Characterization of hdpe/ha Composites Treated with Titanate and Zirconate Coupling Agents

The development of new materials for bone substitution has been of great interest for the scientific community in the last years. High-density polyethylene (HDPE) and hydroxyapatite (HA) composites have been used in biomedical applications without any inflammatory response. However, the differences in nature of both materials have motivated the use of coupling agents to improve their interfacial interactions. In this work, the effects of adding three different commercial coupling agents (NZ12, Lica01, Lica12) to high-density polyethylene (HDPE)/hydroxyapatite (HA) composites were studied. Composites containing 20 parts per hundred (phr) of HA previously treated with the already mentioned coupling agents were characterized by mechanical tests and their morphologies were analyzed afterwards. Composites with 0.3 and 0.5 wt% of NZ12 unfolded an increase in their Young's modulus and tensile strength, as a consequence of an improved dispersion of the filler into the polymeric matrix. Analysis of the samples by XPS showed that the zirconate coupling agent interacted more with the HA, as reflected in the lower binding energies of the corresponding oxygen atoms, which agrees with their better performance from the mechanical point of view.     

Effect of Electron Beam Irradiation and Ethylene Vinyl Acetate Copolymer on the Properties of NBR/HDPE Blends

The mechanical and physical properties of blends based essentially on nitrile butadiene rubber (NBR) and different ratios of high density polyethylene (HDPE) up to 25 parts per hundred part of rubber (phr) before and after electron beam irradiation were investigated. The values of tensile strength (TS), tensile modulus at 50% elongation (M₅₀), hardness and gel fraction % (GF%) of NBR/HDPE blends were increased with both irradiation dose and by increasing the content of HDPE in the blends. On the other hand, the values of elongation at break (E _b ) were decreased with both irradiation dose and the content of HDPE in the blends. By loading NBR/HDPE (100/25) blend with ethylene vinyl acetate (EVA) copolymer the mechanical and physico-chemical properties were improved. Moreover, the degree of improvement is proportional to the loading content of EVA.     

Grafting polypropylene and treatment of calcium carbonate to improve structure and properties of polypropylene composites

In this paper, calcium carbonate was chemically treated with two kinds of dicarboxylic acids before compounding with polypropylene in the presence of dicumyl peroxide (DCP). It was observed that the mixture of dicarboxylic acids could improve the crystallization and impact strength properties of calcium carbonate/polypropylene composite. With further addition of DCP, more PP-g-MA was produced in the blend, resulting in PP composites with larger β-phase content and improved mechanical properties. In the experiments, the maximum K _β value of 52.0 % was obtained. The elongation at break of composite increased from 252 % for PP composite with untreated calcium carbonate to 444 % for PP composite with chemically treated calcium carbonate.     

Interaction of Silane Coupling Agents with CaCO3

A study of eight silane coupling agents showed very different effect of these compounds on the mechanical properties of PP/CaCO₃composites. The application of aminofunctional silane coupling agents resulted in the reactive coupling of the two inactive components leading to increased strength and decreased deformability. A detailed study of the interaction between CaCO₃and the various coupling agents was carried out in order to find an explanation for the strong coupling effect. The amount of coupling agent creating a monolayer coverage was determined by a dissolution method for each coupling agent. The obtained values changed between 0.3 and 1.0 wt% calculated for the CaCO₃. An attempt was made to determine the orientation of the adsorbed molecules to the filler surface. Most of the coupling agents are oriented perpendicularly to the surface with the exception of a methacryl functional silane compound. Possible interactions between hydrolyzed or condensed silane coupling agents and the filler were studied by Fourier transform infrared spectroscopy using transmitting (FTIR-TS) and diffuse reflectance (DRIFT) modes, as well as gel permeation chromatography (GPC). The results showed that bulky organofunctional groups form a caged, polycyclic, low-molecular-weight structure on the surface, while silanes with smaller groups tend to condense into open, ladder type, high-molecular-weight polysiloxane chains. Polymer/filler adhesion, however, depends primarily on the chemical character of the organofunctional group. Aminofunctional silane coupling agents adhere well to the filler surface and react also with the polymer. In the case of similar functionality the size of the organofunctional group determines the strength of the adhesion.     

