Manufacture and research of TPS/PE biocomposites properties

In this paper the process of native starch preparing for modification by extrusion and manufacture of biocomposites is presented. The first aim of this study was to determine the mixing and granulating condition of native starch to obtain granulated native starch. For mixing and granulation of native starch Intensive Mixer manufactured by Maschinenfabrik Gustav Eirich was used. Mixing and granulation in a single process is a new method of preparation of powders for other processing. The main task of granulation is the elimination of dust emissions and the increase in density of powders. Granules are easy for dosage and more handy for transport and storage than powders, which is important from a technological point of view.The second aim of this study was to manufacture TPS/PE biocomposites. At first thermal modification of waxy maize starch was carried out with the use of a co-rotating twin screw extruder. During extrusion native starches have been deprived of their crystallinity and the obtained starch (TPS) has fully amorphous structure. XRD analysis revealed that semi crystalline phase of native starch after extrusion disappeared. During extrusion crystal structure of native starch is transformed into amorphous structure of thermoplastic starch (TPS), which was confirmed by XRD analysis.Reactive extrusion of obtained thermoplastic starch and high density polyethylene (HDPE) in the presence of polyethylene-grafted maleic anhydride (PE-g-MA) was done. To modify properties of TPS/PE blend polycaprolactone (PCL) was added in amount of 5 and 10 wt.%. The mass flow rate, static mechanical properties, thermal properties and morphology of obtained biocomposites were examined. The results show that the increased amount of TPS caused an increase in tensile strength and modulus of elasticity of prepared biocomposites. Addition of PCL to TPS/PE blends decreased tensile strength and modulus of elasticity. Moreover, higher amount of TPS and PCL in TPS/PE blends caused decrease of the elongation at break. On the other hand, using of PE-g-MA in TPS/PE blends cause increasing phase compatibility, which was confirmed by mechanical properties and morphology measurements.Biocomposites filled with higher TPS content (45 and 60 wt.%) possess lower resistance to hydrolytic degradation, which cause decrease of mechanical properties.It was found that higher amount of TPS in TPS/PE blends have small effect on mass flow rate and thermal properties estimated by differential scanning calorimetry (i.e. melting temperature, degree of crystallinity, melting enthalpy). This phenomenon have significant influence on processing of obtained biocomposites.     

Studies on the structure and properties of thermoplastic starch/luffa fiber composites

Thermoplastic starch (TPS)/luffa fiber composites were prepared using compression molding. The luffa fiber contents ranged from 0 wt.% to 20 wt.%. The tensile strength of the TPS/luffa fiber composite with 10 wt.% of luffa fiber had a twofold increase compared to TPS. The temperature values of maximum weight loss of the TPS/luffa fiber composites were higher than for TPS. The water absorption of the TPS/luffa fiber composites decreased significantly when the luffa fiber contents increased. The strength of adhesion between the luffa fiber and the TPS matrix was clearly demonstrated by their compatibility presumably due to their similar chemical structures as shown by scanning electron microscope (SEM) micrographs and Fourier transform infrared (FTIR) spectra.     

The influence of starch gelatinization on the rheological,thermal, and morphological properties of poly(ɛ-caprolactone) with corn starch blends

Blends of poly(ɛ-caprolactone) (PCL) with gelatinized and nongelatinized corn starch (PCL/starch ratios of 75/25, 50/50, and 25/75 wt.%) were prepared by mechanical processing and characterized by their melt flow index (MFI), water absorption (WA), differential scanning calorimetry (DSC), and light microscopy (LM). The MFI showed that the viscosity of the blends increased with increasing starch content and that gelatinized starch made the blends less viscous. Starch made the blends more susceptible to WA. The rupture of the starch granules caused by gelatinization increased the WA and the loss of soluble matter. DSC showed that starch reduced the crystallinity of PCL in the blends. LM showed good dispersion of the starch in the PCL matrix and also showed that the blends with nongelatinized starch had poor interfacial adhesion.     

Melt blend studies of nanoclay-filled polypropylene (PP)–high-density polyethylene (HDPE) composites

The objective of this work is to study how the rheological factors of unfilled and nanoclay-filled HDPE–PP blend series influence the structure, morphology, and mixing characteristics. For this study, a series of HDPE–PP blends (0–100 wt % HDPE), with and without nanoclay, was prepared by using melt-mixing method. Nanoclay was varied from 0 to 5 wt % in all the blend and polymer series. The rheological properties were examined by melt viscosity, scanning electron microscopy, and theory of mixing. The result indicated that the viscosity of the blend increased as HDPE and nanoclay content increased, and also affected the structure and morphology of the resulting blend. The thermal properties were examined by using differential scanning calorimetry and suggest improved crystalline and melting characteristics of PP and PP-rich phase of blend. The structure of nanoclay-filled blend was examined by X-ray diffraction and transmission electron microscopy, confirming the formation of nanocomposite with improved tensile properties.     

Experimental and theoretical studies on the properties of injection moulded glass fibre reinforced mixed plastics composites

Recycled mixed post-consumer and post-industrial plastic wastes consisting of HDPE, LDPE and PP were injection moulded with short glass fibre (10–30% by weight) to produce a new generation composite materials. Intensive experimental studies were then performed to characterise the tensile, compression and flexural properties of glass fibre reinforced mixed plastics composites. With the addition of 30 wt.% of glass fibre, the strength properties and elastic modulus increased by as much as 141% and 357%, respectively. The best improvement is seen in the flexural properties due to the better orientation of the glass fibres in the longitudinal direction at the outer layers. The randomness and length of the glass fibre were accounted to modify the existing rule of mixture and fibre model analysis to reliably predict the elastic and strength properties of glass fibre reinforced mixed plastics composites.     

Effect of different polypropylenes and compatibilizers on the rheological,mechanical and morphological properties of nylon 6/PP blends

In this work, the rheological, mechanical and morphological properties of nylon 6/polypropylene compatibilized blends were investigated. Two types of polypropylene were used. One with MFI of 40 g/10 min (PP H103) and the other with MFI of 3.5 g/10 min (PP H503). The compatibilizers used were polypropylene grafted with 6% of acrylic acid (PPgAA) and polypropylene grafted with 1% of maleic anhydride (PPgMA). The blends composition was 80/20 (wt%) for the PA6/PP binary blends and 80/10/10(wt%) for the nylon 6/PPgAA/polypropylene and nylon 6/PPgMA/polypropylene ternary blends. Torque rheometry analysis showed that when PPgAA and PPgMA were added to nylon 6/polypropylene blends, there was an increase in the torque, indicating that reactive compatibilization has occurred. There is no influence of the polypropylene MFI on the mechanical properties of the uncompatibilized and compatibilized blends. The impact strength of the blends containing PPgMA were greater than those of the blends containing PPgAA. The blends containing PPgAA are unstable. SEM analysis showed that PPgMA improves considerably the adhesion between PA6/PP phases, leading to good mechanical properties.     

Changes in the mechanical and thermal properties of high impact polystyrene (HIPS) in the presence of low polypropylene (PP) contents

The final properties of recycled polymers greatly depend on the presence of impurities, which can be detected by differential scanning calorimetry. For the purpose of the present study a total of five high impact polystyrene (HIPS)/polypropylene (PP) blends (100/0; 97.5/2.5; 95/5; 92.5/7.5; 90/10) were prepared and injected at a temperature in the 220–250 °C range. The subsequent mechanical characterization indicates a reduction of tensile strength, elongation at break and impact strength. Scanning Electron Microscopy (SEM) was used in the morphological analysis of the different blends. Finally the variations in the flow measurements and glass transition temperature were analysed using melt flow index (MFI) and differential scanning calorimetry (DSC), respectively. The presence of impurities may have a negative effect on the mechanical properties of the material, but may improve material performance during processing.     

Thermo-mechanical characteristics of thermally aged polyethylene/polypropylene blends

Polyethylene (PE), polypropylene (PP) and their blends have attracted a lot of attention due to their potential industrial applications. Therefore, the current work has been carried out with the main objective of investigating the impact of the thermal aging/treatment and blend ratio (composition range) on the mechanical (tensile and hardness) and thermal characteristics (using thermogravimetric analysis in a dynamic air atmosphere) of PE, PP and PE/PP binary blends. Samples of PE/PP blends containing 100/00, 75/25, 50/50, 25/75 and 0/100 wt.% were prepared via injection moulding technique and thermally treated/aged at 100 °C for 0, 2, 4, 7, 14 days. The tensile measurements indicated that the yield strength and the modulus decrease with increasing PE content. It was also observed that PE, PP and their blends deform in ductile modes. They undergo a uniform yielding over a wide range of deformation, which is followed by strain hardening and then failure. The strain to break for pure PE is found to be much higher than that for pure PP and for their blends, intermediate values have been observed. The hardness measurements have also revealed that increasing PE content in PE/PP blends reduced the hardness value of PP, however, thermal aging at 100 °C has not affected the polymers hardness which holds also true for the tensile properties, showing a good correlation between tested mechanical properties. The thermogravimetric analysis (TGA) in a dynamic air atmosphere and derivative thermogravimetric analysis (DTA) were conducted to study the thermal degradation and stability of thermally unaged and aged PE, PP and PE/PP blends in terms of the initial (T_d and T_d(1%)) and final (T_d(99%)) decomposition temperatures and maximum decomposition rate temperature (T_max). All polymers start to decompose at no less than 365 °C. As for mechanical properties, the blend ratio has affected the thermal properties however, aging time has not.     

Reinforcement of polyethylene with polypropylene by a blending and deformation process

The blending of polymers to achieve either unique or intermediate properties has become a rather common practice. High density polyethylene (HDPE) and isotactic polypropylene (PP) are immiscible in the melt state and phase segregate. This behaviour and their difference in melting point (132 against 165° C) has been exploited to produce a uniaxial reinforcement of HDPE with PP fibres by a process of melt blending, and tensile drawing followed by annealing. Tensile drawing of the blends results in the transformation of each phase to a fibrous structure having an increased modulus and tensile strength. The annealing of this material to melt and recrystallize the HDPE converts it to a lower modulus ductile lamellar structure which is reinforced with the fibrous PP regions. Both the modulus and tensile strength in the fibre direction fit simple composite theory for isotropic HDPE filled with higher modulus PP fibres over the entire composition range.     

超高韧半晶聚合物PP多相体系的结构及脆韧转变的研究

通过严格控制工艺条件，得到了不同分散相含量和不同粒径的ＰＰ／ＥＰＤＭ／ＨＤＰＥ和ＰＰ／ＥＰＤＭ共混体。利用ＳＥＭ分析了ＰＰ／ＥＰＤＭ／ＨＤＰＥ的结构特点，通过测量Ｉｚｏｄ缺口冲击强度，得到了ＰＰ／ＥＰＤＭ／ＨＤＰＥ的脆韧转变主曲线，证明其符合脆韧性转变规律；同时利用ＳＥＭ照片，分析了主曲线不同区域的增韧机理。     

High density polyethylene and poly(ethylene terephthalate) in situ sub-micro-fibril blends as a matrix for wood plastic composites

Wood plastic composites were prepared based on in situ formed poly(ethylene terephthalate) (PET) sub-micro-fibril reinforced high density polyethylene (HDPE) matrices, using a two-step reactive extrusion technology. The use of ethylene-glycidyl methacrylate (E-GMA) copolymer improved phase compatibility in the sub-micro-fibril blends (SMFBs) with 75% HDPE and 25% PET. Most of in situ formed PET fibrils were less than 500 nm in diameter. The PET fibrils obviously increased mechanical properties of the blend, especially the moduli. The subsequent addition of 40 wt.% wood flour did not influence the size and morphology of PET fibrils, and the fibrils and wood fibers had a synergic reinforcement effect on composite properties. Compared with the HDPE/wood composites, the SMFB/wood system had 65% higher tensile strength, 95% higher tensile modulus, 42% higher flexural strength, and 64% higher flexural modulus, respectively. The technology offers a way to use engineering plastics (i.e., PET) for high performance WPC manufacturing.     

TiO2/淀粉/PCL共混材料的制备及表征

目的以玉米双磷脂淀粉和聚己内酯（PCL）为原料,甘油为增塑剂,改性纳米TiO₂为抗菌剂,制备一种具有抗菌性能的可降解材料,并对不同淀粉/PCL质量比和不同纳米TiO₂添加量下制得的共混材料进行表征,以探究最佳共混比例。方法将不同质量比的淀粉/PCL混合,添加一定量的甘油作为增塑剂,并添加不同含量的纳米TiO₂作为抗菌剂,熔融共混并热压成型,利用力学、红外、紫外、SEM、DSC、水接触角等方法对所制备的共混材料进行性能表征。结果随着PCL含量的增加,共混材料的断裂伸长率先下降后上升,拉伸强度逐渐上升,PCL质量分数为100%时共混材料的拉伸强度较未添加提高了104%,对紫外光的屏蔽作用增强,接触角从78.2°下降到53.3°;DSC显示当淀粉的比例相对较大时,整个体系的结晶度较低,但PCL的结晶速率加快。TiO₂的加入未使体系发生化学变化,对共混材料的拉伸强度无明显影响,断裂伸长率先增加后减小,在TiO₂质量分数为0.9%时,达到最大为51.69%。TiO₂...     

Investigation of the effect of addition of calcium stearate on the properties of low-density polyethylene/poly(ε-caprolactone) blends

Low-density polyethylene (LDPE) was blended with poly(ε-caprolactone) (PCL), prepared in proportions of 75/25, 50/50, and 25/75 (LDPE/PCL, wt/wt%). The effect of the addition of calcium stearate (CaSt) of these polymers was assessed by melting flow index, differential scanning calorimetry, tensile test, scanning electron microscopy (SEM), biodegradation in simulated soil with calcium determination, and enzymatic degradation. The addition of CaSt reduced the MFI of the PCL and of the 75/25 blend. The incorporation of 25 % of PCL slightly increased the T _m of LDPE. The tensile strength had no significant changes with the addition of CaSt and the polymers showed that they are incompatible according to this property. SEM showed poor interfacial interaction between PCL and LDPE, as well as that they are immiscible, and showed no significant changes on the morphology of the materials with the addition of CaSt. The results show that polymer samples after biodegradation in simulated soil present more calcium content than initial samples polymer. The soil analysis shows that the soil that contains the polymers submitted to thermal aging show smaller calcium content than the samples that were not aged. Lipase enzyme reinforced its specificity over PCL, and the addition of CaSt reduced the degradation of PCL and the 75/25 PCL/LDPE blend, however, it increased the rate of degradation of 50/50 and 25/75 blends.     

高密度聚乙烯/顺丁橡胶共混物的耐环境应力开裂性的研究

用定应变方法和定拉力方法研究了高密度聚乙烯(HDPE)及其共混物的耐环境应力开裂性(ESCR)。结果表明,丁基橡胶(IIR)和顺丁橡胶(BR)都可以提高HDPE的ESCR。对HDPE/橡胶二元共混物,BR的效果不如IIR。在改性剂DX-2或DX-3存在下,HDPE/BR共混体系的ESCR有大幅度提高,三元共混物在初始应力强度因子K_0为0.2MPam~1/2时,断裂时间可达到HDPE断裂时间的4倍左右,断面形貌的扫描电镜照片呈网孔状,表明断裂过程具有韧性特点。     

Elastomer modified polypropylene–polyethylene blends as matrices for wood flour–plastic composites

Blends of polyethylene (PE) and polypropylene (PP) could potentially be used as matrices for wood–plastic composites (WPCs). The mechanical performance and morphology of both the unfilled blends and wood-filled composites with various elastomers and coupling agents were investigated. Blending of the plastics resulted in either small domains of the minor phase in a matrix of major phase or a co-continuous morphology if equal amounts of HDPE and PP were added. The tensile moduli and yield properties of the blends were clearly proportional to the relative amounts of HDPE and PP in the blends. However, the nominal strain at break and the notched Izod impact energies of HDPE were greatly reduced by adding as little as 25% of the PP. Adding an ethylene–propylene–diene (EPDM) elastomer to the blends, reduced moduli and strength but increased elongational properties and impact energies, especially in HDPE-rich blends. Adding wood flour to the blends stiffened but embrittled them, especially the tougher, HDPE-rich blends, though the reductions in performance could be offset somewhat by adding elastomers and coupling agents or a combination of both.     

