Eco-friendly flame-retardant bamboo fiber/polypropylene composite based on the immobilization of halloysite nanotubes by tannic acid-Fe3+ complex.

Bamboo fibers (BF), as an important sustainable natural material, are becoming a hot alternative to synthetic fibers for the reinforcement of polypropylene (PP)-based composites. However, the weak interfacial compatibility between BF and PP as matrix and their inherent flammability limit the practical application of BF/PP composites (BPC). Here, a fire-safe BPC was fabricated by constructing flame-retardant interfacial layers containing tannic acid (TA)-Fe3+ complex and halloysite nanotubes (HNTs) on the fiber matrix followed by a hot-pressing process. The results showed that the interfacial chelating of TA with Fe3+ improved the dispersion of HNTs on the fibers and the interfacial interactions within the fiber matrix, resulting in the as-fabricated composite with significantly improved mechanical properties and water resistance. In addition, the flame-retardant composite exhibited higher thermal stability and enhanced residual char content. Moreover, the composite possessed significant flame-retardant performances with a reduction of 23.75 % in the total heat release and 32.44 % in the total smoke production, respectively, owing to the flame retarding in gaseous phase and condensed phase of TA-Fe3+@HNTs layers. This work offers a green and eco-friendly strategy to address the inherent problems of BPC material in terms of fire safety and interfacial compatibility, thus broadening their applications in the automotive interior and construction industries.

Mechanical and Fire Properties of Flame-Retardant Laminated Bamboo Lumber Glued with Phenol Formaldehyde and Melamine Urea Formaldehyde Adhesives.

This study investigated the effects of different adhesives, phenol formaldehyde (PF) and melamine urea formaldehyde (MUF), on the mechanical and fire properties of flame-retardant laminated bamboo lumber (LBL). The results demonstrated that the flame-retardant treatment using phosphorus-nitrogen-boron compounds endowed the LBL with excellent flame retardancy and smoke suppression properties, even though the bending strength and bond shear strength were slightly reduced. The PF-glued LBL exhibited superior mechanical and shear properties to the MUF-glued ones, primarily due to its higher processing temperature and deeper adhesive penetration. In addition, the MUF-glued flame-retardant LBL displayed better heat release reduction and smoke suppression properties than the PF-glued LBL, which resulted from the synergistic flame retardancy between the melamine element in MUF and the applied flame retardant. The analysis of the influence of adhesive type on the mechanical and fire properties of flame-retardant LBL holds significant importance for the future design and production of high-performance LBL material.

Eco-friendly bamboo pulp foam enabled by chitosan and phytic acid interfacial assembly of halloysite nanotubes: Toward flame retardancy, thermal insulation, and sound absorption.

Lightweight, porous cellulose foam is an attractive alternative to traditional petroleum-based products, but the intrinsic flammability impedes its use in construction. Herein, an environmentally friendly strategy for scalable fabrication of flame-retardant bamboo pulp foam (BPF) using a foam-forming technique followed by low-cost ambient drying is reported. In the process, a hierarchical structure of halloysite nanotubes (HNT) was decorated onto bamboo pulp fibers through layer-by-layer assembling of chitosan (CS) and phytic acid (PA). This modification retained the highly porous microcellular structure of the resultant BPF (92 %-98 %). It improved its compressive strength by 228.01 % at 50 % strain, endowing this foam with desired thermal insulation properties and sound absorption coefficient comparable to commercial products. More importantly, this foam possessed exceptional flame retardancy (47.05 % reduction in the total heat release and 95.24 % reduction in the total smoke production) in cone calorimetry, and it showed excellent extinguishing performance, indicating considerably enhanced fire safety. These encouraging results suggest that the flame retardant BPF has the potential to serve as a renewable and cost-effective alternative to traditional foam for applications in acoustic and thermal insulation.

Fabrication of High-Performance Bamboo-Plastic Composites Reinforced by Natural Halloysite Nanotubes.

Bamboo-plastic composites (BPCs) as new biomass-plastic composites have recently attracted much attention. However, weak mechanical performance and high moisture absorption as well as low thermal stability greatly limit their industrial applications. In this context, different amounts of halloysite nanotubes (HNTs) were used as a natural reinforcing filler for BPCs. It was found that the thermal stability of BPCs increased with increasing HNT contents. The mechanical strength of BPCs was improved with the increase in HNT loading up to 4 wt% and then worsened, while the impact strengths were slightly reduced. Low HNT content (below 4 wt%) also improved the dynamic thermomechanical properties and reduced the water absorption of the BPCs. Morphological studies confirmed the improved interfacial compatibility of the BPC matrix with 4 wt% HNT loading, and high-concentration HNT loading (above 6 wt%) resulted in easy agglomeration. The results highlight that HNTs could be a feasible candidate as nanoreinforcements for the development of high-performance BPCs.

