Effect of the nanosilica content in the shell of coextruded wood‐plastic composites to enhance the ultraviolet aging resistance

Weathering durability of wood‐plastic composites (WPCs) is a significant issue for outdoor applications. Nanosilica is widely used to enhance the ultraviolet (UV) aging resistance of composites. In this study, the effects of nanosilica (0%, 1%, 2%, 5%, and 10%) added into the shell of coextruded WPCs were investigated after 2500‐hour UV exposure. Discoloration, durability, degradation, and photooxidation of the composites were studied by colorimetry, mechanical testing, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X‐ray photoelectron spectroscopy (XPS). The samples with 2% nanosilica addition (the N2 samples) provided optimal color protection, showing the lowest ΔE* (color difference) and ΔL* (lightness) values in all samples. The surface of N2 samples was less oxidized after UV exposure as revealed by FTIR and XPS analysis, and showed fewer cracks in SEM images compared with controls and other samples. In addition, N2 samples provided best flexural properties. In summary, the addition of 2% nanosilica was most effective in protecting WPCs from UV degradation. Moreover, obtained results provide a theoretical development for adopting the nanosilica as a reinforcing agent in WPCs and applying coextruded WPCs in outdoors.     

Ultraviolet weathering of HDPE/wood-flour composites coextruded with a clear HDPE cap layer

This study examined the effect coextruding a clear HDPE cap layer onto HDPE/wood-flour composites has on the discoloration of coextruded composites exposed to accelerated UV tests. Chroma meter, FTIR-ATR, XPS, SEM, and UV vis measurements accounted for the analysis of discoloration, functional groups, and degree of oxidation of both uncapped (control) and coextruded composites before and after UV exposures. Two separate discoloration characteristics occurred in the discoloration of composites. For uncapped WPCs (control), chemical changes due to photooxidation resulted in darkening followed by physical changes, including loss of colored wood components from the surface, as well as increased roughness on the surface, which led to lightening of WPCs. By contrast, because a hydrophobic cap layer prevented the loss of colored components from the surface, coextruding a clear hydrophobic HDPE cap layer over WPCs significantly decreased the discoloration during the weathering process. Photooxidation of wood components at the interface accounted for the discoloration of coextruded WPCs before the failure of cap layer. Moreover, as the cap layer absorbed a specified amount of UV light and reduced oxygen available to interface, it decreased the photooxidation rate at the interface compared to that at the WPCs surface.     

Physical properties of PVC/aminosilane‐treated wood flour/organoclay composites

Most physical properties of a wood plastic composite (WPC) with poly(vinyl chloride) (PVC) matrix are lower than those of corresponding neat PVC because of poor interfacial adhesion between hydrophobic PVC and hydrophilic wood. In this study, to improve the interfacial adhesion, wood flour was pre‐treated with N‐2(aminoethyl)‐3‐aminopropyltrimethoxysilane, and the surface modification was characterized and confirmed by X‐ray photoelectron spectroscopy (XPS). Furthermore, to improve the performance of PVC/wood composites, a type of organoclay was added as nanofiller. PVC/wood/clay composites were prepared by melt blending a heavy metal‐free PVC compound, the aminosilane‐treated wood flour, and the organoclay, and their physical properties were tested by universal testing machine and thermal gravimetric analyzer. X‐ray diffractometer (XRD) analyses of the WPCs showed an intercalated structure of the organoclay. The scanning electron microscope images for the fracture surfaces of the WPCs confirmed the positive effect of the aminosilane pre‐treatment by showing reduced debonding of wood flour from the PVC matrix. The performance of the WPCs was improved by the aminosilane pre‐treatment of the wood flour and the organoclay. Copyright © 2011 John Wiley & Sons, Ltd.     

Accelerated weathering of polypropylene/wood flour composites

Wood-plastic composites (WPCs) have received increasing attention during the last decades, because of many advantages related to their use. Some of their main applications are represented by outdoor furnishing and decking; therefore, it is important to assess their behaviour under UV exposure. In this work, polypropylene/wood flour composites were prepared and their resistance to photooxidation investigated. The composites were prepared by extrusion and compression moulding, and were subjected to mechanical tests, FTIR analysis and molecular weight measurements. The results showed that the composites retained a higher fraction of the original mechanical properties after accelerated weathering; the wood flour did not significantly degrade throughout the irradiation time slot of the investigation and the composites kept a higher percentage of the original molecular weight.     

