The influence of chemical surface modification on the performance of sisal‐polyester biocomposites

This article concerns the effectiveness of various types and degrees of surface modification of sisal fibers involving dewaxing, alkali treatment, bleaching cyanoethylation and viny1 grafting in enhancing the mechanical properties, such as tensile, flexural and impact strength, of sisal‐polyester biocomposites. The mechanical properties are optimum at a fiber loading of 30 wt%. Among all modifications, cyanoethylation and alkali treatment result in improved properties of the biocomposites. Cyanoethylated sisal‐polyester composite exhibited maximum tensile strength (84.29 MPa). The alkali treated sisal‐polyester composite exhibited best flexural (153.94 MPa) and impac strength (197.88 J/m), which are, respectively, 21.8% and 20.9% higher than the corresponding mechanical properties of the untreated sisal‐polyester composites. In the case of vinyl grafting, acrylonitrile (AN)‐grafted sisal‐polyester composites show better mechanical properties than methyl‐methacrylate (MMA)‐grafted sisal composites. Scanning electron microscopic studies were carried out to analyze the fiber‐matrix interaction in various surface‐modified sisal‐polyester composites.     

接枝丙烯酸对SF/PP复合材料性能的影响

分别对短切剑麻纤维(SF)和聚丙烯(PP)进行接枝丙烯酸(AA)预处理后，采用片状层压工艺制备了SF／PP、SF／PP-g-AA、SF-g-AA／PP复合材料；测试了复合材料的力学性能，并观察了复合材料的断面形态。结果表明：SF／PP-g-AA复合材料的综合力学性能比SF／PP复合材料有明显提高，而SF-g-AA／PP复合材料的综合力学性能反而比SF／PP复合材料差。     

Preparation and properties of L‐lactide‐grafted sisal fiber–reinforced poly(lactic acid) composites

Pretreatment of the sisal fiber (SF) grafting with L‐lactide (LA) monomer via a ring‐opening polymerization catalyzed by a Sn(II)‐based catalyst was performed to improve the interfacial adhesion between SF and poly (lactic acid) (PLA). Biocomposites from LA‐grafted SF (SF‐g‐LA) and PLA were prepared by compression molding with fiber weight fraction of 10, 20, 30, and 40%, and then were investigated in contrast with alkali‐treated sisal fiber (ASF) reinforced PLA composites and untreated SF reinforced PLA composites. PLA composites reinforced by half‐and‐half SF‐g‐LA/untreated SF (half SF‐g‐LA) were prepared and studied as well, considering the disadvantages of SF‐g‐LA. The results showed that both the tensile properties and flexural properties of the SF‐g‐LA reinforced PLA composites were improved noticeably as the introduction of SF‐g‐LA, compared with pure PLA, untreated SF reinforced PLA composites and ASF reinforced PLA composites. The mechanical properties of the half SF‐g‐LA reinforced PLA composites were not worse, even better in some aspects, than the SF‐g‐LA reinforced PLA composites. Fourier transform infrared analysis and differential scanning calorimetry analysis exhibited that both the chemical composition and crystal structure of the SFs changed after LA grafting. In addition, the fracture surface morphology of the composites was studied by scanning electron microscopy. The morphological studies demonstrated that a better adhesion between LA‐grafted SF and PLA matrix was achieved. POLYM. COMPOS., 37:802–809, 2016. © 2014 Society of Plastics Engineers     

Graft copolymerization studies. III. Methyl methacrylate onto polypropylene and polyethylene terephthalate

The tert‐butoxy radical‐facilitated grafting of methyl methacrylate (MMA) onto commercial polypropylene (PP) pellets and fiber was investigated in heterogeneous conditions similar to practical systems. Free‐radical grafting of several other monomers onto PP fiber was also investigated. Also, preliminary data from the grafting of MMA onto poly(ethylene terephthalate) pellets is presented. The PP‐graft‐PMMA residues were detected by solid‐state ¹³C‐NMR and photoacoustic IR spectroscopy. There was a good correlation between the degree of grafting (DG) determined from these spectroscopic techniques and the results from gravimetric methods. A maximum grafting efficiency of over 50% was found, whereas DG (20%) remained constant at various PP pellet, initiator, and monomer concentrations. However, at relatively low PP fiber concentrations, the DG was 27%; the increase was most likely due to the greater surface area of the fiber. There was also a reduction in DG (14%) at relatively low initiator concentrations. The reaction conditions were altered to favor grafting by the addition of more polymer substrate. When the ratio of tert‐butoxy radicals to PP was decreased, more of the substrate remained unmodified, and empirical calculations showed the formation of grafts with up to 40 monomer units. At high initiator concentrations, calculations showed that the graft residues were 1–2 units long. Therefore, variation of the polymer, initiator, and monomer concentrations was shown to have a significant effect on grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 898–915, 2002     