Characterization of recycled polyamide 6: Effect of polypropylene and inorganic contaminants on mechanical properties

Recycled polyamide 6 (PA6) from post-industrial waste fibers (PIW) and post-consumer carpet waste (PCW) are characterized in this study. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) indicate the presence of polypropylene (PP) in PCW. Furthermore, measured ash content of PCW is ca. 6 wt.%, while PIW has only 0.5 wt.% inorganic content. X-ray fluorescence (XRF) and X-ray diffraction (XRD) show that inorganic contaminants of PCW and PIW are calcium carbonate (CaCO₃) and titanium dioxide (TiO₂), respectively. Due to higher inorganic filler content, PCW exhibits higher melt viscosity and higher storage modulus than that of PIW. PIW has 20% higher tensile strength than that of PCW. However, a drastic 70% drop is observed in vibration weld strength of PCW, which is attributed to its PP contamination. The negative effect of PP on the weld strength of recycled PA6 is also confirmed by measuring the mechanical properties of model compounds.     

Unsaturated hyperbranched polyester as a surface modifier of CaCO3 and enhanced effect on mechanical properties of HDPE/CaCO3 composites

The unsaturated hyperbranched polyester (UH20) based on Boltorn™ H20 (H20) end‐capped with methacrylate groups and carboxylic acid groups was introduced to treat calcium carbonate (CaCO₃) as a new type of surface modifier by a wet‐coating technique. The interaction between CaCO₃ and modifier was proven to be due to the ionic character by FT‐IR after the extraction with acetone. The maximum amount of tightly bonded UH20 modifier was determined to be around 9% by thermogravimetric analysis (TGA). The incorporation of CaCO₃ coated with UH20 into high‐density polyethylene (HDPE) decreased the mechanical performance of HDPE/CaCO₃ composite in comparison with CaCO₃ coated with stearic acid. In the presence of a small amount of dicumyl peroxide (DCP), a greatly improvement of the notched impact strength as well the tensile strength of HDPE/CaCO₃ coated with UH20 composite was obtained. An enhanced effect in the mechanical performance of the composite between CaCO₃ coated with UH20 and HDPE matrix in the existence of DCP was suggested. Moreover, the morphological structures of impact fracture surface of the HDPE/CaCO₃ composites were studied by scanning electron microscopy (SEM) to confirm the possible mechanism for explaining the improvement of mechanical properties of the composite. Copyright © 2005 John Wiley & Sons, Ltd.     

Implications of LDPE Branching and Mw on Thermal and Mechanical Properties of PP/LDPE Blends

Summary: The influences of short chain branching (SCB) and molecular (M_w) weight of low density polyethylene (LDPE) on the solid state properties of polypropylene (PP)-LDPE blends were investigated by mechanical and thermal techniques. DSC analysis of all blends exhibit a double melting peak at all compositions studied thus suggesting that both PP and LDPE crystals exist separately in the solid state. It was found that the SCB and Mw of LDPE influenced the modulus and ultimate tensile strength of the blends. However, elongation at break seems to be independent of the molecular characteristics of the pure homopolymer especially at PP blend composition greater than 50%. LDPE with high SCB showed broader melting peaks. Addition of a small amount of a low Mw LDPE (10%) resulted in a higher elongation at break than a high Mw LDPE. There is likely a correlation between the presence of a new peak in the thermograms of PP-rich blends and the observed poor elongation at break.     

The effect of gamma irradiation and particle size of CaCO3 on the properties of HDPE/EPDM blends

Mechanical blends formed of 50 wt% of high-density polyethylene (HDPE) and 50 wt% of ethylene–propylene–diene-monomer (EPDM) elastomer have been loaded with 50 wt% of three different particle size of CaCO₃, namely CaCO₃ 300, CaCO₃ 700, and CaCO₃ 2000 whereby the latter has the smallest particle size of ～311, 82 μm. Mechanical, physico-chemical and thermal properties were followed up as a function of irradiation dose for loaded and unloaded blends. The results obtained indicated that the values of tensile strength, tensile modulus at 50% elongation, gel fraction and decomposition temperature increase with increasing irradiation dose. On the other hand elongation at break, permanent set and swelling number were found to decrease with increasing irradiation dose. Moreover, the effect of particle size of CaCO₃ was observed in a limited but apparent upgrading of mechanical, physico-chemical, and thermal properties. The order of semi-reinforcing capacity of three different types of CaCO₃ is as follow: CaCO₃ 2000 > CaCO₃ 700 > CaCO₃ 300 > unloaded blend. Whereby CaCO₃ 2000 has the smallest particle size.     

