Surface characteristics of coated soft- and hardwoods due to UV-B ageing

Wood is a valuable building material, but it is susceptible to degradation if left unprotected especially when using less durable species. Protection is commonly achieved by applying a suitable finish that should exhibit sufficient penetration, good adhesion and resistance to photo-degradation and weathering. The performance of wood coatings is largely influenced by the adhesion between the coating and substrate and any degradation of the substrate will also affect the coating. The aim of this study was to determine the degree to which the substrate degrades despite the coating and adds to the ageing of the coating from the interface. This effect can be expected to differ for soft- and hardwoods. Coated wood samples from pine and meranti wood - a soft- and hardwood - were irradiated with UV-B light to detect surface changes at various length scales and to assess the impact of the underlying wood substrate on the ageing performance of a commercially available acrylic coating. Surface modifications were determined with atomic force microscopy, Fourier transform infrared spectroscopy, colour spectroscopy, static contact angle and a surface roughness profiler.     

Weathering of copper-amine treated wood

In this study, the effect of ultraviolet light (UV) irradiation and water spray on color, contact angle and surface chemistry of treated wood was studied. Southern pine sapwood (Pinus Elliottii.Engelm.) treated with copper ethanolamine (Cu-MEA) was subjected to artificially accelerated weathering with a QUV Weathering Tester. The compositional changes and the surface properties of the weathered samples were characterized by Fourier transform infrared (FTIR) spectroscopy, color and contact angle measurements. FTIR indicated that MEA treatment was not found to slow down wood weathering. FTIR spectrum of MEA-treated sample was similar to that of the untreated SP. However, the Cu-MEA treatment retarded the surface lignin degradation during weathering. The main changes in FTIR spectrum of Cu-MEA treatment took place at 915, 1510, and 1595 cm⁻¹. The intensity of the bands at 1510 and 1595 cm⁻¹ increased with the Cu-MEA treatment. Both untreated and MEA-treated exhibited higher ΔE than the Cu-MEA treated samples, indicating that MEA treatment did not retard color changes. However, ΔE decreased with increasing copper concentration, suggesting a positive contribution of Cu-EA to wood color stability. The contact angle of untreated and MEA-treated samples changed rapidly, and dropped from 75 ± 5° to 0° after artificial weathering up to 600 h. Treatment with Cu-MEA slowed down the decreasing in contact angle. As the copper concentration increases, the rate of change in contact angle decreases.     

基于近红外光谱技术的紫外光老化落叶松木材表面材色变化的定性和定量研究

自然光中的紫外光在木材表面产生复杂的光化学反应,是木材在自然环境中老化降解速度最快,反应最强的化学过程。基于近红外光谱(NIRs)技术探讨了落叶松表面材色在340 nm波长紫外光照射条件下的老化状况。不同时间(180,540,900,1 080 h)试材弦切面经紫外光人工老化后,测量木材表面材色色度学指数,并采集NIRs信息。由NIRs二阶导数及其差谱图反映的信息,定性分析和讨论了木材表面化学组分基团的变化;定量建立基于偏最小二乘法(PLS)结合留一交叉验证的木材表面材色预测模型。结果表明：(1) 随着人工老化时间延长,木材表面明度值L*降低,红绿指数a*与黄蓝指数b*出现先增加后缓慢降低的趋势,表明发色基团的形成随着紫外光照射时间的延长而减少,在辐射时间540 h达到最大值,此外,色差值ΔE*与紫外光照射时间成正相关。(2) NIRs二阶导数在6 996,6 773以及6 287 cm-1等分别反映木材中纤维素非结晶区、半结晶区和结晶区的光谱吸光度随着老化时间的延长而增加,而5 986 cm-1反映木质素特征性谱带吸收峰随着紫外光老化时间的延长而降低,表明木质素出现降解。通过紫外光照射1 080 h与对照材的差谱分析发现,纤维素和半纤维素基团的特征峰差谱值为正,表明紫外光辐射后木材表面的纤维素和半纤维素相对含量增加,而木质素基团特征峰差谱值为负,表明经紫外光辐射后,木质素的降解导致其相对含量减少。这些结果与色度值测量结果相一致。(3) 基于NIRs建立的紫外光照射落叶松表面材色预测模型中,L*交叉验证模型决定系数(R2)为0.949,相对分析误差(RPD)为4.42;a*交叉验证模型R2是0.928,RPD是3.73;b*的交叉验证模型R2是0.831,RPD为2.43,建立的材色预测模型满足预测要求。     

