Comparison of the effects of polyethylenimine and maleated polypropylene coupling agents on the properties of cellulose‐reinforced polypropylene composites

The desire to improve the properties of cellulose‐reinforced composites while producing them by methods as similar as possible to those used on an industrial scale is one of the driving forces in this field of research. In this work, extensive research for determining the mechanical, thermal, rheological, and physical properties of novel cellulose‐reinforced polypropylene composites containing a polyethylenimine (PEI) coupling agent was conducted. A comparison of their properties with those of reference composites without any coupling agent or containing a maleated polypropylene (MAPP) coupling agent was also carried out. The presence of the PEI coupling agent mainly gave rise to a substantial increase in the tensile and flexural strengths and elongations as well as the impact strength, heat deflection temperature (HDT), melt volume flow index, and water absorption of PEI‐containing composites in comparison with composites without any coupling agent added. However, the increases achieved in the tensile and flexural composite strengths and HDT were lower than those achieved with the MAPP coupling agent mainly for composites containing 50 wt % cellulose fibers. On the other hand, PEI‐containing composites exhibited, in most cases, larger elongations and energies required to break in tensile tests as well as larger impact strengths, melt volume flow indices, and water absorption percentages than MAPP‐containing composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Maleic anhydride grafted polypropylene as a coupling agent for polypropylene composites filled with ink‐eliminated waste paper sludge flour

Ink‐eliminated sludge flour (IESF), a waste residue from the recycling treatment of waste paper, is a promising new kind of filler for thermoplastic polymers with a good price/performance ratio and advantages for environmental protection. In this study, high‐impact polypropylene (PP) and maleic anhydride grafted polypropylene (MAPP) were chosen as a polymer matrix and a coupling agent, respectively, for the preparation of IESF/PP composites, and the structures and properties of the obtained composites were also investigated. The experimental results revealed that IESF not only induced the crystallization orientation of PP along the b axis but also had a restraining effect on the formation of the β phase during the recrystallization of PP from the melt; the addition of MAPP further strengthened this effect to some extent. In addition, the proper addition of MAPP was helpful for improving the thermal stability of the IESF/PP composites. With the strengthening of the interfacial interaction between the IESF and PP matrix by MAPP, the resultant efficient stress transfer from the PP matrix to the IESF particles led to increased tensile and flexural strength. However, the original greater rigidity of MAPP, with respect to PP, reduced the toughness of the composites and caused some negative effects on the impact strength and the elongation at break. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2320–2325, 2004     

New hyperdispersant agent for polypropylene/CaSO4 composites

A new hyperdispersant agent with Si? OH as an anchoring group and poly(butyl acrylate) as a solvatable chain was synthesized, and its effect on the properties of polypropylene (PP)/CaSO₄ composites was investigated. Fourier transform infrared spectroscopy results showed that the hyperdispersant agent reacted on the CaSO₄ surface and the modified CaSO₄ particles. The tensile strength and impact strength of the PP/CaSO₄ composites increased about 14 and 34%, respectively, versus that of PP/CaSO₄ (filled with the same unmodified fraction). According to surface analysis by scanning electron microscopy, the CaSO₄ particles were buried well in the PP matrix when CaSO₄ was coated with the hyperdispersant agent. CaSO₄ significantly increased the crystallization temperature and crystallization rate of PP by differential scanning calorimetry, but the addition of hyperdispersant‐agent‐modified CaSO₄ did not lead to the formation of crystalline PP through X‐ray diffraction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cellulose/syndiotactic polypropylene composites: Effects of maleated polypropylene as a compatibilizer and silanized cellulose on the morphology and tensile properties

