Photodegradation at the wood-clearcoat interface

Summary Western red cedar panels, one coated with a soft latex-based acrylic polymer clear coating and the other uncoated, were exposed outdoors under a series of cut-off filters for 50 weeks. FTIR-ATR spectra of the panels showed that the extent of delignification increased with decreasing wavelengths of the solar radiation incident at the wood surface. The results support the proposal that it is the UV component of sunlight that is primarily responsible for the degradation of lignin. The extent of loss of lignin from the surface of the exposed coated panel was significantly less than that for the exposed uncoated panel suggesting that the coating confers some protection from weathering to the underlying timber. Colorimetric measurements also showed that the degree of discoloration of the panels is related to the wavelength of the radiation penetrating the wood surface.This work was supported financially by ICI Dulux Australia and the Australian Research Council. The authors also express their appreciation for helpful discussions with G. J. Wilson of the Commonwealth of Australia Scientific and Industrial Research Organization (C.S.I.R.O.) and I. Leaver of Dulux Australia     

Spectral sensitivity in the photodegradation of fir wood (Abies alba Mill.) surfaces: colour changes in natural weathering

Activation spectra of wood under natural irradiation were investigated in detail in this work. The main purpose was to study colour changes on the wood surface over time and into the depth during natural light exposure and thus to further contribute to the optimization of surface-protecting treatments. In a natural weathering test, three 80-μm-thick strips of fir wood forming the surface layer of a wood composite were exposed to light under a series of glass cut-off filters. Samples were withdrawn at intervals and tested for colour changes. Identification of the most detrimental wavebands of light causing photodegradation was performed based on recorded colour changes. With chronological development of exposure, the colour changes shifted ever deeper into the surface and further into the visible region of the spectrum. A relatively narrow waveband from 360 to 435 nm was identified in the activation spectra to be the most active band, causing the greatest proportion of recorded colour changes. However, also visible light of wavelengths up to 515 nm significantly contributed to colour changes of the surface layers.     

UV‐B radiation constrains the photosynthesis of Quercus robur through impacts on the abundance of Microsphaera alphitoides

Quercus robur saplings were exposed at an outdoor facility in the UK to supplemental levels of UV‐B radiation (280–315 nm) under arrays of cellulose diacetate‐filtered fluorescent lamps which also produced UV‐A radiation (315–400 nm). Saplings were also exposed to supplemental UV‐A radiation under arrays of polyester‐filtered lamps and to ambient levels of solar radiation under arrays of unenergized lamps. The UV‐B treatment was modulated to maintain a 30% elevation above the ambient level of erythemally weighted UV‐B radiation. Naturally occurring infections by oak powdery mildew (Microsphaera alphitoides) were more abundant, and developed more rapidly, on lammas leaves of saplings which were exposed to treatment levels of UV‐B radiation than on leaves of saplings exposed to supplemental UV‐A or to ambient levels of solar radiation over 12 weeks in summer and autumn 1996. An analysis of leaf photosynthetic capacities revealed that M. alphitoides infection reduced the quantum efficiency of photosystem (PS) II by 14% at moderate irradiance. Although there was no direct effect of UV‐B radiation on PSII photochemistry, exposure of saplings to supplemental UV‐A radiation under polyester‐filtered lamps resulted in a 17.5% decrease in PSII quantum efficiency, compared with saplings exposed to ambient solar radiation. The results from our study suggest that photosynthesis of Q. robur may be constrained by exposure to UV‐B radiation in the natural environment through impacts on the abundance of M. alphitoides.     

