Effect of nanofillers on flame retardancy, chemical resistance, antibacterial properties and biodegradation of wood/styrene acrylonitrile co-polymer composites

Wood polymer nanocomposites (WPNCs) based on simul wood (Bombex ceiba, L.) were prepared by impregnation of styrene acrylonitrile copolymer, γ-methacryloyloxy trimethyl silane-modified TiO₂, SiO₂ nanoparticles and nanoclay intercalating mixture through vacuum impregnation. The impact of nanofillers on the physical properties, flame retardancy, water resistance, anti-swelling efficiency and biodegradability of the resultant WPNCs was investigated. Remarkable enhancement in wood properties such as flame retardancy, water resistance and anti-swelling efficiency was achieved with the treatment. The results showed that all the properties were maximum for wood samples treated with SAN/TiO₂ (0.5 %)/SiO₂ (0.5 %)/nanoclay (0.5 %). The presence of TiO₂ nanoparticles in WPNC exhibited antibacterial activity. The resistance to biodegradation was observed by incorporation of nanofillers into wood.     

Ultraviolet resistance and other physical properties of softwood polymer nanocomposites reinforced with ZnO nanoparticles and nanoclay

Wood polymer nanocomposites (WPNCs) based on nano-ZnO and nanoclay were prepared by impregnation of melamine formaldehyde–furfuryl alcohol copolymer, 1,3-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU), a cross-linking agent and a renewable polymer obtained as a gum from the plant Moringa oleifera under vacuum condition. Fourier transform infrared spectroscopy (FTIR) and X-ray diffractometry (XRD) studies were employed for the characterization of modified ZnO and WPNCs. The change in crystallinity index (CrI) value of the cellulose in wood and the distribution of ZnO nanoparticles in composites were determined using FTIR and XRD. Scanning electron microscopy and Transmission electron microscopy showed the presence of nanoparticles and nanoclay in the cell lumen or cell wall of wood. An enhanced UV resistance property was shown by the treated wood samples as judged by lower weight loss, carbonyl index, lignin index, cellulose CrI values, and mechanical property loss compared to the untreated wood samples. Wood polymer composites treated with 3 phr each of nanoclay, ZnO, and the plant gum showed an improvement in mechanical properties, flame-retarding properties, thermal stability, and lower water uptake capacity.     

Chemical modification of simul wood with styrene–acrylonitrile copolymer and organically modified nanoclay

Simul wood (Salmalia malabarica) was chemically modified by treatment with styrene–acrylonitrile copolymer (SAN), glycidyl methacrylate (GMA), and organically modified nanoclay. The physical properties of wood polymer composites (WPC) were improved due to the addition of GMA and nanoclay. XRD analysis indicated a decrease in crystallinity in WPC. FTIR study confirmed the presence of clay in WPC. The presence of clay in cell lumen and cell wall was evidenced by SEM study. WPC containing lower percentage of clay showed better thermal stability compared to WPC loaded with higher percentage of clay.     

Improvement of wood properties by urea-formaldehyde resin and nano-SiO2

In order to improve wood properties of triploid clones of Populus tomentosa, urea-formaldehyde (UF) resin was compounded with nano-SiO₂, coupling agents and flame retardants in different ways to prepare five kinds of modifiers. The poplar wood samples were impregnated with the modifiers and heated to prepare UF-SiO₂-wood composites. The antiswelling efficiency, resistance of water absorption, oxygen index and hardness of the composites were measured. Results show that all of the modifiers reduced water absorption of poplar wood and enhanced flame resistance and hardness. Nano-SiO₂ showed a marked effect in improving the hardness of wood. In addition, all of the modifiers, except UF-C-SiO₂-polymer, improved the dimensional stability of poplar wood. The UF resin and nano-SiO₂ compound improved general properties of poplar wood. __________ Translated from Journal of Beijing Forestry University, 2006, 28(2): 123–128 [译自: 北京林业大学学报]     

不同改性剂对木塑复合材料性能的影响研究

采用木材纤维分别与PE、PS、ABS、SAN四种塑料制成木塑复合材料，根据物理力学性能的检测，研究了不同改性剂对木塑复合材料性能的影响。结果表明：加入改性剂能改善木材纤维与所用塑料交接性能，改性剂可以提高复合材料的力学强度；不同的改性剂对复合材料的性能产生不同的影响，异氰酸酯胶改性效果比较好。木塑复合材料既保持了木质材料原来的优良品质，又具有塑料的一些特性，其防水性、尺寸稳定性、力学强度等指标均有较大改善。图5参6。     

