Effect of filler content and surface treatment on the tensile properties of glass‐bead‐filled polypropylene composites

The tensile properties of polypropylene (PP) filled with two A‐glass beads with the same size, PP/3000 (glass bead surface pretreated with a silane coupling agent) and PP/3000U (no surface pretreatment), have been measured by using an Instron materials testing machine at room temperature, to identify the effects of the filler surface pretreatment and its content on the tensile properties of these composites. The results show that the Young's modulus E_c of the composites increases non‐linearly with increasing volume fraction of glass beads ϕ_f, while the tensile yield strength σ_yc and tensile stress at break σ_bc of the composites decrease with an increase of ϕ_f, in the ϕ_f range 0–30%. Furthermore, the values of E_c and σ_bc of the PP/3000 system are somewhat higher than those of the PP/3000U system under the same test conditions, but this is in contrast to the tensile strain at break ε_bc and tensile fracture energy E_bc, especially at higher ϕ_f values. Good agreement is shown between the measured tensile strength and the predicted value by using an equation proposed in previous work. In addition, ε_bc and E_bc reach maximum values at ϕ_f = 25% for both systems. This indicates that there is a brittle–ductile transition for the composites in tension. © 2000 Society of Chemical Industry     

中空无机微珠填充PP复合材料的流动性能

应用熔体流动指数仪，考察了温度（T），载荷（P），填料含量及粒径（d)对中空无机微珠填充聚丙烯复合材料流动性的影响。结果表明，试样的熔体流动指灵敏（MI）随着T或P的增加而提高。而MI随中空无机微珠体积分数的变化不太明显。当P小于5kg时，MI随着微珠d的增加而轻微提高；而当P大于5kg后，MI则随d的增加有所下降。     

PVC/HGB拉伸性能的研究

应用Instron材料试验机在室温下测量了空心玻璃微珠（HGB）填充聚氯乙烯（PVC）复合材料（PVC／HGB）拉伸性能。结果表明：试样的弹性模量随着HGB体积分数（φf)的增加而线性增大；而屈服拉伸强度（σyc)和拉伸断裂能则随着φf的增加而缓慢下降，当φf为5％－20％时，PVC／HGB的断裂拉伸强度（σbc)均高于未填充PVC；HGB粒径对试样的σyc和σbc的影响不太明显。当φf为5％时，PVC／HGB的拉伸强度均高于PVC/CaCO3复合材料。     

Hygrothermal aging and tensile behavior of injection‐molded rice husk‐filled polypropylene composites

The effect of the filler volume fraction on the tensile behavior of injection‐molded rice husk‐filled polypropylene (RH–PP) composites was studied. Hygrothermal aging behavior was also investigated by immersing the specimens in distilled water at 30 and 90°C. The kinetics of moisture absorption was studied from the amount of water uptake by specimens at regular interval times. It was found that the diffusion coefficient and the maximum moisture content are dependent on the filler volume fraction and the immersion temperatures. Incorporation of RH into the PP matrix has led to a significant improvement in the tensile modulus and a moderate improvement in the tensile strength. Elongation at break and energy at break, on the other hand, decreased drastically with the incorporation of the RH filler. The extent of deterioration incurred by hygrothermal aging was dependent on the immersion temperature. Both the tensile strength and tensile modulus deteriorated as a result of the combined effect of thermal aging and moisture attack. Furthermore, the tensile properties were not recovered upon redrying of the specimens. Scanning electron microscopy was used to investigate the mode of failure of the RH–PP composites. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 742–753, 2001     

Crystallization behavior of glass bead‐filled low‐density polyethylene composites

The effects of the filler content and the filler size on the crystallization and melting behavior of glass bead‐filled low‐density polyethylene (LDPE) composites have been studied by means of a differential scanning calorimeter (DSC). It is found that the values of melting enthalpy (ΔH_c) and degree of crystallinity (x_c) of the composites increase nonlinearly with increasing the volume fraction of glass beads, ϕ_f, when ϕ_f is greater than 5%; the crystallization temperatures (T_c) and the melting temperatures (T_m) of the composites are slightly higher than those of the pure LDPE; the effects of glass bead size on x_c, T_c, and T_m are insignificant at lower filler content; but the x_c for the LDPE filled with smaller glass beads is obviously greater than that of the filled system with bigger ones at higher ϕ_f. It suggests that small particles are more beneficial to increase in crystallinity of the composites than big ones, especially at higher filler content. In addition, the influence of the filler surface pretreated with a silane coupling agent on the crystallization behavior are not too outstanding at lower inclusion concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 687–692, 1999     