To improve the interaction between syndiotactic polypropylene (SPP) and fibrous cellulose (FC), the effects of the addition of maleated polypropylene (MAPP) and FC surface modification with 3‐aminopropyltriethoxysilane (APTES) on SPP/FC composites were studied with respect to the morphology and the tensile properties. The addition of MAPP brought about an improvement in the interfacial adhesion between SPP and FC according to scanning electron microscopy observations and tensile testing. This improvement was, however, less effective than the improvement in the interfacial adhesion between isotactic polypropylene (IPP) and FC. SPP and MAPP partially or microscopically phase‐separated because of the IPP‐like polymer chain structure of MAPP. With respect to the compatibility between SPP and FC, FC surface modification with APTES was more suitable. The increase in Young's modulus was remarkable in the SPP/silanized FC composite with APTES. The tensile strength of the SPP/silanized FC composite with APTES was, however, considerably lower than that of the SPP/FC/MAPP composite. These results suggest that interfacial improvement between SPP and FC requires a compatibilizer or a surface modifier with a suitable primary structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Interface adhesion properties of syndiotactic polypropylene/cellulose group composite: Relationship between chemical structure of coupling agent and reactivity for cellulose group

Reinforcement of interfacial adhesion between syndiotactic polypropylene (SPP) and fibrous pure cellulose (FC) was performed by the FC silanizations with 3‐aminopropyltrimethoxysilane (APTMS), with hexyltrimethoxysilane (HTMS) and by an addition of a SPP grafted with dimethyl itaconate (SPP‐g‐DMI: number‐average molecular weight = 3.3 × 10⁴, DMI cont. = 0.11 wt %), respectively. The adhesion and the morphology were improved by them, respectively. However, their behavior was considerably different. The hexyl group in the HTMS converted the FC surface into hydrophobicity, leading to the hindrance of the interhydrogen bonding in the FC. The silanized FC was embrittled with the increase of the degree of the silanization. In the case of the APTMS, the inter hydrogen bonding was kept because of the existence of the amino group. Whereas, the SPP‐g‐DMI was unable to penetrate into the cellulose because of its higher molecules, and the interhydrogen bonding was not hindered. The keeping the inter hydrogen bonding was important for the reinforcement of the tensile properties such as Young's modulus and tensile strength in the composite. Furthermore, the interfacial adhesion between the SPP and holocellulose (HC) was studied as well as the SPP/FC. Although the tensile properties were slightly improved by the APTMS silanization and by the addition of the SPP‐g‐DMI, respectively, the reactivity of the HC was much less than that of the FC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improvement in impact property of continuous glass mat reinforced polypropylene composites

The toughened polypropylene (PP) was obtained by the blending of PP with ethylene‐propylene diene monomer (EPDM). The impact property of continuous glass mat‐reinforced polypropylene was adjusted through three ways: different toughness PPs and their blends were used as matrices, the functionalized polypropylene was added into the matrix to control the interfacial adhesion; the ductile interlayer was introduced at the fiber/matrix interphase by the grafting and crosslinking of rubber chains on fiber surface. The effect of PP toughness, interfacial adhesion, and ductile interlayer on the mechanical properties of composite systems was studied. The impact toughness of GMT increased with increasing the matrix toughness, whereas the flexural strength and modulus decreased. The good interfacial adhesion resulted in the low impact toughness. However, GMT composite with high strength, modulus, and impact toughness could be obtained by the introduction of a ductile interlayer at fiber/matrix interphase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2680–2688, 2002     

Effects of wheat straw fiber content and characteristics,and coupling agent concentration on the mechanical properties of wheat straw fiber‐polypropylene composites