LC-DAD/ESI-MS/MS study of phenolic compounds in ash (Fraxinus excelsior L. and F. americana L.) heartwood. Effect of toasting intensity at cooperage

The phenolic composition of heartwood extracts from Fraxinus excelsior L. and F. americana L., both before and after toasting in cooperage, was studied using LC-DAD/ESI-MS/MS. Low-molecular weight (LMW) phenolic compounds, secoiridoids, phenylethanoid glycosides, dilignols and oligolignols compounds were detected, and 48 were identified, or tentatively characterized, on the basis of their retention time, UV/Vis and MS spectra, and MS fragmentation patterns. Some LMW phenolic compounds like protocatechuic acid and aldehyde, hydroxytyrosol and tyrosol, were unlike to those for oak wood, while ellagic and gallic acid were not found. The toasting of wood resulted in a progressive increase in lignin degradation products with regard to toasting intensity. The levels of some of these compounds in medium-toasted ash woods were much higher than those normally detected in toasted oak, highlighting vanillin levels, thus a more pronounced vanilla character can be expected when using toasted ash wood in the aging wines. Moreover, in seasoned wood, we found a great variety of phenolic compounds which had not been found in oak wood, especially oleuropein, ligstroside and olivil, along with verbascoside and isoverbascoside in F. excelsior, and oleoside in F. americana. Toasting mainly provoked their degradation, thus in medium-toasted wood, only four of them were detected. This resulted in a minor differentiation between toasted ash and oak woods. The absence of tannins in ash wood, which are very important in oak wood, is another peculiar characteristic that should be taken into account when considering its use in cooperage.     

Comparative study of the photo-discoloration of moso bamboo (Phyllostachys pubescens Mazel) and two wood species

Bamboo or bamboo products undergo surface degradation during outdoor exposure resulting in lower quality in service. In this study, the effect of UV-vis light irradiation on changes in color and surface chemistry of moso bamboo (Phyllostachys pubescens Mazel) was investigated. For comparison purpose, two wood species (a soft and a hardwood) were also studied to present their differences in degradation performance. Color characterization was performed by measuring CIELab parameters (L*, a*, b* and ΔE*), and Fourier transform infrared (FTIR) spectroscopy was used to analyze the chemical changes induced by irradiation. The results showed that the surface color of bamboo changed rapidly during the irradiation process. Compared with the wood species, bamboo was less influenced by photo-irradiation. Chemical analysis indicated that irradiation altered the chemical structures of bamboo surfaces. Lignin was the most sensitive component to photo-degradation and the intensities of its characteristics bands decreased significantly during the irradiation process. This was accompanied by formation of new carbonyl groups at 1735 cm⁻¹. The rate of lignin degradation and carbonyl formation in bamboo was relatively lower compared with the wood species. The color changes (ΔE*) was well correlated with lignin degradation and carbonyl formation regardless bamboo or the wood species.     

Surface roughness and color characteristics of wood treated with preservatives after accelerated weathering test

Wood samples treated with ammonium copper quat (ACQ 1900 and ACQ 2200), chromated copper arsenate (CCA), Tanalith E 3491 and Wolmanit CX-8 have been studied in accelerated weathering experiments. The weathering experiment was performed by cycles of 2 h UV-light irradiation followed by water spray for 18 min. The changes on the surface of the weathered samples were characterized by roughness and color measurements on the samples with 0, 200, 400 and 600 h of total weathering.

The objective of this study was to investigate the changes created by weathering on impregnated wood with several different wood preservatives. This study was performed on the accelerated weathering test cycle, using UV irradiation and water spray in order to simulate natural weathering.

Surface roughness and color measurement was used to investigate the changes after several intervals (0–200–400–600 h) in artificial weathering of treated and untreated wood.     