空心玻璃微珠/环氧复合材料的制备及性能研究

制备了空心玻璃微珠/环氧复合材料。通过力学性能、固化收缩率、热性能等测试考察了空心玻璃微珠粒径、填充量、硅烷偶联剂处理对树脂及固化物性能的影响。结果表明,硅烷偶联剂改善了空心玻璃微珠与树脂基体的相容性。复合材料的力学性能随着空心微珠粒径减小而增大。随着空心微珠填充量的加大,固化物拉伸强度有所降低,冲击强度和弯曲强度在空心玻璃微珠质量分数为2%时达到最大值,比纯树脂分别提高了30%和34.2%,同时材料的固化收缩率和密度降低,玻璃化转变温度升高。     

Mechanical properties and morphology of glass bead–filled polypropylene composites

The effects of the filler content and size on the mechanical properties such as tensile modulus, E_c, yield strength, σ_yc, and impact strength, S_IC, of glass bead–filled polypropylene (PP) composites have been investigated employing an Instron materials tester and a Ceast impact tester at room temperature. With increasing concentration of glass beads, E_c and S_IC increase, but σ_yc decreases non–linearly, within a filler volume fraction range of 0%−20%; under the same test conditions, the values of E_C and σ_yc for PP with bigger beads are somewhat lower than those of PP with smaller ones; the maximum values of S_IC for the composites are about 1.4 times as high as the unfilled PP; the interface between the matrix and the beads is a weak bond. The results indicate that the stiffness and the toughness of the PP composites are effectively improved by addition of glass beads.     

Phenolic rigid organic filler/isotactic polypropylene composites. II. Tensile properties

A novel phenolic rigid organic filler (KT) was used to modify isotactic polypropylene (iPP). The influence of KT particles on the tensile properties of PP/KT microcomposites was studied by uniaxial tensile test and the morphological structures of the stretched specimens were observed by scanning electron microscopy (SEM) and polarized optical microscopy (POM). We found that the Young’s modulus of PP/KT specimens increased with filler content, while the yield and break of the specimens are related to the filler particles size. The yield stress, the breaking stress and the ultimate elongation of PP/KT specimens were close to those of unfilled iPP specimens when the maximal filler particles size is less than a critical value, which is 7 μm at a crosshead speed of 10 mm/min and 3 μm at 200 mm/min, close to that of glass bead but far more than those of other rigid inorganic filler particles. The interfacial interaction was further estimated from yield stress, indicating that KT particles have a moderate interfacial interaction with iPP matrix. Thus, the incorporation of small KT particles can reinforce iPP matrix and simultaneously cause few detrimental effects on the other excellent tensile properties of iPP matrix, due to their organic nature, higher specific area, solid true-spherical shape and the homogenous dispersion of the ROF particles in microcomposites.     

Mechanical properties of glass bead‐ and wollastonite‐filled isotactic‐polypropylene composites modified with thermoplastic elastomers

Mechanical properties of the isotactic‐polypropylene/glass bead (iPP/GB) and iPP/wollastonite (iPP/W) composites modified with thermoplastic elastomers, the poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) copolymer (SEBS) and corresponding block copolymer grafted with maleic anhydride (SEBS‐g‐MA), were investigated. An increase in toughness of iPP with the elastomers was associated with a decrease in rigidity and strength. Mechanical performance of iPP increased more with acicular W than with spherical GB due to reinforcing effect of W. Comparing the (iPP/GB)/SEBS and (iPP/W)/SEBS composites having the separate microstructure, strength and toughness values of the iPP/GB and iPP/W composites increased more with SEBS‐g‐MA at the expense of rigidity due to the core‐shell microstructure with strong interfacial adhesion. Moreover, the iPP/W composite exhibited superior mechanical performance with 2.5 and 5 vol% of SEBS‐g‐MA because of a positive synergy between the core‐shell microstructure and reinforcing effect of acicular W. The extended models revealed that the elastomer and filler particles in the (iPP/GB)/SEBS and (iPP/W)/SEBS composites acted individually due to the separate microstructure. However, the rigid GB and W particles encapsulated with the thick elastomer interlayer (R₀/R₁ = 0.91) in the (iPP/GB)/SEBS‐g‐MA and (iPP/W)/SEBS‐g‐MA composites acted like neither big elastomer particles nor like individual rigid particles, inferring more complicated failure mechanisms in the core‐shell composites. POLYM. COMPOS., 31:1285–1308, 2010. © 2010 Society of Plastics Engineers     

