Biodegradable thermoplastic elastomer comprising PLLCA and CaCO<Subscript>3</Subscript> whiskers: mechanical properties,thermal stability and shape memory properties

A biodegradable and thermoplastic elastomer—poly(L-lactide-co-ε-caprolactone) (PLLCA)—was reinforced with 5, 10, 20, and 30 wt% of CaCO₃ whiskers. We assessed the influence of the CaCO₃ whisker content on the mechanical and thermal properties of the PLLCA/CaCO₃ whisker composites. Scanning electron microscopy (SEM) revealed that the CaCO₃ whiskers were uniformly distributed in the composite matrices. The results of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that the glass transition temperatures (T _g) of the composites increased slightly with increasing CaCO₃ whisker content. At low CaCO₃ whisker contents, the tensile strengths of the composites increased sharply with increasing CaCO₃ content, the Young’s moduli also increased, and the elongation at break values gradually decreased. Thermogravimetric analysis (TGA) showed that the CaCO₃ whiskers can promote the thermal degradation of PLLCA. Shape memory test results indicated that an appropriate amount of CaCO₃ whiskers can improve the shape memory properties of PLLCA.     

Effect of particle size and surface modification on mechanical properties of poly(para‐dioxanone)/inorganic particles

Poly(para‐dioxanone) (PPDO)‐based composites have been prepared by blending PPDO with three different types of CaCO₃ particles, CC1 (nano‐CaCO₃), CC2 (CaCO₃ whisker), and CC3 (silane‐coated CaCO₃ whisker). The effects of particles size, interface adhesion, and crystallinity of composites on mechanical properties were discovered through analysis of the morphology of fracture surfaces, thermal characteristics, and crystalline structure. DSC revealed that the CaCO₃ particles acted as a nucleating agent and promoted crystallinity of PPDO. The effect of CaCO₃ particles on crystallization of PPDO was clearly revealed by using the nucleating efficiency. Smaller size particles exhibit greater nucleating efficiency. Adhesion between PPDO and the CaCO₃ particles plays major roles on the mechanical properties of composites. The tensile strength of PPDO was improved over 54%. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Preparation of PMMA grafted calcium carbonate whiskers and its reinforcement effect in PVC

In this study, calcium carbonate (CaCO₃) whiskers were grafted with poly(methyl methacrylate) (PMMA) by in situ emulsion polymerization using γ‐methacryloxy propyl trimethoxyl silane (γ‐MPS) as a coupling agent, and the properties of resultant whisker were determined using Fourier transform infrared (FTIR) spectroscopy, energy dispersive spectroscopy (EDS), X‐ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The results show that PMMA has been successfully grafted onto the surface of CaCO₃ whiskers and the maximum grafting degree (Gd) is 3.75%. The scanning electron microscopy (SEM) micrographs of the tensile‐fractured surfaces show that modified CaCO₃ whiskers have strong interfacial adhesion to the poly(vinyl chloride) (PVC) matrix. The tensile strength increases from 44.0 MPa for PVC composite with unmodified whisker to 49.5 MPa for that with grafted whisker. The dynamic mechanical analysis (DMA) and TGA results indicate that the composites reinforced by modified CaCO₃ whiskers have much higher modulus, glass transition temperature, and better thermal stability than their counterparts reinforced by unmodified CaCO₃ whiskers. POLYM. COMPOS., 38:2753–2761, 2017. © 2015 Society of Plastics Engineers     

Mechanical properties,thermal stability,and thermal degradation kinetics of silicone rubber/ethylene-vinyl acetate copolymer/magnesium sulfate whisker composites compatibilized by ethylene-acrylic acid copolymer

