibre mat polypropylene composites (NMT) could surpass the values of glass mat reinforced thermoplastic (GMT) on fibre weight basis. The tensile and flexural strength could reach values of up to 65% of the GMT strength values, however, very much dependent on the fibre physical structure. This study deals with the Charpy impact and the thermo-mechanical properties of flax NMT materials. The trend is that the Charpy impact strength decreases with increasing fibre internal bonding and enhanced fibre-matrix adhesion, which is opposite to the trend for the tensile and flexural properties. The impact strength of the NMT materials is lower than generally reported for GMT materials. Dynamic mechanical thermal analysis reveals that with increasing temperature the storage modulus of the NMT materials reduces more slowly when the fibre internal bonding and the fibre-matrix adhesion are improved. In order to approach the tensile, flexural and impact strength of GMT materials, composites should be based on the strong elementary flax fibres. The axial tensile strength of elementary fibres approaches the strength of glass fibres and the lateral strength of the elementary fibres is higher than the technical flax fibres lateral strength. The thermo-mechanical properties can probably be improved when non-cellulosic material can be removed from the flax fibre surface without damaging the fibre.     

玻璃纤维与聚丙烯界面性能的研究

利用小跨度变曲的方法研究了玻璃纤维增强PP复合材料的层间剪切强度(ILSS)。进行了偶联剂的评选,考察了偶联剂和接核物PP-g-MAH用量对层间剪切强度的影响。试验表明,玻璃纤维经偶联剂处理后,提高了与PP的层间剪切强度,PP-g-MAH在玻璃纤维与PP之间起到了较好的增容作用,研究了接技物PP—g—MAH的增容效果。     

Synergetic toughness and morphology of poly(propylene)/nylon 11/maleated ethylene‐propylene diene copolymer blends

Polypropylene (PP)/nylon 11/maleated ethylene‐propylene‐diene rubber (EPDM‐g‐MAH) ternary polymer blends were prepared via melt blending in a corotating twin‐screw extruder. The effect of nylon 11 and EPDM‐g‐MAH on the phase morphology and mechanical properties was investigated. Scanning electron microscopy observation revealed that there was apparent phase separation for PP/EPDM‐g‐MAH binary blends at the level of 10 wt % maleated elastomer. For the PP/nylon 11/EPDM‐g‐MAH ternary blends, the dispersed phase morphology of the maleated elastomer was hardly affected by the addition of nylon 11, whereas the reduced dispersed phase domains of nylon 11 were observed with the increasing maleated elastomer loading. Furthermore, a core‐shell structure, in which nylon 11 as a rigid core was surrounded by a soft EPDM‐g‐MAH shell, was formed in the case of 10 wt % nylon 11 and higher EPDM‐g‐MAH concentration. In general, the results of mechanical property measurement showed that the ternary blends exhibited inferior tensile strength in comparison with the PP matrix, but superior toughness. Especially low‐temperature impact strength was obtained. The toughening mechanism was discussed with reference to the phase morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melting and crystallization behaviors,morphology, and mechanical properties of β‐polypropylene/polypropylene‐graft‐maleic anhydride/calcium sulfate whisker composites

The melting and crystallization behaviors, morphology, and mechanical properties of polypropylene (PP)/surface‐treated calcium sulfate (CaSO₄) whisker (T‐CSW), β‐PP/T‐CSW, and β‐PP/polypropylene‐graft‐maleic anhydride (PP‐g‐MAH)/T‐CSW composites had been investigated via differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized light microscopy (PLM), scanning electron microscopy (SEM), and mechanical tests. We found that T‐CSW was an α‐nucleating agent and increased the crystallization temperatures of PP, but PP‐g‐MAH and high loadings of T‐CSW had weakly negative effects on the crystallization rates of PP. The T‐CSW restrained the formation of β‐spherulites, and the spherulitic size decreased in the composites. PP‐g‐MAH improved the compatibility and adhesion between T‐CSW and the matrix. The notched impact strength was improved, and the tensile strength was enhanced at low levels of T‐CSW, while the flexural modulus was weakened for β‐PP/T‐CSW and β‐PP/PP‐g‐MAH/T‐CSW composites versus PP/T‐CSW composites. POLYM. COMPOS., 37:2121–2132, 2016. © 2015 Society of Plastics Engineers     

Dynamically cured polypropylene/Novolac blends compatibilized with maleic anhydride‐g‐polypropylene

In this article, the dynamic vulcanization process was applied to polypropylene (PP)/Novolac blends compatibilized with maleic anhydride‐grafted PP (MAH‐g‐PP). The influences of dynamic cure, content of MAH‐g‐PP, Novolac, and curing agent on mechanical properties of the PP/Novolac blends were investigated. The results showed that the dynamically cured PP/MAH‐g‐PP/Novolac blend had the best mechanical properties among all PP/Novolac blends. The dynamic cure of Novolac improved the modulus and stiffness of the PP/Novolac blends. The addition of MAH‐g‐PP into dynamically cured PP/Novolac blend further enhanced the mechanical properties. With increasing Novolac content, tensile strength, flexural modulus, and flexural strength increased significantly, while the elongation at break dramatically deceased. Those blends with hexamethylenetetramine (HMTA) as a curing agent had good mechanical properties at HMTA content of 10 wt %. Scanning electron microscopy (SEM) analysis showed that dynamically cured PP/MAH‐g‐PP/Novolac blends had finer domains than the PP/MAH‐g‐PP/Novolac blends. Thermogravimetric analysis (TGA) results indicated that the incorporation of Novolac into PP could improve the thermal stability of PP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of the compatibilizer on the morphology and properties of dynamically cured PP/POE/epoxy blends

