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     

Effects of glass bead content and surface treatment on viscoelasticity of filled polypropylene/elastomer hybrid composites

The dynamic mechanical properties of A‐glass bead filled polypropylene (PP)/ethylene–propylene–diene monomers polymer (EPDM) ternary composites have been measured over a temperature range from −80 °C to 100 °C and at a fixed frequency of 1 Hz, using a dynamic mechanical analyser (DMA), to identify the effects of the filler content and its surface treatment with a silane coupling agent on the dynamic viscoelastic behaviour. The results show that the storage modulus (E′_c) and loss modulus (E ″_c) of these composites with 10% volume fraction of EPDM at 25 °C increase non‐linearly with increasing volume fraction of glass beads (ϕ_g). At the same test conditions, the E′_c value of the PP/EPDM filled with pretreated glass beads is higher than that of the uncoated glass bead filled PP/EPDM system, especially at higher ϕ_g, while the difference in E ″_c between both systems is very small. The mechanical damping for the former decreases with increasing ϕ_g, but the opposite is true for the latter. The glass transition temperature of these composites varies irregularly with ϕ_g. The dynamic complex viscosity increases nonlinearly with an increase of ϕ_g. In addition, the interfacial structure between the matrix and inclusions has been observed by means of a scanning electron microscope. © 1999 Society of Chemical Industry     

Crystallization of glass fiber‐reinforced poly(p‐phenylene sulfide) nanocomposites

Ternary composites of glass fiber‐reinforced poly(p‐phenylene sulfide) (PPS/GF) filled with nanometric calcium carbonate (nano‐CaCO₃) were prepared by means of a twin‐screw extruder. The nano‐CaCO₃ surface was treated with stearate and treated with titanate, the composites being called SI composite system and SII composite system, respectively. The crystallization and heatproof properties of the PPS/GF/nano‐CaCO₃ composites were measured using a differential scanning calorimeter, to investigate the influence of the nanometric filler content on the crystallinity. The results show that the variation of the starting crystallization temperature, crystallization temperature and crystallinity with an increase of the particle weigh fraction (?_f) of SI composite system is different from that of SII composite system. When ?_f is less than 4 wt%, the crystallinity of the two composite systems increases and then decreases slightly with increasing ?_f. Moreover, the crystallization behavior and mechanisms are discussed. Copyright © 2011 Society of Chemical Industry     

Tensile properties and morphology of PP/EPDM/glass bead ternary composites

The tensile properties of three types of injection molded glass bead (GB) filled polypropylene (PP)/ethylene-propylene-diene monomer (EPDM) ternary composites have been determined at room temperature by using an Instron materials testing machine. The effects of the filler surface treatment, the glass bead (GBI) pretreated with a silane coupling agent and the EPDM (EPDM-MA) modified with a maleic anhydride, and the filler content on the tensile mechanical properties of the ternary PP composites have been investigated. The Young's modulus (E_c) increases while the yield stress (σ_yc) and tensile fracture strength (σ_bc) of the composites decrease with increasing the volume fraction of glass beads (ϕ_g) when the volume fraction of EPDM is constant (ϕ_e = 10%). The (E_c) values of PP/EPDM/GBI and ϵ_bc for PP/EPDM-MA/GB2 (no surface pretreated) systems are the highest at the same ϕ_g. The tensile fracture energy (E_bc) and tensile fracture strain (ϵ_bc) of PP/EPDM/GBI and PP/EPDM/GB2 systems appear to peak at ϕ_g = 25%. However, the E_bc and ϵ_bc of PP/EPDM-MA/GB2 system show little changes with increasing ϕ_g. The fracture surfaces of ternary composites have been examined in a scanning electron microscope. The correlation between the tensile properties and morphologies of these materials have been discussed.     