Silane treatment in polypropylene composites: Adsorption and coupling

The study of the effect of eight silane coupling agents on mechanical properties of PP/CaCO₃ composites showed that the application of certain compounds leads to the reactive coupling of the components. The adsorption of the silanes on the surface of the filler was studied by a dissolution method, while the structure of the adsorbed layer was determined by FTIR spectroscopy and GPC measurements. Model reactions and an FTIR study were carried out to reveal possible coupling reactions of PP and the active silanes. The results showed that amino-functional silane coupling agents adsorb on the surface of the filler, polycondensation taking place and a polysiloxane layer of high molecular weight forms as a result. The model reactions indicated that during processing, PP oxidizes even in the presence of stabilizers and oxygen-containing functional groups form on the polymer chains. These easily react with the amino functionality of the silane coupling agents strongly bonding the polymer to the treated filler.     

动态固化聚丙烯/环氧树脂共混物的研究

将动态硫化技术应用于热塑性树脂 热固性树脂体系 ,制备了动态固化聚丙烯 (PP) 环氧树脂共混物 .研究了动态固化PP 环氧树脂共混物中两组分的相容性、力学性能、热性能和动态力学性能 .实验结果表明 ,马来酸酐接枝的聚丙烯 (PP g MAH)作为PP和环氧树脂体系的增容剂 ,使分散相环氧树脂颗粒变细 ,增加了两组分的界面作用力 ,改善了共混物的力学性能 .与PP相比 ,动态固化PP 环氧树脂共混物具有较高的强度和模量 ,含 5 %环氧树脂的共混物拉伸强度和弯曲模量分别提高了 30 %和 5 0 % ,冲击强度增加了 15 % ,但断裂伸长率却明显降低 .继续增加环氧树脂的含量 ,共混物的拉伸强度和弯曲模量增加缓慢 ,冲击强度无明显变化 ,断裂伸长率进一步降低 .动态力学性能分析 (DMTA)表明动态固化PP 环氧树脂共混物是两相结构 ,具有较高的储能模量 (E′)     

Photocrosslinking of EVA/inorganic filler blends and characteristics of related properties

The blends of EVA filled with talc, calcium carbonate, and glass ball (GB) have been photocrosslinked by UV irradiation in the presence of benzophenone (BP) as a photoinitiator and triallyl isocyanurate (TAIC) as a crosslinker. The various factors affecting the crosslinking process and the related properties have been studied by gel determination, heat extension test, mechanical and thermal aging test, UV spectroscopy, and scanning electron microscopy. The results show that the EVA/talc, EVA/CaCO₃, and EVA/GB samples of 1 mm thickness filled with 25 phr inorganic filler can be photocrosslinked to gel content of above 70 wt% by 5 sec UV‐irradiation under optimum conditions, which is sufficient for some applications of EVA blend materials. The crosslinking rate and final gel content level are in the order of EVA/GB > EVA/talc > EVA/CaCO₃. The data from mechanical and thermal aging tests give evidence that the photocrosslinked EVA/talc, EVA/CaCO₃, and EVA/GB samples are of much better tensile strength and thermal aging properties than those of the unphotocrosslinked ones. Copyright © 2009 John Wiley & Sons, Ltd.     

Toughness mechanism of polypropylene/elastomer/filler composites

The toughening mechanisms of polypropylene filled with elastomer and calcium carbonate (CaCO₃) particles were studied. Polypropylene/elastomer/CaCO₃ composites were prepared on a twin‐screw extruder with a particle concentration of 0–32 vol %. The experiments included tensile tests, notched Izod impact tests, scanning electron microscopy, and dynamic mechanical analysis. Scanning electron microscopy showed that the elastomer and CaCO₃ particles dispersed separately in the matrix. The modulus of the composites increased, whereas the yield stress decreased with the filler concentration. The impact resistance showed a large improvement with the CaCO₃ concentration. At the same composition (80/10/10 w/w/w), three types of CaCO₃ particles with average diameters of 0.05, 0.6, and 1.0 μm improved the impact fracture energies comparatively. The encapsulation structure of the filler by the grafting elastomer had a detrimental effect on the impact properties because of the strong adhesion between the elastomer and filler and the increasing ligament thickness. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1113–1123, 2005     