Wheat straw fiber‐polypropylene (PP) composites were prepared to investigate the effects of wheat straw fiber content (10, 20, 30, 40, and 50 wt %), fiber size (9, 28, and 35 mesh), and maleic anhydride grafted polypropylene (MAPP) concentration (1, 2, 5, and 10 wt %) on the static and dynamic mechanical properties of the wheat straw fiber‐PP composites in this study. The tensile modulus and strength of the composites increased linearly with increasing wheat straw fiber content up to 40%, whereas the elongation at break decreased dramatically to 3.78%. Compared with the composites made of the longer wheat straw fiber, the composites made of the fines (>35 mesh) had a slightly higher tensile strength of 31.2 MPa and tensile elongation of 5.39% at break. With increasing MAPP concentration, the composites showed an increase in tensile strength, and the highest tensile strength of 34.0 MPa occurred when the MAPP concentration reached 10 wt %. As wheat straw fiber content increased from 0 to 40%, the flexural modulus of the composites increased gradually from 1335 to 3437 MPa. The MAPP concentration and wheat straw fiber size distribution had no appreciable effect on the static flexural modulus of the composites. The storage flexural modulus of the composites increased with increasing wheat straw fiber content. The scanning electron microscopy (SEM) observation on the fracture surface of the composites indicated that a high wheat straw fiber content (>30 wt %) resulted in fiber agglomeration and a reduction in interfacial bonding strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ink‐eliminated waste paper sludge flour‐filled polypropylene composites with different coupling agent treatments

Ink‐eliminated sludge flour (IESF), waste residue from the recycling treatments of waste paper, was utilized as a new kind of filler to reinforce polypropylene (PP) in this research work. Different coupling agents, including maleated anhydride grafted PP (MAPP), stearic acid (SA), and titanate (NDZ‐101), were used to increase the compatibility between IESF and PP. By using different measurements, the microstructure, morphology, thermal behaviors, and mechanical properties of the IESF/PP composites were investigated in detail. It was found that IESF, as a nucleation agent, not only induced the crystallization orientation of PP but also accelerate the crystallization rate of PP. Just as indicated in the experiments, the presence of IESF has shown the advantages of increasing the dimensional stability, the hardness and the flexural property, and the presence of coupling agents has a favorable effect on the improvement of dimensional stability. Moreover, the coupling agent has minor influence on the mechanical property, even causes some decrease in the impact strength. Among these three coupling agents, MAPP is found to be the best coupling agent for increasing the interfacial adhesion between IESF and PP, and the MAPP addition makes the PP composite possess the quickest crystallization rate and greatest tensile strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 513–520, 2003     

Mechanical,thermal, and morphological properties of maleic anhydride‐g‐polypropylene compatibilized and chemically modified banana‐fiber‐reinforced polypropylene composites

Composites were prepared with chemically modified banana fibers in polypropylene (PP). The effects of 40‐mm fiber loading and resin modification on the physical, mechanical, thermal, and morphological properties of the composites were evaluated with scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Infrared (IR) spectroscopy, and so on. Maleic anhydride grafted polypropylene (MA‐g‐PP) compatibilizer was used to improve the fiber‐matrix adhesion. SEM studies carried out on fractured specimens indicated poor dispersion in the unmodified fiber composites and improved adhesion and uniform dispersion in the treated composites. A fiber loading of 15 vol % in the treated composites was optimum, with maximum mechanical properties and thermal stability evident. The composite with 5% MA‐g‐PP concentration at a 15% fiber volume showed an 80% increase in impact strength, a 48% increase in flexural strength, a 125% increase in flexural modulus, a 33% increase in tensile strength, and an 82% increase in tensile modulus, whereas the heat deflection temperature increased by 18°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of the chemical foaming agents,injection parameters,and melt‐flow index on the microstructure and mechanical properties of microcellular injection‐molded wood‐fiber/polypropylene composites