Properties of coconut shell powder‐filled polylactic acid ecocomposites: Effect of maleic acid

Ecocomposites were produced by incorporating coconut shell powder (CSP) into polylactic acid (PLA) resin. The effect of filler content and chemical modification on the mechanical properties, thermal properties, and morphology of PLA/CSP ecocomposites were investigated. The addition of filler has decreased the tensile strength and elongation at break of PLA/CSP ecocomposites. However, tensile strength and modulus of elasticity of PLA/CSP ecocomposites were enhanced by maleic acid treatment. Meanwhile, glass transition temperature (T_g) and crystallinity (X_c) of PLA/CSP ecocomposites increased at 30 php of filler content and increased the presence of maleic acid (MA). However, the melting temperature (T_m) and crystallization temperature (T_c) were not significantly changed with the filler content and MA modification The thermal stability of PLA/CSP ecocomposites increased with the CSP content. The MA modification improved the thermal stability of PLA/CSP ecocomposites through better filler–matrix interaction. The improvement was confirmed by scanning electron microscope study. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Crystallization and melting behavior of HDPE in HDPE/teak wood flour composites and their correlation with mechanical properties

The nonisothermal crystallization behavior and melting characteristics of high‐density polyethylene (HDPE) in HDPE/teak wood flour (TWF) composites have been studied by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) methods. Composite formulations of HDPE/TWF were prepared by varying the volume fraction (?_f) of TWF (filler) from 0 to 0.32. Various crystallization parameters evaluated from the DSC exotherms were used to study the nonisothermal crystallization behavior. The melting temperature (T_m) and crystallization temperature (T_p) of the composites were slightly higher than those of the neat HDPE. The enthalpy of melting and crystallization (%) decrease with increase in the filler content. Because the nonpolar polymer HDPE and polar TWF are incompatible, to enhance the phase interaction maleic anhydride grafted HDPE (HDPE‐g‐MAH) was used as a coupling agent. A shift in the crystallization and melting peak temperatures toward the higher temperature side and broadening of the crystallization peak (increased crystallite size distribution) were observed whereas crystallinity of HDPE declines with increase in ?_f in both DSC and WAXD. Linear correlations were obtained between crystallization parameters and tensile and impact strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The influence of filler treatment on the properties of TPU/PP blends: I. Thermal properties and stability

Commercially available organosilane (3‐glycidoxypropyltrimethoxysilane (GPTMS)) coupling agent was used to treat talc in order to improve the affinity relative between the filler and the polymer in composites as well as filler and polymer in the thermoplastic polyurethane/polypropylene (TPU/PP) blends (talc content was 5 wt%). The talc particles were first modified with GPTMS and then introduced into TPU, PP as well as TPU/PP blends with different weight ratios of polymers using blending method and subsequently injection molded in a hydraulic press. The aim was to report the effect of silane coupling agent on the thermal and morphological properties of talc filled composites and blends. The results showed that the thermal properties of the TPU, PP composites and TPU/PP blends were improved with the addition of silane treated talc (higher melting (T_m), crystallization (T_c) temperatures and degree of crystallinity (χ_c)). The glass transition temperature (T_g) obtained by dynamic mechanical analysis (DMA) of the TPU soft segments in TPU/PP blends increased with the addition of untreated and silane treated talc due to lower mobility of the soft segments in TPU and better miscibility of TPU and PP. TPU/PP blends with the silane treated talc show better thermal stability than the TPU/PP blends with untreated talc. POLYM. ENG. SCI., 55:1920–1930, 2015. © 2014 Society of Plastics Engineers     

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.     

Viscoelastic properties and characterization of inorganic particulate‐filled polymer composites

To identify effects of glass bead (GB) content on the dynamic mechanical properties of filled low‐density‐polyethylene (LDPE) composites, the storage modulus, loss modulus, glass transition temperature, and mechanical damping of these composites were measured using a Du Pont dynamical mechanical analysis instrument in temperature range from ?150 to 100°C. It was found that the storage modulus increased nonlinearly with an increase of the GB volume fraction. On the basis of Eshelby's method and Mori's work, an equation describing the relationship between the relative storage modulus (E′_R) and filler volume fraction for polymeric composites was proposed, and the E′_R of LDPE/GB composites were estimated by means of this equation at temperatures of ?25, 0, and 25°C, and the calculations were compared with the experimental data, good agreement was showed between the predictions and the measured data. Furthermore, this equation was verified by the experimental from Al(OH)₃ filled EPDM composites at glassy state reported in a reference. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Die–swell behavior of glass bead‐filled low‐density polyethylene composite melts at high extrusion rates

