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Laboratory evaluation of borate amine: Copper derivatives in wood for fungal decay
2010 - IRG/WP 10-30543
The aims of this study were to evaluate borate: amine: copper derivatives in wood for fungal decay protection as well as the permanence of copper and boron in wood. Wood treated with each of four derivatives of borate:amine:copper prevented fungal decay. Disodium tetraborate ecahydrate (Borax):amine:copper derivatives with retentions of 0.61 to 0.63% after water leaching prevented decay by Gloeophylum trabeum (Gt) and 0.64% by Trametes versicolor (Tv). Leaching did not decrease decay resistance to both Gt and Tv. Disodium octaborate tetrahydrate(DOT):amine:copper derivatives with retentions of 1.14 to 2.93% after water leaching prevented decay by Gt and 0.54 to 1.19 % by Tv. Leaching decreased decay resistance to Gt but not to Tv. Higher copper and boron in disodium borax:amine:copper derivatives contributed to more decay resistance to Gt and Tv than that of DOT:amine:copper derivatives as evidenced by elemental analysis. Infrared spectra (IR ) of wood treated with 5% borate: amine: copper derivatives after water leaching showed that increased absorption at 1632-1635 cm-1 compared with the control. The increased absorption at 1632-1635 cm-1 was partly attributable to carbonyl of copper carboxylates from oxidation of hemiacetals of hemicelluloses and cellulose by copper (II) ions, and carbonyls of copper (II) quinone methides by oxidation of guaicyls by copper (II) ions. It was also partly attributable to carbonyls of copper carboxylates from hemicelluloses and phenolates from lignin through ion exchange reactions. The above oxidation and ion exchange reactions of copper with wood components may account for their efficacy and long term performance.
G Chen


Borate Redistribution in Glulam in an Above Ground Field Test
2014 - IRG/WP 14-30652
Researchers have refocused on the use of boratesin the wood protection industry in the last two decades due to their broad spectrum effectiveness against fungi and insects, and favourable environmental characteristics. This study was designed to determine borate distribution in a limited number of samples from a large field test of composites protected by a combination of coating and borate treatment by two processes.The intended application of these products was exterior components of buildings with considerable protection by design, but the test method was designed to be a much more severe exposure. A variety of structural composites had been machined into ɣ-joint test samples, then borate-treated by two methods: a surface-applied penetrating process, and a dip treatment with borate/glycol plus insertion of copper/borate rods.After application of the coating the test samples had been installed in a long-term above-ground outdoor weathering trial at FPInnovations’ Maple Ridge, British Columbia test site. After seven years of exposure, selected glulam beams of black spruce, white spruce, and Douglas-fir samples were destructively sampled and analyzed for borate retention and penetration, with results compared to unexposed material.Results showed that borateshad migrated from the surface of exposed samples to inside the wood, as deep as 50 mm, and in many samples were present in concentrations that would be sufficient to prevent fungal decay.
P I Morris, A Temiz, J Ingram


Effectiveness and synergistic effects between copper and polymer betaine
1996 - IRG/WP 96-30097
Different formulations of "Copper Amine" and Polymer Betaine were studied. During laboratory tests a synergism between both active ingredients against soft rot and dry rot has been found. The efficacy against soft rot according to the "BAM method" and the European Standard ENV 807 depends only on the amount of copper. Long term tests in a fungus cellar for determining the relative protective effectiveness in ground contact show similar results as CCA-treated wood.
H Härtner, V Barth


Contribution of wood components on the absorption of copper amine
2000 - IRG/WP 00-30216
The contribution of wood components on the absorption of copper amine was investigated. Holocellulose, lignin and xylan absorbed significant amount of copper. The amount of copper absorbed by cellulose was almost negligible. The removal of extractive also decreased the amount of copper absorption. This study clearly indicates the importance of lignin, hemicellulose in the absorption of copper amine in wood.
D P Kamdem, Jun Zhang