Evaluation of dynamic elastic properties of wood‐filled polypropylene composites

Dynamic modulus of elasticity (MoE) and shear modulus of wood‐filled polypropylene composite at various filler contents ranging from 10% to 50% was determined from the vibration frequencies of disc‐shaped specimens. Wood filler was used in both fiber form (pulp) and powder form (wood flour). A novel compatibilizer, m‐isopropenyl‐α,α‐dimethylbenzyl‐isocyanate(m‐TMI) grafted polypropylene with isocyanate functional group was used to prepare the composites. A linear increase in dynamic MoE, shear modulus, and density of the composite was observed with the increasing filler content. Between the two fillers, wood fiber filled composites exhibited slightly better properties. At 50% filler loading, dynamic MoE of the wood fiber filled composite was 97% higher than that of unfilled polypropylene. Halpin‐Tsai model equation was used to describe the changes in the composite modulus with the increasing filler content. The continuous improvement in elastic properties of the composites with the increasing wood filler is attributed to the effective reinforcement of low‐modulus polypropylene matrix with the high‐modulus wood filler. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1706–1711, 2006     

Influence of grafted polypropylene on the mechanical properties of mineral‐filled polypropylene composites

The purpose of this work was to study how mineral fillers would behave in a polypropylene (PP) matrix when PP modified with maleic anhydride (MA) and/or itaconic acid (IA) was used as a coupling agent in the preparation of mineral‐filled PP composites. The composites were characterized with tensile mechanical measurements and morphological analysis. The optimum amount of the coupling agent to be used to obtain composites with improved mechanical properties was established. The results indicated that these coupling agents enhanced the tensile strength of the composites significantly, and the extent of the coupling effect depended on the nature of the interface that formed. The incorporation of coupling agents enhanced the resistance to deformation of the composite. The behavior of IA‐modified PP as a coupling agent was similar to that of a commercial MA‐modified PP for the filled PP composites. Evidence of improved interfacial bonding was revealed by scanning electron microscopy studies, which examined the surfaces of fractured tensile test specimens; their microstructures confirmed the mechanical results with respect to the observed homogeneous or optimized dispersion of the mineral‐filler phase in these composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2343–2350, 2007     

中空微球填充PP复合材料传热的有限元分析

应用ANSYS软件对中空微球填充聚丙烯复合材料单元中的热传递进行了有限元模拟，并计算出等效导热系数(keff)。结果表明，keff随着中空微球体积分数的增加呈线性函数形式下降，且随着微球粒径的增加有所减小。此外，三维有限元模拟的keff值高于二维，两者的差异随着中空微球体积分数的增加而增大。     

Tensile properties and creep response of polypropylene fibre composites with variation of fibre diameter

The mechanical properties and morphology of polypropylene (PP) long‐fibre reinforced random poly(propylene‐co‐ethylene) (PPE) composites (50/50 % vol/vol) have been investigated with reference to the fibre diameter with constant length. There is an improvement in the mechanical properties of PPE matrix by incorporation of long PP fibres into the matrix. The elastic modulus of the composite increased with decrease in the fibre diameter to 50 µm, to 0.91 GPa, which was 5 times higher than for pure PPE. However, composite stiffness decreased with decreasing fibre diameter of less than 50 µm and this is discussed in term of the fibre stiffness, packing, stress concentration and aspect ratio. Creep resistance of the composites showed the same behaviour. Morphology of the composites was investigated using scanning electron microscopy. This showed that there was a thin layer of matrix on the reinforcement, which was attributed to good impregnation and wetting of the fibres. Moreover, prediction of tensile modulus using the Cox model correlated well with experimental data. Copyright © 2004 Society of Chemical Industry     

Preparation and mechanical properties of high‐performance short ramie fiber‐reinforced polypropylene composites

Short ramie fiber (RF) was used to reinforce the polypropylene (PP). The composites were prepared in a twin‐screw extruder followed by injection molding. The experimental results showed that both the strength and the modulus of the composites increase considerably with increasing RF content. The tensile strength and flexural strength are as high as 67 and 80 MPa by the incorporation of ramie up to 30 wt %. To the best of our knowledge, this is one of the best results for short natural fiber‐reinforced PP composites. However, the preparation method in this study is more simple and economic. This short RF‐reinforced PP composites extend the application field for short‐nature fiber‐reinforced PP composites. Morphological analysis revealed that it is the high aspect ratio of the fiber and good interfacial compatibility that result in the high performance of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical behavior of agro‐residue‐reinforced polypropylene composites