基于拉曼光谱的电线绝缘材料老化状态评估

电线绝缘材料老化状态的准确评估有助于减少因电线绝缘老化引起的火灾,该实验基于拉曼光谱检测平台及自行搭建的老化设备,对13种电线绝缘材料(聚偏氟乙烯、聚丙烯、聚四氯乙烯、尼龙、亚大尼龙、聚氨酯、乳胶、聚全氟乙丙烯树脂、橡胶、聚乙烯、聚氯乙烯、硅胶、进口硅胶)进行加速温度老化以及加速紫外老化试验并定期检测,温度老化10个时间段,时间间隔为32 h,每个老化时间15个样本数据,获得温度老化的每种材料共150个样本光谱数据;紫外老化13个时间段,时间间隔16 h,每个老化时间15个样本数据,获得紫外老化的每种材料共195个样本光谱数据。依据老化时间段,温度老化分为10类,紫外老化分为13类,采用线性回归分类和支持向量机对原始光谱数据进行分类,两种分类算法准确率均在80%以上的材料有尼龙、聚氨酯、特氟龙、橡胶等,但部分材料的分类准确率却低于70%,在对原始光谱数据进行支持向量机分类时,由于样本数量多以及光谱维度高,支持向量机分类所需时间较长,为进一步提升分类准确率以及分类速度,对原始光谱数据进行迭代自适应加权惩罚最小二乘法、五点三次平滑等预处理方法,采用PCA压缩,样本光谱维数从2 048维降至...     

Mechanical Properties and Solid-State Structure of Photodegraded Polyoxymethylene and Effect of UV Stabilizers Modification

Ultraviolet (UV) light exposure can lead to photodegradation of polyoxymethylene (POM), resulting in a change of its physical and chemical properties. Benzophenone UV absorber (UV-9), benzotriazole light stabilizer (UV-327), and hindered amine light stabilizer (LD-622) were used as UV stabilizers to improve the photostabilization of POM. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize POM before and after aging. The change of its solid-state structure during the aging process was investigated. The surface molecular weight and the mechanical properties of modified POM after UV aging were also determined. The results showed that the degradation of amorphous molecules mainly occurred at the surface, while crystalline reorganization occurred in the interior part of the sample as a result of the UV irradiation, both of which led to an increase of the crystallinity. After UV irradiation for 1000 h, the elongation at break and notched Charpy impact strength were only 16.6% and 27.4% of the initial sample, respectively. However, 1%–3% of the additives could reduce the chain scission and restrain the recrystallization of POM after UV irradiation. Furthermore, mechanical properties were maintained to a certain degree by adding the UV stabilizers.     

Paraloid文物保护材料光老化的红外光谱研究

Paraloid(乳胶粘合剂)是一系列丙烯酸树脂的商品名称,是文物保护领域中最常用的保护材料之一,主要用于文物的加固、封护和粘接,适用文物材质范围非常广泛。其中以Paraloid B-72最具代表性,在国内外的文物保护中被大量使用,相关的应用案例、性能评价及其老化机理研究都有较多报道,而Paraloid系列的其他产品却鲜有关注,在国内应用较少,老化性能研究尚未开展工作。该研究系统评价了Paraloid B-72, Paraloid B-44, Paraloid B-48N和Paraloid B-67的光老化性能,采用红外光谱跟踪紫外辐照3 864 h过程中Paraloid材料分子结构变化,对光老化机理进行了深入解析和半定量评测。结果显示,4种Paraloid系列丙烯酸树脂材料中,B-72老化前后颜色和光泽度均没有发生明显变化,B-48N和B-67老化前后色差较大,B-44光泽度降低最多。丙烯酸树脂老化过程中高分子材料内部发生断链反应以及一定程度的交联反应,表现在主要官能团吸收的减弱和羰基指数(CI)的增加。根据主要官能团吸收峰CO相对强度的半定量分析结果反映出,B-72的光稳定性最好,...     

Determination of wood grain direction from laser light scattering pattern

Laser light scattering patterns from the grains of wood are investigated in detail to gain information about the characteristics of scattering patterns related to the direction of the grains. For this purpose, wood samples of Scots pine (Pinus sylvestris L.) and silver birch (Betula pubescens) were investigated. The orientation and shape of the scattering pattern of laser light in wood was found to correlate well with the direction of grain angles in a three-dimensional domain. The proposed method was also experimentally verified.     

