Utilization of linseed cake as a postagricultural functional filler for poly(lactic acid) green composites

Linseed cake (LC), a byproduct of linseed oil extraction, is used as a functional filler for production of biodegradable composites. To determine the influence of residual linseed crude oil contained in lignocellulosic filler on the properties of the poly(lactic acid) (PLA)-based composites with 5–30% filler content, two types of LC were analyzed: a defatted and an unmodified one. Complex analysis of the composites' properties change was conducted in relation to their structure modification caused by the addition of a waste filler. It was found that the addition of LC resulted in simultaneous plasticization and improved crystallization of PLA. Lignocellulosic particles and crude linseed oil contained in the LC powder provided a modifying effect, influencing the level of crystallinity and mechanical and thermomechanical properties. Using LC may thus overcome one of the main drawbacks of PLA, which is brittleness and low crystallinity. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47152.     

A comparative study on selective properties of Kraft lignin–natural rubber composites containing different plasticizers

Effect of plasticizer type on the kraft lignin–natural rubber composite microstructure and selected properties was determined. The composites were prepared with addition of a commonly used naphthenic oil plasticizer to study the decomposition product of polyurethane (glycerolysate) and its characteristics. Kraft lignin powder was incorporated into the natural rubber matrix in amounts of 10 and 40 parts per 100 parts of natural rubber (phr). The reference samples were prepared without any lignin present. The chemical interaction between the filler particles and natural rubber macromolecules was analyzed by Fourier transform infrared spectroscopy (FTIR) and the adhesion was characterized by scanning electron microscopy (SEM). The results of the adhesion measurements confirmed poor distribution of lignin particles into the natural rubber matrix with increasing filler content. Optimal lignin content in the composites was 10 phr in the case of both plasticizers. Moreover, the results of FTIR verified the formation of non-covalent bonds and the need for modification of the filler to enhance the reinforcing effect in the natural rubber matrix. Dynamic mechanical analysis (DMA) and mechanical measurements proved that the specimen containing 10 phr of lignin with the use of glycerolysate as plasticizer displayed the highest mechanical performance. It was demonstrated that glycerolysate and naphthenic oil as plasticizing agents showed similar effect on the thermal properties of the prepared composites. Also, the measured mechanical properties, such as tensile strength, hardness, resilience, and abrasiveness confirmed these findings.     

Effect of surface treatment on the physicomechanical and thermal properties of high‐density polyethylene/olive husk flour composites

In this study, a particular interest was focused on the recovery of lignocellulosic waste of olive husk flour (OHF) by its incorporation as filler in manufacturing composite materials based on high‐density polyethylene (HDPE) matrix with various filler contents (10, 20, and 30 wt %). The problem of incompatibility between the hydrophilic filler and the hydrophobic matrix was treated with two methods: the first method consists of using maleic anhydride‐grafted polyethylene (MAPE) as compatibilizer in HDPE/OHF composites. The second method, was focused on the chemical modification of OHF by vinyl‐triacetoxy‐silane (VTAS). Fourier transform infrared spectroscopy is used to analyze both grafting and silanization reactions involved. Scanning electron microscopy was used to show the morphology of the flour surface. Furthermore, the physicomechanical and thermal characteristics of the various composite samples were investigated as a function of filler contents and treatment types. The results showed that the properties of the composite materials are positively affected by the silanization treatment of OHF and also by MAPE addition. However, better mechanical and thermal properties with less moisture absorption were obtained for the composite materials compatibilized with MAPE. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characterization of composite materials based on LDPE loaded with agricultural tunisian waste

This study investigated the use of an available agricultural Tunisian vine stem waste as a filler material. Composites of green materials were prepared using vine stems as filler and low density polyethylene (LDPE) as a matrix. A series of composite films was prepared by different loadings of the vine stem waste with 10–50% of the filler in 10% intervals. The ensuing materials were characterized by several techniques. The morphology of the composites was investigated using scanning electron microscopy (SEM). The thermal and mechanical properties were studied using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), respectively. The results indicated that vine‐stem based particles enhanced the thermo‐mechanical properties of the thermoplastic matrix and demonstrated that this available lignocellulosic biomass of vine stems can be considered to be a promising filler material. However, the obtained result of water absorption indicated that the maximum limit of the filler content should not exceed 30% of vine stems. POLYM. COMPOS., 36:817–824, 2015. © 2014 Society of Plastics Engineers     

Studies on the physico‐mechanical,thermal, and morphological behaviors of high density polyethylene/coleus spent green composites

This study is aimed at utilizing nutraceutical industrial waste and reducing carbon footprints of plastics. Eco‐friendly “green composites” of high density polyethylene (HDPE) were fabricated using coleus spent (CS)—a nutraceutical industrial waste as reinforcing filler and maleic anhydride‐graft‐polyethylene (MA‐g‐PE) as compatibilizer. Composites were fabricated with 5, 10, 15, and 20% (w/w) of CS by extrusion method. The fabricated HDPE/CS composites were evaluated for mechanical and thermal behavior. A slight improvement of about 5% in tensile strength and marked improvement of about 25% in tensile modulus for 20 wt % CS filled HDPE composites was noticed. The effect of CS content on rheological behavior was also studied. Thermal characteristics were performed using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA thermogram indicated increased thermal stability of CS‐filled composites. From TGA curves the thermal degradation kinetic parameters of the composites have been calculated using Broido's method. The enthalpy of melting (ΔH_m) obtained from DSC curves was reduced with increase in CS content in HDPE matrix, due to decrease in HDPE content in composite systems. An increase in CS loading increased the water absorption behavior of the composites slightly. Morphological behavior of cryo‐fractured composites has been studied using scanning electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effectiveness of functionalized polyolefins as compatibilizers for polyethylene/wood flour composites

The effects of various types of compatibilizers on the mechanical properties of high‐density polyethylene/wood flour (HDPE/WF) composite were investigated. Functionalized polyolefins such as maleated and acrylic acid grafted polyethylenes, maleated polypropylene (PPgMA) and styrene‐ethylene/butylene‐styrene triblock copolymer (SEBSgMA) were incorporated to reduce the interfacial tension between the polyethylene matrix and the wood filler. Among them, it was found that maleated linear low‐density polyethylene (LLDPEgMA) gave maximum tensile and impact strength of the composites, presumably because of better compatibility with the HDPE matrix. Similar but less enhanced improvements in the mechanical properties, depending on the compatibilizer loading, were seen for the SEBSgMA system. Whereas acrylic acid grafted high‐density polyethylene (HDPEgAA) and maleated polypropylene (PPgMA) only slightly improved tensile modulus and tensile strength; and they both increased with increasing loadings of compatibilizers. A scanning electron microscopic study was employed to reveal the interfacial region and confirm these findings. In addition, dynamical mechanical thermal measurements also revealed the interaction between filler and matrix, and FTIR spectroscopy was used to assign the chemical fixation and the various chemical species involved at the surface of the wood fillers before and after surface treatment.     

Mechanical properties and microstructure of HDPE/AL(OH)3/silicone oil composite

The effect of surface modification on the mechanical properties and microstructure of the composites of high‐density polyethylene (HDPE), silicone oil, and aluminum hydroxide [Al(OH)₃] was investigated. The dispersion of silicone oil in the HDPE composites was studied by scanning electric microscope (SEM) and differential scanning calorimetry (DSC). In the HDPE/Al(OH)₃/silicone oil composites, two types of dispersion structure of silicone oil were observed resulting from different surface modifications. In the composites surface modified with titanate NDZ‐130, calcium stearate, or oleic acid, silicone oil encapsulates around Al(OH)₃ particles, and both the notched impact strength and the elongation at break are very high. However, in the composites surface modified with silane KH‐550 or silane‐g‐HDPE, silicone oil and Al(OH)₃ particles separately disperse in HDPE, and both the notched impact strength and the elongation at break are very low. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1896–1903, 2002     

Mechanical,dynamic mechanical,and thermal characterization of fly ash and nanostructured fly ash‐waste polyethylene/high‐density polyethylene blend composites

Disposal of polyethylene used as carry bags is the greatest challenge increasing day by day. Composite materials were prepared by mixing Fly ash (FA) and nanostructured fly ash (NFA) from thermal power station as filler and blends of Waste polyethylene (WPE)(carry bags) collected from municipal solid waste (MSW) with virgin high‐density polyethylene (HDPE) as matrix. Different modifications were induced to improve the overall properties of these composites. At first, the WPE/HDPE blend matrix was modified by grafting with maleic anhydride (MA) and the composite prepared with FA/NFA. Then, the WPE/HDPE‐FA/NFA composite as a whole was treated with electron beam irradiation at 250 kGy radiation dose and finally the FA/NFA filler was treated with radiation dose of 250 kGy and the composite prepared. Significant enhancement in tensile strength, flexural strength, flexural modulus, and hardness are observed for MA modified and irradiated composites, the increase being more prominent in irradiated composites. Furthermore, an increase in storage/loss moduli with enhanced thermal stability was observed with the addition of FA/NFA and upon modifications. The analysis of the tensile fractured surfaces by scanning electron microscopy was in well correlation with the mechanical properties obtained. In summary, after analyzing the effects of the three different modifications on mechanical, dynamic mechanical and thermal properties, the irradiation on to the WPE/HDPE‐FA/NFA composites investigated was selected as the most appropriate for future applications. POLYM. COMPOS., 37:3256–3268, 2016. © 2015 Society of Plastics Engineers     

Thermo-mechanical properties of high density polyethylene with zinc oxide as a filler

This study investigates the microstructural, thermal, and mechanical behavior of high density polyethylene (HDPE)-based composites prepared using compression molding technique. HDPE was mixed with either micro-size zinc oxide (bulk ZnO) or zinc oxide nanoparticles (nano-ZnO) as fillers’ contents at 0, 10, 20, 30, and 40 wt%. The structural, morphological, and thermal properties of the composites were identified using X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectrophotometer (FTIR), and thermal gravimetric analysis (TGA). The results showed good dispersion and interaction mechanisms between HDPE and the fillers at low weight percentage. The thermal stability of HDPE was enhanced by adding both bulk and nano-ZnO, especially for higher filler loading. Tensile tests at different speeds and Vickers microhardness tests conducted at different indentation loads (0.25–5 N) at t = 60 s were performed to realize how the mechanical properties of the composites were influenced. The values of stiffness, ultimate tensile strength, and yield stress increased by increasing the filler loading to 20 wt% of either bulk ZnO or nano-ZnO. The values of ultimate tensile strain and ductility were deteriorated by increasing the filler loading. Nano-ZnO, at 20 wt% content in composite, showed higher mechanical properties than bulk composite, so it has been recommended for a better tensile performance at higher strain rates. Vickers microhardness measurements showed that the tested samples exhibited reverse indentation size effect (RISE) behavior. The obtained results were analyzed using Meyer’s law which was a preferred approach for analysis of HDPE/ZnO composite.     

Properties of high‐density polyethylene filled with waste crosslinked foam

Crosslinked polyethylene foam is widely used in packaging and as an insulation material. Finely ground waste of such crosslinked foam mesh size 7 or particle size less than 2815 μm is used as a filler in high‐density polyethylene (HDPE) of two different grades (7.5 and 21 MFI). Mechanical, thermal, and morphological properties of filled composites is studied experimentally. Waste foam powder concentration was varied up to 40% by weight basis. Impact strength of base HDPE increased by a factor of six. The overall changes in mechanical properties are similar to the crosslinking effect. It is believed that waste foam particles act as a point of entanglement with different chains of polyethylene. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 110–114, 2004     

Mechanical properties of high‐density polyethylene/scrap rubber powder composites modified with ethylene–propylene–diene terpolymer,dicumyl peroxide,and silicone oil

The effect of ethylene–propylene–diene terpolymer (EPDM), dicumyl peroxide (DCP), and dimethyl silicone oil on the mechanical properties of high‐density polyethylene (HDPE) composites filled with 60 mesh cryogenically scrap rubber powder (SRP) was studied. The addition of 10 wt % EPDM, 0.2 wt % DCP, and 4 wt % dimethyl silicone oil significantly increased both the impact strength and elongation at break of the HDPE/SRP composites. After the modification, the impact strength increased by 160%, and the elongation at break increased by 150% for the composites containing 40 wt % SRP. The impact load–time curves showed that the increase of impact energy for the modified composites was attributed to the increase of the maximum force at yield point and the ductile deformation after yielding. The rheological behavior, dynamic mechanical properties, and morphology observation suggested that an enhanced adhesion between SRP and polymer matrix formed in the modified HDPE/SRP composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2020–2027, 2003     

A novel polymer composite with double positive‐temperature‐coefficient transitions: effect of filler–matrix interface on the resistivity–temperature behavior

BACKGROUND: Sn–Pb alloy‐filled high‐density polyethylene (HDPE) composites exhibit double positive‐temperature‐coefficient (PTC) behavior, with the first transition at the melting point of HDPE and the second at that of Sn–Pb alloy. The objective of this study is to improve the reversibility and reproducibility of double‐PTC transitions of these composite materials by enhancing the filler–matrix interface. RESULTS: Fourier transform infrared spectroscopy, surface wettability and dynamic mechanical and rheological measurements confirm that surface‐treating Sn–Pb with titanate concentration ≤1 wt% enhances the interface adhesion between Sn–Pb alloy and HDPE matrix. Surface‐treating Sn–Pb with titanate concentration ≤1 wt% increases the PTC transition temperature, reduces the PTC intensity and improves the reversibility and reproducibility of the double‐PTC behavior of Sn–Pb/HDPE composites. CONCLUSION: It is demonstrated that adjusting the filler–matrix interface is an effective means to modify the double‐PTC behavior of Sn–Pb alloy‐filled HDPE composites. Copyright © 2007 Society of Chemical Industry     

Mechanical Properties of High Density Polyethylene/Modified Calcium Silicate Composites

High density polyethylene (HDPE)/calcium silicate (CS) composites containing vinyltriethoxysilane treated calcium silicate contents varying from 0–10 phr were prepared by injection molding. Thus obtained HDPE/CS composites were characterized by the thermal analyses. The mechanical properties were evaluated. It was found that the incorporation of the calcium silicate into high density polyethylene resulted in a slight increase in the yield stress (6.85–11.76 %) as well as tensile strength (7.02–12.84 %). However, the elongation at yield and the elongation at break decreased by 9.23–24.87 % and by 11.03–60.73 %, respectively, with the increasing calcium silicate content. The vinyltriethoxysilane modified CS exhibited the dispersibility in HDPE matrix arising from the compatibility between high density polyethylene matrix and the disperse phase (treated calcium silicate particles) which led to the effect on the mechanical properties of the composites. It could be concluded that the modified calcium silicate played a role in reinforcing the mechanical properties into the high density polyethylene.     

The comparison of properties of (rubber tree seed shell flour)‐filled polypropylene and high‐density polyethylene composites

The effect of varied rubber tree seed shell flour (RSSF) filler loadings on processing torque, mechanical, thermal, water absorption, and morphological properties of polypropylene (PP) and high‐density polyethylene (HDPE) composites has been studied. The addition of RSSF in the composites increased the stabilization torque in both PP‐ and HDPE‐based composites. Tensile strength, elongation at break, flexural strength, and impact strength show significant reduction when higher loading of RSSF was incorporated, while tensile modulus and flexural modulus were improved. The phenomenon was noted for both matrices, PP and HDPE, but HDPE‐based composites showed clear effects on the reduction of the mechanical properties compared with RSSF‐filled PP. Scanning electron microscopy of tensile fracture specimens revealed the degree of dispersion of RSSF filler in the matrices. At higher filler loadings, agglomerations and poor dispersion of RSSF particles were spotted, which induce the debonding mechanism of the system. Thermogravimetric analysis thermograms showed that both PP‐ and HDPE‐based composite systems with higher RSSF content have higher thermal stability, initial degradation temperature, degradation temperature, and total weight loss. Water absorption ability of the composites increases as the filler loading increases for both matrices. J. VINYL ADDIT. TECHNOL., 22:91–99, 2016. © 2014 Society of Plastics Engineers     

Polyethylene composite fibers. I. Composite fibers of high‐density polyethylene

Polymer matrix composites are generally studied in the form of bulk solids, and very few works have examined composite fibers. The research described here extended such bulk studies to fibers. The question is whether or not what has been reported for bulk polymers will be the same in fibers. In this article are reported studies of high‐density polyethylene (HDPE), whereas those of linear low‐density polyethylene are reported in part II of this article series. Two types of filler were used, that is, organically modified montmorillonite (OMMT), in which the nanosized filler particles had a high aspect ratio, and microsized calcium carbonate (CaCO₃), with an aspect ratio nearer to unity. Composite fibers of both as‐spun and highly drawn forms were prepared, and their structures, morphology, and mechanical properties were studied. It was found that the microsized particles gave HDPE composite fibers with mechanical properties that were the same as those of the neat polymer. In the case of clay composite fibers, the clay interfered with the yield process, and the usual yield point could not be observed. The particle shape did not affect the mechanical properties. The fibers showed different deformation morphologies at low draw ratios. The CaCO₃ composite fibers showed cavities, which were indicative of low interaction between the polymer and the filler. The OMMT composite fibers showed platelets aligned along the fibers and good polymer–filler interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