Silicone rubber/ethylene-vinyl acetate copolymer/magnesium sulfate whisker composites containing ethylene-acrylic acid copolymer (MS/SR/EVM/EAA) as a compatibilizer were successfully prepared. Moreover, the magnesium sulfate whisker surface was modified with 3 wt% of silane coupling agent (KH570), resulting in composites including (unmodified magnesium sulfate whisker) uMS/SR/EVM, (modified magnesium sulfate whisker) mMS/SR/EVM, and mMS/SR/EVM/EAA were compared. The values of thermal decomposition activation energy (E_a) calculated by the two different methods (Kissinger and Friedman methods) show that the composites filled with 5 and 20 phr whiskers have lower values of activation energy (E_a) than the SR/EVM blend. The tensile strength of composites with a 5 phr modified whisker is 14.5 MPa, which is higher than that of the SR/EVM blend and uMS5/SR/EVM composite. The tear strength of the composite with 20 phr mMS is 51.6 kN m⁻¹, much higher than that of the composite with 20 phr uMS and SR/EVM blend. The mechanical properties were also investigated after thermal aging of the composites at 85°C for 48 h. The thermal conductivity of the composites with high filler loading was studied.     

Influence of functionalized calcium carbonate nanofillers on the properties of melt-extruded polycarbonate composites

In an effort toward developing better tribological properties of polycarbonate (PC), a reinforcement with calcium carbonate (CaCO₃) nanoparticles (3% by weight), in the size range of 30–60?nm, functionalized using stearic acid, was carried out by melt extrusion method. It was established that scratch resistance of PC/CaCO₃ composites (PCC) improved by 30% in comparison with pure PC. Nevertheless, an assessment of thermal properties using thermogravimetric analysis and differential scanning calorimetry (DSC) indicated an inferior thermal stability of PCC. Thermomechanical properties as obtained from dynamic mechanical analysis revealed an improvement in storage modulus for PCC but loss tangent (tan δ) results indicated lower glass transition (T_g) values in agreement with DSC results. To comprehend the thermal behavior of PCC, degradation kinetics was studied using the model-free method, and it was observed that the presence of organically modified nanoparticles resulted in catalysis of degradation, thus, lowering apparent activation energy (E_α) for PCC at the initial stages of degradation.     

High density polyethylene/micro calcium carbonate composites: A study of the morphological,thermal, and viscoelastic properties

High density polyethylene (HDPE) with micro calcium carbonate (CaCO₃) masterbatch was pelletized by using a twin screw extruder and different ASTM specimens were molded by an injection molding machine. The morphology of the composites was characterized by scanning electron microscopy (SEM) and Image Analysis software. The dispersion and interfacial interaction between CaCO₃ and the polymer matrix were also investigated by SEM. The thermal properties of HDPE and its composites were investigated by differential scanning calorimetry (DSC). The crystallization process of the composites samples was found to be slightly different than that of the neat HDPE. Otherwise, the presence of CaCO₃ did not have a considerable effect on the melting behavior of the composites. Thermogravimetric analysis (TGA) revealed that the composites had better thermal stability than the neat HDPE resin as indicated by a higher temperature of 50% weight loss (T_50%) for the composites as compared to that of the neat resin. The viscoelastic properties of the composites and HDPE were also investigated via torsional and rotational techniques. The presence of CaCO₃ increased the shear modulus at low frequency of the composites at 80°C over that of the neat resin. However, at higher frequencies, the difference between the neat resin and the composites' shear modulus was less than that at low frequencies. The complex viscosity of the composite increased upon the addition of CaCO₃. However, the shear sensitivities of the neat resin and the microcomposite were similar. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical and thermal behavior of polycarbonate composites reinforced with aluminum borate whiskers

Inorganic aluminum borate (Al₁₈B₄O₃₃) whisker was employed in this study to reinforce polycarbonate (PC). The composites were prepared in a single-screw extruder, followed by injection molding. The whiskers were pretreated with tetrabutyl orthotitanate prior to compounding. The tensile, dynamic mechanical, impact, and thermal properties of the composites were studied. Tensile results showed that the modulus of PC–Al₁₈B₄O₃₃ composites increased markedly with increasing whisker content. However, the tensile stress of the composite decreased slightly with the addition of 5 wt % whisker; thereafter, it increased slowly with increasing whisker content. Differential thermal analysis and thermogravimetric measurements showed that the glass transition temperature (T_g) and 5% weight loss temperature (T_−5%) of the composite shift rapidly to lower temperature regimes with the addition of Al₁₈B₄O₃₃ whiskers up to 10 wt %. Thereafter, the T_g and T_−5% of PC–Al₁₈B₄O₃₃ composites tended to decrease slowly with increasing whisker content. The mechanical and thermal properties of PC–Al₁₈B₄O₃₃ composites were compared with those of PC–potassium titanate (K₂Ti₆O₁₃) whisker composites. The reinforcing effect of Al₁₈B₄O₃₃ and K₂Ti₆O₁₃ whiskers on PC was discussed and contrasted. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2247–2253, 1999     

