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Effect of Nano and Micronized Particles as Wood Preservatives for Termite Control
2013 - IRG/WP 13-30620
Subterranean termites are a major factor in the biodegradation of wood constructor products. In this study the efficacy of wood treated with micronized copper, zinc oxide and their mixture was compared to that of wood treated with soluble amine copper oxide with subterranean termites in a laboratory test. All of the formulations tested were effective in controlling wood degradation by the termites, with the copper being slight more effective than zinc and micronized copper being slightly more effective that amine copper.
M Akhtari, D Nicholas, A Rowlen, M Arefkhani

Effect of Nano and Micronized Particles as Wood Preservatives for Termite Control
2013 - IRG/WP 13-30620
Subterranean termites are a major factor in the biodegradation of wood constructor products. In this study the efficacy of wood treated with micronized copper, zinc oxide and their mixture was compared to that of wood treated with soluble amine copper oxide with subterranean termites in a laboratory test. All of the formulations tested were effective in controlling wood degradation by the termites, with the copper being slight more effective than zinc and micronized copper being slightly more effective that amine copper.
M Akhtari, D Nicholas, A Rowlen, M Arefkhani

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

Buffered Amine Oxide Treatment Systems for Ammonical Copper Wood Preservatives
2014 - IRG/WP 14-40685
Wood is the most versatile, practical and sustainable building material in the world. In modern countries, wood is a well-managed renewable resource that has a small carbon footprint. Wood does suffer from a lack of durability against invasive organisms such as insects and fungi. Steel, aluminum and composites have emerged as viable alternative building materials. These sectors market the deficiencies of wood to better position their products. As these materials continue to take market share away from wood, the need to cost-effectively increase the durability of wood remains an always present target within the forest products industry. The use of chemical treatments to impart fungal and insect resistance into wood has been utilized for over a century. Today, many of these preservatives are delivered into the wood using the same decades-old methods and chemicals. The development of buffered amine oxides treatment systems (known commercially as TRU-CORE® Technology) for use in wood preservation has allowed significant modernization of the application and preservation process. The buffered amine oxides allow for a chemically based infusion process that is capable of delivering key wood protectants completely throughout the wood. This waterbased system imparts a minimal amount of added moisture into the wood during the process, so there is no need to dry after treatment. A short activation period is utilized to achieve full penetration. For larger wood profiles, such as decking members and railroad crossties, the use of pressure/vacuum impregnation accelerates the penetration. The Buffered Amine Oxide Treatment System is in commercial use in the United States, New Zealand and Australia; where numerous programs have been developed for residential and industrial wood products. The most modern buffered amine oxide treatment system was designed to impart ammonical copper based wood preservatives into decking profiles.
R W Clawson Jr

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

Rapid leaching test
1991 - IRG/WP 2367
An accelerated test which is suitable for measuring the extent of metal fixation in both chromium and non chromium containing preservatives is described.
J A Cornfield, M Bacon, A Lyman, C Waldie, M R Gayles

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

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

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

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

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

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

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

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

Copper preservative systems: A rapid investigation into effects of co-biocides and used treating solutions
2010 - IRG/WP 10-30541
The efficacy of various micronized and amine copper preservative systems was evaluated using soil block testing with the copper tolerant brown rot fungi, Postia placenta. The American Wood Protection Association E22 protocol was used to compare the relative efficacy of preservatives by monitoring compressive strength losses of the systems in southern pine wood. As information, the weight losses were also measured and the relative ranking of the systems was the same by either methodology. Generally, the micronized and amine systems with co-biocides performed very well while systems without a cobiocide did not. Used treating liquids obtained from operating plants did not show any significant differences in performance compared to virgin liquids of the same system.
T F Shupe, K Ragon, Q Wu, M H Freeman, C R McIntyre

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

Studies on Effect of pH on Copper Availability in Copper-Based Preservatives
2010 - IRG/WP 10-30549
Laboratory methods have been employed to investigate the pH effect on the copper solubility of basic copper carbonate. The pH was controlled using two different approaches. One was with the adjustment of pH of the solutions by acid or base using sulfuric acid or sodium hydroxide until the solution equilibriums were obtained for each defined pH. A second approach was to control pH with buffer solutions to provide the designated pH range. Differences in copper solubility at the same pH with these two approaches were observed. The results generated from this study are compared with previously presented data and are discussed in terms of the influence of methodology, potential interactions of component(s) and the effect of the pH control agents.
L Jin, P Walcheski, A F Preston