表面改性剂和硅油对HDPE/Al(OH)3力学性能的影响

探讨了各种表面改性剂和硅油对高填充HDPE/Al（OH)3复合材料力学性能的影响。研究表明,使用经特殊表面改性剂处理的Al（OH)3作填料并加入硅油时,可以大幅度提高HDPE/Al（OH)3复合材料的缺口冲击强度和断裂伸长率。利用扫描电镜和差示扫描量热仪研究了Al（OH)3的表面改性对硅油分布的影响,观察到硅油的两种分布类型;包覆Al(OH）3粒子和以液滴形式与Al(OH）3粒子单独分散于HDPE中,并将硅油的分布状况与材料的力学性能作了对比分析。     

Effects of Durian Seed Flour on Processing Torque,Tensile, Thermal and Biodegradation Properties of Polypropylene and High Density Polyethylene Composites

Composites containing various percentage of durian seed flour (DSF) in the polypropylene (PP) and high density polyethylene (HDPE) have been compounded using an internal mixer. The processing torque, tensile, thermal and biodegradation properties have been determined. The incorporation of DSF increases stabilization torque and had adversely affected the mechanical properties by reducing the tensile strength and elongation at break, while the elastic modulus is increased, as starch content increases. At similar filler content, DSF filled PP showed higher tensile strength and elastic modulus, while lower in elongation at break than DSF-filled HDPE. The scanning electron microscopy (SEM) of tensile fracture specimens revealed good adhesion and dispersion of the DSF granules in the polymer matrix. However, the SEM results showed agglomeration of the DSF at higher filler content in the polymer and hence revealed poor wetting between DSF granules and polymer. The TGA results showed that both of the composites systems with higher filler content have higher initial degradation temperatures, T₀, degradation temperatures, T_deg and total weight loss. A simple biodegradability test conducted on each composite system shows that composites are subjected to biodegradation, judging by the significant increase in carbonyl and hydroxyl index of the composites after the test.     

Structure and properties of phase change materials based on HDPE,soft Fischer‐Tropsch paraffin wax,and wood flour

Phase‐change materials based on high density polyethylene (HDPE), soft Fischer‐Tropsch paraffin wax (M3), and alkali‐treated wood flour (WF) were investigated. The blend and composite samples were prepared by melt mixing using a Brabender Plastograph, followed by melt pressing. They were characterized in terms of their morphology, as well as thermal, mechanical, thermo‐mechanical, and water absorption properties. Although SEM micrographs showed some evidence of intimate contact between the WF particles and the HDPE matrix as a result of alkali treatment, poor filler dispersion, and interfacial adhesion were also observed. Partial immiscibility of the HDPE and the M3 wax was noticed, with the WF particles covered by wax. There was plasticization of the HDPE matrix by the wax, as well as partial cocrystallization, inhomogeneity and uneven wax dispersion in the polymer matrix. The HDPE/WF/M3 wax composites were more homogeneous than the blends. The presence of wax reduced the thermal stability of the blends and composites. Both the presence of M3 wax and WF influenced the viscoelastic behavior of HDPE. The HDPE/M3 wax blends showed an increase in the interfacial amorphous content as the wax content increases, which resulted in the appearance of a β‐relaxation peak. The presence of M3 wax in HDPE reduced the mechanical properties of the blends. For the composites these properties varied with WF content. An increase in wax content resulted to a decrease in water uptake by the composites, probably because the wax covered the WF particles and penetrated the pores in these particles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Green composites using switchgrass as a reinforcement for a conjugated linseed oil‐based resin

Switchgrass (SWG) has been used as a filler to produce conjugated linseed oil‐based green composites. The effect of the amount of the SWG; the matrix crosslink density; and the incorporation of a compatibilizer, maleic anhydride (MA), on the structure, water absorption, and thermal and mechanical properties of the composites has been investigated. The thermal stability of the composites is primarily dependent on the amount of the SWG fibers, which are far less thermally stable than the linseed oil‐based resin. For the most part, improvements in the mechanical properties can be achieved by increasing the amount of SWG (up to 70 wt %), increasing the amount of the crosslinker, and adding MA to increase the filler–matrix interaction. The uptake of water in the composites is mostly influenced by the loading of the SWG fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013