Loading and Sustained Release of Benzyl Ammonium Chloride (BAC) in Nano-Clays.

Benzyl ammonium chloride (BAC) is a broad-spectrum bactericide, but vulnerable to leaching by water. In this paper, halloysite nanotubes (HNT) and montmorillonite (MMT) were used as drug carriers to load BAC, in order to achieve good anti-mildew activity and long-term sustained release properties. The HNT and MMT nano-composites were characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and nitrogen adsorption/desorption. XRD results showed that BAC intercalated the interlayer of MMT, and expanded the interlayer spacing from 1.15 nm to 1.75 nm. Pore analysis showed that BAC decreased the cavity of halloysite nanotubes to a certain extent, which indicated that BAC loaded inside the lumen of HNT successfully. TG analysis showed that the loading capacity of MMT to BAC was higher than HNT. The accelerated-release experiments revealed both two clays have significant sustained-release effects on BAC, and the releasing rate of HNT was relatively lower. Both HNT and MMT have promising application prospects as sustained-release carriers. The inhibition test showed that BAC in nano-clay has good anti-mildew resistance performance.

In Situ Formation of Ag Nanoparticles in Mesoporous TiO2 Films Decorated on Bamboo via Self-Sacrificing Reduction to Synthesize Nanocomposites with Efficient Antifungal Activity.

We developed a novel green approach for the in situ fabrication of Ag NPs in mesoporous TiO2 films via the bamboo self-sacrificing reduction of Ag(NH3)2+ ions, which can inhibit fungal growth on the bamboo surface. Mesoporous anatase TiO2 (MT) films were first synthesized on bamboo via a hydrothermal method. Then, Ag NPs with a 5.3 nm mean diameter were incorporated into the pore channels of optimal MT/bamboo (MTB) samples at room temperature without the addition of reducing agents, such that the Ag NPs were almost entirely embedded into the MT films. Our analysis indicated that the solubilized lignin from bamboo, which is rich in oxygen-containing functional groups, serves as a green reductant for reducing the Ag(NH3)2+ ions to Ag NPs. Antifungal experiments with Trichoderma viride under dark conditions highlighted that the antifungal activity of the Ag/MT/bamboo samples were greater than those of naked bamboo, MTB, and Ag/bamboo, suggesting that these hybrid nanomaterials produce a synergistic antifungal effect that is unrelated to photoactivity. The inhibition of Penicillium citrinum effectively followed a similar trend. This newly developed bamboo protection method may provide a sustainable, eco-friendly, and efficient method for enhancing the antifungal characteristics of traditional bamboo, having the potential to prolong the service life of bamboo materials, particularly under dark conditions.

In situ deposition of MOF199 onto hierarchical structures of bamboo and wood and their antibacterial properties.

Tremendous efforts have been dedicated to developing functionalized cellulose materials by synthesis with copper-based metal-organic frameworks (MOF199), also known as HKUST-1. However, few studies have explored the deposition of MOFs on woody materials due to the complex chemical compositions of these materials (cellulose, hemicellulose, lignin) and their difficulty of bonding with MOF crystals. In this article, for the first time, MOF199 was successfully synthesized onto two different woody materials, moso bamboo and balsa wood, via in situ deposition at room temperature. The results show that the diverse surface roughness and the hierarchical structures of woody materials have significant effects on the size of MOF199 crystal. Additionally, bamboo and wood coated with MOF199 exhibited better antibacterial activities against Staphylococcus aureus (S. aureus) than Escherichia coli (E. coli); they could minimize S. aureus colony levels to 2.08 from 8.98 CFU cm-2. This study provides a facile method for the functionalization of woody materials with MOFs for antibacterial applications.

Functionalization of halloysite nanotubes by enlargement and layer-by-layer assembly for controlled release of the fungicide iodopropynyl butylcarbamate.

Iodopropynyl butylcarbamate (IPBC) is currently one of the most important fungicides widely used for industrial coatings and bamboo treatment. In this work, a controlled release composite with IPBC for inhibition of mold and stain fungi was prepared using enlarged halloysite nanotubes (HNTs) with layer-by-layer (LbL) assembly of polyelectrolyte multilayers. The acid-treated HNTs retained their tubular structure with increased internal diameter, and IPBC loading efficiency was therefore increased to 24.4%, approximately three times the amount of raw HNTs (8.4%). In vitro drug release assay showed that IPBC could be released from HNTs in a sustainable manner with a total release amount of 33.8% over a period of 35 days. The release rate of IPBC could be further controlled by adjusting the number of LbL layers on the tubes and the released amount of IPBC could be limited to less than 10% in 100 days. An inhibition zone test indicated the as-prepared nanocomposites exhibited significant anti-fungal performance against three mold fungi (Aspergillus niger, Trichoderma viride, and Penicillium citrinum) and one stain fungus (Botryodiplodia theobromae). The results support the potential use of HNTs for a prolonged service life of bamboo products.

