Gas-diffusion microextraction combined with HPLC-DAD for the comprehensive analysis of volatile carbonyl compounds in wood-based panels.

This work presents a novel application of gas-diffusion microextraction (GDME) combined with high-performance liquid chromatography with diode-array detection (HPLC-DAD) for the comprehensive analysis of volatile carbonyl compounds released from wood-based panels. GDME is a simple, fast, and environmentally friendly technique that allows the simultaneous extraction and derivatization of volatile carbonyls directly from solid samples. Commercial particleboards were analysed together with particleboard panels specifically produced using controlled conditions, materials, and reagents, to evaluate the differences in the emission profile of volatile carbonyl compounds. The effect of different production parameters, such as the type of wood particle, resin, and moisture content, on the emission profile of volatile carbonyls from particleboards was investigated using principal component analysis (PCA). The results showed that GDME-HPLC-DAD could successfully differentiate particleboards according to their emission of carbonyl compounds, such as formaldehyde, furfural, benzaldehyde, and other aliphatic carbonyls. Besides the differences on the emission of formaldehyde caused by the type of resin used, UF (urea-formaldehyde) and mUF (UF fortified with melamine), it was found that pine (Pinus pinaster Ait.) particleboards exhibit higher emissions of compounds such as acetaldehyde or hexanal when compared to the higher emissions of compounds such as furfural or benzaldehyde on the recycled particleboards.

Development of an Innovative Lightweight Composite Material with Thermal Insulation Properties Based on Cardoon and Polyurethane.

The search for innovative and sustainable solutions to improve the energy efficiency of the construction industry has been a hot topic for researchers due to the tremendous impact of insulator materials in the thermal comfort of buildings. In the present work, an innovative lightweight composite material with thermal insulation properties was developed, for the first time, by using cardoon particles and polyurethane. The formulation of the composite material was optimized in terms of cardoon fraction and the polyol/isocyanate ratio, to achieve the best compromise between internal bond (IB) strength and thickness swelling (TS). The best performing composite was PU75-CP45, with 45 wt% of cardoon particles and 75% of isocyanate, achieving an IB of 0.41 MPa and a TS of 5.3%. Regarding insulation properties, the PU75-CP45 composite material exhibits a promising performance when compared to conventional construction industry materials by tuning its thickness. Additionally, the composite material presented very low emissions of volatile organic compounds and formaldehyde (bellow to legislation levels) and high resistance to biological degradation.

Grape Canes (Vitis vinifera L.) Applications on Packaging and Particleboard Industry: New Bioadhesive Based on Grape Extracts and Citric Acid.

The main by-product generated in the wine industry are the grape canes, derived from the pruning process. In order to increase the valorisation possibilities of this highly polyphenolic lignocellulosic material, this work focuses on its applicability in the materials industry. As a first step, we demonstrate the viability of using grape cane particles as raw material for particleboard production, combined with a melamine formaldehyde urea (MFU) binder. In addition, looking for the application of these particleboards in the food packaging industry, particleboards based on grape canes were also produced using a new bioadhesive, obtained from the grape cane extract and citric acid. The self-condensation reaction of the grape cane extracts, and the curing reaction with citric acid, were studied by FTIR-ATR and ABES showing the feasibility of this new bioadhesive formulation. Looking for a zero-waste process, the effect of the type of raw material (fresh grape cane, solid by-product of the extraction) and of the extract used on the properties of particleboard were also studied. Citric acid was demonstrated to be a good crosslinking agent for grape cane extract. This work shows that it is possible to produce a new lignocellulosic product based only on grape cane particles using a binder based on grape cane extracts and citric acid. The implemented methodology allowed producing particleboards with applicability in the food-packaging industry, minimizing the waste generated in the process.

The Potential of Visible Spectroscopy as a Tool for the In-Line Monitoring of Lignin Methylolation.

Out of the 50 to 70 million tons of lignin that are produced annually, only 1 to 2% are used for value-added products. Currently, 90% of the total market of this compound corresponds to lignosulphonates (LS). The most successful industrial attempts to use lignin for wood adhesives rely on using it as a partial substitute in phenol-formaldehyde or urea-formaldehyde resins. However, lignin's aromatic ring presents a low number of reactive sites. Several methods have been proposed to improve its reactivity, such as prior methylolation with formaldehyde. Off-line methods are commonly applied to monitor this reaction's progress, but this introduces a significant delay in the analysis. This study proposes a new method for in-line monitoring of the methylolation reaction using visible spectroscopy. In order to monitor the reaction progress, principal component analysis was applied to the spectra, and the obtained scores were analyzed. When these results were plotted against those obtained by the off-line methods, a satisfactory regression was obtained at 50 °C (R2 = 0.97) and 60 °C (R2 = 0.98) for two different LS samples. Therefore, it was concluded that visible spectroscopy is a promising technique for studying lignin methylolation.