Na2O-SiO2 wood-inorganic composites prepared by the sol-gel process and their fire-resistant properties

For enhancing fire-resistant properties, a binary system to prepare wood-inorganic composites was studied by adding sodium methoxide (SM) or sodium acetate (SA) to a reaction system for SiO₂ composites. Compared with the SiO₂ composites, both the Na₂O-SiO₂ composites prepared could be greatly improved up to 600°C-700°C (glowing). From scanning electron microscopic observations, this enhanced fire resistance was assumed to be due to chemical and physicochemical effects, such as dehydration and carbonization of wood by Na₂O gel. The glassy layer and intumescent structure formed over the cell walls were thought to prevent oxidation and heat transfer from proceeding into the inner portion of the wood cell walls. However, the reaction medium with SM to prepare Na₂O-SiO₂ composites was basic, whereas that with SA was rather neutral. In addition, in the latter composites, most of the inorganic gel was formed within the cell wall, retaining the porous structure characteristic of wood. Therefore, the Na₂O-SiO₂ composites prepared with SA can be concluded to be preferable for practical purposes.Part of this report was presented at the 50th annual meeting of the Japan Wood Research Society, Kyoto, April 2000     

改性剂对木塑复合材料力学性能影响的研究

采用木材纤维,分别与PE、PS、ABS、SAN等热塑性高分子聚合物,经热压复合工艺制成木塑复合板材,通过加入不同的改性剂以及改变改性剂的加入量,研究它们对木塑复合材料力学性能的影响。结果表明:改性剂的加入能使木材纤维与各种热塑性高分子聚合物很好地胶接;改性剂不同对木塑复合材料的性能产生不同的影响;改性剂的加入量为木材纤维用量的5%时,该法制作的木塑复合板材力学性能最佳。     

Improved interaction between wood and synthetic polymers in wood/polymer composites

Summary This article describes the properties of wood polymer composites consisting of linear low density polyethylene (LLDPE) and wood flour (WF). In an attempt to improve the interfacial adhesion between the matrix and the filler, different compatibilizers were used. The interaction between polymer and wood were studied by comparing LLDPE/WF composites with composites when compatibilizer was added. The experimental measurements were conducted by impact and tensile strength testing and Scanning Electron Microscopy (SEM). The mechanical properties of the composites were improved with SEBS triblock copolymer modified with maleic anhydride and with the ionomer polymer, Surlyn, as compatibilizers. SEM fractography confirmed better adhesion between wood particles and LLDPE matrix when SEBS was present.This study was financed by the Swedish National Board for Industrial and Technical Development (NUTEK) which is gratefully acknowledged     

Investigation on physical and mechanical properties of pulp–plastic composites from bagasse

High-density polyethylene (HDPE), bagasse fibers treated by four pulping processes (AS-AQ (alkaline sulfite anthraquinone), SODA-AQ (soda anthraquinone), MEA (monoethanolamine) and chemical–mechanical pulping (CMP)), three levels of nano-SiO₂ (0, 2, and 5?wt%), and maleic anhydride polyethylene as coupling agent were used to produce pulp–plastic composites (PPCs) by injection molding. The physical and mechanical properties of corresponding composites were evaluated according to ASTM standards. The results showed that compared to untreated bagasse/HDPE composite, the addition of bagasse pulp fibers increased significantly the mechanical properties such as tensile strength and modulus, flexural strength and modulus, and hardness. The chemical pulps-reinforced composites showed better mechanical strengths than that of CMP-reinforced composites, but in some properties, CMP pulp composites have comparable results to the chemical pulp-reinforced composites. Natural fibers (untreated and treated) increased water absorption and thickness swelling of composites compared to pure HDPE. The addition of nano-SiO₂ particles showed both increasing and decreasing trends on physical and mechanical properties ofPPCs.     