The extrudate swell behavior of glass bead‐filled low‐density polyethylene (LDPE) composite melts was investigated using a constant rate type of capillary rheometer at high extrusion rates and test temperatures varied from 140 to 170°C. The results show that the die swell ratio (B) of the melts increases nonlinearly with increasing apparent shear rates for the system filled with the surface of glass beads pretreated with a silane coupling agent, while the B for the system filled with uncoated particles remains almost constant when the true wall shear rate is greater than 2000 s⁻¹ at a constant temperature. The values of B for both the pure LDPE and the filled systems decreases linearly with an increase of the temperature and an increase of the die diameter at fixed shear rates, and the sensitivity of B on the die diameter and temperature for the former is higher than that of the latter. Furthermore, the effect of the filler content on B is insignificant, while the values of B decreases, obviously, with an increasing glass bead diameter (d) when d is smaller than 50 μm; then B varies slightly with d. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 419–424, 2000     

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     

Isothermal cold crystallization and melting behaviors of poly(L‐lactic acid)s prepared by melt polycondensation

The isothermal cold crystallization and melting behaviors of poly(L ‐lactic acid)s (PLLAs, weight average molecular weight, M_w, 6000–80,000) prepared via melt polycondensation were studied with differential scanning calorimeter in this work. It is found that the crystallization rate increased with decreasing M_w, reached a maximum at M_w of ca. 21,000 and then decreased again. The crystallinity of PLLA can be controlled in the range 30–50% by crystallization temperature (T_c) and time to fulfill the requirement of subsequent solid state polycondensation. The melting behavior strongly depends on T_c. The samples crystallized at high T_c melted with a single peak but those crystallized at low T_c melted with double peaks. The higher melting point (T_mH) kept almost constant and the lower melting point (T_mL) increased clearly with T_c. But the T_mL changed in jumps and a triple melting peak appeared at the vicinity of a characteristic crystallization temperature T_b, possibly because of a change of crystal structure. The equilibrium melting temperature of PLLA with M_w of 21,300 was extrapolated to be 222°C with nonlinear Hoffman‐Weeks method. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The Melt Flow Properties of Poly(propylene)/Glass Bead Composites

The effects of filler content and its surface treatment on the melt flow properties of A‐glass bead‐filled poly(propylene) (PP) composites have been investigated using a capillary rheometer at a wide apparent shear rate scope of 150 to 7 200 s^–1 and a temperature range of 160 to 200°C. It was found that the melt shear flow obeyed roughly the power law. The melt shear viscosity (η_w) of the treated glass bead‐filled system with a silane coupling agent was somewhat higher than that of the raw glass bead‐filled system when both the systems were subjected to the same test conditions. The increase of the resistance to flow and flow satiability for the former system can be attributed to the improvement of the compatibility and interfacial adhesion between the filler and matrix as well as the dispersion of the filler in the matrix due to the surface treatment of the glass beads. The dependence of η_w on temperatures can be expressed with an Arrhenius relationship. The temperature sensitivity of η_w for the composite melts is greater than that of the unfilled PP. Furthermore, η_w increases obviously with the volume fraction (ϕ_f) of the fillers at lower shear rates, while the dependence of η_w on ϕ_f decreases with the increase of shear rates. This is attributable to the increase of the ability of relative movement between the filler and matrix melt at high extrusion rates.     