Polystyrene/CaCO3 composites with different CaCO3 radius and different nano‐CaCO3 content—structure and properties

The Archimedes' principle and physical theory are attempted to analysis the densification and structure of the polystyrene (PS) composites by melt compounding with CaCO₃ having different particle size. The difference between the measured specific volume (ν) andthe theoretically calculated specific volume (ν_mix), Δν = ν−ν_mix, can reflect the densification of the composites. It is clearly demonstrated that the PS composites become more condensed with the reduction of the CaCO₃ particle size. Especially, when the content for nano‐CaCO₃ achieves 2 wt%, the Δν value of the composites reaches the least, which shows the best densification. Meanwhile, the glass transition temperature (T_g) reaches the maximum value of about 100°C by differential scanning calorimetry (DSC) and thermal mechanical analysis (TMA), which indirectly reveals the composites microstructure more condensed. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) reveal that 2 wt% nano‐CaCO₃ uniformly disperses in PS composites. The CaCO₃ selected in this experiment has certain toughening effect on PS. The impact and tensile strength increase with addition of nano‐CaCO₃, but the elongation at break decreases. When nano‐CaCO₃ content achieved 2 wt%, the impact and tensile strength present the maximum value of 1.63 KJ/m² and 44.5 MPa, which is higher than the pure PS and the composites filled with the same content of micro‐CaCO₃. POLYM. COMPOS., 31:1258–1264, 2010. © 2009 Society of Plastics Engineers     

Crystallization behavior,morphology, and mechanical properties of poly(lactic acid)/tributyl citrate/treated calcium carbonate composites

In this article, poly(lactic acid) (PLA) composites containing titanate coupling agent treated calcium carbonate (T‐CaCO₃) and tributyl citrate (TBC) were prepared via melt blending. The crystallization, morphology, mechanical properties, and nonisothermal cold crystallization kinetics of PLA composites were studied by means of differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized light microscopy (PLM), scanning electron microscopy (SEM), and mechanical tests, respectively. The results show that TBC promotes crystallization of PLA. Both T‐CaCO₃ and TBC significantly decrease the spherulitic size, but the crystal structure of PLA is not changed. A synergistic toughening effect is obtained by the combination of T‐CaCO₃ and TBC. The nonisothermal cold crystallization kinetics of PLA composites is well described by Mo's method. The activation energies (ΔE) of nonisothermal cold crystallization were calculated by Kissinger and Takhor methods, respectively. It is found that the addition of T‐CaCO₃ and TBC increases ΔE, but it also increases the cold crystallization rate. POLYM. COMPOS., 35:1570–1582, 2014. © 2013 Society of Plastics Engineers     

Aluminum‐borate‐whiskers‐reinforced bismaleimide composites. 1: preparation and properties

Aluminum‐borate‐whiskers‐reinforced bismaleimide (BMI/Al₁₈B₄O₃₃) composites were prepared, and the mechanical and thermal properties were investigated. Results show that the coupling agent used for surface treatment of whiskers has a great effect on the properties of these materials. Composites containing surface‐untreated whiskers, or silane‐compound‐KH 921‐treated whiskers, exhibited initially only a slight increase in the flexural strength when the whiskers weight content increased up to 5 wt%; thereafter, they showed a sharp decrease when the whiskers content was higher than 5 wt%. On the other hand, impact strength tests showed that the addition of the two kinds of whiskers decreased the impact strength of the composites. However, studies of the composite containing borate (BE4)‐treated whiskers showed that its flexural strength greatly increased with increasing whisker content. Moreover, the composite showed initially an increase in impact strength with a whisker content up to 10 wt%, then showing a slight decrease when the whisker content reached 15 wt%. Scanning electron microscopy observations revealed that the two coupling agents (KH 921 and BE4) employed in this work tend to change the fracture features of the composites from brittleness to that of ductile behaviour. Copyright © 2004 Society of Chemical Industry     