Tailoring of interface of polypropylene/polystyrene/carbon nanofibre composites by polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene

Mechanical and physical properties of polypropylene (PP)/polystyrene (PS) blend, PP/PS/polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) ternary blend and their composites with carbon nanofibers (CNF) were investigated. Composites of ternary blend exhibited superior properties compared to those of binary blends. Mechanical performance of nanocomposites was intimately related to their phase morphology. PP/PS/SEBS/0.1 wt% CNF hybrid composites exhibited excellent impact strength (Four-fold increase compared to PP/PS blend) and ductility (12-fold increase in elongation at break, with respect to PP/PS blend). Moreover, these composites displayed good tensile strength and modulus (15% increase in Young's modulus, compared to PP/PS/SEBS blend) and are suitable for various end-use applications including automobile applications. Although crystallinity of PP phase is decreased by the incorporation of CNF, thermal stability of the composites remained almost unaffected. Contact angle measurements revealed that ternary composites exhibited maximum hydrophobicity.     

Structural and mechanical studies on modified reused tyres composites

Reused tyres powder was used as reinforcement in HDPE-reused tyre composites. In order to improve the compatibility between both components, several pre-treatments performed over the rubber tyres were applied: sulphuric acid etching, use of a silane coupling agent and chlorination with trichloroisocyanuric acid (TCI). Mechanical properties of the resulting materials (e.g. tensile strength, Young’s Modulus, toughness and elongation at break) were studied and compared. Chemical modifications on the surface of reused tyres were monitored by FTIR and physical modifications and behaviour to fracture were followed by means of SEM. The influence of rubber pre-treatment was assessed by comparing the results of treated and untreated composites with those for neat HDPE. Reused tyre rubber, added to the HDPE in small quantities, acts as a filler, improving the stiffness and providing a more brittle behaviour. Pre-treatment with TCI gave poor results in terms of mechanical properties obtaining lower values than neat HDPE in some cases and always worst properties than sulphuric or silane coupling agent. Treatments with H₂SO₄ and silane coupling agent improve the ability of rubber to interact with the HDPE, increasing the material’s stiffness and its tensile strength. Sulphuric acid modificates chemical and physically the particles’ surface improving mainly mechanical adhesion, whereas silane acts as a compatibilizer developing chemical matrix-reinforcement interactions.     

丁醛等离子体处理填料对填充聚烯烃拉伸应力应变行为的影响

将经过丁醛等离子体处理的云母粉填充到高密度聚乙烯(HDPE)或聚丙烯(PP)中,考察填充聚合物的拉伸行为和断口形貌。结果表明,丁醛等离子体处理云母能够显著提高云母填充HDPE和PP的拉伸弹性模量和断裂伸长率,改善填充HDPE的低温韧性,在一定程度上缓解由填充导致的拉伸断裂强度的下降趋势。处理的上述影响是由于处理使填料与基体的结合性以及基体的延展性改善,填充体系致密性提高。     

Phase morphology, crystallisation behaviour and mechanical properties of isotactic polypropylene/high density polyethylene blends

The phase morphology, crystallisation behaviour and mechanical properties of isotactic polypropylene (iPP)/high density polyethylene (HDPE) blends were investigated. It was found that the properties are intimately related to each other. The morphology of the blends showed a two phase structure in which the minor phase was dispersed as domains in the major continuous matrix phase. The domain size of the dispersed phase increased with increasing concentration of that phase due to coalescence. It was also found that the domain size of the dispersed phase depends on the viscosity difference between the two phases. For a given HDPE/iPP blend, where HDPE is the matrix and iPP is the dispersed phase, the iPP domains were smaller than HDPE domains of the corresponding iPP/HDPE blend where iPP is the matrix and HDPE is the dispersed phase. A co-continuous morphology was observed at 50/50 PP/HDPE composition. Crystallinity studies revealed that blending has not much effect on the crystalline melting point of polypropylene and high density polyethylene. The crystallisation enthalpy and heat of fusion values of HDPE and PP in the blend were decreased as the amount of the other component increased. The variation in percent crystallinity of HDPE and PP in the blend was found to depend on the morphology of the blend. All the mechanical properties except Young's modulus and hardness showed negative deviation from the additivity line. This is due to the incompatibility of these blends.     