Tensile,flow, and thermal properties of CaCO3‐filled LDPE/LLDPE composites

Calcium carbonate (CaCO₃)‐filled low‐density polyethylene (LDPE)/linear low‐density polyethylene (LLDPE) composites were fabricated by means of a twin‐screw extruder, and the tensile mechanical properties of the tubing with thickness of 0.5 mm made from these composites were measured at room temperature to identify the effect of the filler concentration on the properties of these composites. The results showed that the tensile elastic modulus increased roughly linearly with increasing weight fraction (?_f) of the fillers. The tensile fracture strength (σ_b) along longitudinal direction was obviously higher than that along transverse direction under the same test conditions, especially at higher filler concentration. The values of σ_b of the specimens along both the two directions achieved minimum at ?_f = 20%. Furthermore, the melt flow rate (MFR) and heat enthalpy (ΔH) of the composite materials were measured. It was found that both the MFR and the ΔH decreased with the addition of ?_f. The ΔH for the composite with LDPE/LLDPE ratio of 70/30 was higher than that of the composite with LDPE/LLDPE ratio of 50/50 at the same filler concentration, but contrary to the MFR. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1692–1696, 2007     

Highly reversible and repeatable PTCR characteristics of PMMA/Ag‐coated glass bead composites based on CTE mismatch phenomena

Positive temperature coefficient of resistivity (PTCR) behavior of poly(methyl methacrylate) PMMA/silver (Ag)‐coated glass bead composites has been investigated with reference to the conventional PMMA/carbon black (CB) composites. The PMMA/CB composites showed a sudden rise in resistivity (PTC trip) at 115°C, close to the glass transition temperature (T _g, 113°C) of the PMMA. However, the PTC trip temperature (92°C) of PMMA/Ag‐coated glass bead composites was appeared well below the T _g of PMMA. The room temperature resistivity and PTC trip temperature of the composites were also very much stable upon thermal cycling. Addition of 1 phr of nanoclay increased the PTC trip temperature of PMMA/CB composites to 120°C, close to the T _g (118°C) of PMMA/clay nanocomposites, while PMMA/clay/Ag‐coated glass bead nanocomposites showed the PTC trip at 98°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between PMMA and glass beads played a key role that led to a disruption in continuous network structure of Ag‐coated glass beads even at a temperature well below the T _g of PMMA. The decrease in dielectric permittivity of PMMA/Ag‐coated glass bead composites on increasing frequency indicated possible use of the PTC composites as dielectric material. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Tensile and Impact Properties of Hollow Glass Bead‐Filled PVC Composites

The tensile and notched Izod impact properties of poly(vinyl chloride) (PVC) composites filled with hollow glass beads (HGB) were measured at room temperature by means of an Instron materials testing machine to investigate the effects of the filler content and size on these mechanical properties. The results showed that the tensile yield strength (σ_yc) decreased gently with increasing HGB volume fraction (ϕ _f), while the tensile break strength (σ_bc) of the composites was somewhat greater than that of the unfilled PVC within ϕ _f = 0–20%. In addition, the dependence of σ_bc on ϕ _f was not obvious. The effect of HGB size on both σ_yc and σ_bc was insignificant. When ϕ _f < 5%, the notched impact strength (σ_IC) of the composites decreased quickly with increasing ϕ _f, and then it decreased slightly with the increase of ϕ _f. Similarly, the influence of the filler size on the impact properties was insignificant. Furthermore, the σ_yc of the samples was estimated using a tensile equation proposed in a previous paper. A good agreement was shown between the calculations and the measured data.     

Isothermal crystallization behavior of metallocene‐catalyzed isotactic polypropylene

Isothermal crystallization behavior of isotactic polypropylene (iPP) synthesized using metallocene catalyst was investigated in this work. The isotacticity of the polypropylene was characterized by ¹³C‐NMR spectroscopy. It was found that the melting temperature (T_m) of the iPP is 123.51°C and the crystallization temperature (T_c) is 93°C. The iPP synthesized in this work did not show a general increase of T_m with an increase of crystallization temperature T_c, due to the short crystallization time of 20 min and low molecular weight (number average molecular weight = 6,300). The iPP showed a tendency of increasing heat of fusion (ΔH_f) with decreasing crystallization temperature. All the spherulites of iPP samples showed negative birefringence. For the iPP sample crystallized at the highest T_c (= 123°C, just below T_m), the spherulite showed a pronounced Maltese Cross and a continuous sheaf‐like texture aligning radially, which suggests that R‐lamellaes are dominant in this spherulite. The crystalline structure of the iPP was also investigated by X‐ray diffraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 231–237, 2005     