Wood‐fiber‐reinforced plastic profiles are growing rapidly in nonstructural wood‐replacement applications. Most manufacturers are evaluating new alternative foamed composites, which are lighter and more like wood. Foamed wood composites accept screws and nails better than their nonfoamed counterparts, and they have other advantages as well. For example, internal pressures created by foaming give better surface definition and sharper contours and corners than nonfoamed profiles have. In this study, the microfoaming of polypropylene (PP) containing hardwood fiber was performed with an injection‐molding process. The effects of different chemical foaming agents (endothermic, exothermic, and endothermic/exothermic), injection parameters (the mold temperature, front flow speed, and filling quantity), and different types of PP (different melt‐flow indices) on the density, microvoid content, physicomechanical properties, surface roughness, and microcell classification of microfoamed PP/wood‐fiber composites were studied. A maleic anhydride/polypropylene copolymer (MAH‐PP) compatibilizer was used with the intention of improving the mechanical properties of microfoamed composites. The microcell classification (from light microscopy) and scanning electron micrographs showed that an exothermic chemical foaming agent produced the best performance with respect to the cell size, diameter, and distance. The polymer melt‐flow index and the variation of the injection parameters affected the properties and microstructure of the microfoamed composites. The density of the microfoamed hardwood‐fiber/PP (with a high melt‐flow index) composites was reduced by approximately 30% and decreased to 0.718 g/cm³ with an exothermic chemical foaming agent. Tensile and flexural tests were performed on the foamed composites to determine the dependence of the mechanical properties on the density and microvoid content of the foamed specimens, and these properties were compared with those of nonfoamed composites. MAH‐PP improved the physicomechanical properties up to 80%. With an increase in the mold temperature (80–110°C), the surface roughness was reduced by nearly 70% for the foamed composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1090–1096, 2005     

Deformation mechanism of polypropylene composites filled with magnesium hydroxide

The fracture behavior and deformation mechanism of polypropylene (PP) composites filled with magnesium hydroxide [Mg(OH)₂] were investigated. The incorporation of Mg(OH)₂ particles into the PP matrix led to an increase in Young's modulus and a significant reduction in the tensile yield strength and elongation at break. Surface modification on filler particles with stearic acid could reduce the interfacial adhesion between the filler and PP matrix and improve the stress transferability. The deformation mechanism of the Mg(OH)₂/PP composites depended on the interfacial adhesion and the deformability of ligaments between microvoids caused by debonding. The deformability of the ligaments could be significantly improved by surface modification on the particle surface. The dependence of the deformation behavior of the Mg(OH)₂/PP composites on the filler content was in accordance with percolation theory. The agglomeration of microvoids and fibrillation of ligaments in the PP composites with excessive filler content indicated the weak resistance of the polymer matrix to crack propagation and premature fracture in a brittle manner. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1922–1930, 2005     

Thermal degradation of epoxy resin reinforced with polypropylene fibers

The influence of polypropylene fibers on the thermal degradation of epoxy composites was investigated with thermogravimetric analysis. Three composites with 5, 10, or 15 wt % polypropylene fibers were prepared with epoxy as a matrix material. The polypropylene fibers, used as reinforcing materials, retarded the thermal decomposition, and increasing the weight percentage of the fiber material increased the thermal stability to a certain extent. Of the three composites, the 10 wt % polypropylene fiber/epoxy resin composite showed very good thermal stability, which was indicated by the increase in the resin decomposition temperature from 280°C for the 5 wt % polypropylene fiber/epoxy resin composite to 375°C for the 10 wt % polypropylene fiber/epoxy resin composite. The Horowitz–Metzger method was used to calculate the activation energies, and the results were tabulated. A morphological analysis was carried out with scanning electron microscopy to evaluate the dispersion of the fibers in the epoxy matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 500–503, 2007     

Effect of oxidized polypropylene as a new compatibilizer on the water absorption and mechanical properties of wood flour–polypropylene composites

The effect of oxidized polypropylene (OPP) as new compatibilizer on the water absorption and mechanical properties of wood flour–polypropylene (PP) composites were studied and compared with maleic anhydride grafted polypropylene (MAPP). The oxidation of PP was performed in the molten state in the presence of air. Wood flour, PP, and the compatibilizers (OPP and MAPP) were mixed in an internal mixer at temperature of 190°C. The amorphous composites removed from the mixer were then pressed into plates that had a nominal thickness of 2 mm and nominal dimensions of 15 × 15 cm² with a laboratory hydraulic hot press at 190°C. Physical and mechanical tests showed that the wood flour–PP composites with OPP exhibited higher flexural and impact properties but lower water absorption than MAPP. All of the composites with 2% compatibilizers (OPP and MAPP) gave higher flexural and impact properties and lower water absorption compared to those with 4% compatibilizers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characteristics of composites of high‐crystalline cellulose with polypropylene: Effects of maleated polypropylene and cellulose content