Dynamic vulcanization was successfully applied to epoxy resin reinforced polypropylene (PP)/ethylene‐octene copolymer (POE) blends, and the effects of different compatibilizers on the morphology and properties of dynamically cured PP/POE/epoxy blends were studied. The results show that dynamically cured PP/POE/epoxy blends compatibilized with maleic anhydride‐grafted polypropylene (MAH‐g‐PP) have a three‐phase structure consisting of POE and epoxy particles dispersed in the PP continuous phase, and these blends had improved tensile strength and flexural modulus. While using maleic anhydride‐grafted POE (MAH‐g‐POE) as a compatibilizer, the structure of the core‐shell complex phase and the PP continuous phase showed that epoxy particles could be embedded in MAH‐g‐POE in the blends, and gave rise to an increase in impact strength, while retaining a certain strength and modulus. DSC analysis showed that the epoxy particles in the blends compatibilized with MAH‐g‐PP were more efficient nucleating agents for PP than they were in the blends compatibilized with MAH‐g‐POE. WAXD analysis shows that compatibilization do not disturb the crystalline structure of PP in the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of fiber/matrix chemical modification on the mechanical properties and water absorption of extruded flax/polypropylene composite

Compound of flax/polypropylene (PP) is characterized concerning the mechanical properties of stiffness, strength, and impact in addition to the water absorption behavior. Manufacturing takes place by twin‐screw extruder. The extruder screw layout is modified through different kneading elements to get high fiber aspect ratio. Sodium hydroxide solution was used as a washing solution for the flax fibers' surfaces. Both fiber and matrix are chemically modified. Selected groups of the fibers were further treated using trimethoxyvinylsilan TMVS and acrylic acid AA. The PP matrix is also treated with different coupling agents; namely, maleated PP MAPP, TMVS‐MAPP, and acrylic acid‐functionalized PP AAPP. The combinations of different fiber/matrix are extruder compounded, injection molded, and finally tested. Fiber modification seems to be positive with AA‐modified surface. AAPP matrix modification improves the stiffness four times that of the untreated flax/PP. Till 30 and 40 wt %, the more the fiber is the more the strength and stiffness, respectively. MAPP‐modified matrix improves the mechanical properties and keeps low water absorption values. AAPP‐modified matrix shows the best stiffness values. TMVS‐MAPP does not seem to have distinguished improvement compared with MAPP. NaOH‐TMVS/MAPP and NaOH‐TMVS/AAPP systems can serve as alternatives to the normal NaOH/MAPP treatment. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PP/蒙脱土纳米复合材料的制备、结构与性能

采用聚丙烯(PP)与甲基丙烯酸甲酯(MMA)、马来酸酐(MAH)、丙烯酸丁酯(BA)三单体的固相接枝共聚物(TMPP)作为相容剂，通过熔融共混法制备了PP／蒙脱土纳米复合材料，对纳米复合材料的热稳定性能和阻燃性能进行了研究，用X射线衍射分析和透射电镜表征了该纳米材料的结构。结果表明，少量TMPt，的加入，可明显提高复合材料的力学性能，其拉伸强度提高10％，冲击强度提高88％，弯曲模量提高90％；蒙脱土在PP基体中主要以插层形式存在，同时存在少量的剥离结构。     

用PP—g—MAH改进PP／GF带材性能的研究

用红外光谱法表征了接枝物的存在,考察了不同马来酸酐(MAH)用量和加工设备对接枝率的影响,并将接技物加入到聚丙烯/玻璃纤维(PP/GF)体系中挤出带材。通过测试,发现PP接枝物的加入提高了带材的弯曲强度,表明PP-g-MAH提高了相界面的作用力。     

沉淀法制备EPDM-g-MAZn离聚物及其对膨胀阻燃聚丙烯性能的影响

针对膨胀阻燃剂在有效提高聚丙烯(PP)阻燃性能的同时会大大降低PP力学性能的问题,以自制的马来酸酐(MAH)接枝三元乙丙橡胶锌离聚物(EPDM-g-MAZn)作为PP/IFR阻燃材料的改性剂,研究其对PP/IFR阻燃性能以及力学性能的影响及其机理.结果表明,EPDM-g-MAZn离聚物能在保持PP/IFR材料良好阻燃性能并在基本不损失拉伸强度的同时使PP/IFR材料的冲击强度提高4.46倍,拉伸强度的保留率明显高于PP/EPDM-g- MAH/IFR.ZnO与EPDM-g-MAH上的MAH形成的离子键作用可以形成以ZnO连接很多EPDM的交联结构,在PP与IFR之间起交联剂和补强剂的作用,提高界面结合强度,从而有效提高PP/IFR材料的力学性能.     