Effects of rosin‐type nucleating agent and low density polyethylene on the crystallization process of polypropylene

In this article, the influence of rosin‐type nucleating agent (Nu–Na) and low density polyethylene (LDPE) on the crystallization process of polypropylene (PP) from the melt state was studied by differential scanning calorimeter and polarization microscope. It was found that LDPE obstructed the crystallization of PP, decreased the crystallization rate of PP. The rosin‐type nucleating agent Nu–Na substantially improved the rate of crystallization, and decreased the size of spherulites also. The cooperative effect of LDPE and Nu–Na made the crystallization rate of PP increase greatly, the spherulites of PP became much smaller and dispersed more uniformly, and the transparency of PP was further improved evidently. The crystallization temperature (T_c) and melting temperature (T_m) of PP and LDPE in PP/LDPE/Nu–Na (97:3:0.5) were not affected by the number of mixed passes—the nuclei migration from PP to PE had not happened in the mixed passes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2804–2809, 2003     

Nonisothermal crystallization of metallocene propylene–decene‐1 copolymers

The nonisothermal crystallization behavior of one metallocene‐based isotactic polypropylene and three propylene–decene‐1 copolymers was studied. The effects of comonomer content and cooling rate were investigated. It was found that comonomer units enchained systematically reduce the crystallization temperature (T_c), melting temperature (T_m), fusion enthalpy (ΔH_f), and crystallinity (X_c). Such an effect becomes more evident at a faster cooling rate. With increasing comonomer content, the supercooling required for crystallization increases and the overall crystallization rate is reduced. The Avrami equation is applicable to describe the nonisothermal crystallization kinetics of propylene–decene‐1 copolymer. It was shown that, although the reduced crystallization rate constant Z_c increases with comonomer content, the Avrami exponent decreases with comonomer content and cooling rate, leading to the smaller overall crystallization rate and larger crystallization half‐time of the copolymer with higher comonomer content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1724–1730, 2004     

Effect of nanoclay on positive temperature coefficient to resistivity characteristics of high density polyethylene/silver‐coated glass bead composites

Positive temperature coefficient to resistivity characteristics of high density polyethylene (HDPE)/silver (Ag)‐coated glass bead (45 wt%) composites, without and with nanoclay, has been investigated with reference to HDPE/carbon black (CB) (10 wt%) composites. Plot of resistivity versus temperature of HDPE/CB (10 wt%) composites showed a sudden rise in resistivity (PTC trip) at ≈128°C, close to the melting temperature (T_m) of HDPE. However, for HDPE/Ag coated glass bead (45 wt%) composites, the PTC trip temperature (≈88°C) appeared well below the T_m of HDPE. Addition of 1 phr clay in the composites resulted in an increase in PTC trip temperature of HDPE/Ag‐coated glass bead (45 wt%) composites, whereas no significant effect of clay on PTC trip temperature was evident in HDPE/CB/clay composites. We proposed that the PTC trip temperature in HDPE/Ag‐coated glass bead composites was governed by the difference in coefficient of thermal expansion of HDPE and Ag‐coated glass beads. The room temperature resistivity and PTC trip temperature of HDPE/Ag‐coated glass bead (45 wt%) composites were found to be very stable on thermal cycling. Dynamic mechanical analyzer results showed higher storage modulus of HDPE/Ag‐coated glass bead (45 wt%) composites compared with the HDPE/CB (10 wt%) composites. Thermal stability of HDPE/Ag‐coated glass bead (45 wt%) composites was also improved compared with that of HDPE/CB (10 wt%) composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers