Influence of graphite and wood-based fillers on the flammability of flexible polyurethane foams

The aim of this work was to verify the influence of graphite and wood-based fillers on the flammability of flexible polyurethane foams (FPF). Expandable graphite (EG) and cellulose (C) fillers were added to FPFs to improve their thermal stability and reduce their flammability. Four types of foams have been compared: FPF, FPF with the addition of EG, FPF with the addition of C and FPF with the addition of both fillers. Linear flammability tests and pyrolysis combustion flow calorimetry (PCFC) were performed to assess the flammability of these materials. It was found that the addition of cellulose does not improve the fire reaction, but a combination of both the EG and C fillers mixed together was able to achieve a small reduction in flammability, as confirmed by a linear flammability test and PCFC. The best properties observed by PCFC were from FPFs with EG. Usage of cellulose filler separately is not a good method for the assessment of higher thermal stability and lower flammability of FPFs. Thermal properties were measured by thermogravimetric analysis and dynamic mechanical analysis. These results showed that especially EG addition allows to achieve a positive effect on the thermal stability of the tested materials. Mechanical and physical tests (density, hardness, flexibility and irreversible strain) showed that the presence of graphite or cellulose filler results in changes in the properties of the FPFs, but these changes are not extensive. Fourier transform infrared spectroscopy analysis showed that only small changes exist in the chemical structure with the addition of the fillers. The introduction of EG and EG+C fillers into an FPF may reduce its flammability.     

Failure mechanics in ternary composites of polypropylene with inorganic fillers and elastomer inclusions

The effects of phase morphology, interfacial adhesion and filler particle shape and volume fraction on the fracture toughness of polypropylene (PP) filled with CaCO₃ or Mg(OH)₂ and ethylene-propylene elastomer (EPR) were investigated. Separation of the inorganic filler and elastomer particles was achieved using maleic-anhydride-grafted PP (MPP) to enhance the inorganic filler-matrix adhesion. Encapsulation of the rigid filler by the elastomer was achieved by using maleic-anhydride-grafted EPR (MEPR) to increase the inorganic filler-elastomer adhesion. The two limiting morphologies differed significantly in fracture toughness under impact loading at the same material composition. A model for a mixed mode of failure, accounting for the plane strain and plane stress contributions to the strain energy release rate,G _c, was used to predict the upper and lower limits forG _c for the two limiting morphologies over an interval of elastomer volume fractions,v _e, from 0–0.2 at a constant filler volume fraction,V _f = 0.3, and over the filler volume fraction from 0–0.4 at constant EPR content. The role of material yield strength in controlling fracture toughness has been described successfully using Irwin's analysis of plastic zone size. The presence of elastomer enhances both the critical strain energy release rate for crack initiation,G _c, and the resistance to crack propagation as expressed by Charpy notched impact strength for the two limiting morphologies. Satisfactory agreement was found between the experimental data and predictions of upper and lowerG _c limits.     

The mechanical properties of ternary composites of polypropylene with inorganic fillers and elastomer inclusions

The effect of elastomer volume fraction and phase morphology on the elastic modulus of ternary composites polypropylene (PP)/ethylene-propylene rubber (EPR)/inorganic filler containing 30 vol % of either spherical or lamellar filler has been investigated. Phase morphology was controlled using maleated polypropylene (MPP) and/or maleated ethylene-propylene elastomer (MEPR). As revealed by SEM observations, composites of MPP/EPR/filler exhibit separation of the filler and elastomer and good adhesion between MPP and the filler, whereas composites of PP/MEPR/filler exhibit encapsulation of the filler by MEPR. Composite models were utilized to estimate upper and lower bounds for the elastic modulus of these materials, which is strongly dependent on the morphology of the ternary composite. A model based on the Kerner equation for perfect separation of the soft inclusions and rigid fillers gives a good prediction of the upper limit for relative elastic modulus as a function of filler and elastomer volume fractions. The lower limit, achieved in the case of perfect encapsulation, depends significantly on the particle shape. Good agreement was found between experimental data and lower limits predicted using the Halpin-Tsai equation for lamellar filler and the Kerner-Nielsen equation for spherical filler. In order to calculate reinforcing efficiency of the core-shell inclusions, the finite element method (ANSYS 4.4A, GT STRUDL) has been used.     