Effect of stacking sequence on mechanical properties of hybrid flax/jute fibers reinforced thermoplastic composites

In this study, the hybrid composites were prepared by stacking jute/PP nonwoven and flax/MAPP woven fabrics in defined sequences. Polypropylene (PP) and maleic anhydride grafted polypropylene (MAPP) were used as matrix materials. Jute and flax fibers were treated with alkali solution in order to improve the interface properties of the resultant composites. The mechanical properties of these hybrid composites were analyzed by means of tensile, flexural, and drop‐weight impact tests. The effect of fabric stacking sequence on the mechanical properties of the composites was investigated. The stacking of nonwovens at the top and in alternate layers has resulted in maximum flexural strength, flexural stiffness, and impact force. It was also shown that hybrid composites have improved tensile, flexural, and impact properties in comparison to neat PP matrix. POLYM. COMPOS., 36:2167–2173, 2015. © 2014 Society of Plastics Engineers     

The effect of graft copolymers of maleic anhydride and epoxy resin on the mechanical properties and morphology of PP/ABS blends

In this work, maleic anhydride‐grafted polypropylene (PP‐g‐MAH) and maleic anhydride‐grafted poly(acrylonitrile‐butadiene‐styrene) (ABS‐g‐MAH) at 2 : 1 mass ratio were added as a compatibilizer in the PP/ABS blends. The compatibilizing effect was evaluated by adding the graft copolymers together with epoxy resin/imidazole curing agent (E51/2E4MZ). The reaction in reactive extrusion, morphological structure, and properties of PP and ABS blends were investigated by using infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray spectrum, transmission electron microscope (TEM), dynamic thermomechanical analysis (DMA), differential scanning calorimetry (DSC), and mechanical properties tests. The results showed that the compatibilizing effect was greatly improved because of the addition of the graft copolymers together with epoxy resin/imidazole curing agent (E51/2E4MZ) because the link structure of PP‐g‐MAH and ABS‐g‐MAH was formed by the reaction of anhydride group with epoxy group catalyzed by the imidazole. The size of the dispersed phase decreased dramatically, the interfacial adhesion between ABS particles and PP matrix was improved, and the tensile strength and flexural modulus of the PP/ABS blends increased further. The optimizing properties were obtained at 3 phr E51/2E4MZ. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40898.     

Dynamically cured polypropylene/epoxy blends

The dynamic vulcanization process, usually used for the preparation of thermoplastic elastomers, was used to prepare polypropylene (PP)/epoxy blends. The blends had crosslinked epoxy resin particles finely dispersed in the PP matrix, and they were called dynamically cured PP/epoxy blends. Maleic anhydride grafted polypropylene (MAH‐g‐PP) was used as a compatibilizer. The effects of the reactive compatibilization and dynamic cure were studied with rheometry, capillary rheometry, and scanning electron microscopy (SEM). The crystallization behavior and mechanical properties of PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends were also investigated. The increase in the torque at equilibrium for the PP/MAH‐g‐PP/epoxy blends indicated the reaction between maleic anhydride groups of MAH‐g‐PP and the epoxy resin. The torque at equilibrium of the dynamically cured PP/epoxy blends increased with increasing epoxy resin content. Capillary rheological measurements also showed that the addition of MAH‐g‐PP or an increasing epoxy resin content increased the viscosity of PP/epoxy blends. SEM micrographs indicated that the PP/epoxy blends compatibilized with PP/MAH‐g‐PP had finer domains and more obscure boundaries than the PP/epoxy blends. A shift of the crystallization peak to a higher temperature for all the PP/epoxy blends indicated that uncured and cured epoxy resin particles in the blends could act as effective nucleating agents. The spherulites of pure PP were larger than those of PP in the PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends, as measured by polarized optical microscopy. The dynamically cured PP/epoxy blends had better mechanical properties than the PP/epoxy and PP/MAH‐g‐PP/epoxy blends. With increasing epoxy resin content, the flexural modulus of all the blends increased significantly, and the impact strength and tensile strength increased slightly, whereas the elongation at break decreased dramatically. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1437–1448, 2004     

聚丙烯/马来酸酐接枝聚丙烯/超细云母的界面增容及其断面形态研究

:针对 PP/云母相界面缺乏亲和力 ,云母对 PP力学性能改善不明显的缺陷 ,采用偶联剂KH- 570与 PP- g- MAH并用的技术对超细云母进行表面处理并与 PP共混增容。结果表明 ,云母能同时有效提高 PP的强度、模量、硬度和冲击强度。其中 ,由于 PP- g- MAH导致的界面强度提高和界面层厚度增加 ,使 KH- 570与 PP- g- MAH并用的 PP/PP- g- MAH/云母 - 4#材料比单用 KH- 570的PP/云母 - 4# 材料的改性效果更加明显。同时发现 ,云母对 PP的结晶过程具有较明显的成核作用 ,使改性 PP的结晶温度和熔融温度提高