Recent Advances on the Development of Protein-Based Adhesives for Wood Composite Materials—A Review

The industrial market depends intensely on wood-based composites for buildings, furniture, and construction, involving significant developments in wood glues since 80% of wood-based products use adhesives. Although biobased glues have been used for many years, notably proteins, they were replaced by synthetic ones at the beginning of the 20th century, mainly due to their better moisture resistance. Currently, most wood adhesives are based on petroleum-derived products, especially formaldehyde resins commonly used in the particleboard industry due to their high adhesive performance. However, formaldehyde has been subjected to strong regulation, and projections aim for further restrictions within wood-based panels from the European market, due to its harmful emissions. From this perspective, concerns about environmental footprint and the toxicity of these formulations have prompted researchers to re-investigate the utilization of biobased materials to formulate safer alternatives. In this regard, proteins have sparked a new and growing interest in the potential development of industrial adhesives for wood due to their advantages, such as lower toxicity, renewable sourcing, and reduced environmental footprint. This work presents the recent developments in the use of proteins to formulate new wood adhesives. Herein, it includes the historical development of wood adhesives, adhesion mechanism, and the current hotspots and recent progress of potential proteinaceous feedstock resources for adhesive preparation.     

Polymer structure of cured alkaline phenol–formaldehyde resol resins with respect to resin synthesis mole ratio and oxidative side reactions

A wood adhesive-type phenol–formaldehyde (PF) resol resin synthesized with a typical formaldehyde to phenol mol ratio of 2.10 was thoroughly cured and studied by the solid-state crosspolarization/magic angle spinning ¹³C nuclear magnetic resonance (CP/MAS NMR) spectroscopy. The methylene group/phenol mol ratio values found were between 1.35 and 1.46, close to the value of a completely cured PF polymer structure. The amount of formaldehyde emitted during resin curing was very small. Other formaldehyde-derived groups determined from CP/MAS NMR spectra and relatively high levels of oxidation products of formaldehyde determined from water extracts of cured resin raised the total formaldehyde-derived groups/phenol mol ratio value to close to that of the synthesis mol ratio. Technological implications of these findings are discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3275–3285, 1997     

木材种类的近红外光谱和模式识别

木材的种类识别是木材加工和贸易的一个重要环节,传统的木材种类识别方法主要有显微检测法和木材纹理识别法,其操作繁琐,耗时长,成本高,不能满足当前需求。本研究利用木材的近红外光谱(NIRS)结合模式识别方法,以期实现木材种类的快速准确识别。采用近红外光谱结合主成分分析法(PCA)、偏最小二乘判别分析法(PLSDA)和簇类独立软模式法(SIMCA)三种模式识别对58种木材进行种类鉴别研究;5点平滑、标准正态变量变换(SNV)、多元散射校正(MSC)、Savitzky-Golay一阶导数(SG 1st-Der)和小波导数(WD)五种光谱预处理方法用于木材光谱的预处理;校正集和测试集样品的正确识别率(CRR)用于模型的评价。采用PCA方法,通过样品的前三个主成分空间分布图分辨木材种类的聚类情况。在建立PLSDA模型,原始光谱的正确识别率最高,分别为88.2%和88.2%;5点平滑处理的光谱校正集和测试集的CRR分别为88.1%和88.2%;SNV处理的光谱校正集和测试集的CRR分别为84.4%和84.5%;MSC处理的光谱校正集和测试集的CRR分别为83.1%和84.2%;SG 1st-Der处理的光谱校正集和测试集的CRR分别为81.8%和82.7%;WD(小波基为“Haar”,分解尺度为80)处理的光谱校正集和测试集的CRR分别为87.3%和87.2%。可知,在PLSDA模型中,木材光谱未经预处理种类识别效果最后好。在建立SIMCA模型过程中,原始光谱的校正集和测试集的CRR分别为99.7%和99.4%;5点平滑处理的光谱校正集和测试集的CRR分别为100%和100%;SNV处理的光谱校正集和测试集的CRR分别为99.5%和99.1%;MSC处理的光谱校正集和测试集的CRR分别为99.0%和98.4%;SG 1st-Der的光谱校正集和测试集的CRR分别为81.8%和82.7%;WD处理的光谱校正集和测试集的CRR分别为100%和100%。可知,在SIMCA模型中,木材光谱经平滑和小波导数处理后的识别效果最好,且光谱的校正集和测试集CRR都为100%。采用三种模式结合五种不同的预处理方法对木材近红外光谱进行定性建模识别时,由于木材样本属性复杂,主成分分布图相互交织,PCA无法识别出58种木材;原始光谱的PLSDA模型可以得到较好的判别模型,但校正集和测试集的CRR只有88.2%和88.2%;木材光谱经过5点平滑或WD预处理后的SIMCA模型可达到最好的识别效果,校正集和测试集的CRR均为100%,且WD-SIMCA模型因子数比5点平滑SIMCA模型小,模型更为简化,故WD-SIMCA为58种木材种类识别的最优模型。研究表明光谱预处理方法可以有效的提高木材种类识别精度,有监督模式识别方法SIMCA可以用来建立有效的木材识别模型,近红外光谱结合模式识别可以为木材种类的识别提供一种快速简便的分析方法。     

XPS characterization of naturally aged wood

Wood deterioration over time (by a simultaneously biological, chemical or physical attack) is an inevitable continuous process in the environment. This process destroys all heritage resulting in a loss of valuable old wooden structures and their properties. What type of deterioration occurs and how these processes impact the wood are important questions that need consideration if old wooden structures are to be studied and properly preserved.X-ray photoelectron spectroscopy (XPS) was employed to analyze the undegraded (sound wood of ∼6 years) and degraded lime wood (∼150 years, ∼180 years, ∼250 years) from painting supports, differing in terms of the provenance, conservation status and environmental conditions of storage. Elaborated XPS analysis (comparison of C and O individual spectra, decomposition for each atomic component, calculation of O/C ratio) provided a view of the composition of the sample surfaces analyzed. On the basis of these results, it was confirmed that significant changes occurred in the first period of ageing, the ∼150 years lime wood sample having the highest percent of the carbon atoms and the lowest percentage of oxygen atoms and, respectively O/C ratio. According to our previous studies (X-ray diffraction, FTIR spectroscopy, analytical pyrolysis combined with gas chromatography/mass spectrometry and ESR-spectroscopy results), these features could be attributed to the fact that hemicelluloses and amorphous cellulose are degraded in time, whereas the crystalline fraction of cellulose decreases more slowly than the amorphous one. Consequently, the observation may be made that lignin is not so easily degraded under the environmental conditions where paintings are frequently exposed.     

Characterisation of archaeological waterlogged wood by pyrolytic and mass spectrometric techniques

Two techniques based on analytical pyrolysis and mass spectrometry, direct exposure-MS (DE-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), were used to characterise waterlogged archaeological wood and to study degradation patterns of wood in aqueous environments. The two techniques were applied to samples from the excavation of the Site of the Ancient Ships of Pisa San Rossore in Pisa (Italy), and data were compared to those relative to native sound wood of the same species (pine, elm, beech). Both the methods result valuable in the analysis of ancient wood artefacts, avoiding the long wet-chemical procedures that are commonly used in wood analysis, and allowing us to use a minimal sample size. DE-MS achieves a global mass spectral fingerprint of lignin and polysaccharides pyrolysis compounds in few minutes, and the results have been interpreted with the support of principal component analysis (PCA) of mass spectra. Py-GC/MS permits detailed molecular analysis of pyrolysis compounds and highlights some chemical modifications of lignin in archaeological samples, as demethylation of both guaiacyl and syringyl lignin units. Both the techniques demonstrate consistent loss of polysaccharides in archaeological wood.     