Study on antibacterial molecular drugs in Eucalyptus granlla wood extractives by GC-MS.

Eucalyptus granlla, which was one of dominant plantations in south China, was deemed as the important wood bio resources. However, the small molecules of Eucalyptus granlla wood weren't effectively reused. Thus the molecules of wood extractives in Eucalyptus granlla were extracted and studied so as to further utilize the resources. The result suggested that the optimal extraction time of ethanol/methanol extraction, petroleum ether/acetic ether extraction, and benzene/alcohol extraction were 5h, 7h and 4h, respectively. The wood extractives included hexanedioic acid, bis (2-ethylhexyl) ester, 3,3,7,11-tetramethyltricyclo[5.4.0.0(4,11)] undecan-1-ol, squalene, etc. and wood extractives of Eucalyptus granlla was suitable for extraction of 1,5-hexadien-3-yne and squalene.

Analysis on active molecules in Populus nigra wood extractives by GC-MS.

Populus nigra has been introduced and largely planted in China, and the waste wood was still abandoned. Therefore, the wood extractives of Populus nigra were studied to further utilize the bio-resources. The result shown that the optimal extraction time of ethanol/methanol extraction, petroleum ether/acetic ether extraction, and benzene/alcohol extraction were 1h, 7h and 3h, respectively. Among sequential extractions, EPB extraction was the optimum extraction mode for the LR was 17.32%. The wood extractives included hexanedioic acid, bis(2-ethylhexyl) ester, phthalic acid derivatives, squalene, 3,3,7,11- tetramethyltricyclo [5.4.0.0(4,11)]undecan-1-ol, other rare drug and biomedical activities. The wood extractives of Populus nigra was fit to extract rare dibutyl phthalate and squalene.

[Discrimination of wood biological decay by soft independent modeling of class analogy (SIMCA) pattern recognition based on principal component analysis].

Wood, as a biomass materials, tends to be attacked by microorganisms, and its structure could be rapidly destroyed by biological decay. Therefore, it's significant to rapidly and accurately detect or identify biological decay in wood. Recently, extensive research has demonstrated that near infrared spectroscopy (NIR) and soft independent modeling of class analogy (SIMCA) can be used to discriminate or detect a wide variety of food, medicine and agricultural products. The use of NIR coupled with principal component analysis (PCA) and SIMCA pattern recognition to detect wood biological decay was investigated in the present paper. The results showed that NIR spectroscopy coupled with SIMCA pattern recognition could be used to rapidly detect the biological decay in wood. The discrimination accuracy by the SIMCA model based on the training set for the non-decay, white-rot and brown-rot decay samples were 100%, 82. 5% and 100%, respectively; and that for the samples for the test set were 100%, 85% and 100%, respectively. However, some white-rot decay samples were mis-discriminated as brown-rot decay, for which the main reasons might be that the training set does not have enough typical samples, and there's a slight difference between white-rot and brown-rot decay during the early stage of decay.

[Rapid determination of Klason lignin content in bamboo by NIR].

Lignin is one of the main components of lignocellulosic materials. The main purpose of wood cooking and bleaching is to remove lignin by chemical agent in paper industry. Whereas the lignin content shows wide variations depending on its tree specie, site condition, part and so on, it is essential to analyze the lignin content of different raw material. The aim of this paper is to develop a rapid near infrared (NIR) reflectance spectroscopic method to characterize the Klason lignin content of bamboo. Fifty four samples from three growth years, two positions along the longitudinal directions and three positions along the radial directions within a bamboo pole were prepared. The Klason lignin contents of 54 samples were analyzed according to traditional chemical method, the spectra of these samples were collected by NIR in the range of 350 to 2500 nm, and the relationship between the lignin content and the spectra of these samples was established by multivariate statistical technique. After second derivative pretreatment of raw spectra, the Klason lignin contents of the bamboo samples were quantified using partial least-squares statistical analysis (PLS1) and full cross validation in the range of 1011-1675 nm and 1930-2488 nm. High coefficients of correlation (r) were obtained between the predicted NIR results and those obtained from traditional chemical method. The correlation coefficient of calibration model and prediction model was 0.99 and 0.97, respectively. The standard error of calibration (SEC) and standard error of prediction (SEP) was 0.36% and 0.59%, respectively. It was found that the lignin content in bamboo could be determined rapidly with reasonable accuracy by the NIR method.