水性丙烯酸聚氨酯涂料中反应性缓蚀剂掺入及其耐蚀性能

利用磷酸和双酚A环氧树脂反应得到功能性缓蚀剂羟基环氧磷酸酯(HEP). 将其添加到水性羟基丙烯酸树脂中,再与水性异氰酸酯固化剂交联,制备了水性羟基环氧磷酸酯/丙烯酸聚氨酯复合涂层(HEP-APU). 由于磷酸酯基团可以与金属基体发生反应,在金属表面形成一层磷化膜,极大的提升了金属的抗闪蚀能力. 利用电化学阻抗谱和极化曲线研究HEP-APU复合涂层对Q235碳钢在3.5wt% NaCl溶液中耐蚀性能. 结果表明,HEP-APU涂料对Q235碳钢具有优越的钝化和耐腐性能,且当HEP在水性丙烯酸聚氨酯涂料中质量分数为0.5%时,所得到的复合涂层的防腐性能最佳.     

Color changes in wood during heating: kinetic analysis by applying a time-temperature superposition method

This paper deals with the kinetics of the color properties of hinoki (Chamaecyparis obtusa Endl.) wood. Specimens cut from the wood were heated at 90–180°C as accelerated aging treatment. The specimens completely dried and heated in the presence of oxygen allowed us to evaluate the effects of thermal oxidation on wood color change. Color properties measured by a spectrophotometer showed similar behavior irrespective of the treatment temperature with each time scale. Kinetic analysis using the time-temperature superposition principle, which uses the whole data set, was successfully applied to the color changes. The calculated values of the apparent activation energy in terms of L ^*, a ^*, b ^*, and DE^*_ab\Delta E^{*}_{ab} were 117, 95, 114, and 113 kJ/mol, respectively, which are similar to the values of the literature obtained for other properties such as the physical and mechanical properties of wood.     

人工降解饱水木材制备方法与光谱研究

考古出土/出水的饱水木质文物保存状态千差万别,内部降解不均匀、差异大,又有取样的限制,造成许多必需的材性定性定量分析和保护效果评价测试难以进行,因此亟需开发实验室可控制备的人工降解饱水木材技术,以获取大量重复性好、性质均匀的样品供研究使用。以健康黄松为原料,探索使用NaOH-真空浸渍-高压水热的联用法制备人工降解饱水木材,取得了初步的成功。制备的人工降解饱水木材的最大含水率（MWC）为260%,340%和575%,分别达到国际上普遍认定的低、中、高度降解饱水考古木材的MWC水平。红外光谱（FTIR）显示制备的人工降解饱水木材纤维素结构保存较为完好,氢键部分断裂;半纤维素显著降解,主链、侧链有断裂现象,1 732 cm-1特征峰消失;木质素有部分降解,1 508 cm-1处木质素芳香环骨架振动等吸收峰相对强度降低并发生偏移。近红外反射光谱（NIR）显示,制得的样品的三大素均发生降解,半纤维素降解程度最高,木质素次之,木质素相对含量升高,表现为C═O相对含量增加。在1 536～1 580 nm区域形成宽峰且峰强度降低,表明纤维素结晶区分子内部、分子间氢键结构均发生断裂。NaOH-真空浸渍-水热联用法与国际上现用的常压高浓度NaOH浸渍法相比,所需NaOH溶液浓度从50%以上降低到1%、处理时间从数月缩短至10 h,制备效率大大提升,所制得的饱水木材的最大含水率显著增大,与考古木材相近,细胞壁化学结构降解程度显著增大。NaOH-真空浸渍-水热联用法有望实现在实验室可控、快速、大量制备不同降解程度的人工降解饱水木材,对饱水木质文物保护水平的提高具有一定的促进意义。     