Lignosulphonates as an Alternative to Non-Renewable Binders in Wood-Based Materials.

Lignin is a widely abundant renewable source of phenolic compounds. Despite the growing interest on using it as a substitute for its petroleum-based counterparts, only 1 to 2% of the global lignin production is used for obtaining value-added products. Lignosulphonates (LS), derived from the sulphite pulping process, account for 90% of the total market of commercial lignin. The most successful industrial attempts to use lignin for wood adhesives are based on using this polymer as a partial substitute in phenol-formaldehyde or urea-formaldehyde resins. Alternatively, formaldehyde-free adhesives with lignin and lignosulphonates have also been developed with promising results. However, the low number of reactive sites available in lignin's aromatic ring and high polydispersity have hindered its application in resin synthesis. Currently, finding suitable crosslinkers for LS and decreasing the long pressing time associated with lignin adhesives remains a challenge. Thus, several methods have been proposed to improve the reactivity of lignin molecules. In this paper, techniques to extract, characterize, as well as improve the reactivity of LS are addressed. The most recent advances in the application of LS in wood adhesives, with and without combination with formaldehyde, are also reviewed.

Effect of Panel Moisture Content on Internal Bond Strength and Thickness Swelling of Medium Density Fiberboard.

Wood-based products usually have serious limitations concerning contact with water, both because wood is a hygroscopic material and because the commonly used binder has low moisture resistance. This paper studies the effect of panel moisture content (MC) on the physico-mechanical properties of medium density fiberboards (MDF). Several commercial MDF boards produced in Europe were stored at room temperature and relative humidity (RH) for 9 weeks (approx. range 15-20 °C and 50-85% RH). Every week, a strip of each MDF board was cut out, divided into 5 × 5 cm test pieces and its internal bond strength (IB) was measured. A strong influence of MDF moisture content on internal bond strength was observed and therefore IB test pieces were stored in a climatic chamber (either at 20 °C, 55% RH and at 20 °C, 70% RH). A decreasing linear relation was established between IB and MC. It was found that this effect is reversible: after drying, internal bond strength rises again (following a slight hysteresis). This work reinforces the importance of conditioned storage before board properties analysis, as described in European Standard EN 319.

Biosourced Disposable Trays Made of Brewer's Spent Grain and Potato Starch.

Single-use plastic items made of non-biodegradable and fossil-based materials have been identified as a major environmental problem in modern society. Food packaging materials represent an important fraction of these, and replacement with biosourced, sustainable and low-cost alternatives, is a key priority. In the present work, and for the first time, trays suitable for some food packaging applications were produced by the hot-pressing of brewer's spent grains (BSG, a low added-value byproduct of the beer industry), bound with potato starch. Expanded polystyrene (EPS) trays were used as reference, since this material has been widely used in food packaging trays. The results demonstrated that all trays produced with varying proportions of BSG and potato starch have appropriate flexural strength, with values ranging between 1.51 ± 0.32 MPa, for 80% BSG content, and 2.62 ± 0.46 MPa, for 40% BSG content, which is higher than for EPS, 0.64 ± 0.50 MPa. Regardless of BSG content, flexural strength and modulus decreased significantly after contact with water, due to starch plasticization, attaining values below EPS. Trays produced with 60% BSG, and also with the addition of chitosan and glyoxal presented the highest flexural strength, both before and after contact with water, 3.75 ± 0.52 MPa and 0.44 ± 0.11 MPa, respectively. The latter is reasonably close to the reference value obtained for EPS.

Copolymerization of UF Resins with Dimethylurea for Improving Storage Stability without Impairing Adhesive Performance.