Ten year field test with a copper-borate ground line treatment for poles
1993 - IRG/WP 93-30017
A wood preservative paste consisting of borax and copper naphthenate has been tested to determine its efficiency in protecting wood from decay fungi and insects. The paste was applied to polyethylene-backed wraps that were fastened to the below-ground portions of unseasoned southern pine pole stubs. After 4 years of exposure in Mississippi, the untreated control stubs were completely deteriorated. The below-grade portions of the treated stubs remained sound after nearly 6 years of exposure due to movement of copper and diffusion of the borate throughout the cross section. Borate and copper also moved vertically in the stubs and was present in sufficient amounts to protect sections of the stubs as high as 3 feet above grade. After 9 years of exposure, the below-grade portions of the treated stubs had limited areas of decay and no termite damage; the majority of the cross section remained sound. Wood analysis indicated that concentrations of borate in the sound areas were about 1/10 the estimated toxic threshold. A visual examination and push test indicated that the treated stubs continued to be protected at groundline after 10 years of exposure. It is hypothesized that the continued protection of the below-grade portions of the stubs against both decay fungi and subterranean termites is the result of copper-borate complexes that have formed in the wood.
T L Amburgey, M H Freeman


A Preliminary Report on the Properties of Engineered Wood Composite Panels Treated with Copper Naphthenate
2005 - IRG/WP 05-40294
This paper reports on our preliminary investigation of the properties of randomly oriented strandboard which had waterborne or powdered copper naphthenate (CuN) incorporated into the board during manufacture. When compared to zinc borate-treated controls (ZnB), the mechanical properties of strandboard (MOR, MOE, work-to-maximum load, internal bond strength) were not adversely affected by treatment with either form of copper naphthenate. In general, values for mechanical properties followed the trend untreated controls > waterborne CuN = powdered CuN > ZnB. Water absorption and dimensional properties followed a similar trend. This preliminary study suggests that CuN is a viable alternative treatment for engineered wood composites.
J W Kirkpatrick, H M Barnes


Evaluation of the corrosivity of the treated wood - Laboratory vs field test methodologies
2000 - IRG/WP 00-20211
The corrosivity of treated wood to fasteners has been evaluated using laboratory test procedures, including AWPA Standard E12-94. The standard method was modified in order to allow detailed study of commercial metal fasteners in terms of sample types, installation configuration and exposure conditions. Parallel field tests were also performed. The experimental results generated from these tests suggest that the laboratory test methods accelerate metal corrosion relative to the field performance conditions for only certain preservative treatments. The influence of performance properties of water repellent treated wood on the corrosivity testing methods is also discussed.
L Jin, A F Preston


Evaluating the natural durability of native and tropical wood species against Reticulitermes flavip
2004 - IRG/WP 04-10539
Environmental pressures to eliminate arsenate from wood preservatives has resulted in voluntary removal of CCA for residential applications in the United States. A new generation of copper organic preservatives has been formulated to replace CCA for decking and in-ground applications but there is no guarantee that these preservatives represent a permanent solution to all related problems. Therefore, it is still necessary to evaluate alternative treatments, as well as naturally durable wood species, in order to be prepared for future changes in the field. In this study, six hardwoods and six softwoods have been evaluated for their ability to resist termite damage by Reticulitermes flavipes in a 4-week laboratory no-choice test. In addition, moderately resistant Douglas-fir and southern pine wood blocks were evaluated after treatment with copper borate, copper naphthanate, and N,N-naphthaloylhydroxylamine (NHA). Erisma, juniper, ipe and white-cedar were shown to be highly resistant. NHA protected Douglas-fir and southern pine as effectively as copper borate or copper naphthanate. These results suggest that some naturally durable wood species, both tropical and native, can inhibit R. flavipes as effectively as preservative treatment.
R A Arango, F Green III, K Hintz, R B Miller


Remedial ground-line treatment of CCA poles in service. Results of chemical and microbiological analyses 6 months after treatment
1986 - IRG/WP 3388
CCA-treated poles in service with incipient internal soft rot were remedially treated by inserting borate rods, brushing with a boron/glycol solution and injecting boric acid paste, copper/creosote paste or a commercial product (DFCK paste). The spread of active chemicals in the treated zone as well as the change in microflora have been studied with time. After six months chemicals had spread to most parts of the pole in the ground-line zone and the microflora had been changed - in some cases drastically. The test is still in progress. Chemical and microbiological analyses after 12, 28 and 60 months will be published at a later date.
B Henningsson, H Friis-Hansen, A Käärik, M-L Edlund


Adsorption of ACQ and CuMEA Wood Preservatives in Red pine
2005 - IRG/WP 05-30374
The rates of stabilization or fixation of ACQ subcomponents (CuO, DDAC and MEA) in red pine (Pinus resinosa) were compared for different solution concentrations (0.75%, 1.5%, 2.25% and 3% ACQ-D) and post treatment conditioning temperatures. Preservative solutions were impregnated into red pine sapwood by a full-cell treatment. Copper and MEA adsorptions from copper monoethanolamine solutions without DDAC were also evaluated for comparison. After the treatments, samples were conditioned without drying either at 22° C for seven weeks or at 50° C for one week. At different times after treatment, expressate from the specimen blocks was analyzed for copper, DDAC and MEA. Copper and MEA adsorption by the wood cell walls followed similar trends. The equilibrium copper adsorption ranged from 44% at high ACQ retentions to about 95% for the lowest retention while the values in the CuMEA system were slightly higher for the higher retentions, ranging from about 54% to 93%. This suggests that DDAC may compete with CuMEA for reaction sites at high ACQ concentrations. Adsorption of DDAC into the wood cell wall matrix was rapid; at all solution concentrations, more than 80% of DDAC was adsorbed by red pine sapwood within minutes after treatment.
C Tascioglu, P A Cooper, Y T Ung


Field performance of novel antisapstain formulations
1997 - IRG/WP 97-30125
The effectiveness as antisapstain formulations of combinations of oxine copper (Cu-8), carbendazim, hexaconazole, cyproconazole, flusilazole, didecyldimethyl ammonium chloride (DDAC), an alkanolamine borate (SB), benzalkonium chloride (BAC), 2-n-octylisothiazolin -3-one (isothiazoline) and p-chlorophenyl-3-iodopropagilformal (CPIPF) was determined for freshly sawn, block-stacked radiata pine in three 18-week field trials: 1. Established in summer 1992 evaluating combinations of hexaconazole, carbendazim and DDAC. 2. Established in autumn/winter 1994 evaluating combinations of hexaconazole, carbendazim, DDAC, BAC and SB. 3. Established in autumn/winter 1995 evaluating combinations of triazoles, DDAC, Cu-8, carbendazim, CPIPF, isothiazoline and SB. Reference standards included: Cu-8; Cu-8 + carbendazim; IPBC + DDAC and TCMTB. In all tests, formulations containing carbendazim + hexaconazole + DDAC gave better protection for 12 and 18 weeks than most other experimental formulations and were equal to or better than commercial standards.
D R Eden, R N Wakeling, C M Chittenden, J G Van der Waals


Tests with ammoniacal copper and alkyl ammonium compounds as wood preservatives
1984 - IRG/WP 3299
Formulations based on copper and alkyl ammonium compounds in ammonia solution have been tested in a fungus cellar on Pinus radiata and Fagus sylvatica. This type of products gives promising results as wood preservatives, especially on hardwood and are safe to destroy by e.g. combustion. The best results were achieved with a dialkyl ammonium compound, Cu/octyldecyl dimethyl ammonium chloride (NH3). The optimal weight ratio of Cu/AAC is for Pinus radiata = 0.2-0.4 and Fagus sylvatica = 1.0 based on cost-effectiveness. Fixation and leaching of coppertetrammine are discussed in detail. The leaching of active components from the Cu/AAC/NH3-systems is very low.
C-E Sundman


The effect of pretreatments on the impregnation of air-dried sawn Belgian spruce
1988 - IRG/WP 3490
In general the impregnation of airdried spruce results in a variable treatment and limited penetration. This is the result of pit aspiration that occurs during drying of the spruce sapwood and heartwood. Spruce timber is becoming of greater importance in Belgium and hence research for better treatment of this vulnerable wood species is needed. Squared airdried timber of different dimensions were extracted from 10 winter-felled logs (Picea abies (L.) Karst) and impregnated with preservative used for constructional purposes. Partly the material was presteamed or waterlogged. Prior to the preservative treatment both groups were reconditioned to the same moisture content as the reference material (airdried). Retention and different penetration parameters showed better figures when only modifying the treating cycle rather than using a pretreatment. Both pretreatments seemed to have no positive effect on the treatability of airdried material. Increasing the strength of the initial vacuum parameters of the full-cell processes improved the degree and homogenity of the penetration of the preservative components.
J Van Acker, M Stevens