Accelerated weathering of unbleached and bleached Kraft wood fibre reinforced polypropylene composites

In this paper, combined moisture/ultraviolet (UV) weathering performance of unbleached and bleached Kraft wood fibre reinforced polypropylene (PP) composites was studied. Composites containing 40 wt% fibre with 3 wt% of a maleated polypropylene (MAPP) coupling agent were fabricated using extrusion followed by injection moulding. Composite mechanical properties were evaluated, before and after accelerated weathering for 1000 h, by tensile and impact testing. Differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) were also carried out to assess the changes occurring during accelerated weathering. Bleached fibre composites initially showed higher tensile and impact strengths, as well as higher thermal stability and greater crystallinity. During accelerated weathering, both unbleached and bleached fibre composites reduced tensile strength (TS) and Young's modulus (YM), with the extent of the reduction found to be similar for both unbleached and bleached fibre composites. Evidence supported that the reduction of TS and YM was due to PP chain scission, degradation of lignin and reduced fibre-matrix interfacial bonding.     

Quantitative characterization of chemical degradation of heat‐treated wood surfaces during artificial weathering using XPS

The X‐ray photoelectron spectroscopy (XPS) study of three heat‐treated North American wood species (jack pine, birch and aspen) was carried out to evaluate chemical modifications occurring on the wood surface during artificial weathering for different times. The results suggest that the weathering reduces lignin content (aromatic rings) at the surface of heat‐treated wood, consequently, the carbohydrates content increases. This results in surfaces richer in cellulose and poorer in lignin. Heat‐treated wood surfaces become acidic due to weathering, and the acidity increases as the weathering time increases. Three possible reasons are given to account for the increase of acidity during weathering. The lignin content increases, whereas the hemicelluloses content decrease due to heat treatment. Heat‐treated woods have lower acidity to basicity ratios than the corresponding untreated woods for all three species because of the decrease in carboxylic acid functions mainly present in hemicelluloses. The wood composition changes induced by weathering are more significant compared to those induced by heat treatment at wood surface. Exposure to higher temperatures causes more degradation of hemicelluloses, and this characteristic is maintained during weathering. However, the wood direction has more effect on chemical composition modification during weathering compared to that of heat treatment temperature. The heat‐treated jack pine is affected most by weathering followed by heat‐treated aspen and birch. This is related to differences in content and structure of lignin of softwood and hardwood. The use of XPS technique has proved to be a reliable method for wood surface studies. Copyright © 2012 John Wiley & Sons, Ltd.     

木粉/聚乙烯复合材料的等离子体表面处理——等离子体处理时间对复合材料表面特性的影响

为改善木粉/聚乙烯复合材料的表面粘接性,实现木粉/聚乙烯复合材料的无缝连接,利用低温等离子体处理技术,对木粉/聚乙烯复合材料进行了表面处理.采用接触角测试、傅立叶变换红外光谱分析(FTIR)以及X射线光电子能谱分析(XPS)研究了等离子体处理前后复合材料表面性能的变化.试验结果表明,经等离子体处理后,复合材料表面的接触角减小,表面润湿性得以改善;FTIR分析结果表明,经等离子体处理后,复合材料表面有—OH、—C=O和—O—C=O基团生成;XPS分析表明,经等离子体处理后,复合材料表面含氧基团的含量增加,在较短的时间内表面氧元素含量增加会达到平衡,且生成大量的—O—C=O基团。     

Properties of poly(vinyl chloride)/wood flour/montmorillonite composites: Effects of coupling agents and layered silicate

Organomodified montmorillonite (OMMT) was prepared using cetylalkyl trimethyl amine bromide. OMMT and wood flour (WF) were surface-modified by silane coupling agent. They were melt-blended with polyvinyl chloride (PVC) and extruded into wood-plastic composite samples using one conical twin screw extruder. The effects of their contents on the composite mechanical properties were investigated. X-ray diffraction, transmission electron microscopy and scanning electron microscopy observed intercalation and dispersion of the OMMT. FTIR and X-ray photoelectron spectroscopy were used to analyze the silane-modification effects. The possible reaction mechanisms were proposed. After wood flour was modified by 1.5 phr silane, the impact strength and the tensile strength of wood flour-PVC composite were increased by 14.8% and 18.5%, respectively. Mechanical tests showed that the addition of OMMT did not enhance the untreated wood flour-PVC composites. However, adding 0.5% OMMT did improve the mechanical properties of the treated ones. The grafting improved the interfacial compatibility between components producing higher properties of the composites. Further addition of OMMT reinforced the composites. Too higher contents of silane and OMMT impaired some properties because of weak interfacial layer and higher concentrated stress. Cone calorimetry showed that the fire flame retardancy and smoke suppression of composites were strongly improved with the addition of OMMT.     