Binary composites of high‐crystalline fibrous cellulose with polypropylene (PP) or maleic anhydride‐grafted polypropylene (MAPP) were prepared by melt‐mixing with different contents of cellulose from 0 to 60 wt %. Ternary composites of cellulose with PP and MAPP were also prepared to investigate the effects of MAPP as a compatibilizer between cellulose and PP. Scanning electron microscopy revealed that the addition of MAPP generates strong interactions between a PP matrix and cellulose fibers: All cellulose fibers are encapsulated by layers of the matrix and connected tightly within the matrix. Thus, the tensile strength and Young's modulus of MAPP‐containing composites increase with an increase in MAPP and cellulose content, in contrast to the decrease in tensile strength of a PP‐based binary composite with an increase in cellulose. Cellulose fibers act as a nucleating agent for the crystallization of PP, which is promoted by the addition of MAPP through an increase of the crystallization temperature of PP in the composite. Accordingly, both cellulose and MAPP facilitate the thermooxidative stability of PP composites in the following order: MAPP/cellulose > PP/MAPP/cellulose > PP/cellulose > PP. Relative water absorption increases with an increase in cellulose content, decreasing with the addition of MAPP. MAPP‐containing cellulose composites have high potential for applications as environmentally friendly materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 337–345, 2003     

Using hop bines as reinforcements for lightweight polypropylene composites

Whole hop bines (HBs), the peeled outer bark (OB) of HBs, and fibers chemically extracted from hop bark (HFs) were used as reinforcements to make lightweight composites with polypropylene (PP) webs or fibers as the matrix materials. Using discarded HBs for composites not only increases the value of hop crops but also provides a green, sustainable, and biodegradable material for the composite industry. Lightweight composites are preferred, especially for automotive applications because of the potential energy savings. In this research, the effects of the processing parameters on the properties of PP composites reinforced with HBs were studied. The composites reinforced with OB without any chemical treatment showed better properties than the composites reinforced with HFs or HBs. Compared with jute–PP composites of the same density (0.47 g/cm³), composites reinforced with OB had 43% higher flexural strength, 46% higher impact resistance, 56% higher Young's modulus, similar modulus of elasticity, 33% lower tensile strength, and better sound‐absorption properties. OB–PP composites with optimized properties have the potential to be used in industrial applications such as support layers in automotive interiors, ceiling tiles, and office panels. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Evaluation of interfacial compatibility in wood flour/polypropylene composites by grafting isocyanate silane coupling agent on polypropylene

In this paper, the polypropylene was functionalized by isocyanate silane coupling agent grafted polypropylene (IS-g-PP), various characterization methods were conducted to evaluate the interfacial compatibility of WF/PP. The results indicated that IS-g-PP remarkably enhanced the interfacial adhesion between WF and PP with improved mechanical property, tensile strength was improved by 96.1%, and flexural strength was also increased apparently. According to the DSC results, the crystallization temperature of PP was decreased due to its enhanced interfacial adhesion. Most importantly, the use of IS-g-PP reinforced the storage modulus, loss modulus, and complex viscosity of WF/PP. These results demonstrated that IS-g-PP enhanced the interfacial interaction, and the mobility of PP chain was restrained, and was further confirmed by SEM analysis.     