A comparative study of the effect of different rigid fillers on the fracture and failure behavior of polypropylene based composites

Polypropylene (PP) composites with 5 wt% of different rigid particles (Al₂O₃ nanoparticles, SiO₂ nanoparticles, Clay (Cloisite 20A) nanoparticles or CaCO₃ microparticles) were obtained by melt mixing. Composites with different CaCO₃ content were also prepared. The effect of fillers, filler content and addition of maleic anhydride grafted PP (MAPP) on the composites fracture and failure behavior was investigated. For PP/CaCO₃ composites, an increasing trend of stiffness with filler loading was found while a decreasing trend of strength, ductility and fracture toughness was observed. The addition of MAPP was beneficial and detrimental to strength and ductility, respectively mainly as a result of improved interfacial adhesion. For the composites with 5 wt% of CaCO₃ or Al₂O₃, no significant changes in tensile properties were found due to the presence of agglomerated particles. However, the PP/CaCO₃ composite exhibited the best tensile behavior: the highest ductility while keeping the strength and stiffness of neat PP. In general, the composites with SiO₂ or Clay, on the other hand, displayed worse tensile strength and ductility. These behaviors could be probably related to the filler ability as nucleating agent. In addition, although the incorporation of MAPP led to improved filler dispersion, it was damaging to the material fracture behavior for the composites with CaCO₃, Al₂O₃ or Clay, as a result of a higher interfacial adhesion, the retardant effect of MAPP on PP nucleation and the lower molecular weight of the PP/MAPP blend. The PP/MAPP/SiO₂ composite, on the other hand, showed slightly increased toughness respect to the composite without MAPP due to the beneficial concomitant effects of the presence of some amount of the β crystalline phase of PP and the better filler dispersion promoted by the coupling agent which favor multiple crazing. From modeling of strength, the effect of MAPP on filler dispersion and interfacial adhesion in the PP/CaCO₃ composites was confirmed.     

Compatibilizing effect of mesoporous fillers on the mechanical properties and morphology of polypropylene and polystyrene blend

Polypropylene(PP)/Polystyrene(PS) (PP/PS = 80/20) blend with different types of fillers were prepared by using melt method. Four different types of fillers, namely mesoporous MCM-41 (without template), nano-SiO₂, Polymethylmethacrylate (PMMA)/MCM-41 and PMMA/SiO₂ were considered. For PMMA/MCM-41 filler, the synthesis of the filler consisting of entrapped strand of PMMA within the pores of mesoporous MCM-41 (without template) was described. The mechanical properties of the blend determined as the nano-fillers contents and the different types of blend were found to vary with the different interface between fillers and the matrix. SEM revealed a good interaction between the matrix phases and PMMA/MCM-41 or MCM-41 (without template). The decreased T_g of PS implied that the good adhesion between PP and PS blend was obtained by adding PMMA/MCM-41 nano-filler.     

Hybrid effects on tensile properties of hybrid short-glass-fiber-and short-carbon-fiber-reinforced polypropylene composites

Hybrid composites of polypropylene reinforced with short glass fibers and short carbon fibers were prepared using extrusion compounding and injection molding techniques. The tensile properties of these composites were investigated taking into account the effect of the hybridization by these two types of short fibers. It was noted that the tensile strength and modulus of the hybrid composites increase while the failure strain of the hybrid composites decreases with increasing the relative carbon fiber volume fraction in the mixture. The hybrid effects for the tensile strength and modulus were studied by the rule of hybrid mixtures (RoHM) using the tensile strength and modulus of single-fiber composites, respectively. It was observed that the strength shows a positive deviation from that predicted by the RoHM and hence exhibits a positive hybrid effect. However, the values of the tensile modulus are close to those predicted by the RoHM and thus the modulus shows no existence of a hybrid effect. Moreover, the failure strains of the hybrid composites were found to be higher than the failure strain of the single carbon fiber-reinforced composite, indicating that a positive hybrid effect exists. Explanations for the hybrid effects on the tensile strength and failure strain were finally presented.     