Synthesis,characterization, and electrorheological properties of polyindene/calcium carbonate composites

In this study, synthesis, characterization, and electrorheological (ER) properties of polyindene (PIn) and PIn/calcium carbonate (PIn/CaCO₃) conducting composites were carried out by free radical polymerization. In the experiments, FeCl₃ was used as oxidizing agent and the ratio of salt:monomer was 2:1. First, PIn was synthesized and obtained with 70% yield. Then, PIn/CaCO₃ composites containing various amounts of PIn were prepared. PIn and PIn/CaCO₃ composites were characterized by FTIR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), dynamic light scattering (DLS) methods, Gouy Balance, and dielectric measurements. Suspensions of PIn and PIn/CaCO₃ composites were prepared in silicone oil (SO), at a series of concentrations (c = 10–25%, m/m) and their sedimentation stabilities were determined. The effects of dispersed particle concentration, particle size, shear rate, external electric field strength, frequency, and temperature onto ER activities of suspensions were investigated. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Investigation on β‐polypropylene/PP‐g‐MAH/ surface‐treated calcium carbonate composites

β‐Polypropylene composites containing calcium carbonate treated by titanate coupling agent (T‐CaCO₃) and maleic anhydride grafted PP (PP‐g‐MAH) were prepared by melt compounding. The crystallization, morphology and mechanical properties of the composites were investigated by means of differential scanning calorimetry, wide‐angle X‐ray diffraction, polarized light microscopy, scanning electron microscopy and mechanical tests. It is found that both T‐CaCO₃ and NT‐C are able to induce the formation of β‐phase, and NT‐C greatly increases the β content and decreases the spherulitic size of PP. PP‐g‐MAH facilitates the formation of β‐form PP and improves the compatibility between T‐CaCO₃ and PP. Izod notched impact strength of β‐PP/T‐CaCO₃ composite is higher than that of PP/T‐CaCO₃ composite, indicating the synergistic toughening effect of T‐CaCO₃ and β‐PP. Incorporation of PP‐g‐MAH into β‐PP/T‐CaCO₃ composite further increases the content of β‐crystal PP and improves the impact strength and tensile strength when T‐CaCO₃ concentration is below 5 wt%. The nonisothermal crystallization kinetics of β‐PP composites is well described by Jeziorny's and Mo's methods. It is found that NT‐C and T‐CaCO₃ accelerate the crystallization rate of PP but the influence of PP‐g‐MAH on crystallization rate of β‐PP composite is marginal. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Crystallization behavior of polypropylene filled with surface-modified calcium carbonate

Polypropylene (PP) and calcium carbonate (CaCO₃) were mixed in a two-roll mill. The mixed compounds were molded on the plate by using a compression press heater. To improve the affinity of the relation between CaCO₃ and the PP matrix, we modified the CaCO₃ surface through chemical reaction with alkyl dihydrogen phosphates. The CaCO₃ content and size modification affected the crystallization behavior of the filled PP composites. The crystallization temperature in the nonisothermal crystallization process increased with the increase of CaCO₃ content and the decrease of CaCO₃ size. The crystallization temperature revealed the function of log (1 + T_s) (T_s, total surface area of CaCO₃) irrespective of CaCO₃ content and size for modified and unmodified systems, respectively. The shoulder or double crystallization peak of PP composites is recognized for the unmodified system (particle sizes: 1.0 and 4.5 μm).     