PP-g-(GMA-co-St)增容PC/PP共混体系的形态与性能

运用分级注入方法制备了不同配比的PC/PP-g-(GMA-co-St)/PP共混物。通过力学性能测试、扫描电子显微镜观察、高压毛细管流变测试等方法考察了增容剂PP-g-(GMA-co-St)对PC/PP共混体系的形态与性能的影响。PP-g-(GMA-co-St)的加入提高了两相界面结合力,降低了分散相粒子尺寸,有效地改善了共混体系的相容性;同时PC/PP-g-(GMA-co-St)/PP体系的拉伸性能得到显著的提高,体系表观黏度提高,对剪切应力的敏感性降低。     

Characterisation of blends between poly(ε-caprolactone) and polysaccharides for tissue engineering applications

In this work, bioartificial binary blends between poly(ε-caprolactone) (PCL) and a polysaccharide (chitosan (CS) or starch (S)) with different contents of the natural polymer (5–30 wt.%) were produced. Melt-mixing and double-precipitation were the methods used for the obtainment of PCL/S and PCL/CS blends, respectively. Tubular scaffolds were produced from bioartificial blends by melt-extrusion. Physico-chemical characterisation was performed by differential scanning calorimetry analysis (DSC), thermogravimetry (TGA), scanning electron microscopy (SEM), infrared analysis (FTIR-ATR and micro-ATR mapping), atomic force microscopy (AFM) and stress–strain tests. Blends were not miscible, phase-separated systems, showing a homogeneous composition and morphology only at low polysaccharide content (≤ 10 wt.%). The biocompatibility of bioartificial guides was investigated by culturing NIH-3T3 mouse fibroblasts. Cells response showed the following order: PCL/S > PCL > PCL/CS. For each blend type, biocompatibility increased with decreasing the polysaccharide content. In vitro cell tests using S5Y5 neuroblastoma cells, carried out on the most biocompatible blends, assessed their absence of cytotoxicity towards these model cells of the nervous tissue. Results showed that blends with a low chitosan or starch content (≤ 10 wt.%) are promising for the regeneration of tissues requiring tubular scaffolds, such as the peripheral nerves.     

The effects of cross-linked starch on the properties of thermoplastic starch

In order to improve the poor tensile properties and high water absorption of thermoplastic starch (TPS), cross-linked starch was added into the TPS matrix. The cross-linked starch contents ranged from 0 wt% to 20 wt%. The TPS/cross-linked starch composites were analyzed for the morphology of their fractured surfaces, the thermal decomposition temperatures, ability to absorb water and mechanical properties. The results showed that the incorporation of cross-linked starch into the TPS matrix caused considerable improvement to tensile strength. The maximum tensile strength was obtained with addition of 20 wt% cross-linked starch. Moreover, water absorption of the TPS samples was clearly reduced by the inclusion of cross-linked starch. The thermal degradation temperatures of the composites were also higher than those of the TPS matrix.     

Blends of biodegradable polyesters by reactive blending: preparation, characterisation and properties

Blends of poly--caproIactone (PCL) and poly--hydroxybutyrate (PHB) were prepared by mixing the two polymers in the presence of dicumylperoxide (DCPO) in solution of chlorobenzene. Similarly blends were obtained by mixing the two polymers with no peroxide added. The blends were prepared in a break of composition, from 85% wt PHB/15% wt PCL to 15% wt PHB/85% wt PCL, respectively. Also pure polymers were reacted with DCPO in the same way of the blends. Thermal (DSC), spectroscopic, mechanical (tensile tests) and morphological SEM)analyses were performed on the blends and on the pure polymers. Significant differences were found in the chemical-physical characteristics of the blends with and without peroxide.     

复合增塑剂增塑红苕淀粉的研究

采用双螺杆挤出机制备了红苕热塑性淀粉(TPS)和高密度聚乙烯(HDPE)/塑化淀粉共混材料.通过X射线衍射和扫描电镜分析了甘油/尿素/乙醇胺复合增塑剂的增塑效果和结晶行为,结果表明,复合增塑剂可以使淀粉塑化,能明显抑制红苕淀粉的重结晶.甘油含量的增多可以改善TPS与HDPE的相容性,同时会引起少量重结晶,但是不会影响到材料的使用性能.此外,共混材料随热塑性淀粉中甘油含量的增多,拉伸强度逐渐下降,而断裂伸长率逐渐增大.