Effect of morphology on the behaviour of ternary composites of polypropylene with inorganic fillers and elastomer inclusions

The effects of phase morphology, interfacial adhesion, rigid filler particle shape and elastomer volume fraction on the tensile yield strength of polypropylene (PP) filled with inorganic filler (CaCO₃ or Mg(OH)₂) and ethylene-propylene elastomer (EPR) were investigated. Separation of the filler and elastomer particles was achieved using maleic-anhydride-grafted PP (MPP) to enhance the filler-matrix adhesion. Encapsulation of the rigid filler by the elastomer was achieved using maleic-anhydride-grafted EPR (MEPR) to increase the filler-elastomer adhesion. The two limiting morphologies differ significantly in mechanical properties under tensile loading at the same material composition. Elastomer particles separately dispersed in the matrix enhance the shear banding in the bulk matrix which prevents the crazes growing from the filler surface from becoming unstable and, thus, increases the ductility of the material. Encapsulation by an elastomer layer on the filler surface relieves triaxial stresses at the filler surface, changing the major local failure mechanism from crazing to shear yielding and, hence, increasing the ductility of the material. Increase of the elastomer volume fraction also causes, in both cases, an increase in matrix ductility. Composite models are used to predict upper and lower limits of yield strength (_y) for the two limiting morphologies over an interval of elastomer volume fractions (V _e) from 0 to 0.2 at a constant filler loading of 30 vol.% and over a filler volume fraction from 0 to 0.4 at a constant EPR content in the matrix. Satisfactory agreement was found between the experimental data and theoretical predictions.     

Influence of additives on the global mechanical behavior and the microscopic strain localization in wood reinforced polypropylene composites during tensile deformation investigated using digital image correlation

The structural integrity of polypropylene (PP) matrix composites reinforced by natural wood fibers is investigated by digital image correlation (DIC) coupled with tensile tests. The use of the material as an alternative construction material requires extensive understanding of its micromechanical properties, which primarily define its performance. Addition of several additives such as coupling agents is common practice for such materials. These ingredients improve the performance of these materials mainly by improvement of the chemical and physical interactions between the nonpolar matrix and the polar wood fibers. These interactions facilitate the transfer of the applied deformation particularly in the interphase region between the polymer matrix and the reinforcing fibers. Such localized changes can influence the performance of the material specially its micromechanical behavior. The DIC via photogrammetry was used to study the spatial distribution of the accumulated plastic surface strain, which is based on pattern recognition of the surface before and after straining. The heterogeneous strain distribution reveals a structural inhomogeneity of the material. The magnitude of local strain was much higher than the global strain, suggesting preferred regions for plastic deformation formed by the microstructure.     

Wear behavior of light-cured resin composites with bimodal silica nanostructures as fillers

To enhance wear behavior of resin composites, bimodal silica nanostructures including silica nanoparticles and silica nanoclusters were prepared and proposed as fillers. The silica nanoclusters, a combination of individually dispersed silica nanoparticles and their agglomerations, with size distribution of 0.07–2.70 μm, were fabricated by the coupling reaction between amino and epoxy functionalized silica nanoparticles, which were obtained by the surface modification of silica nanoparticles (~ 70 nm) using 3-aminopropyl triethoxysilane (APTES) and 3-glycidoxypropyl trimethoxysilane (GPS) as coupling agents, respectively. Silica nanoparticles and nanoclusters were then silanized with 3-methacryloxypropyl trimethoxysilane (γ-MPS) to prepare composites by mixing with bisphenol A glycerolate dimethacrylate (Bis-GMA) and tri (ethylene glycol) dimethacrylate (TEGDMA). Experimental composites with various filler compositions were prepared and their wear behaviors were assessed in this work. The results suggested that composites with increasing addition of silica nanoparticles in co-fillers possessed lower wear volume and smoother worn surface. Particularly, the composite 53:17 with the optimum weight ratio of silica nanoparticles and silica nanoclusters presented the excellent wear behavior with respect to that of the commercial Esthet-X, although the smallest wear volume was achieved by Z350 XT. The introduction of bimodal silica nanostructures as fillers might provide a new sight for the design of resin composites with significantly improved wear resistance.     