Study of electrical,mechanical, and nanoscale free‐volume properties of NBR and EPDM rubber reinforced by bentonite or kaolin

The effect of Na bentonite, Ca bentonite, and kaolin fillers on the macrostructure and microstructure of acrylonitrile butadiene rubber, ethylene propylene diene rubber, and their blend (50/50) was studied through electrical and mechanical measurements, as well as with positron annihilation lifetime spectroscopy. The real part of permittivity (ε′), dielectric loss (ε″), and the crosslinking density were found to increase with increasing filler content. The increase of crosslinking density of the blend with increasing amount of fillers reflects a decrease in the equilibrium swelling up to 21.50 wt % compared with that of the unfilled blends. The mechanical investigation showed pronounced increase in the tensile strength, and in elongation at break with the addition of up to 21.50 wt % of filler. In addition, comparing between different fillers showed that the reinforcing effect of Na bentonite is more effective than Ca bentonite and kaolin but the physico‐mechanical of Ca bentonite is less than that for kaolin. The positron annihilation lifetime measurements revealed that the free‐volume properties were strongly affected by the amount and type of filler, in particular, the free‐volume fraction was dramatically decreased with increasing filler content. Furthermore, correlations were made between the free‐volume parameters and both electrical and mechanical properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1825–1838, 2009     

The influence of CaCO3 filler component on thermal decomposition process of PP/LDPE/DAP ternary blend

Polypropylene‐low density polyethylene (PP‐LDPE) blends involving PP‐LDPE (90/10 wt%.) with (0.06 wt%) dialkyl peroxide (DAP) and different amounts (5, 10, 20 wt%) of calcium carbonate (CaCO₃) were prepared by melt‐blending with a single‐screw extruder. The effect of addition of CaCO₃ on thermal decomposition process and kinetic parameters, such as activation energy and pre‐exponential factor of PP‐LDPE blend with DAP matrix, was studied. The kinetics of the thermal degradation of composites was investigated by thermogravimetric analysis in dynamic nitrogen atmosphere at different heating rates. TG curves showed that the thermal decomposition of composites occurred in one weight‐loss stage. The apparent activation energies of thermal decomposition for composites, as determined by the Tang method (TM), the Kissinger–Akahira–Sunose method (KAS), the Flynn–Wall–Ozawa method (FWO), and the Coats–Redfern (CR) method were 156.6, 156.0, 159.8, and 167.7 kJ.mol^?1 for the thermal decomposition of composite with 5 wt% CaCO₃, 191.5, 190.8, 193.1, and 196.8 kJ.mol^?1 for the thermal decomposition of composite with 10 wt% CaCO₃, and 206.3, 206.1, 207.5, and 203.8 kJ mol^?1 for the thermal decomposition of composite with 20 wt% CaCO₃, respectively. The most likely decomposition process for weight‐loss stages of composites with CaCO₃ content 5 and 10 wt% was an A_n sigmoidal type. However, the most likely decomposition process for composite with CaCO₃ content 20 wt% was an R_n contracted geometry shape type in terms of the CR and master plots results. It was also found that the thermal stability, activation energy, and thermal decomposition process were changed with the increase in the CaCO₃ filler weight in composite structure. Copyright © 2009 John Wiley & Sons, Ltd.     

PPC／NBR弹性体的结构与性能

本文研究了聚丙撑碳酸酯(PPC)/丁腈橡胶(NBR)弹性体结构形态、动态力学性能、力学性能、耐油、耐热氧老化及耐化学介质稳定性。发现PPC/NBR弹性体呈现IPN结构特征,加入PPC使NBR拉伸强度、扯断伸长率大幅度提高。PPC/NBR弹陸体具有优良的耐油及耐热氧老化稳定性。     

Influence of chitosan on the mechanical and biological properties of HDPE for biomedical applications

High density polyethylene (HDPE) is widely used in biomedical field, except when strong cell-material interactions and high mechanical properties are required. To address this pitfall, two kinds of chitosan in different amounts were used as filler in the present research. Composites were prepared by melt extrusion process and their microstructural, thermal and mechanical properties were widely investigated. Also roughness and wettability were studied, as features of paramount importance in dictating cell response.Both types of chitosan endowed HDPE with higher Young modulus and lower elongation at break. Interestingly, fibroblast adhesion and viability were enhanced when a low amount of filler was used. The interaction of HDPE/chitosan composites with biological environment was investigated for the first time in order to assess the feasibility of these composites as materials for biomedical application.