Processability,morphology, thermal,and mechanical properties of rigid PVC composites with liquid macromolecular modifier‐coated CaCO3

Rigid poly(vinyl chloride) (PVC)/CaCO₃ and PVC/liquid macromolecular modifier (LMM) coated CaCO₃ (PVC/LCC) composites were both fabricated by melt mixing. The processability, micro‐structure, dynamic mechanical behavior and mechanical properties of PVC/CaCO₃ and PVC/LCC composites were studied by using torque rheometer, scanning electron microscope (SEM), dynamic mechanical analysis (DMA), and universal mechanical testing machine. The results showed that the synergistic effect of LMM and CaCO₃ particles accelerated the plasticization of PVC resins. The processability of PVC/LCC composites was improved. The dispersion of LCC in PVC matrix was improved by the modification of CaCO₃ particles with LMM. The T_gs of PVC/LCC composites were enhanced by filling with LCC. Because of the synergistic toughening of LMM and CaCO₃ particles, the PVC/LCC composites exhibited excellent notched impact properties at the optimum value of LCC particles content. POLYM. COMPOS., 36:1286–1292, 2015. © 2014 Society of Plastics Engineers     

Nonisothermal crystallization behavior and crystals morphology of poly(trimethylene terephthalate)/nano‐calcium carbonate composites

Nonisothermal crystallization behavior and crystal morphology of poly(trimethylene terephthalate) (PTT) composites filled with modified nano‐calcium carbonate (CaCO₃) had been investigated by using differential scanning calorimetry and polarized optical microscopy. The modified Avrami equation and Ozawa theory were used to investigate the nonisothermal crystallization, respectively. The particles of nano‐CaCO₃, acting as a nucleation agent in composites, accelerated the crystallization rate by decreasing the half‐time of crystallization or increasing the parameters of Z_c and K(T). Moreover, the nano‐composite with 2 wt% nano‐CaCO₃ exhibited the highest crystallization rate. The Avrami and the Ozawa exponents, n and m of the nano‐composites, were higher than those of neat PTT, suggesting more complicated interaction between molecular chains and the nanoparticles that cause the changes of the nucleation mode and the crystal growth dimension. The effective activation energy calculated from the Friedman formula was reduced as nano‐CaCO₃ content increased, suggesting that the nano‐CaCO₃ made the molecular chains of PTT easier to crystallize during the nonisothermal crystallization process. The optical micrographs showed that much smaller or less perfect crystals were formed in composites because of the presence of the nano‐CaCO₃ particles. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

The effect of whisker orientation in SiC whisker-reinforced Si3N4 ceramic matrix composites

Si₃N₄ ceramic matrix composites reinforced by nearly unidirectionally aligned SiC whiskers have been prepared by extrusion and hot pressing. Unlike the case in traditional Si₃N₄ ceramic matrix composites reinforced by random SiC whiskers, the mechanical properties of the composites exhibit a significant dependence on whisker orientation. In the direction of whisker alignment for SiC(w)/Si₃N₄ composites, increments in bending strength and fracture toughness of 200 MPa and 3 MPa·m^1/2 are obtained respectively, compared to the values in the direction perpendicular to whisker alignment. Based on microscopic fractographic observation and micromechanics analyses, the effects of whisker orientation on toughening mechanisms are discussed. The results indicate that the whisker orientation, θ, is a decisive factor for the essential toughening mechanisms of whiskers. Only in the case of small θ and weak interface can whisker pullout occur, and whisker has maximum toughening effect. The results show that effects of whisker strengthening and toughening can be improved simultaneously through whisker oriented alignment. ©     

Crystallization kinetics of polypropylene composites filled with nano calcium carbonate modified with maleic anhydride

The subject of this study was the crystallization behavior and thermal properties of polypropylene (PP)/maleic anhydride (MAH) modified nano calcium carbonate (nano‐CaCO₃) composites. In this study, 5 wt % nano‐CaCO₃ modified with different contents of MAH was filled into a PP matrix. X‐ray diffraction and differential scanning calorimetry were used to characterize the crystal morphology and crystallization kinetics of a series of composites. The results demonstrate that the nano‐CaCO₃ modified with MAH had an important effect on the thermal and morphological properties of the nanocomposites. The Avrami exponent of the pure PP was an integer, but those of the composites were not integers, but the crystallization rate constant decreased as the content of MAH in the nano‐CaCO₃ filler increased in isothermal crystallization. In nonisothermal crystallization, the kinetic parameter F(T) and the degree of crystallinity of pure PP were compared with those of the PP composites filled with nano‐CaCO₃. We suggest that heterogeneous nucleation existed in the PP composites and that the transformation and retention of the β‐form crystal into the α‐form crystal took place in the composite system and the β‐form crystal had a higher nucleation rate and growth process than the α‐form crystal in the PP composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization properties of polycaprolactone composites filled with nanometer calcium carbonate