Photostable wood–inorganic composites prepared by the sol-gel process with UV absorbent

To enhance the photostability of wood against ultraviolet (UV) light, a UV absorbent, 2,2,4-trihydroxy-4-[2-hydroxy-3-(3-trimethoxysilylpropoxy)propoxy]benzophenone (BP), was applied to the reaction system for preparing SiO₂ wood–inorganic composites by sol–gel reaction. The BP–SiO₂ wood–inorganic composites obtained were examined for photostability by scanning electron microscope observations, color changes, and diffuse reflectance infrared fourier transform analyses. The results clearly indicated that compared with SiO₂ composites, BP–SiO₂ composites improved the photostability of wood. In addition, BP was stable against UV light without degradation so that the BP–SiO₂ composite should provide sustainable and high photostability of treated wood.Part of this report was presented at the 51st Annual Meeting of the Japan Wood Research Society at Tokyo, April, 2001     

Several SiO2 wood-inorganic composites and their fire-resisting properties

Summary In a study on the SiO₂ wood-inorganic composites prepared by the sol-gel process with tetraethoxysilane (TEOS), it is more appropriate to use safer agents than TEOS, considering the operational and processing environments. In this study, therefore, methyltrimethoxysilane (MTMOS) was used to prepare the SiO₂ wood-inorganic composites, and comparative studies were made with TEOS. Resultingly, SiO₂ wood-inorganic composites could be successfully prepared from MTMOS reaction system, as in TEOS system, with its lower concentration, and both composites had SiO₂ gels specifically formed within the cell walls from moisture-conditioned wood specimens. On this SiO₂ composites, the water-repellent properties were added most effectively with a molar ratio of 2-heptadecafluorooctylethyltrimethoxysilane (HFOETMOS) to alcohol being 1/250 and 1/180 for TEOS and MTMOS reaction systems, respectively. On the other hand, fire-resisting properties were tried to add to SiO₂ composites with several fire-resisting agents. The fire-resisting agents in the obtained composites are not, however, stable and leached out readily. Therefore, a small addition of HFOETMOS was tested to the MTMOS and TEOS reaction systems with fire-resisting agents. The obtained results clearly indicated that HFOETMOS could restrain the fire-resisting agents to be leached from the composites, and that composites from MTMOS system were superior to TEOS system on the antileachability. Therefore, MTMOS can be appropriate for displacement of TEOS as a chemical agent to prepare SiO₂ wood-inorganic composites.This research has been performed in Department of Wood Science and Technology, Faculty of Agriculture, Kyoto University, Kyoto, Japan.This research was supported by a Grant-in-Aid for Scientific Research (B) (No. 06453176, 1994.4–1996.3) from the Ministry of Education, Science, and Culture, Japan.     

Fire-resisting properties in several TiO2 wood-inorganic composites and their topochemistry

Summary A study of the wood-inorganic composites prepared by the sol-gel process with a metal alkoxide indicated that an inorganic modification of wood with TiO₂ gels from tetraisopropoxytitanium (TPT) can not improve its properties due to the formation of the gels in the cell lumina by high hydrolysis rate of TPT. In this study, therefore, titanium alkoxides or titanium chelates which have the lower rate of hydrolysis and subsequent polycondensation than TPT were used for preparing TiO₂ wood-inorganic composites to study the topochemical effects of the TiO₂ gels for the property enhancement of wood. As a result, it was found by SEM-EDXA analysis that the TiO₂ gels deposited within the cell walls could improve the properties of wood in dimensional stability and fire-resistance, whereas for the gels in the cell lumina, property enhancement could not be achieved, as observed in SiO₂ wood-inorganic composites.This research has been performed in Dept. of Wood Sci. & Technol., Kyoto UniversityThis research was supported by a Grant-in-Aid for Scientific Research (B) (No. 06453176, 1994.4–1996.3) from the Ministry of Education, Science, and Culture, Japan. The authors were grateful to Nippon Soda Co., Ltd. for providing titanic reagents.     

Effect of organoclay platelets on the mechanical properties of wood–plastic composites formulated with virgin and recycled polypropylene

Abstract

This study investigated the effects of organoclay platelet contents (0, 3 and 5 wt%) and polypropylene type (virgin and recycled) on the mechanical properties of polypropylene/wood flour composites. Composite samples were made by melt compounding and consequent injection moulding. The tensile, flexural and impact properties of resultant composites were determined. X-ray diffraction (XRD) analysis of composites with 3 and 5% nanoclay content was also conducted. The results indicated that tensile and flexural properties of the composites increased with the addition of nanoclay particles up to 3 wt% and decreased thereafter. The impact strength of the composites, however, decreased with the incorporation of nanoclay. The mechanical properties of the recycled polypropylene-based nanocomposites were statistically comparable with those based on virgin polypropylene. XRD analysis revealed that the degree of intercalation in the nanocomposites containing 3% nanoclay was higher than in those containing 5%. Based on these results, it can be concluded that recycled polypropylene could be used instead of virgin polypropylene in the production of value-added products with no significant adverse effects on the mechanical properties.     

The influence of surface-treated nano-TiO2 (rutile) incorporation in water-based acrylic coatings on wood protection

The aim of this research was to synthesize surface-treated nano-titanium dioxide (TiO₂) particles and incorporate them into water-based acrylic systems, which could offer long-term protection for UV-sensible wood substrates. To suppress the photocatalytic activity, the surface of TiO₂ nanoparticles in rutile crystal structure was coated with amorphous silica (SiO₂) layer. The amounts of SiO₂ were 5 and 10 wt%, respectively. Formation of SiO₂ layer on TiO₂ surface was analyzed using scanning and transmission electron microscopy. SiO₂ layer thickness increases as a function of precursor loading. In addition, the influence of SiO₂ loading on rutile UV-protective properties was determined. Transparent UV-protective coatings were developed by incorporating surface-treated nano-TiO₂ into water-based acrylic stain. The particle size distribution was determined using dynamic light-scattering measurements, which indicate that the suspension of surface-treated rutile is stable against agglomeration. Furthermore, the color change and ability of protection against UV light of coatings after nanoparticles incorporation were determined. TiO₂, surface treated with 10 wt% of SiO_2, yielded coatings of higher transparency; however, TiO_2, surface treated with 5 wt% of SiO_2, improved UV protection.     

Cellulose esters as compatibilizers in wood/poly(lactic acid) composite

One of the important issues relevant to wood/plastic composite molding is the compatibility between hydrophilic wood and hydrophobic plastic. Polyolefins modified with maleic anhydride, which have been frequently used for wood and polyolefin composites, are not effective for poly(lactic acid) composites. Because compounds with both hydrophilic and hydrophobic groups are potential compatibilizers, cellulose esters of several carboxylic acids, RCOO-cellulose (R = CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₁₁H₂₃), were synthesized and their effects as compatibilizers of wood/poly(lactic acid) composites (WPLC) were examined in this study. The mechanical properties of WPLC were improved with a small amount of added cellulose esters, especially cellulose butyrate or cellulose valerate. The relevant effect of added cellulose esters on the thermal properties of wood/PLA composite was analyzed by measuring dynamic viscoelasticity. Part of this report was presented at the 56th Annual Meeting of Japan Wood Research Society, Akita, August 2006 and the 9th International Conference on Frontiers of Polymers and Advanced Materials, Cracow, Poland, July, 2007     

Property of nano-SiO2/urea formaldehyde resin

In this paper, we discuss the effects of a nanometer silicon dioxide (nano-SiO₂) coupling agent, dispersal methods and the amount of nano-SiO₂/urea formaldehyde resin. The results of our study indicate that when nano-SiO₂, using KH-550 silane as a coupling agent, was added to UF resin by discontinuous ultrasonic vibration, its properties improved effectively. When the content of nano-SiO₂ was below 1.5%, the amount of free formaldehyde decreased, and the viscosity and bonding strength of resin increased with an increase in the added nano-SiO₂, which did not prolong the curing time. The performance indices of plywood, particleboard and medium density fiberboard (MDF), hot-pressed by nano-SiO2 (1%)/UF resin (F/U molar ratio=1.2), exceeded the requirements of the National Standard. Their free formaldehyde emission reached E1 grade. Finally, we analyzed the mechanism of the strengthening effects of nano-SiO₂ on UF resin by means of infrared spectrum analysis and X-ray photoelectronic spectrum (XPS). __________ Translated from Scientia Silvae Sinicae, 2005, 41(2) [译自: 林业科学, 2005, 41(2)]     