Weathering characteristics of hardwood surfaces

Summary Four hardwoods, red oak, white oak, yellow-poplar, and sweetgum, were exposed to outdoor weathering and to artificial ultraviolet (UV) light with wavelengths of >220 and >254 nm. Discoloration and loss of brightness were observed from all specimens regardless of their exposure conditions. White oak and sweetgum changed color at a slower rate than did red oak and yellow-poplar. SEM micrographs showed that all wood species exhibited surface deterioration after 30 days exposure to sunlight or 500 hrs to UV light. Loss of middle lamella, separation of procumbent cells, and damage of pit structures were observed on transverse sections for all species. ESCA studies revealed a high oxygen content at the wood surfaces indicating severe oxidation of wood exposed either outdoors or to artificial UV light. The generation of new chromophoric groups such as carbonyls, carboxylic acids and quinones, and the loss of lignin at the oxidized surface were demonstrated experimentally by infrared studies.This study was supported by cooperative research funds provided by the U.S. Forest Products Laboratory, Madison, Wisconsin. The authors wish to acknowledge this support     

Degradation of wood surfaces during natural weathering. Effects on lignin and cellulose and on the adhesion of acrylic latex primers

Summary Radiata pine veneers and blocks were exposed to natural weathering under Australian summer conditions over a period of 30 days. Infrared spectroscopy revealed that there was perceptible surface delignification after 4 hours exposure, substantial surface delignification after 3 days exposure and almost complete surface delignification after 6 days. Rapid lignin degradation was also suggested by measurements of the acid insoluble lignin content of weathered veneers. Viscometry determinations on holocellulose samples from weathered veneers and unweathered controls indicated significant depolymerisation of cellulose after 4 days exposure. A tape test was used to assess the adhesion of acrylic latex primers to weathered blocks. The adhesion of exterior acrylic primers decreased on weathered wood surfaces and was significantly lower on specimens that were weathered for 5 to 10 days. An oil-modified acrylic primer showed greater adhesion to weathered wood surfaces. Primer adhesion was lower on weathered radial surfaces than on similarly exposed tangential surfaces. The practical implications of these findings for the coating of exterior wood with acrylic latex primers are discussed briefly.The authors wish to thank Dr. A. J. Michell for FTIR spectral determinations and the Australian Research Council small grants scheme for financially supporting part of the work     

Chemical characteristics of surfaces of hardwood and softwood deteriorated by weathering

The factors that cause weather-induced deterioration of wood surfaces were determined by chemical and spectroscopic analyses. Albizzia (Paraserianthes falcata Becker.) and sugi (Cryptomeria japonica D. Don) were exposed to two temperate conditions of natural weathering with and without rainfall and to accelerated conditions of artificial weathering coupled with ultraviolet (UV) light irradiation and water flashing. Infrared spectroscopic analysis showed that the oxidative reaction of lignin was observed under all conditions of weathering for both wood species. However, a marked decrease in lignin and hemicellulose content were recognized when albizzia woods were exposed to weathering with water. Lignin content in the softwood sugi did not decrease as much as in albizzia even in the presence of water, but the modification of lignin macromolecules was assumed to be accelerated by water, as seen by electron spin resonance spectroscopy. These results showed that the presence of water promotes the weathering deterioration of wood under UV irradiation.     

Natural weathering of Scots pine (Pinus sylvestris L.) wood treated with epoxidized linseed oil and methyltriethoxysilane

In this study, the effect of natural weathering on the performance of Scots pine sapwood treated with epoxidized linseed oil (ELO) and methyltriethoxysilane (MTES) was investigated by measuring water uptake, colour, check propagation and chemical changes. Boards were impregnated in a pilot-scale autoclave under various conditions. After the treatments, pairs of samples were cut from the treated boards and exposed at 45° angle facing south for a long-term test of natural weathering above ground in Uppsala (Sweden). The effect of solar radiation and humidity on the colour changes, water uptake, check propagation and chemical alterations was assessed during 20 months of exposure. The obtained results can serve as indication for the viability of the treatments. Samples impregnated with low retentions of ELO showed similar performance regarding check propagation and moisture uptake as samples with higher retentions. No significant difference between these samples was found regarding colour change which is mainly caused by blue stain fungi on the surface. In opposite, samples treated with MTES exhibited no consistent water uptake and check propagation unproportioned to the applied retentions. The spectra of ELO- and MTES-treated wood after weathering showed a significant decrease of the peak at 1510 cm^?1 indicating delignification of wood surface caused by weathering.     