Analysis of tensile and flexural modulus in hemp strands/polypropylene composites

This research focuses on the behavior of the tensile and flexural modulus of polypropylene/hemps strands composites. The intrinsic tensile modulus of the hemp strands was computed using Hirsch model and experimental data of the tensile modulus of the polypropylene composites at the 20–50 wt.% hemp strands content. The modified rule of mixtures was used to evaluate the efficiency factor. Square packing distribution was assumed and the length factor was fixed by Cox–Krenchel’s model. The mean value of the orientation efficiency factor was found to be 0.55. Tensile and flexural modulus were compared concluding that its value was independent of the manner the composite was loaded. Finally the Tsai–Pagano model was applied to predict the behavior of the composite’s tensile modulus.     

Investigation on double yielding behavior under tensile loading in isotactic polypropylene

In this article, a peculiar phenomenon of double yielding was first discovered in isotactic polypropylene (iPP) under tensile loading. The results of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and polarized light microscopy (PLM) show that all the three samples, which were subjected to different crystallization procedures, only form α-crystals that are composed of radial lamellae and tangential lamellae. These α-PP samples display different double yield behaviors under tensile loading. PP-quenched sample exhibits double yield points when stretched at low cross-head speed (CHS), while one single yield point appears accompanied with a marked shear band when stretched at high CHS. However, in the case of PP-annealed, only one yield point appears at low CHS accompanied with the formation of a large number of crazes in the necked region, meanwhile, a second yield point gradually develops with increasing CHS. Furthermore, as for PP-isotherm, only one yield point is observed with homogenous deformation and concomitant whitening along the whole sample at any CHS. Based on the characterization of crystalline structure changes after yielding, we propose two plastic processes that contribute cooperatively in the yield process of α-PP, namely the inter-spherulitic deformation and intra-spherulitic deformation. The inter-spherulitic deformation which is prone to be initiated in the sample of strong spherulites is predominant in the first yield process, while the intra-spherulitic deformation enters into action after the appearance of the second yield point in the case of weak spherulites. Moreover, due to the polydispersity of lamellae thickness, the two deformation processes are co-existed and operate competitively in double yielding of α-PP.     

正交铺设陶瓷基复合材料单轴拉伸行为

采用细观力学方法对正交铺设陶瓷基复合材料单轴拉伸应力-应变行为进行了研究。采用剪滞模型分析了复合材料出现损伤时的细观应力场。采用断裂力学方法、 临界基体应变能准则、 应变能释放率准则及Curtin统计模型4种单一失效模型确定了90°铺层横向裂纹间距、 0°铺层基体裂纹间距、 纤维/基体界面脱粘长度和纤维失效体积分数。将剪滞模型与4种单一损伤模型结合, 对各损伤阶段应力-应变曲线进行了模拟, 建立了复合材料强韧性预测模型。与室温下正交铺设陶瓷基复合材料单轴拉伸应力-应变曲线进行了对比, 各个损伤阶段的应力-应变、 失效强度及应变与试验数据吻合较好。分析了90°铺层横向断裂能、 0°铺层纤维/基体界面剪应力、 界面脱粘能、 纤维Weibull模量对复合材料损伤及拉伸应力-应变曲线的影响。      