In situ observation of polypropylene composites reinforced by nonmetals recycled from waste printed circuit boards during tensile testing

A great amount of work has been done over the past few years to reuse the nonmetals recycled from waste printed circuit boards in polypropylene (PP) composites. This is because of the very fast generation rate of nonmetal pollution in the world each year and the very fast growing rate of PP applications in industries. This work focuses on the dynamic effects of nonmetals of different particle sizes on the tensile properties and reinforcing mechanisms of nonmetal/PP composites by in situ scanning electron microscopy tensile testing. The observed results show that the dominant deformation mechanism in pure PP is shear yielding. When fine nonmetals are filled into PP, mass microcracks are initiated. The glass fibers first resist the cracks and undertake the loading when they propagate. The crazes propagate slowly and then break the glass fibers. When coarse nonmetals are filled into PP, interfacial debonding and mass microcracks are initiated. A crack is either terminated when it meets another fiber–particulate bundle or branched into finer mass crazing. Interfacial debonding, crack initiation and propagation, and fiber pullout and breakage dissipate tremendous energy. These factors cause improvements in the strength and rigidity of nonmetal/PP composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical,flammability, and crystallization behavior of polypropylene composites reinforced by aramid fibers

In this article, we report the mechanical and thermal properties, together with the crystallization and flammability behaviors, of pure polypropylene (PP) and PP/aramid fiber (AF) composites with AF loadings of 5, 10, 20, 30, and 40 wt %. The mechanical properties of the samples were evaluated by tensile and izod notched impact tests, and the results show that the tensile strength of the composites could reach up to 67.8 MPa and the izod notched impact strength could rise to 40.1 kJ/m². The structure and morphology were observed by scanning electron microscopy and polarized optical microscopy, respectively. This demonstrated that a solid interface adhesion between the matrix and fibers was formed. The thermal and crystalline behaviors of the PP/AF composites were also investigated by thermogravimetric analysis and differential scanning calorimetry analysis, and the results show that the char residue of the PP/AF composites improved greatly with increasing AF loading, and the highest value could reach up to 23.7% in the presence of 40 wt % AF. The supercooling degree, initial crystallization temperature, and crystallization percentage were used to characterize the crystallization behavior of the PP/AF composites, and the results indicate that the AFs had positive effects on the promotion of PP nucleation, which can usually improve the mechanical properties of composites. Moreover, the flammability analysis of the PP/AF composites demonstrated that the presence of AFs could significantly decrease the peak heat release rate and the total heat release and reduce the melt-dripping of the PP/AF composites. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of chemical structure of silane coupling agent on interface adhesion properties of syndiotactic polypropylene/cellulose composite

To improve interaction between syndiotactic polypropylene (SPP) and fibrous cellulose (FC), effects of chemical structure of silane coupling agent on the reactivity for the surface hydroxyl group on the FC were studied by X‐ray photoelectron spectroscopy (XPS) measurement. Among the three kinds of the silane coupling agent, the 3‐aminopropyltrimethoxysilane (APTMS) showed the highest reactivity with the surface hydroxyl group on the FC, and the linear silane compound with methoxyl group was found to be suitable for the reaction. Although the morphology of the SPP/FC composite is hardly affected by the difference in the kinds of the silane coupling agent, the tensile properties were considerably different. In particular, in the case of using higher silane coupling agent solution (over 3 wt %), the chemical structure of silane coupling agent certainly affected the tensile properties of the SPP/silanized FC composite. It was found that the tensile properties were distinctly affected by the reactivity between the surface hydroxyl group on FC and the silane coupling agent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of bark flour content on the hygroscopic characteristics of wood–polypropylene composites

The effects of the bark content on the water absorption and thickness swelling of wood–plastic composites prepared from polypropylene, wood flour, and bark flour were studied. Samples were made with a laboratory twin‐screw extruder. The results showed that among composites free of maleic anhydride polypropylene, those composites containing a higher bark flour content exhibited lower water absorption and lower thickness swelling. Maleic anhydride polypropylene reduced water absorption and thickness swelling in composites containing wood flour and a lower content of bark flour but had no influence on the hygroscopic properties of composites made with higher bark contents. Adding maleic anhydride polypropylene had no effect on the water diffusion coefficients and swelling rate parameters of composites made with a higher bark flour content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008