Design of wood/montmorillonite (MMT) intercalation nanocomposite

Studying new wood composites through nano science and technology (NSC) will develop new compounding theory of wood, and accelerate the combination of new technology, wood science, material science and other disciplines. The compounding of wood and inorganic MMT on nanoscale molecular level has high potential to greatly improve the mechanical properties, fire retardance, abrasion resistance, decay resistance, dimensional stability and other properties of wood. Based on the great achievements of polymer/montmorillonite (MMT) nanocomposites, this paper reviewed nano intercalation compounding methods (i.e. in-situ intercalative polymerization and direct polymer intercalation), and discussed the structure, properties and modification of montmorillonite (MMT). According to the main chemical components and particular structure of wood, the authors discussed the liquefaction and plasticization of wood, compared the dissolvability and meltability between wood and polymer, and then systematically put forward the basic idea, technological processes and schematic diagram to prepare wood/MMT nanocomposites (WMNC). The key technology to prepare WMNC is either to introduce delaminated MMT nanolayers into wood with the help of some intermediate polymers, or to obtain liquefied wood or plasticized wood from the complicated natural composite. It is applicable and effective to realize wood/MMT nanoscale compounding with the help of proper intercalation agent and medium polymer through the proposed “one-step” or “two-step” impregnating processes.     

Preparation,physical properties and ultraviolet resistance of wood nanocomposites based on modified soybean oil and bentonite

ABSTRACT

Safer environmental requirements have resulted in significant interest in natural polymer-based materials to increase sustainability. In this perspective, wood polymer nanocomposites are of particular interest. Wood polymer nanocomposites were prepared from modified soybean oil, wood flour and cetyl trimethylammonium bromide modified bentonite using the compression-molding technique. Fourier transform infrared spectroscopy and X-ray diffractometric studies were used to confirm the successful modification of bentonite. Incorporation of 3?wt% of bentonite in the composites produced significant improvement in properties compared to those of 1 and 5?wt%. Furthermore, in comparison to the unfilled nanocomposites, nanoclay-filled ones showed an enhanced UV resistance property as judged by lower weight loss and carbonyl index. The decrease in mechanical properties of UV-exposed unfilled composites was more significant compared to those of nanoclay-filled composites. Scanning electron microscope and transmission electron microscope were used to study the surface morphology and distribution of the bentonite into the composites. In addition, with the incorporation of bentonite, significant increase in thermal, mechanical and flame-retarding properties was observed.     

Preliminary observations of hydrothermal growth of nanomaterials on wood surfaces

A hydrothermal method of fabricating nanomaterials at wood surfaces is described in this paper. Nanomaterials with different morphologies including spherical anatase TiO₂, amorphous SiO₂, wurtzite ZnO nanorod arrays, intertwining MnO₂ nanowires, shuttle-shaped CaCO₃ nanorods, and rhombic and cubic NaCl were deposited at wood surfaces. TiO₂–ZnO compound nanoparticles and CuO nanoparticles were also created. The surface morphologies and crystalline structures of the prepared samples were characterized by scanning electron microscopy and X-ray diffraction, respectively. No obvious changes in the color of wood were caused by the hydrothermal process except those nanomaterials of Mn or Cu deposited at surfaces.     

Modeling moisture absorption process of wood-based composites under over-saturated moisture conditions using two-part equations

The objective of this study was to investigate the moisture absorption process for wood-based composites subjected to over-saturated moisture conditions. Two stages are comprised in the moisture transfer process at the over-saturated moisture conditions, an initial stage which is the moisture transfer process mainly under fiber saturation point (FSP), and a second stage which is the moisture transfer process beyond the FSP. A model was developed based on two-part equations to describe the process, from which three coefficients (k ₁ , k ₂₁ , and k ₂₂) can be used to quantitatively describe the moisture transfer process under the conditions. Two different wood-based composites, wood fiberboard and wood fiber/polymer composites (polymer content: 30%), were used to test the model at four different ambient temperatures (30, 45, 62, and 80°C). It was shown that the two-part equation can accurately describe the moisture absorption process under over-saturated moisture conditions. The moisture absorption rate in the initial stage was about 30–60% greater than that in the second stage for most of the cases evaluated in this study. The higher the temperature, the greater moisture absorption parameters were obtained. At both moisture absorption stages (below FSP and above FSP), the calculated activation energy for the moisture absorption rate of wood fiberboard was very close to that of wood fiber/polymer composites.