Polycaprolactone (PCL) composites filled with nanometer calcium carbonate (nano‐CaCO₃) were prepared by means of a twin‐screw extruder in this study. The nano‐CaCO₃ surface treated with stearate. The crystalline properties of the PCL/nano‐CaCO₃ composites were measured with a differential scanning calorimeter to identify the influence of the nanometer filler content on the crystalline properties. The results show that the crystallization onset temperature, crystallization temperature, and crystallization end temperature of the composites were obviously higher than those of the unfilled PCL resin, and the crystallization degree (χ_c) of the composites increased with increasing particle weight fraction (?_f) when ?_f was more than 1%. When ?_f was 1%, χ_c of the composite was less than that of the unfilled PCL resin. Moreover, the dispersion of the inclusions in the matrix was observed by means of scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigation of the microstructures,properties, and toughening mechanism of polypropylene/calcium carbonate toughening masterbatch composites

The morphologies, crystallization and melting behaviors, and mechanical, thermal and processing properties of polypropylene (PP)/CaCO₃ toughening masterbatch (CTM) composites were investigated. The good dispersion of CaCO₃ particles via appropriate surface encapsulation in the composites is proven by density measurements and scanning electron microscopy images. The crystallinity and tensile strength of PP decrease with the addition of CTM. The flexural modulus and storage modulus (E′) at 23 °C increase with CTM content, implying improved stiffness. A sharp increase in the Izod notched impact strength can be observed for the composites, and the critical ligament thickness (τ_c) is calculated to be 1.31 and 2.46 μm for PP (S1003) and PP (001 G) composites, respectively. The morphologies of the impact‐fractured surfaces of the specimens were observed, and the shear deformation is enhanced by the addition of CTM. The presence of CTM also increases the melt flowability and decreases the shrinkage of the composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45515.     

Study on mechanical and flow properties of acrylonitrile‐butadiene‐styrene/poly(methyl methacrylate)/nano‐calcium carbonate composites

Acrylonitrile‐butadiene‐styrene (ABS)/poly(methyl meth‐acrylate) (PMMA)/nano‐calcium carbonate (nano‐CaCO₃) composites were prepared in a corotating twin screw extruder. Four kinds of nano‐CaCO₃ particles with different diameters and surface treatment were used in this study. The properties of the composites were analyzed by tensile tests, Izod impact tests, melt flow index (MFI) tests, and field emission scanning electron microscopy (FESEM). This article is focused on the effect of nano‐CaCO₃ particles' size and surface treatment on various properties of ABS/PMMA/nano‐CaCO₃ composites. The results show that the MFI of all the composites reaches a maximum value when the content of nano‐CaCO₃ is 4 wt%. In comparison with untreated nano‐CaCO₃ composites, the MFI of stearic acid treated nano‐CaCO₃ composites is higher and more sensitive to temperature. The tensile yield strength decreases slightly with the increase of nano‐CaCO₃ content. However, the size and surface treatment of nano‐CaCO₃ particles have little influence on the tensile yield strength of composites. In contrast, all of nano‐CaCO₃ particles decrease Izod impact strength significantly. Stearic acid treated nano‐CaCO₃ composites have superior Izod impact strength to untreated nano‐CaCO₃ composites with the same nano‐CaCO₃ content. Furthermore, the Izod impact strength of 100 nm nano‐CaCO₃ composites is higher than that of 25 nm nano‐CaCO₃ composites. POLYM. COMPOS., 31:1593–1602, 2010. © 2009 Society of Plastics Engineers