Structural properties and mechanical behavior of injection molded composites of polypropylene and sisal fiber

Composites based on isotactic polypropylene (PP) and sisal fiber (SF) were prepared by melt mixing and injection molding. The melt mixing characteristics, thermal properties, morphology, crystalline structure, and mechanical behavior of the PP/SF composites were systematically investigated. The results show that the PP/SF composites can be melt mixed and injection molded under similar conditions as the PP homo‐polymer. For the composites with low sisal fiber content, the fibers act as sites for the nucleation of PP spherulites, and accelerate the crystallization rate and enhance the degree of crystallinity of PP. On the other hand, when the sisal fiber content is high, the fibers hinder the molecular chain motion of PP, and retard the crystallization. The inclusion of sisal fiber induces the formation of β‐form PP crystals in the PP/SF composites and produces little change in the inter‐planar spacing corresponding to the various diffraction peaks of PP. The apparent crystal size as indicated by the several diffraction peaks such as L_(110)α, L_(040)α, L_(130)α and L_(300)β of the α and β‐form crystals tend to increase in the PP/SF composites considerably. These results lead to the increase in the melting temperature of PP. Moreover, the stiffness of the PP/SF composites is improved by the addition of sisal fibers, but their tensile strength decreases because of the poor interfacial bonding. The PP/SF composites are toughened by the sisal fibers due to the formation of β‐form PP crystals and the pull‐out of sisal fibers from the PP matrix, both factors retard crack growth.     

剑麻纤维及其复合材料研究进展

介绍了剑麻纤维(SF)的结构特点、物理力学性能以及纤维改性处理方法,从纤维形态及增强基质出发综述了长、短SF及SF混杂纤维增强复合材料以及SF增强热塑性、热固性树脂和弹性体复合材料方面的研究与开发,指出了SF增强复合材料今后的研究方向。     

表面处理对PP/Al2O3性能与结晶的影响

为了改善无机粒子在聚合物基体中的分散性与相容性 ,采用 2种表面处理方法 :硅烷偶联剂KH5 70表面处理Al2 O3粒子得到烷基化粒子 ;另外在此基础上采用溶液聚合法在烷基化Al2 O3粒子表面进行MMA与单体的接枝聚合 ,制备PMMA包覆Al2 O3复合粒子Al2 O3-g -PMMA。采用XPS、IR研究烷基化粒子与复合粒子表面结构 ,同时通过无机粒子直接填充法与PP基体复合获得Al2O3/PP复合材料并研究其力学性能与结晶行为     

聚烯烃弹性体对剑麻纤维增强聚丙烯复合材料性能的影响

为提高剑麻(SF)增强聚丙烯(PP)复合材料的韧性,分别采取乙烯-辛烯共聚物(POE)和马来酸酐接枝POE(POE-g-MAH)二种弹性体对其进行增韧改性;研究了弹性体和纤维用量的变化对SF/PP/弹性体三元复合体系力学性能的影响及其内在原因。结果表明:POE和POE-g-MAH对剑麻增强聚丙烯复合材料均有良好的增韧效果;仅从增韧效果而言,在弹性体用量较低阶段POE优于POE-g-MAH,但当弹性体增至30%以后,POE-g-MAH则好于POE;在拉伸强度、拉伸模量、弯曲强度及弯曲模量方面,POE-g-MAH均比POE效果更好。     

Natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) blends

The grafting of the methyl methacrylate (MMA) monomer onto natural rubber using potassium persulfate as an initiator was carried out by emulsion polymerization. The rubber macroradicals reacted with MMA to form graft copolymers. The morphology of grafted natural rubber (GNR) was determined by transmission electron microscopy and it was confirmed that the graft copolymerization was a surface‐controlled process. The effects of the initiator concentration, reaction temperature, monomer concentration, and reaction time on the monomer conversion and grafting efficiency were investigated. The grafting efficiency of the GNR was determined by a solvent‐extraction technique. The natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) (NR‐g‐MMA/PMMA) blends were prepared by a melt‐mixing system. The mechanical properties and the fracture behavior of GNR/PMMA blends were evaluated as a function of the graft copolymer composition and the blend ratio. The tensile strength, tear strength, and hardness increased with an increase in PMMA content. The tensile fracture surface examined by scanning electron microscopy disclosed that the graft copolymer acted as an interfacial agent and gave a good adhesion between the two phases of the compatibilized blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 428–439, 2001     

剑麻纤维/长玻纤混杂增强PP复合材料的力学性能研究

采用剑麻纤维(SF)和长玻璃纤维(LGF)混杂增强聚丙烯(PP)复合材料,考察了SF/LGF的比例和含量对PP复合材料力学性能的影响。结果表明:SF/LGF在聚丙烯树脂基体中呈交叉网状分布,这有利于提高复合材料的冲击强度、弯曲模量、拉伸强度和软化点。在SF/LGF质量比为2 2∶,二者总质量分数为30%时,SF/LGF混杂增强PP复合材料的综合力学性能较好。     

Modification of sisal fiber by in situ coating steam explosion and electromagnetic interference shielding effectiveness of sisal fiber/PP composites

The technology of steam explosion was adopted to modify sisal fiber (SF) material and two different carbon particles, expanded graphite and conductive carbon black (CCB), were in situ coated on the surface of SF during steam explosion process. The DC conductivity and electromagnetic interference shielding effectiveness (SE) of the modified SF/polypropylene (PP) composites were studied and the measurement of electromagnetic interference (EMI) SE was conducted in two frequency ranges of 400–1,000 MHz and 1–18 GHz. The experimental results showed that this novel coating technology could improve the SE of the modified SF/PP composites significantly, which has a strong dependence on the loadings of the expanded graphite modified sisal fiber (SF‐EG) and conductive carbon black modified sisal fiber (SF‐CCB). When the loadings of SF‐EG and SF‐CCB reached 50 wt%, the maximum values of the SE were 33 dB and 51 dB, respectively. For the modified SF/PP composites, the experimental EMI SE values are in good correlation with the theoretical calculation values in far field of electromagnetic radiation. POLYM. COMPOS., 35:1038–1043, 2014. © 2013 Society of Plastics Engineers     

Preparation and characterization of EVA–sisal fiber composites

In this work, composites of an EVA polymer matrix and short sisal fiber were characterized. The physical‐morphological as well as chemical interactions between EVA and sisal were investigated. When the samples were prepared in the presence of dicumyl peroxide, the results suggest that crosslinking of EVA as well as grafting between EVA and the sisal fibers took place. Morphological changes were studied by scanning electron microscopy (SEM). Results from Hg‐porosimetry, SEM, Fourier transform infrared spectroscopy, surface free energy, and gel content strongly indicate grafting of EVA onto sisal under the composite preparation conditions, even in the absence of peroxide. The grafting mechanism could not be confirmed from solid‐state ¹³C NMR analysis. The grafting had an impact on the thermal and mechanical properties of the composites, as determined by differential scanning calorimetry and tensile testing. Thermogravimetric analysis results show that the composites are more stable than both EVA and sisal fiber alone. The composite stability, however, decreases with increasing fiber content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1607–1617, 2006     

Studies on mechanical properties of sisal fiber/phenol formaldehyde resin in‐situ composites

Phenol formaldehyde resin (PF) reinforced with short sisal fibers (SF) were obtained by two methods, direct‐mixing and polymerization filling. Impact and bending properties of resulting composites were compared. Under the same compression molding conditions, polymerization filled composites showed better mechanical properties than those of direct‐mixed composites. The influences of fiber modifications on the mechanical properties of SF/PF in‐situ (polymerization filled) composites have been investigated. Treated‐SF‐reinforced composites have better mechanical properties than those of untreated‐SF‐reinforced composites. The effects of SF on water absorption tendencies of SF/PF composites have also been studied. In addition, sisal/glass (SF/GF) hybrid PF composites of alkali‐treated SF were prepared. Scanning electron microscopic studies were carried out to study the fiber‐matrix adhesion. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Production of leather-like composites using short leather fibers. II. Mechanical characterization

Leather-like composites were prepared by addition of chemically modified short leather fibers (SLF) into a plasticized polyvinyl chloride (pPVC) matrix. The fibers were subjected to chemical modification by emulsion polymerization to achieve good interfacial adhesion between SLF and the pPVC matrix. The SLF with chemical modification were obtained from three different reaction conditions where these SLF have different percentages of grafted and deposited PMMA polymer onto the fiber surface. The incorporation of the SLF into the thermoplastic matrix was carried out using a torque-rheometer and the composites obtained were molded by compression. Tensile and tear mechanical tests were performed on composite samples, and the morphology of the fractured surfaces was analyzed using scanning electron microscopy (SEM). The results show that the incorporation by grafting of polymethyl metacrylate (PMMA) onto the fibers produced a significant improvement of their interfacial adhesion to pPVC, promoting the compatibilization between the fiber surface and matrix. The findings are discussed and interpreted in terms of enhanced adhesion at phase boundaries. Overall, the results confirm that it is possible to produce modified leather composites based on a pPVC matrix, which exhibit relatively high tensile strength, tear resistance and flexibility. These composites are very suitable candidate materials for applications in the footwear industry.     

A low‐cost,low‐fiber‐breakage,injection molding process for long sisal fiber reinforced polypropylene

Composites of polypropylene (PP) and non‐treated sisal fiber (SF) were prepared in a non‐conventional two‐step process that offers significant advantages. Maleic anhydride–grafted polypropylene (MA‐g‐PP) was used as a coupling agent, to improve adhesion between the polar sisal fiber and the non‐polar polypropylene continuous matrix. At a first step, SF/MA‐g‐PP pellets with large aspect ratio and very high fiber content are prepared by extrusion impregnation and coating of a continuous SF yarn, followed by cooling and cutting. The composite pellets are thus dry blended with regular PP pellets in the injection machine hopper, and injected to obtain composite tensile specimens with a minimum quantity of expensive MA‐g‐PP, minimum fiber breakage and thermal degradation, and excellent mechanical properties. The SF/MA‐g‐PP pellets have a fiber content of 70% (w/w). The composite tensile specimens have final fiber contents ranging from about 3.5% to 24.5% (w/w). The PP tensile strength rises by about 44%. The tensile modulus increases by 126%, and the heat distortion temperature (HDT) is raised by about 35 K. FT‐IR spectroscopy and SEM micrographic observation show that the MA‐g‐PP is covalently bonded to SF through esterification. Besides the improvement in mechanical and thermal properties, costs are reduced because of the lower content of very expensive MA‐g‐PP, and the use of a single‐screw extruder at high production rates. Polym. Eng. Sci. 44:1766–1772, 2004. © 2004 Society of Plastics Engineers.     

The influence of fiber surface modification on the mechanical properties of coir‐polyester composites

Coir, an important lignocellulosic fiber, can be incorporated in polymers like unsaturated polyester in different ways for achieving desired properties and texture. But its high level of moisture absorption, poor wettability and insufficient adhesion between untreated fiber and the polymer matrix lead to debonding with age. In order to improve the above qualities, adequate surface modification is required. In our present work, fiber surface modification was effected through dewaxing, alkali (5%) treatment, aqueous graft copolymerization of methyl methacrylate (MMA) onto 5% alkali treated coir for different extents using CuSO₄ – NaIO₄ combination as an initiator system and cyanoexhylation with a view to improve the mechanical performance of coir‐polyester composites. Mechanical properties like tensile strength (PS), flexural strength (ES) and impact strength (IS) of the composites as a function of fiber loading and fiber surface modification have been evaluated. Composites containing z5 wt% of fiber (untreated) improved tensile and flexural strength by 30% and 27% respectively in comparison to neat polyester. The work of fracture (impact strength) of the composite with 25 wt% fiber content was found to be 967 J/m. The elongation at break of the composites exhibits an increase with the introduction of fiber, All types of surface modification result In improved mechanical properties of the composites. Significant improvement in mechanical strength was also observed for composites prepared from 5% PMMA grafted fiber.     

Injection molding of long sisal fiber–reinforced polypropylene: Effects of compatibilizer concentration and viscosity on fiber adhesion and thermal degradation

A two‐step process was used to obtain long sisal fiber‐polypropylene (SF/PP)–reinforced thermoplastic composites, using maleic anhydride grafted polypropylene (MA‐g‐PP) as a compatibilizer. At a first stage, modified polypropylenes (mPP) were used for an extrusion impregnation process, for the preparation of composite pellets containing about 70 wt% of SF. SF/mPP pellets with a large aspect ratio were prepared by continuous extrusion impregnation of a continuous SF yarn, using a single screw extruder and an adequate impregnation die. The mPP used were MA‐g‐PP and regular polypropylene (PP), modified by reaction with different amounts of an organic peroxide. The composite pellets were thus dry blended with regular PP pellets in an injection machine hopper, and injection molded to obtain composite tensile specimens with a minimum quantity of modified polypropylene, minimum fiber breakage and thermal degradation, and excellent mechanical properties. It is shown that the fiber breakage is reduced to a minimum, even for recycled composites, due to the presence of the low‐viscosity polymer layer wetting the SF fibers. The bulk composite effective viscosity and the fiber breakage extent and thermal degradation during the injection‐molding step are found to be closely related. Blending with much less expensive mPP at the impregnation stage optimizes the amount of expensive MA‐g‐PP. POLYM. ENG. SCI., 45:613–621, 2005. © 2005 Society of Plastics Engineers     

剑麻纤维/聚丙烯木塑复合材料的热氧老化性能研究

以剑麻纤维(SF)、聚丙烯(PP)为原料,经熔融共混、模压成型工艺制备木塑复合材料。探讨了SF/PP复合材料的力学性能、热性能随老化时间和SF含量的变化规律,借助扫描电镜对复合材料老化前后的冲击断面进行微观结构分析。结果表明:老化后复合材料的冲击强度、弯曲强度和弯曲模量随剑麻含量的增加而降低;同时,复合材料中PP相的结晶速率、结晶度也有所降低,但复合材料的热稳定性基本没有变化。     

Electrical conductivity and electromagnetic interference shielding effectiveness of carbon black/sisal fiber/polyamide/polypropylene composites

The effects of hybrid fillers on the electrical conductivity and electromagnetic interference (EMI) shielding effectiveness (SE) of polyamide 6 (PA6)/polypropylene (PP) immiscible polymer blends were investigated. Carbon black (CB) and steam exploded sisal fiber (SF) were used as fillers. CB was coated on the surface of SF, and this was exploded by water steam to form carbon black modified sisal fiber (CBMSF). CB/SF/PA6/PP composites were prepared by melt compounding, and its electromagnetic SE was tested in low‐frequency and high‐frequency ranges. We observed that SF greatly contributed to the effective decrease in the percolation threshold of CB in the PA6/PP matrix and adsorbed carbon particles to form a conductive network. Furthermore, an appropriate CB/SF ratio was important for achieving the best shielding performance. The results indicate that CBMSF was suitable for use as electronic conductive fillers and the CB/SF/PA6/PP composites could be used for the purpose of EMI shielding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42801.     

Use of preimpregnated sisal yarn in woven reinforced polypropylene sheets: Thermoformability and mechanical properties

Thermoplastic composites were made from polypropylene (PP) and long sisal fibers (SF) by using different processing techniques. Four sets of composites specimens were made with a 60/40 (wt/wt) SF/PP ratio: the first set was made by melt‐blending PP and SF and compression molding 2‐mm‐thick flat sheets; a second set was made by melt‐blending PP, SF, and maleic anhydride grafted polypropylene (MA‐g‐PP); the third set was made by compression molding knitted SF yarns, preimpregnated with PP, between PP sheets; the fourth set was also made by compression molding knitted SF yarns, preimpregnated with diluted MA‐g‐PP, between PP sheets. The bidirectional array of fibers, containing 60% of SF well‐impregnated with a small quantity of MA‐g‐PP, increases the flexural modulus by 600%, the tensile modulus by 475%, and the tensile strength by 300% compared with unfilled PP. The composites sheets were successfully thermoformed with small wall thickness reductions to obtain a three‐dimensional (3D) shape with very low forming energy, outstanding mechanical properties, and excellent surface finish. POLYM. ENG. SCI., 45:976–983, 2005. © 2005 Society of Plastics Engineers