Changes in surface properties of tropical wood species exposed to the Indonesian climate in relation to mold colonies

Changes in mold populations and genera on the exposed surfaces of tropical hardwoods — albizia (Paraserianthes falcata), kapur (Dryobalanop lanceolata), mahoni (Switenia macrophylla), nangka (Artocarpus heterophyllus), puspa (Schima wallchii) — were investigated. The wood specimens were exposed to the Indonesian climate for 32 weeks. Properties including mass loss, wettability, mold growth (colony-forming units), and mold genera were evaluated. The change in properties after exposure was significantly affected by the wood species, but there was no clear relation between mass loss and the initial chemical components or between wettability and wood density. The number of mold populations was different by exposure period and wood species, but there was no significant effect of climate conditions, such as rainfall and ultraviolet radiation. Of the genera identified,Aureobasidium, Cladosporium, andPenicillium were dominant molds on the exposed wood surfaces.     

Fungal colonisation of outside weathered modified wood

Specimens of Scots pine sapwood (Pinus sylvestris L.) and beech wood (Fagus sylvatica L.) were treated with an amino-alkyl-functional oligomeric siloxane, a sodium water glass solution and 1,3-dimethylol-4,5-dihydroxyethylene urea (DMDHEU). Treated and untreated wood specimens were exposed outdoors without ground contact. After 9?months of outside exposure, all specimens showed discolouration caused by infestations of mould and staining fungi on the exposed wood surface. Fungi grown on the sample surface were isolated and identified by microscopic technique and sequencing of PCR-amplified DNA from the ITS region. Primarily, an infestation by ascomycetes and related deuteromycetes was found. The most dominant fungi were Trichoderma sp. and Epicoccum sp.. An infestation of Aureobasidium pullulans was only detected on untreated and DMDHEU-treated samples. There were only marginal differences of fungal infestation between the two wood species.     

Depth profiling of weathered tropical wood using Fourier transform infrared photoacoustic spectroscopy

Depth profiling analysis of wood samples using Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) was carried out to obtain information on the chemical changes caused by weathering. The test samples used for PAS measurements were tropical wood species, puspa (Schima wallichii Korth) and kapur (Dryobalanop lanceolata Burck), that were exposed outdoors for periods of 2–32 weeks. FTIR-PAS spectra of the weathered surfaces were recorded at various moving-mirror velocities in the range from 0.081 to 0.56cm/s (linear-scan method) to provide the depth profiling analysis. The band intensity of vibrations attributed to phenyl groups clearly decreased as weathering proceeded and demonstrated a tendency to be reduced with a decrease in the photoacoustic probing depth during relatively short weathering periods. The bands of C=O groups also exhibited remarkable spectral changes. The PAS spectra of the tropical wood changed considerably during the 32 weeks of weathering, and their spectral contours gradually approached that of pure cellulose (microcrystalline). It was noted that FTIR-PAS is very useful for depth profiling analysis of the wood surface in the early stages of deterioration.     

Effects of radiational heating at low air temperature on water balance, cold tolerance, and visible injury of red spruce foliage

Recent studies have shown that winter needle mortality in red spruce (Picea rubens Sarg.) is increased by exposure to direct solar radiation, possibly as a result of photo-oxidative damage, accelerated winter desiccation, or reduced cold tolerance due to heating of sun-exposed needles. In an experiment at controlled subfreezing air temperatures of -10 to -20 degrees C, visible radiation was less effective than infrared radiation in producing needle desiccation and visible injury during freeze-thaw cycles. However, visible radiation produced a red-brown color in injured needles, similar to natural winter injury, whereas injured needles exposed to infrared radiation were yellow and injured needles kept in darkness were dark brown. Thus, visible radiation was necessary to produce the red-brown color of damaged needles, but not the injury itself. Needle desiccation was not strongly correlated with visible injury, but the pattern of variation in visible injury among trees and the positive correlation between electrolyte leakage and visible injury suggested that freezing damage following freeze-thaw cycles might cause the visible injury. This was confirmed by a second experiment that showed loss of cold hardiness in needles thawed by radiational heating for six consecutive days. Even with a constant nighttime temperature of -10 degrees C, six days of radiational heating of needles to above freezing caused a small (2.8 degrees C) mean decrease in needle cold tolerance, as measured by electrolyte leakage. Continuous darkness at -10 degrees C for six days resulted in an estimated 5.6 degrees C mean increase in needle cold tolerance. Freezing injury stimulated desiccation: cooling at 4 degrees C h(-1) to -43 or -48 degrees C increased the dehydration rate of isolated shoots by a factor of two to three during the first day after thawing. Within three days at 15 to 22 degrees C and 50% relative humidity, the mean water content of these shoots fell to 60% or lower, compared to 90% or greater for unfrozen controls or shoots subject to less severe freezing stress. In some but not all severely freeze-stressed shoots, accelerated needle desiccation and abscission were accompanied by a red-brown color typical of red spruce winter needle injury. We conclude that severe winter desiccation in red spruce may often be due to prior freezing injury, increased as a result of exposure to direct solar radiation. Furthermore, freezing injury in red spruce may sometimes cause desiccation and abscission of green needles.     

Effects of long-term,elevated ultraviolet-B radiation on phytochemicals in the bark of silver birch (Betula pendula)

Long-term outdoor experiments were conducted to investigate the effects of elevated ultraviolet-B (UV-B, 280-320 nm) radiation on secondary metabolites (phenolics and terpenoids) and the main soluble sugars (sucrose, raffinose and glucose) in the bark of silver birch (Betula pendula Roth) saplings. Saplings were exposed to a constant 50% increase in erythemal UV irradiance (UV-B(CIE); based on the CIE (International Commission on Illumination) erythemal action spectrum) and a small increase in UV-A radiation (320-400 nm) for three growing seasons in an irradiation field in central Finland. Two control groups were used: saplings exposed to ambient radiation and saplings exposed to slightly increased UV-A radiation. Concentrations of sucrose, raffinose and glucose in bark were higher in UV-treated saplings than in saplings grown in ambient radiation, indicating that stem carbohydrate metabolism was changed by long-term elevated UV radiation. Saplings in the elevated UV-A + UV-B radiation treatment and the UV-A radiation control treatment had significantly increased concentrations of certain UV-absorbing phenolics, such as salidroside, 3,4'-dihydroxypropiophenone-3-glucoside, (+)-catechin and (-)-epicatechin compared with saplings in ambient radiation. In contrast, the radiation treatments had no effect on the non-UV-B-absorbing terpenoids, papyriferic acid and deacetylpapyriferic acid. We conclude that plant parts, in addition to leaves, accumulate specific phenolic UV-filters in response to UV radiation exposure.     

Influence of wood moisture content and wood temperature on fungal decay in the field: observations in different micro-climates

In this study, Scots pine sapwood (Pinus sylvestris L.) and Douglas fir heartwood (Pseudotsuga menziesii Franco) specimens were exposed in double layer field trials at four different exposure sites and under different exposure conditions (in total ten test sets). The material climate of wood in terms of wood moisture content (MC) and wood temperature was automatically monitored over a period of 6 years and compared with the progress of decay. The aim of this study was to highlight the interrelationship between microclimate, material climate, and decay as a basis for the establishment of dose-response functions to be used for service life prediction of wood and wood-based products. Differences in resulting decay dynamics between the test sites as well as between the different types of exposure were quantified and discussed with respect to corresponding microclimatic and material climatic conditions. The time between the beginning of exposure and the first occurrence of visible decay varied between the sites and influenced the total decay development. The fundamental importance of direct decay factors, such as MC and wood temperature, were underlined and basic requirements for establishing dose-response-functions to be used in service life prediction models were derived.     