Influence of Copper Preservative Type on Earlywood and Latewood Distribution of Copper in Treated Wood
2010 - IRG/WP 10-40507
Some of the new water based copper containing wood preservative systems use particulate “micronized” copper as the primary biocide instead of the more traditional soluble amine copper based systems. Studies were conducted to investigate how this difference in the type of copper system might impact both initial and post drying distribution of the preservatives in wood. Of specific interest was to determine the influence of the copper type on the distribution in earlywood and latewood portions of southern pine lumber, where significant differences in wood density might impact preservative loadings for the soluble and particulate systems. Our results support that the copper distributions were distinctly different between the two systems in air-dried boards, although amine copper treated boards had a similar copper distribution immediately after treatment to that observed in dry micronized copper treated boards. Both the air-dried boards treated with micronized copper and the freshly treated amine copper treated boards had distinctly higher copper concentrations in the early wood bands than in the latewood bands on a wood mass basis. After air-drying, this difference is dramatically reduced in all but the outermost growth rings in the amine copper treated boards, suggesting some copper redistribution on drying, as well as copper binding to the wood substance in direct ratio to the amount of wood substance present.
A Zahora

Standardized Field Trials with Micronized Copper
2011 - IRG/WP 11-30564
In 2008, an extensive review of all available data from standardized tests of micronized copper systems was published and there has been considerable work since then. This paper discusses over 20 field stake trials underway in well-known sites such as Gainesville, FL, Hilo, HI and the Dorman and Saucier sites in MS as well as tests from Australia and New Zealand. In addition, 4 ground proximity tests from HI and 3 ground proximity tests from MS are discussed. The micronized formulations are showing good performance in all of these field trials with standardized tests. In some tests, the micronized formulations are performing better than the amine soluble counterparts.
C R McIntyre, M H Freeman

The potential for using CuO nanoparticles as a wood preservative
2011 - IRG/WP 11-30569
The potential for using nano-copper particles for wood protection was investigated using mini-agar slant and wood block tests with Gloeophyllum trabeum or Trametes versicolor. Nano-copper was more effective against G. trabeum than T. versicolor, although neither of these fungi would be considered copper tolerant. Nano-copper solutions were stable over a 17 week storage period, but precipitated when subjected to a vacuum or when wood was added to the solution. The results suggest that nano-copper has potential as a wood protectant, but much more research will be required to understand the properties of this material.
I S Weitz, K Knani, M Maoz, C Freitag, J J Morrell

Further Studies on the Distribution of Copper in Treated Wood Using an XRF Microscope Technique
2011 - IRG/WP 11-40549
There are two distinct forms of copper in aqueous copper based wood preservative systems that are currently used in the United States for treatment of southern pine lumber. These are systems using either soluble copper (typically amine based) or the more recent particulate or “micronized” copper as the primary biocide. Studies reported last year showed that there were distinct differences in the gross distribution of the copper in the high density late wood and low density early wood with treatments using these two forms of copper. This study was to further investigate these two systems using an x-ray fluorescence (XRF) microscope to provide further data on the qualitative and quantitative distribution of these two forms of copper in southern pine wood and the impact of wood structure on this deposition. Commercially treated lumber treated with ACQ type D, MCQ, and MCA were selected and analyzed by XRF in cross-section in areas showing both a strong color reaction as well as an incomplete or streaky color reaction when tested with a standard spot test copper indicator. Distinctly different patterns of copper distribution were observed with the two forms of copper, with a much more uniform distribution resulting with the soluble copper system than observed with the particulate system. Both systems deposited high concentrations of copper in the resin canals and in rays, but whereas distribution tended to be very uniform across and within the early and latewood bands in the soluble system, with the particulate systems it was comparatively low in the latewood bands, high near the surface, and produced an overall streaky distribution pattern (radial orientation) throughout the treated zone. Discussion is also presented on interpretation of the XRF micrographs including how deep it is detecting copper, as well as influence of sample orientation on results.
A Zahora

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