In this research, fully environment‐friendly, sustainable and biodegradable composites were fabricated, using wheat straw and rice husk as reinforcements for thermoplastics, as an alternative to wood fibers. Mechanical properties including tensile, flexural, and impact strength properties were examined as a function of the amount of fiber and coupling agent used. In the sample preparation, three levels of fiber loading (30, 40, and 50 wt %) and two levels of coupling agent content (0 and 2 wt %) were used. As the percentage of fiber loading increased, flexural and tensile properties increased significantly. Notched Izod results showed a decrease in strength as the percentage of fiber increases. With addition of 50% fiber, the impact strengths decreased to 16.3, 14.4, and 16.4 J/m respectively, for wheat straw‐, rice husk‐, and poplar‐filled composites. In general, presence of coupling agent had a great effect on the mechanical strength properties. Wheat straw‐ and rice husk‐filled composites showed an increase in the tensile and flexural properties with the incorporation of the coupling agent. From these results, we can conclude that wheat straw and rice husk fibers can be potentially suitable raw materials for manufacturing biocomposite products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Steam‐exploded residual softwood‐filled polypropylene composites

Residual softwood sawdust was pretreated by a steam‐explosion technique. It was used as a natural filler in polypropylene (PP)‐based composites. Dynamic mechanical analysis and tensile properties of these materials were studied. The influence of filler loading, steam‐explosion severity, and coating the fiber with a functionalized compatibilizer, such as maleic anhydryde polypropylene (MAPP), on the mechanical behavior of the composite was evaluated. The results were analyzed in relation with scanning electron microscopy observations, and surface energy (dispersive and polar components) and apparent specific area measurements. Experimental data indicate a better compatibility between MAPP‐coated fiber and PP with respect to the untreated one. The coating treatment of the softwood fiber was found to promote interfacial adhesion between both components, and to enhance the tensile properties of the resulting composite. This reinforcing effect was well predicted from theoretical calculations based on a mean field approach (Halpin‐Kardos model). The steam‐explosion pretreatment severity increased the surface energy and apparent specific surface, and resulted in a loss of the fiber entirety. The sorption behavior of these composite materials was also performed. It was found that the composites absorb more water, as the filler content is higher. MAPP coating provided protection from water uptake in the interphase region. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1962–1977, 1999     

Mechanical and thermal properties of glass bead–filled nylon‐6

The mechanical and thermal properties of glass bead–filled nylon‐6 were studied by dynamic mechanical analysis (DMA), tensile testing, Izod impact, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) tests. DMA results showed that the incorporation of glass beads could lead to a substantial increase of the glass‐transition temperature (T_g) of the blend, indicating that there existed strong interaction between glass beads and the nylon‐6 matrix. Results of further calculation revealed that the average interaction between glass beads and the nylon‐6 matrix deceased with increasing glass bead content as a result of the coalescence of glass beads. This conclusion was supported by SEM observations. Impact testing revealed that the notch Izod impact strength of nylon‐6/glass bead blends substantially decreased with increasing glass bead content. Moreover, static tensile measurements implied that the Young's modulus of the nylon‐6/glass bead blends increased considerably, whereas the tensile strength clearly decreased with increasing glass bead content. Finally, TGA and DSC measurements indicated that the thermal stability of the blend was obviously improved by incorporation of glass beads, whereas the melting behavior of the nylon‐6 remained relatively unchanged with increasing glass bead content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1885–1890, 2004     

Flammability and mechanical properties of wood flour‐filled polypropylene composites