E玻璃纤维增强环氧树脂基复合材料轴向拉伸力学性能的应变率效应

采用MTS-810材料试验机、Zwick-HTM5020高速拉伸试验机及分离式Hopkinson拉杆（SHTB）实验装置,并结合数字图像相关性（Digital image correlation,DIC）分析方法,对E玻璃纤维增强环氧树脂基复合材料棒材在10^-3~2 400 s^-1应变率范围内的轴向拉伸力学性能进行了较系统的实验研究,获得了不同应变率下材料的应力-应变曲线,揭示了应变率对材料的拉伸强度和断裂应变的影响规律。通过显微分析拉伸试样的断口形貌,揭示了试样的断裂机制及对应变率的依赖性。实验结果表明：E玻璃纤维增强环氧树脂基复合材料的力学性能具有强烈的应变率效应,归一化拉伸强度随着应变率对数线性增加,而归一化断裂应变则随着对数应变率线性减小;断口显微分析显示：E玻璃纤维增强环氧树脂基复合材料的轴向拉伸断裂模式依赖于应变率,低应变率加载下试样发生沿45°方向的剪切断裂,随着应变率增大,试样断裂模式逐渐过渡到沿轴向的拉伸断裂,特别是在高应变加载下,观察到大量的玻璃纤维丝被拉断,同时环氧树脂基体也发生严重的碎裂现象,这反映了基体材料与玻璃纤维之间相互约束作用在增强。     

Flexural behavior of geopolymer composites reinforced with steel and polypropylene macro fibers

Like ordinary Portland cement concrete, the matrix brittleness in geopolymer composites can be reduced by introducing appropriate fiber reinforcement. Several studies on fiber reinforced geopolymer composites are available, however there is still a gap to understand and optimize their performance. This paper presents the flexural behavior of fly ash-based geopolymer composites reinforced with different types of macro steel and polypropylene fibers with higher aspect ratio. Three types (length-deformed, end-deformed and straight) of steel fibers and another type of length-deformed polypropylene fiber with optimum fiber volume fraction of 0.5% are studied. The effects of different geometries of the fibers, curing regimes (ambient cured and heat cured at 60 °C for 24 h) and concentration of NaOH activator (10 M and 12 M) on the first peak strength, modulus of rupture and toughness of the geopolymer composites are investigated. The quantitative effect of fiber geometry on geopolymer composite performance was also analyzed through a fiber deformation ratio. The compressive strength, splitting tensile strength and flexural toughness are significantly improved with macro fibers reinforcement and heat curing. The results also show that heat curing increases the first peak load of all fiber-reinforced geopolymers composites. End-deformed steel fibers exhibit the most ductile flexural response compared to other steel fibers in both heat and ambient-cured fiber reinforced geopolymer composites.     

Surface microstructural modification and fracture behavior of tensile deformed polypropylene with different percentage crystallinity

Microstructural evolution during tensile deformation of injection molded polypropylene (PP) at the micro- and nano-scale level was studied using atomic force and scanning electron microscopy techniques. Atomic force microscopy (AFM) enabled microstructural changes of tensile deformed PPs with different percentage crystallinity to be captured. AFM of undeformed slow-cooled (SC-PP: high crystallinity) and water-quenched (WQ-PP: low crystallinity) PPs suggested that the fibrils are relatively more closely packed in the SC-PP with higher average surface height of 7.5 nm as compared to 5.4 nm in the case of WQ-PP. Tensile deformed SC-PP and WQ-PP at displacement rates of 125–500 mm/min (strain rates of 0.04 s⁻¹ to 0.16 s⁻¹) indicated that the fibrils/microfibrils are aligned along the tensile axis, with WQ-PP exhibiting enhanced stretching of fibrils/microfibrils/chain-folded lamellae in comparison to SC-PP. Three fracture morphologies were identified at different strain rates, and include crazing/tearing (C), brittle fracture in association with crazing/tearing (B1), and brittle fracture together with ductile pulling of ligaments (B2). The fracture morphology exhibited by both SC-PP and WQ-PP was similar, but the percent area fraction of the three identified morphologies varied. WQ-PP with lower crystallinity was characterized by a decrease in percent of crazing/tearing (C) and brittle+crazing/tearing (B1), and increase in brittle+ductile pulling of ligaments (B2). The fracture characteristics of PPs with differences in crystallinity was consistent with AFM observations.     

Role of micro/nano fillers on mechanical and tribological properties of polyamide66/polypropylene composites

The objectives of this research article is to evaluate the mechanical and tribological properties of polyamide66/polypropylene (PA66/PP) blend, graphite (Gr) filled PA66/PP, nanoclay (NC) filled PA66/PP and NC plus short carbon fiber (NC + SCF) filled PA66/PP composites. All composites were fabricated using a twin screw extruder followed by injection molding. The mechanical properties such as tensile, flexure, and impact strengths were investigated in accordance with ASTM standards. The friction and sliding wear behaviour was studied under dry sliding conditions against hard steel on a pin-on-disc apparatus. Scanning electron micrographs were used to analyze the fracture morphologies. From the experimental investigation, it was found that the presence of NC and SCF fillers improved the hardness of PA66/PP blend. Further, the study reveals that the tensile and flexural strength of NC + SCF filled PA66/PP was higher than that of PA66/PP blend. Inclusion of micro and nanofillers reduced the wear rate of PA66/PP blend. The wear loss of the composites increased with increasing sliding velocity. The lowest wear rate was observed for the blend with nanoclay and SCF fillers. The wear rates of the blends with micro/nanofillers vary from 30–81% and lower than that of PA66/PP blend. The wear resistance of the PA66/PP composites was found to be related to the stability of the transfer film on the counterface. The results have been supplemented with scanning electron micrographs to help understand the possible wear mechanisms.     

Effects of carbon nanotubes and its functionalization on the thermal and flammability properties of polypropylene/wood flour composites

In this article, pristine carbon nanotubes (CNTs) and hydroxylated CNTs (CNT-OH) were employed to enhance the thermal stability and flame retardancy of polypropylene (PP)/wood flour composites (WPC) compatibilzed by maleic anhydride-grafted polypropylene (PP-g-MA). Incorporating 10 wt% PP-g-MA only enhanced the mechanical and thermal properties to some extent, but did not improve the flame retardancy of WPC. Thermogravimetric analysis (TGA) showed that the thermal stability of WPC was further increased with the addition of CNTs or CNT-OH and the increase of their loading level. Cone calorimeter measurements suggested that CNTs and CNT-OH could effectively reduce the peak heat release rate (PHRR) of WPC, and the flame retardancy properties reached the optimum value when both of their loading was 1.0 wt%, for instance, a reduction in PHRR by 16.7% and 25% for CNTs and CNT-OH, respectively. In addition, CNT-OH conferred better flame retardancy on WPC relative to pristine CNTs due to the better interfacial adhesion with wood flour and PP matrix, which was evidenced by scanning electron microscopy (SEM) observations.     

Continuous-glass-fibre-reinforced polypropylene composites: I. Influence of maleic-anhydride-modified polypropylene on mechanical properties

This study investigates the influence of maleicanhydride-modified polypropylene (m-PP) on monotonic mechanical properties of continuous-glass-fibre-reinforced polypropylene (PP) composites. Maleicanhydride-modified polypropylene was added to the PP homopolymer to improve the adhesion between the matrix and the glass fibre. Three-point bending tests were performed on 0° and 90° unidirectional glass-fibre/PP laminates with various weight fractions of m-PP in the PP matrix. These tests showed an increase in both longitudinal and transverse flexural strength up to 10 wt% m-PP, whereas at higher weight fractions of m-PP a decrease in flexural strength was observed. No significant influence of m-PP on composite stiffness was observed. Additional mechanical tests on unidirectional glass/PP composites with 0 wt% and 10 wt% m-PP showed only a small increase in fibre-dominated properties such as longitudinal tensile strength and strain, whereas composite properties that are governed by the interphase, such as transverse, shear and compressive strength, showed significant increases as a result of matrix modification and an enhanced interaction between the glass fibres and the PP matrix.