Laboratory and environmental decay of wood–plastic composite boards: flexural properties

The flexural properties of wood–plastic composite (WPC) deck boards exposed to 9.5 years of environmental decay in Hilo, Hawaii, were compared to samples exposed to moisture and decay fungi for 12 weeks in the laboratory, to establish a correlation between sample flexural properties and calculated void volume. Specimens were tested for flexural strength and modulus, both wet and dry, at 23°C and 52°C. Some specimens degenerated to only 15% of original flexural strength. UV radiation had no impact on flexural properties of field-exposed boards; loss occurred mainly on the side opposite to the sun-exposed surface. The mechanism of the aging process on colonization of WPC by fungi was examined and is consistent with development of slow crack growth in the polyethylene matrix combined with wood decay by fungi. Wood particle decay, moisture, and elevated temperature were the major factors causing composite degradation, indicated by accumulation of voids and a severe decrease in flexural properties. To simulate long-term field impact (including decay) on WPC flexural properties in the laboratory, conditioning of specimens in hot water for an extended period of time is required. Exposure to water (70°C/5 days) was adequate for simulating long-term composite exposure in Hawaii of 4?×?15?×?86 mm³ specimens.     

Weathering durability of CCB-impregnated wood for clear varnish coatings

Outdoor performances of a polyurethane varnish and an alkyd-based synthetic varnish coated over chromium-copper-boron (CCB)-impregnated Scots pine (Pinus sylvestris L.) and chestnut (Castanea sativa Mill.) [10 (R) × 100 (T) × 150 (L) mm] were investigated. These varnishes were also applied to the wood surface as sole coatings or impregnated into wood as water-repellent (WR) solutions. Outdoor exposure was performed in the Black Sea region of northern Turkey (41°N, 39.43°E) where humid weather predominates throughout the year and accelerates decomposition of coated wood surfaces. The wood panels were exposed at 45° south on their tangential surfaces. After 9 months of exposure to summer, autumn, and the following winter season, the color and glossiness changes of the exposed surface, adhesion of the coating layer to the wood surface, water absorption through the coating layers, mass loss, and the hardness of the board surface were studied. CCB impregnation greatly stabilized the surface color of varnish-coated panels of both wood species. Gradual decreases of adhesion between varnished layers and preimpregnated surfaces were attributed to probable weakening of interactions at the interface of the treated wood and the film layer. A superficial cleaning process of treated wood is suggested to improve glossiness and adhesion. The coated wood surface became harder with time on outdoor exposure until a maximum hardness occurred followed by softening, whereas the uncoated surface softened steadily. Polyurethane varnish yielded a harder surface than synthetic varnish. Mass losses of wood panels after 9 months of exposure were negligible for all treatments compared with the untreated controls, which were totally discolored and eroded on the surface. It is concluded that long-term exterior wood protection has been achieved by a successful combination of an appropriate preservative treatment followed by a compatible surface-coating process.     

木材光降解机理及研究进展

木材受紫外可见光照射后易发生降解, 表面的材色和力学性能都会下降, 大大影响木材的使用价值和美学特点。文中针对木材光降解机理进行了讨论, 在提出木质素是木材光降解中关键组分的同时, 强调了抽提物对木材光变色的具体影响; 通过详细叙述光降解过程中木材发生的化学变化, 进一步表明该过程中自由基中间体的生成和新的发色团的产生; 系统总结了影响木材光降解的主要因素, 并提出防治木材表面光降解的技术手段。     

Extractives relating to heartwood color changes in sugi (<Emphasis Type="Italic">Cryptomeria japonica</Emphasis>) by a combination of smoke-heating and UV radiation exposure