Influence of carboxylic acids on LEACHING of copper amine based preservatives
2005 - IRG/WP 05-30365
The importance of chromium free preservatives is increasing. Leaching of copper from wood preserved with such solutions is still higher compared to leaching from wood impregnated with copper chromium ones. In order to decrease leaching, different carboxylic acids (octanoic, 2-etilheksanoic, decanoic) were added to copper/amine/boron aqueous solutions. Experiment of leaching of copper from Norway spruce (Picea abies) was performed according to the modified standard procedure (EN 1250). Results presented in this paper showed, that carboxylic acids significantly improve copper fixation. The best one was determined at specimens impregnated with the preservative solutions consisting of copper, ethanolamine, boric acid and octanoic acid.
M Humar, P Kalan, F Pohleven


Diffusion modeling of inorganic wood preservative leaching in service
2005 - IRG/WP 05-50224-5
To evaluate the potential environmental and health implications of leaching of inorganic wood preservatives in service under different conditions, there is a need for a predictive model that provides estimates of the rate and extent of leaching over a wide range of product dimensions and exposure conditions. In this paper, we show that the leaching behavior of inorganic preservative components from wood in continuous water contact can be characterized by three easily measured parameters: total leachable component (Le) based on intensive leaching of fine ground material; amount of dissolved or dissociated component (Di) in water saturated wood; preservative component diffusion coefficients (Dt,l) in the transverse and longitudinal directions. Use of the applicable D and Di or Le in a diffusion model allows the prediction of total amount leached and emission rate at different times of exposure. Both D and Di increase somewhat with increasing ambient temperature. Laboratory determined parameters for alkaline copper quaternary (ACQ), copper azole (CA), chromated copper arsenate (CCA) and borate (DOT) wood preservatives are used to predict leaching rates from larger lumber samples. Preliminary comparisons of predicted leaching with measured leaching of larger samples in laboratory and natural rain exposure indicate that the approach is surprisingly effective at predicting leaching performance but some model refinements are needed for some components such as copper in CCA to account for the slow dissolving of a component of the preservative available for leaching.
L Waldron, P A Cooper, Y T Ung


Determination of the amine to copper ratio remaining in wood after leaching
2002 - IRG/WP 02-30285
The effectiveness of the protection and the environmental impact of the treated wood are two of the most important aspects that need to be understood for all preservatives. Both are particularly influenced by the loss of biocidal components from treated wood. For amine copper preservatives, copper fixation determines the leaching resistance of the copper and amine compounds formed in wood. Previous research has suggested that the degree of copper fixation may be influenced by the amine-copper formulation (including the type of amine), the copper concentration and the ratio of the amine to copper in the treating solution. However, the relationship between amine and copper concentration and the fixation efficiency is not fully understood. The purpose of this study is to determine the influence of a) the type of amine, b) the concentration of copper, and c) the amine to copper mole ratio, on the fixation chemistry of amine-copper preservatives.
N Lucas, J N R Ruddick