Urea-formaldehyde (UF) resins are the most used resins in the wood industry due to high reactivity and low price. However, their reduced stability during storage is a drawback, imposing strict limits in terms of allowable shipping distances and storage times. This instability, manifested by viscosity increase that renders the resin unusable, occurs due to the progress of condensation reactions between the polymeric species present in the liquid medium. In order to achieve a stable resin formulation, dimethylurea (DMeU) was selected for being less reactive than urea. Dimethylurea is shown to co-polymerize with the UF polymer during the acidic synthesis condensation step. However, during storage it behaves like an end group blocker, due to its lower reactivity at basic pH. By adding 1.25% DMeU, it was possible to obtain a formulation that remained with stable viscosity during two-month storage at 40 °C. The reference UF resin remained stable only for eight days in these conditions. Wood particleboards produced with modified resins showed internal bond strengths of about 0.5 N·mm−2, similar to the fresh reference UF resin, even when the resins were used after the two-month storage period. Formaldehyde content values were below the limit for E1 class, ≤8 mg/100 g oven dry board (EN 13986).

Reinforcement of Thermoplastic Corn Starch with Crosslinked Starch/Chitosan Microparticles.

Microparticles of corn starch and chitosan crosslinked with glutaraldehyde, produced by the solvent exchange technique, are studied as reinforcement fillers for thermoplastic corn starch plasticized with glycerol. The presence of 10% w/w chitosan in the microparticles is shown to be essential to guaranteeing effective crosslinking, as demonstrated by water solubility assays. Crosslinked chitosan forms an interpenetrating polymer network with starch chains, producing microparticles with a very low solubility. The thermal stability of the microparticles is in agreement with their polysaccharide composition. An XRD analysis showed that they have crystalline fraction of 32% with Va-type structure, and have no tendency to undergo retrogradation. The tensile strength, Young's modulus, and toughness of thermoplastic starch increased by the incorporation of the crosslinked starch/chitosan microparticles by melt-mixing. Toughness increased 360% in relation to unfilled thermoplastic starch.

Biosourced Binder for Wood Particleboards Based on Spent Sulfite Liquor and Wheat Flour.

Currently, the majority of binders used in wood particleboard (PB) manufacturing are formaldehyde-based synthetic resins. Because of the toxicity of formaldehyde, there is a strong demand for eco-friendly alternatives with similar performances and economic viability. In this work, thick spent sulfite liquor (TSSL), an industrial byproduct from sulfite pulp mills, is proposed as a binder for fully bio-based PBs. The results showed that PBs bound with TSSL present appropriate mechanical performance, which was further improved when TSSL was combined with wheat flour at an 84:16 dry weight ratio and preheated to 94 °C prior to application. For 13.2% binder content per dry wood weight, the PB internal bond strength was 0.46 N mm-2, which is above the standard requirements for PB type P2 (0.35 N mm-2). Optical microscopy showed that TSSL hinders the gelatinization of starch granules during preheating, allowing the binder mixture to maintain a low viscosity suitable for combination with wood particles and PB production.

Quinolone treatment for pediatric bacterial meningitis: a comparative study of trovafloxacin and ceftriaxone with or without vancomycin.

BACKGROUND: Trovafloxacin is a new fluoroquinolone that exhibits good penetration into the central nervous system and excellent antimicrobial activity against common meningeal pathogens, including beta-lactam-resistant pneumococci. PURPOSE AND DESIGN: A multicenter, randomized clinical trial was conducted in children with bacterial meningitis to compare the safety and efficacy of trovafloxacin with that of ceftriaxone with or without vancomycin therapy. RESULTS: A total of 311 patients, ages 3 months to 12 years, were enrolled, of whom 203 were fully evaluable, 108 treated with trovafloxacin and 95 with the conventional regimen. Both groups were comparable with regard to baseline characteristics: age; cerebrospinal fluid findings; use of dexamethasone; history of seizures; and etiologic agents. No significant differences between trovafloxacin and the comparator, respectively, were detected in any of the following outcome measures: clinical success at 5 to 7 weeks after treatment (79% vs. 81%); deaths (2% vs. 3%); seizures after enrollment (22% vs. 21%); and severe sequelae (14% vs. 14%). Only 4 of 284 children developed joint abnormalities up to 6 months after treatment, 1 (0.9%) child received trovafloxacin and 3 (3.1%) received the comparator regimen. None of the evaluable patients experienced significant abnormalities of liver function during treatment. One nonevaluable patient who received trovafloxacin for 5 days and ceftriaxone for 11 days was readmitted to the hospital with hepatitis of unknown etiology 1 day after discharge. The episode resolved with liver function tests returning to normal within 2 months. CONCLUSIONS: We conclude that trovafloxacin is an effective antibiotic for treatment of pediatric bacterial meningitis. These favorable results support further evaluation of fluoroquinolone therapy for children with meningitis or other serious bacterial infections.