 Sugi green logs with red or black heartwood were smoke-heated, and the changes in the color of the heartwood after ultraviolet (UV) (λ = 365 nm) radiation exposure were then observed. After UV radiation exposure, the redness and yellowness increased in both the red and black heartwoods, whereas the brightness decreased. In the black heartwood, the resulting color turned from yellowish white to reddish brown. Reddening in black heartwood after exposure to a combination of smoke heating and UV radiation is thought to be due to a decrease in brightness and an increase in both redness and yellowness. However, the degree of change in heartwood color by UV radiation exposure was not greatly affected by smoke-heating treatments of various lengths. When methanol extracts were fractionated and exposed to UV radiation, the yellowness increased in the n-hexane-soluble portion and the redness increased in the acetone-soluble fractions from the n-hexane-insoluble portion. These results suggest that the n-hexane-soluble fraction contains the substances that allow heartwood color to change to yellow after UV radiation exposure, and the acetone-soluble-fraction from the n-hexane-insoluble portion contains the substances that allow it to change to red. Received: November 14, 2001 / Accepted: June 3, 2002 Acknowledgment This research was supported in part by a Grant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science. This study was presented in part at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001 Correspondence to:N. Yoshizawa     

Impregnated wooden claddings and the influence of nanoparticles on the weathering performance

Abstract

This work was an investigation of the effect of nanoparticles on the durability of wood specimens exposed to artificial weathering. TiO₂ and clay nanoparticles were mixed with preservative (Wolmanit CX-8) for improving the durability of Norway spruce (Picea abies). Impregnated and untreated specimens were subjected to Atlas Solar Simulator accelerated ageing test chamber for solar radiation and water spray exposure. The effectiveness of the treatment against colour and chemical changes was investigated using CIEL*a*b* colour measurements system and Fourier transform infrared analysis. The present study showed that the wood specimens that had been treated with preservatives containing nanoparticles were slightly more stable against artificial ageing than both untreated specimens and specimens treated with preservative alone.     

The feature of color alteration of bleached oak,beech, and black locust surfaces during artificial xenon radiation

Abstract

In Europe, large quantities of oak wood are available and industrial partners showed interest in bleached oak as oak's reinterpretation in order to reintroduce it on the design furniture market. In the present work besides oak two further wood species beech and black locust were also examined in comparison. Bleaching of beech has a relative well-established technique and can be done with good results with H₂O₂, contrary to oak where bleaching with the same agent results in a spotty discoloration of the surface with high-greenish incrust. A second substance is suggested to be used, to achieve the same significant bleaching effect for oak and black locust as for beech. As bleached wood surfaces are also subject to color changes due to sun radiation, bleached samples of the three wood species were exposed to artificial xenon radiation and their behavior was investigated, with focus on the influence of the type of application. Expecting industrial-scale application the possible influence of application type on the measure of total color change was also investigated. The feature of color development was described as exponential function of time for all three wood species and all three application methods.     

Microclimate and moisture content profile measurements in rain exposed Norway spruce (Picea abies (L.) Karst.) joints

In order to perform service life predictions of rain exposed wood structures, the moisture and temperature conditions in the structure need to be known as well as which degradation that occurs under those exposure conditions. The microclimate (the moisture conditions at the surface) is the boundary condition for moisture transport into the wood and depends on the detail design; joints between two pieces of wood can act as a water trap which give long durations of surface moisture after rain events and hinders drying. This study presents moisture content and microclimate measurements in three types of Norway spruce joints exposed to artificial rain in the laboratory. Both the microclimate (the duration of water on surfaces and in gaps) and the moisture content profiles were monitored. The microclimate was changed by changing the size of the gap between the two boards. The duration of water in the gap depended both on the gap size and on the permeability of the wood (sapwood/heartwood, end grain surface/side grain surface). In many cases, a larger gap width gave shorter durations of high moisture contents since a larger gap gave more favourable drying conditions, but the magnitude of this reduction varied between joint types.