Polypropylene (PP) composites filled with wood flour (WF) were prepared with a twin‐screw extruder and an injection‐molding machine. Three types of ecologically friendly flame retardants (FRs) based on ammonium polyphosphate were used to improve the FR properties of the composites. The flame retardancy of the PP/WF composites was characterized with thermogravimetric analysis (TGA), vertical burn testing (UL94‐V), and limiting oxygen index (LOI) measurements. The TGA data showed that all three types of FRs could enhance the thermal stability of the PP/WF/FR systems at high temperatures and effectively increase the char residue formation. The FRs could effectively reduce the flammability of the PP/WF/FR composites by achieving V‐0 UL94‐V classification. The increased LOI also showed that the flammability of the PP/WF/FR composites was reduced with the addition of FRs. The mechanical property study revealed that, with the incorporation of FRs, the tensile strength and flexural strength were decreased, but the tensile and flexural moduli were increased in all cases. The presence of maleic anhydride grafted polypropylene (MAPP) resulted in an improvement of the filler–matrix bonding between the WF/intumescent FR and PP, and this consequently enhanced the overall mechanical properties of the composites. Morphological studies carried out with scanning electron microscopy revealed clear evidence that the adhesion at the interfacial region was enhanced with the addition of MAPP to the PP/WF/FR composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological behaviors of glass bead‐ and wollastonite‐filled polypropylene composites modified with thermoplastic elastomers

Steady‐ and oscillatory‐shear rheological behaviors of polypropylene/glass bead (PP/GB) and PP/wollastonite (PP/W) melts modified with thermoplastic elastomers, poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) copolymer (SEBS) and the corresponding block copolymer grafted with maleic anhydride (SEBS‐g‐MA), were examined by means of a parallel‐plate rheometer. With adding the elastomers (SEBS and SEBS‐g‐MA) and fillers (spherical GB and acicular W) to PP, viscosity especially at low shear rates and shear‐thinning flow behavior at high shear rates were pronounced as evidenced quantitatively by Carreau–Yasuda (CY) parameters, but Cox–Merz analogy became weakened. Besides, melt‐elasticity in terminal region and relaxation time (t_c) in crossing point increased, indicating an enhancement in quasi‐solid behavior of molten PP. Comparing with the elastomers, rheological behaviors of molten PP were more influenced with adding the rigid fillers, especially with W due to distinct acicular shape of W particles. SEBS‐g‐MA elastomer more affected rheological behaviors of the ternary composites than SEBS elastomer, implying that SEBS elastomer and the filler particles behaved individually (i.e., development of separate microstructure) in (PP/GB)/SEBS and (PP/W)/SEBS ternary composites, but core‐shell microstructure developed with strong interfacial adhesion by adding SEBS‐g‐MA elastomer, and the filler particles encapsulated with the thick SEBS‐g‐MA elastomer interlayer (i.e., core‐shell particles) acted like neither big elastomer particles nor like individual rigid particles in melt‐state. Moreover, effects of SEBS‐g‐MA elastomer reached a maximum on rheological behaviors of (PP/W)/SEBS‐g‐MA ternary composite, indicating a synergy between core‐shell microstructure and acicular W particles. Correlations between oscillatory‐shear flow properties and microstructures of the blends and composites were evaluated using Cole–Cole (CC), Han–Chuang (HC), and van Gurp–Palmen (vGP) plots. COMPOS., 2012. © 2012 Society of Plastics     

An efficient way to improve the mechanical properties of polypropylene/short glass fiber composites

Enhancement of tensile strength, impact strength, and flexural strength of polypropylene/short glass fiber composites by treating the glass fibers with coupling agent, mixing with maleated polypropylene (MPP) for compatibilization and adhesion, and with nucleating agent for improvement of polypropylene crystallization was studied. The results showed that both the silane coupling agent and MPP enhance tensile strength, impact strength, and flexural strength. In the absence of MPP, the effect of silane coupling agent on the mechanical properties of the composites decreases in the following order: alkyl trimethoxy silane (WD‐10) > γ‐methacryloxypropyl trimethoxysilane (WD‐70) > N‐(β‐aminoethyl)‐γ‐aminopropyl trimethoxysilane (WD‐52), whereas in the presence of MPP, the order changes as follows: WD‐70 > WD‐10 > WD‐52. When the glass fibers were treated with WD‐52, 4,4‐diamino‐diphenylmethane bismaleimide (BMI) can further enhance the mechanical properties of the composite. The three kinds of strengths increase with MPP amount to maximum values at 5% MPP. As a nucleating agent, adipic acid is better than disodium phthalate in improving the mechanical properties, except for the notched impact strength. Wide‐angle X‐ray diffraction showed that the adipic acid is an α‐type nucleating agent, whereas disodium phthalate is a β‐type nucleating agent. Blending with styrene–butadiene rubber can somewhat improve the notched impact strength of the composites, but severely lowers the tensile strength and bending strength. Scanning electron micrographs of the broken surface of the composite showed greater interfacial adhesion between the glass fibers and polypropylene in the modified composite than that without modification. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1414–1420, 2005