GMA和共单体对聚乙烯木塑复合材料的直接反应增容

通过甲基丙烯酸缩水甘油酯(GMA)、聚乙烯(PE)、木粉和其它助剂的熔融挤出,实现了GMA及GMA与共单体对PE和木粉的直接反应增容.通过扫描电镜(SEM)观测了PE基木塑复合材料(WPC)的冲击断面形貌.测试了WPC经抽提后所得木粉的傅立叶变换红外光谱(FTIR)和WPC的力学性能及热变形温度(HDT).研究了共单体苯乙烯(St)和抑交联剂亚磷酸三苯酯(TPP)对反应增容的影响.结果显示,经GMA和引发剂反应增容后,有部分PE分子键合到了木粉粒子上,从而增强了木塑两相的结合力;St的加入有利于提高GMA的接枝率,导致更多PE分子键合到了木粉粒子上,而TPP的加入则使GMA的接枝率有所下降.经GMA和引发剂直接反应增容后,WPC的力学性能和HDT均明显改善;St的加入有助于抑制PE的交联,但并未造成WPC力学性能和HDT的明显劣化;同时加入St和TPP后,WPC的HDT有所下降,而断裂伸长率和冲击强度则明显提高.     

Thermal tools in the evaluation of decayed and weathered wood polymer composites prepared by in situ polymerization

This study aims to apply thermal tools in the evaluation of decayed and weathered wood polymer composites prepared by in situ polymerization with and without cross-linkers. Pinewood samples were impregnated with methyl methacrylate using glycidyl methacrylate and methacrylic acid as cross-linkers by vacuum/pressure. The polymerization was carried out in an oven at 90 °C for 10 h using benzoyl peroxide as catalyst. All samples were exposed to decay and artificial weathering tests. The characterization was performed by mass loss, color changes, optical images, wettability, thermogravimetric analysis (by means of DTG) and differential scanning calorimetry analyzes. The mass loss was higher in untreated wood in comparison with the composites, ~2.5–10 times. Cross-linked composites showed the highest resistance to fungal biodeterioration. The reduction in L*, chroma and b* confirmed loss of original yellow tones and increase in dark and dull tones of samples. The wettability was very affected by irregularities of the samples’ surface. Only DTG showed a shifting in the temperature of thermal events related to polysaccharides and lignin after exposure to decay and weathering. DTG was the best thermal technique for evaluation of decaying and weathering of wood composites.     

The effect of wood extractives on the thermal stability of different wood-LLDPE composites

The thermal stability of wood polymer composites made with extractive-free wood from four different wood species was studied. Hot water (HW) extractives, ethanol/cyclohexane (E/C) extractives and both types of extractives were eliminated from A. cyclops, E. grandis, P. radiata and Q. alba. Composites of LLDPE and 10 wt% of wood were prepared, using poly vinyl alcohol-co-ethylene (EVOH) as a compatibilizer. The thermal degradation behavior of the composites was characterized with thermogravimetric analysis (TGA). The obtained results showed that in all cases, the degradation temperatures shifted to higher values after removal of the extractives. The removal of E/C extractives was less effective in its improvement of the thermal stability than the removal of HW extractives. The largest improvement on the thermal stability of WPCs was achieved when both types of extractives (E/C and HW) were removed.     

New PP/PLA/cellulose composites: effect of cellulose functionalization on accelerated weathering behavior (accelerated weathering behavior of new PP/PLA/cellulose composites)

Polylactic acid (PLA) was used as partial replacement for conventional thermoplastic matrix, new composites comprising cellulose, polypropylene (PP), and PLA being realized. In order to obtain a compatible interface between cellulosic pulp and polymeric matrix, two chemical modifications of cellulose with stearoyl chloride and toluene di‐isocyanate (TDI) were performed, structural changes being evidenced by X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The composite materials were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic scanning calorimetry, impact, tensile and melt rheological tests, surface tension, and dynamic vapor sorption. Because promising results for impact strength and Young modulus were recorded when replacing 15% of PP with PLA in blends of PP with the same cellulosic pulp load, the aim of our study was to assess the behavior to accelerate weathering of composites comprising PP, cellulosic pulp, and PLA. Although the slight decrease in the mechanical properties was recorded after accelerated weathering, the use of functionalized cellulose successfully prevented the deterioration of surface materials, especially for composite comprising stearoyl chloride treated cellulose pulp. Copyright © 2015 John Wiley & Sons, Ltd.     

Evaluation of various fire retardants for use in wood flour-polyethylene composites

Wood-plastic composites represent a growing class of materials used by the residential construction industry and the furniture industry. For some applications in these industries, the fire performance of the material must be known, and in some cases improved. However, the fire performance of wood-plastic composites is not well understood, and there is little information regarding the effectiveness of various fire retardants in the public domain. We used oxygen index and cone calorimeter tests to characterize the fire performance of wood flour-polyethylene composites, and compared the results with unfilled polyethylene and solid wood. We then evaluated the effect of five additive-type fire retardants on fire performance. Generally, magnesium hydroxide and ammonium polyphosphate improved the fire performance of WPCs the most while a bromine-based fire retardant and zinc borate improved fire performance the least.     

Effect of thermal-treatment of wood fibres on properties of flat-pressed wood plastic composites

This study aimed to enhance the dimensional stability of flat-pressed wood plastic composites (WPCs) containing fast growing wood fibres by a thermal-treatment method. The wood fibres were treated at three different temperatures (120, 150, or 180 °C) for 20 or 40 min in a laboratory autoclave. The WPC panels were made from dry-blended Eucalyptus camaldulensis wood fibres and polypropylene (PP) powder (50:50 by weight) using a conventional flat-press process under laboratory conditions. Thickness swelling and water absorption of the WPC panels significantly decreased with increasing the treatment temperature and time. The thermal-treatment of eucalyptus wood fibres slightly decreased the screw withdrawal resistance of the WPC panels as compared to the reference panels while the flexural properties and internal bond strength were more seriously affected by the treatment. The present study revealed that the thermal-treatment of the wood fibres significantly improved the dimensional stability of the WPC panels.     

Optical microscopy,Raman spectroscopy,and AFM study of heavy weathered surface of barium crystal glass

Glass samples of barium crystal glass (handmade and produced by automatic technology) were weathered at controlled conditions. On the weathered glass surface, the high number of corrosion products of approximate size of (5–10) μm was found. On the unweathered (native) glass surfaces, only small non-homogeneities were observed. The micro-Raman spectroscopy was used for study of corrosion products observed by the optical microscopy. It was shown that surface roughness determined by atomic force microscopy (AFM) can be used for the quantification of degree of weathering. The stoichiometric corrosion products can be identified by Raman spectroscopy by application of the proper spectral database. The proposed method of quantification of the degree of weathering was confirmed by the coincidence of AFM results obtained for two kinds of glass samples (handmade and automatic produced) with the same chemical composition but with the different character of macroscopic surface irregularities. On the other hand, the micro-Raman spectroscopy confirmed the same chemical character of weathering process in both cases.     

Influence of Accelerated Weathering on the Properties of Polypropylene/Polylactic Acid/Eucalyptus Wood Composites

In the view of producing environmentally friendly materials without compromising properties, new composites containing polypropylene as a matrix and eucalyptus wood, with or without 15% of polylactic acid, were melt processed. In order to improve compatibility between components, a chemical modification of wood with toluene-2,4-diisocyanate (TDI) was realized and evidenced by changes in FT-IR and XPS spectra. The morphological, mechanical, and thermal characterizations of the obtained composites were evaluated before and after accelerating weathering. The results showed that the material comprising 15% TDI-modified wood, PP, and 15% PLA exhibited the best properties.     

Durability of Flame-Retarded,Co-Extruded Profiles Based on High-Density Polyethylene and Wheat Straw Residues

At present, little information is available in the scientific literature related to the durability (weathering resistance) of fire-retarded wood and natural fiber-reinforced thermoplastics. In this work, thermoplastic profiles for façade applications based on high-density polyethylene, wheat straw particles, and fire-retardants were extruded and their reaction-to-fire performance before and after artificial weathering evaluated. Profile geometries were either solid or hollow-core profiles, and fire-retardants (FR) were added either in the co-extruded layer or in the bulk. Various FR for inclusion in the co-extruded layer were screened based on UL-94 tests. For profile extrusion, two types of FR were chosen: a coated intumescent combination based on ammonium polyphosphate (APP) and an APP coated with melamine and without formaldehyde. Before weathering, the peak heat release rate (pHRR) and the total heat release (THR), which were determined using cone calorimeter measurements, were reduced by up to 64% and 67% due to the FR. However, even before weathering, pHRR of the profiles was relatively high, with best (lowest) values between 230 and 250 kW/m² under the test conditions. After 28 days of artificial weathering, changes in reaction-to-fire performance and color were evaluated. Use of the APP in the co-extruded layer worsened color change compared to the formulation without APP but the pHRR was not significantly changed. The influence of weathering on the fire behavior was small compared to the difference between fire-retarded and non-fire-retarded materials. Results from the cone calorimeter were analyzed with regard to ETAG 028, which provides requirements related to the durability of fire performance of building products. In many formulations, increase in THR was less than 20% compared to before weathering, which would place some of the profiles in class C or better (EN 13501-1). However, due to the high pHRR, at best, class D was obtained under the conditions of this study. In addition to cone calorimeter measurements, results from the single flame source test, limiting oxygen index determination and thermogravimetric analysis, are shown and discussed. Strength properties, water uptake and swelling of the profiles, thermal conductivity, and energy dispersive X-ray data are also presented.     

The effect of wood extractives on the thermal stability of different wood species

This study compares the thermal stability of different wood species, which is an important factor for the production of wood–polymer composites (WPCs), and investigates the effect of extraction on thermal properties. The chemical composition of four wood species – Quercus alba, Pinus radiata, Eucalyptus grandis and Acacia cyclops – has been determined, as the species is expected to affect the thermal stability of wood. Subsequently, the hot-water (HW) extractives, ethanol/cyclohexane (E/C) extractives and both extractives were eliminated from the wood via Soxhlet extraction and the thermal stability of the wood determined with thermogravimetric analysis (TGA) under identical conditions. The results suggest that a higher cellulose and lignin content leads to better thermal stability of wood in different temperature regimes. In all cases, the removal of extractives improved the thermal stability of the wood. The effect of combined extractions was more pronounced than of an individual extraction and E/C-extraction caused less improvement in the thermal stability of wood than HW extraction. The degradation of the investigated wood extractives occurred at low rates over a broad temperature range. Pure cellulose exhibited superior thermal stability compared to wood, but differences were observed between the investigated wood species.     

Wastes from Wood Extraction Used in Composite Materials: Behavior after Accelerated Weathering

New materials were obtained by incorporating in polypropylene (PP) matrix 60% wood wastes resulting after extraction with supercritical carbon dioxide, water, and ethanol. Structural, mechanical, thermal, and rheological characterizations, as well as moisture uptake of the composites, were evaluated before and after accelerated weathering. It was found that the extraction method influenced the composite properties due to the hydrophilic-hydrophobic balance. The addition of extracted fibers results in an increase in hardness and tensile properties and a decrease of impact strength as compared to PP.     

Wood plastic composites weathering: Visual appearance and chemical changes

The effects of outside and accelerated (xenon-arc and UVA) weathering on the visual appearance and chemical changes of wood plastic composite (WPC) formulations based on high density polyethylene (HDPE) and polypropylene (PP) were investigated. Colorimetry, scanning electron microscopy, Fourier transform infrared spectroscopy (FT-IR), and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) were employed in this study. The study showed that for both outside and accelerated weathering, longer exposure time increased the degree of color change (and lightness), carbonyl concentrations, and wood loss on weathered WPC surfaces. HDPE-based WPC exhibited decreased lightening, carbonyl concentrations, and wood content loss when compared to PP-based WPC. From this study, relationships between chemical and color changes that occurred during exterior weathering of HDPE-based WPC were established. Oxidation and degradation of wood lignin influenced WPC color changes (lightening) during weathering.