马尾松木材褐腐降解的红外光谱研究

用傅立叶变换红外光谱(FTIR)研究了马尾松木材被茯苓褐腐菌降解过程中化学成分的变化。测量了木质素和综纤维素的相关红外吸收峰的峰高比值,用湿化学方法测定了未褐腐和不同褐腐时间木材的Klason木质素含量和综纤维素含量,分析了红外吸收峰峰高比值与Klason木质素含量和综纤维素含量的相关性。褐腐15周内,1736和1372cm-1处归属于综纤维素的吸收峰强度逐渐减弱,1510和1225cm-1处归属于木质素的吸收峰强度逐渐增强;但褐腐15周后,1736和1372cm-1处的吸收强度却开始略微增强,1510和1225cm-1处吸收强度略微下降。I1510/I1736,I1510/I1372,I1225/I1736和I1225/I1372与Klason木质素和综纤维素含量之间均存在非常好的线性相关,R2为0.96～0.99。I1736/I1510和I1372/I1510与综纤维素含量之间存在高度线性相关,R2=0.96。结果说明用红外光谱技术可以对木材褐腐过程中的综纤维素含量和Klason木质素含量进行准确分析。     

NMR spectroscopy applied to the Cultural Heritage: a preliminary study on ancient wood characterisation

High and low resolution solid state NMR methods have been applied to characterise a few samples of ancient wood. In an ancient larch wood sample, by applying ¹H low resolution NMR methods as a function of the temperature, the average pore size and its distribution have been determined. In addition, high resolution NMR techniques have allowed addressing of the question of the proximity of water pools to cellulose and lignin. In particular, a model can be hypothesized in which water pools are surrounded by thin layers of amorphous cellulose and/or lignin while the crystalline domains of cellulose surround the layers of amorphous cellulose. Preliminary results obtained using a fully non invasive and portable NMR unilateral relaxometer, the Eureka-Mouse10 (EM10), are reported. This instrumentation is shown to be perfectly suitable for characterizing degradation in ancient wood samples. PACS 76.60 k     

Inorganic UV absorbers for the photostabilisation of wood-clearcoating systems: Comparison with organic UV absorbers

Inorganic UV absorbers which are widely used today were originally designed neither as a UV blocker in coatings applications, nor for wood protection. In recent years however, there has been extensive interest in these compounds, especially with regard to their properties as a UV blocker in coating applications.In this work, we carried out a comparative study to look into some inorganic and organic UV absorbers used in wood coating applications. The aim of this study is to determine the photostabilisation performances of each type of UV absorbers, to seek possible synergies and the influences of different wood species. We have also searched to find eventual correlation between these performances and the influence of UV absorbers on the film properties. Our study has compared the performances of the following UV absorbers: hombitec RM 300, hombitec RM 400 from the Sachtleben Company; transparent yellow and red iron oxides from Sayerlack as inorganic UV absorbers; organic UV absorbers Tinuvin 1130 and Tinuvin 5151 from Ciba Company.The study was carried out on three wood species: Abies grandis, tauari and European oak.The environmental constraints (in particular the limitation of the emission of volatile organic compounds VOCs) directed our choice towards aqueous formulations marketed by the Sayerlack Arch Coatings Company.The results obtained after 800 h of dry ageing showed that the Tinuvins and the hombitecs present better wood photostabilisations.On the other hand in wet ageing, with the hombitec, there are appearances of some cracks and an increase in the roughness of the surface. This phenomenon is absent when the Tinuvins are used. With regard to these results, the thermomechanical analyses relating to the follow-up of the change of the glass transition temperature (T_g) of the various coating systems, show a different behaviour between the two types of absorbers. However, contrary to organic UV absorbers, inorganic ones tend to increase T_g during ageing, and, consequently decrease the flexibility of films. These phenomena can lead to the appearance of cracks found in the case of the wet weathering.     