Weathering of copper-amine treated wood
2000 - IRG/WP 00-40155
Copper ethanolamine (Cu-EA) treated southern pine (SP) were artificially weathered with a QUV Weathering Tester. The weathering regime was composed of a continuous UV-light irradiation for 2 hours followed by a water spray for 18 minutes for a total time of 1200 hours. The changes on the surface of the weathered samples were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, color and contact angle measurements. FTIR indicates that Cu-EA treatment can retard the surface degradation during weathering. The reduction of the peak intensity at 1510 cm-1, characteristic of the wood lignin was less pronounced for Cu-Ea treated wood than for untreated or ethanolamine treated wood. This reduction in 1510 cm-1 intensity decreases with the increase of copper EA retention in treated wood. The color change expressed by the value of DE indicated that untreated and Cu-EA treated wood change color rapidly during the first 200 hours irradiation and the color change remained relatively constant thereafter. The values of DE for untreated and ethanolamine treated sample were higher than the values of Cu-Ea treated. Changes in the lightness of wood samples were also observed with the duration of irradiation. The lightness of untreated and Cu-MEA treated samples decreased during the first 100-hour weathering. These samples regained their lightness after 100 hours irradiation. For samples treated with copper concentration above 0.25%, the change in lightness was rather small. The contact angle measurement indicates that the wettability of wood surface increases with the duration of QUV exposure. Untreated and MEA treated wood samples changed contact angles rapidly, and The contact angle of untreated and ethanol amine treated samples dropped from about 75"5 degree to zero after 600 hours artificial weathering. Treatment with Cu-MEA can slow the decreasing in contact angle. After 1200 hours, the contact angle of Cu-EA treated wood dropped from 100 to a minimum between 25 and 60 degree. As the copper concentration increases, the rate of changing contact angle decreases. This study suggests that a copper amine treatment increases the hydrophobic and the resitance to photodegradation.
J Zhang, D P Kamdem


Preservative treatment of green timber by soaking in ammoniacal copper borate
1984 - IRG/WP 3292
Freshly sawn boards of radiata pine sapwood were preservative treated by soaking in ammoniacal copper borate. Optimum schedules were obtained by partially seasoning the boards for one week prior to treatment. This aided the absorption of preservative and reduced the required soaking time to approximately 2 hours. Complete boron penetration was obtained after one week of block storage under cover and air drying. Copper penetration was more limited because of fixation of copper. The preservative treatment system should have particular application in the treatment of coconut timber destined for above-ground use but exposed to the weather.
P Vinden, A J McQuire


Amine copper reaction with wood components: acidity versus copper adsorption
1997 - IRG/WP 97-30161
The bonding sites for copper in wood from CCA, as well as ammoniacal/amine based systems, has long been a topic of investigation. Both phenolic and carboxylic functional groups have been discussed as potential bonding sites for copper. However, no consensus on the adsorption mechanism has been realized. Thus, the selective adsorption of copper in southern yellow pine from ethanolamine-copper solutions and its correlation to wood acidity is currently being investigated. The wood acidity has been determined by acid/base titration, and is due to more than one type of acidic group. The acid(s) can be removed by thermal treatment or extraction techniques, and, interestingly, the selective adsorption of copper was observed to track the presence of particular acid functionalities. The preferential adsorption of copper and the mechanisms behind such will be discussed.
S M Thomason, E A Pasek


Interaction of copper-amine complexes with wood: Influence of copper source, amine ligands and amine to copper molar ratio on copper retention and leaching
1999 - IRG/WP 99-30203
The absorption and leachability of copper in copper amine (Cu-EA) treated wood are influenced by the formulation and the composition of copper amine treating solutions. The sources of copper used, Cu(OH)2, CuCO3, CuSO4 and Cu(NO3)2, in the copper amine complex formulation affect the leachability of copper. Data show that copper amine from CuSO4 and Cu(NO3)2 treated wood has less copper loss during laboratory water leaching than those from Cu(OH)2 and CuCO3 treated wood. Increasing amine to copper molar ratio increases the copper retention by wood, but reduces the leaching resistance of copper. The nature of amine ligands, such as monoethanolamine (primary amine), 2-methylamino-ethanol (secondary amine) and N, N-dimethyl-ethanolamine (tertiary amine), has some effect on copper retention and copper leaching. As the molecular weight of amine ligands increases, copper loss during leaching decreases.
Jun Zhang, D P Kamdem