Recovery of palladium using chemically modified cedar wood powder

Japanese cedar wood powder (CWP) was chemically modified to a tertiary-amine-type adsorbent and studied for the selective recovery of Pd(II) from various industrial waters. Batch adsorption tests performed from 0.1 M to 5 M HCl and HNO₃ systems reveal stable performance with better results in HNO₃ medium. The maximum loading capacity for Pd(II) was studied in HCl as well as in HNO₃. A continuous-flow experiment taking a real industrial solution revealed the feasibility of using modified CWP for the selective uptake and preconcentration of traces of palladium contained in acidic effluents. In addition, stable adsorption performance even on long exposure to γ-irradiation and selective recovery of palladium from simulated high-level liquid waste (HLW) are important outcomes of the study.     

斜投影-不展开薄层色谱法对废木料液化产物乙酰丙酸的过程分析

采用多波长薄层色谱扫描法,不经过传统的薄层色谱展开步骤实现混合体系的快速定量。废木料液化过程产物为混合体系,分别将不同液化反应时间点所取样品点样于硅胶板上。仅对液化过程终点的样本点进行一次展开,分离斜投影建模所需的反射光谱,切割出目标产物(乙酰丙酸)和背景光谱,构造斜投影算子;对其他液化过程中的样品点不展开,采集混合光谱,经斜投影算法分离出其中的目标产物纯光谱,从而实现定量。将该方法的定量结果与高效液相色谱法的定量结果对比,得到两种方法测定乙酰丙酸的相对误差小于3.27%,表明两种方法具有良好的一致性。     

用于木材水分检测的单边核磁共振传感器设计

为了实现对木材水分的无损检测,设计了一种单边核磁共振（unilateral nuclear magnetic resonance,UMR）传感器,该传感器由单边磁体、抗涡流板、射频线圈、阻抗匹配和调谐电路构成．在距离传感器表面上方75 mm处的50 mm×50 mm的平面内,建立了71.1 mT（共振频率为3.027 MHz）的静态磁场．本文详细介绍了该传感器的设计思路和实现方法,并开展了初步的木材水分无损测量实验．对圆柱形树桩的径向水分分布进行了一维扫描测量,观察了水分由树皮向树芯逐步深入过程中横向弛豫时间（T₂）的变化规律,还使用UMR仪对木材干燥过程中水分的挥发进行了测量.实验结果表明,随着干燥的加剧,被测样品T₂谱的长T₂波峰明显左移、积分面积渐减,而且积分面积与木材样品含水率呈正比．本文为木材研究提供了一种便携的NMR测量设备设计方案,且可以实现野外活体树木的无损测量．     

真空热处理人工林落叶松木材吸湿性变化机理研究

热处理是一种环境友好型的木材改性方法,可提高木材的耐腐性和尺寸稳定性。研究以落叶松木材为试验材料,在处理温度200 ℃的条件下,对其进行了不同时间的真空热处理。利用动态水蒸气吸附(DVS)对热处理前后木材吸湿性的变化进行了表征,通过傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)和X射线衍射(XRD)分析了热处理前后木材化学组分和结构变化,通过化学变化分析阐明了热处理木材吸湿性变化的作用机制。结果表明：真空热处理落叶松木材的平衡含水率降低,热处理木材的平衡含水率随热处理时间的延长呈逐渐下降的趋势。结合红外光谱和光电子能谱发现,热处理后木材纤维素和半纤维素等化学成分发生降解,木质素发生交联缩合反应,使得吸湿性基团含量减少,碳元素与氧元素含量发生变化,氧碳比降低,从C原子的结合形式来看,热处理材的C1含量增加,C2和C3含量降低,这些化学变化使得热处理材的吸湿性降低。此外,真空热处理未破坏木材的结晶结构,木材的相对结晶度随真空热处理时间的延长而增大,结晶度的增大减少了纤维素分子链上吸水性基团的数量,从而降低了木材的吸湿性。