UV辐射前后乙酰化木材的化学组分结构变化与微观构造表征

以杨木木粉为试样,进行不同时长的乙酰化处理,利用紫外光加速老化,探讨不同乙酰化度对木材耐光性能的影响,根据FTIR光谱分析试样化学组分特征吸收峰强度的变化规律,建立乙酰化处理时间与木材化学组分变化之间的关系。结果表明：UV辐射前,乙酰化木粉在1 739 cm-1处饱和酯化合物中CO和 1 385 cm-1处乙酸酯基中C—H的特征吸收峰强度均大于原木粉,处理40 min木粉的吸收峰强度最大,增重率最高,木粉的乙酰化效果显著;UV辐射后,乙酰化木粉在1 504 cm-1处木质素中苯环特征吸收峰强度明显大于原木粉,且乙酰化处理40 min木粉的吸收峰强度最大,表明乙酰化处理能够有效抑制木材化学组分的光降解反应,提高木材的耐光老化性能,其中处理40 min的效果最佳;SEM图片显示,乙酰化处理木粉的纤维状表面较原木粉更加均匀,材料粒径更小,乙酰化处理能有效提高木材的稳定性。     

Electroless nickel plating on APTHS modified wood veneer for EMI shielding

A new activation process was developed for electroless plating to prepare wood-based EMI shielding material. Pd(II) was adsorbed on a wood surface modified with γ-aminopropyltrihydroxysilane (APTHS) formed by the hydrolysis of γ-aminopropyltriethoxysilane (APTES). After reduction of Pd(II), electroless plating was successfully initiated and an Ni-P coating was deposited on the wood veneer. The activation process and resulting coating were characterized by XPS, SEM-EDS and XRD. The metal deposition, surface resistivity and electromagnetic shielding effectiveness were measured. XPS analysis proved that Pd(II) was bonded to the amino group of APTHS and was reduced to Pd(0). The Ni-P coating was uniform, compact and continuous, and consisted of 3.39 wt.% phosphorus and 96.61 wt.% nickel. XRD analysis indicated that the coating was crystalline, which is thought to be related to the low phosphorus content. The plated birch veneers exhibited electromagnetic shielding effectiveness greater than 60 dB in the frequency range 10 MHz-1.5 GHz.     

Photocatalytic degradation of methylene blue in water solution by multilayer TiO2 coating on HDPE

A multilayer photocatalytic TiO₂ coating on a high-density polyethylene (HDPE) disk was found to degrade aqueous methylene blue in a batch reactor study. The TiO₂ coating was fabricated by a low-temperature method using polyurethane resin (PU) as a barrier layer for HDPE and as a binding agent for two TiO₂ layers. Adequate adhesion between the HDPE substrate and PU barrier in aqueous environment was ensured with an oxygen plasma treatment.The photocatalytic effect of immersed TiO₂ coating on the degradation of methylene blue in aqueous solution was monitored by UV–vis spectrometry as a function of UV-illumination time. Samples were allowed to adsorb methylene blue in the dark for 1 h before the UV-degradation experiments were started. The percentages of methylene blue degraded during 6 h UV illumination (λ = 365 nm) varied from 80% to 92%. The degradation followed pseudo-first order reaction kinetics, and the observed rate constants (k_obs) were between 0.27 and 0.43 h⁻¹.     

Facile Preparation and Excellent Ultraviolet Shielding Application of Polyurethane-TiO2 Composite Microcapsules

In this work, butyl stearate, isophorone diisocyanate, and glycerol are used to prepare reticulated polyurethane microcapsules using interfacial polymerization. In addition, anatase nano-TiO₂ is added to prepare TiO₂-polyurethane phase change microcapsules during the polymerization process. Polarized light microscope, scanning electron microscope, Fourier-transform infrared spectroscopy, thermogravimetric, differential scanning calorimeter, and other methods demonstrate the successful preparation of microcapsules, and microcapsules with different TiO₂ content have differences in morphology and performance. It is worth noting that the addition of TiO₂ enhances the thermal stability and mechanical strength of the prepared composite microcapsules. In addition, TiO₂ particles allow the microcapsules to have photocatalytic properties and ultraviolet shielding properties, and the prepared TiO₂-polyurethane composite capsules show good catalytic degradation properties for methyl orange solution. Moreover, the ultraviolet absorption performance of the TiO₂-polyurethane composite microcapsule coating is tested, and the results show that the strength of ultraviolet light is weakened after passing through the coating, indicating that the composite microcapsule can enhance the UV resistance of the coating. This work shows the preparation of multifunctional microcapsules and their potential applications in photocatalysis and UV resistance.