Upgrading the fungal resistance of OSB
1999 - IRG/WP 99-40138
There is a perception that oriented strand board (OSB) is less resistant to fungl than plywood under conditions of moderate exposure to moisture. Douglas fir-faced plywood (DFP) has been suggested as a benchmark for acceptable durability under such conditions. This project was initiated to determine the minimum level of low-toxicity chemical treatment needed to upgrade the fungal resistance of OSB, made from aspen, to equal that of DFP. Against a brown-rot fungus in a soil-block test, 0.2% zinc borate (ZB), added during manufacture, and subsequent spray treatment with 10 µg/cm2 oxine copper provided the required performance. Against a white-rot fungus 0.2% ZB alone was sufficient and between 0.1 and 0.2% may have been adequate. For resistance to mould in a humidity chamber, spray treatment of OSB with 10 µg/cm2 oxine copper provided equivalent performance to DFP. The recommended combination of treatments for moderate moisture exposure is 0.2% zinc borate and 10 µg/cm2 oxine copper.
P I Morris, J E Clark, D Minchin, R Wellwood


Copper borate for the protection of engineered wood products
2006 - IRG/WP 06-40334
Copper borate was evaluated for use in protecting oriented strand board (OSB) from mould, decay, and termites. Aspen OSB bonded with either phenolic or isocyanate resin was treated with several formulations of copper borate at various loadings from 0.26 to 4 percent by weight. These panels were then tested to determine the impact of the preservative on mechanical properties as well as resistance to fungal decay, mould, and Formosan termite attack. With proper resin selection, acceptable panels could be produced with both phenolic and isocyanate resin. The 10% copper hydroxide formulation of copper borate provided superior protection against mould, while all formulations tested gave adequate protection against fungal decay and Formosan termite attack. This paper summarizes over 5 years of research and the production of several hundred panels.
R Smart, W Wall


Biological efficacy of micronized copper systems
2008 - IRG/WP 08-30485
Soil block, fungal cellar and field stake test data will be presented for micronized copper systems. The copper portion of the formulations is present as a fine dispersion of "micro" particulates while the co-biocide is present as either a soluble quat or an azole containing emulsion. This testing generally used the amine based counterpart as the control preservative system and the micronized formulations perform as well or better than the amine formulations. In 5 year field stake tests in Gainesville, FL, the micronized copper quaternary formulation significantly outperformed the amine copper quaternary formulations. Strength and fixation testing is also discussed.
C R McIntyre, M H Freeman


Laboratory Studies on Copper Availability in Wood Treated with Soluble Amine Copper and Micronized Copper Systems
2008 - IRG/WP 08-30489
A laboratory method has been employed to investigate the level of soluble copper in wood treated with various copper-based preservative systems, such as micronized copper (particulate copper) and amine copper solutions. This report describes the methodology and preliminary results on determination of the soluble copper in the treating solutions and the treated wood by these systems, as well as the potential impact on performance of such systems against wood decay fungi.
L Jin, P Walcheski, A Preston


Adsorption of ACQ components in wood
2010 - IRG/WP 10-30522
To investigate the chemical adsorption capacity of copper-monoethanolamine (Cu-Mea) components on wood, the Na+ cation exchange capacity (CEC) of red pine (Pinus resinosa Ait.) was determined and compared to the adsorption capacity of free Mea and Cu-Mea complexes. The CEC increased with increasing pH. Free Mea adsorption as a function of pH followed the sodium adsorption curve except at pH over 9, when it exceeded the CEC. Cu-Mea adsorbed up to the CEC at pH 9.0-9.5 apparently as Cu(Mea)+, whereas the complex in solution is predominantly of the form Cu(Mea)2+. For the quaternary ammonium compound, alkyl dimethyl benzyl ammonium chloride (ADBAC) adsorption isotherm showed two different adsorption mechanisms into wood: ion exchange reaction at low concentration and hydrophobic interaction at high concentration. ADBAC adsorbed at solution concentrations below a critical concentration (hemi-micelle concentration) had high leaching resistance while ADBAC adsorbed into wood at above the critical micelle concentration (CMC) had low leaching resistance. The CMC decreased with addition of Mea and Cu-Mea. The anion, Cl- of ADBAC was only adsorbed at solution concentrations above the CMC and was easily leached out. The adsorption capacity of ADBAC into wood by cation exchange reaction did not achieve the cation exchange capacity (CEC) of wood. However, the total adsorption of ADBAC and Cu achieve the CEC of wood in the presence of copper amine, and ADBAC competes with copper to occupy the same sites in wood.
Myung Jae Lee, P Cooper


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