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Influence of different fixation and ageing procedures on the leaching behaviour of copper from selected wood preservatives in laboratory trials
2003 - IRG/WP 03-20264
The paper focuses on the role of different parameters, such as fixation, sample size, wood species, and leaching in internationally standardized ageing procedures for wood preservatives from Europe, Japan and the United States. The leaching protocols used were EN 84, JIS K 1571 and AWPA E11 protocols. The wood species were Scots pine, Sugi and Southern Yellow Pine respectively. Three types of commercially important copper-based wood preservatives were used as model formulations, namely copper/copper-HDO, ammoniacal copper/quat and CCA. The most important factors determining the extent of copper leaching in the different lab trials were the sample size (volume/surface ratio) and the fixation conditions prior to leaching. On the other hand, the wood species and the leaching protocol itself were found to have only minor influence on the copper leaching rate in the test methods included in this study.
J Habicht, D Häntzschel, J Wittenzellner
Problems of fixation of CCA-preservatives in palm-wood
1985 - IRG/WP 3338
Palm-wood may be used for posts and poles where it needs proper treatment for long time use. Based on observations by W. Killmann on low CCA-fixation in palm-wood, samples of Jubaea-palm grown in a Greenhouse at Hamburg, have been treated in two different series with a 4% solution of CCA-type B. After 1-16 weeks of storage the blocks were split into sticks of 1-2 mm² and leached. In all series 50% of the chromium and copper content of the individual blocks was leached independent of the time of storage, whereas simultaneously treated pinewood samples showed complete fixation after 4 weeks of storage.
H Willeitner, K Brandt
The influence of previous anti-blue-stain preservative treatments on the fixation of CC in spruce
1997 - IRG/WP 97-30134
Freshly cut and kiln dried spruce boards were treated with 4 different anti-blue stain preservatives (ABP). After a period of 10 days allowing the samples to dry and fixate, the samples were treated with CC (chromium, copper formulation) using a vacuum pressure cycle. After impregnation the wood was steam fixed. A submersion leaching test showed differences in the leachable quantity of copper and chromium. When related to the retention of both salts after impregnation, no differences could be found between samples previously treated with anti-blue-stain preservatives and untreated samples. However, the retention of CC diminished significantly by application of quaternary ammonium compounds.
M Van der Zee, W J Homan
Copper naphthenate-treated Southern Pine pole stubs in field exposure. -Part 2: Chemical characterization of full size pole stubs 12 years after treatment
2000 - IRG/WP 00-30246
This study examines the influence of pre-treatment and post-treatment steaming on the character and physio-chemical nature of copper naphthenate in hydrocarbon solvent treated pine in larger, pole diameter, pole stub-length samples. This work is the continuation of two projects that began almost a decade ago. Previous reports indicated that certain morphological changes might occur in small laboratory steamed samples of copper naphthenate treated southern pine. Toluene-methanol extraction, UV-Vis spectroscopy, X-ray diffraction (XRD) and environmental scanning electron microscopy (ESEM) were used to investigate the nature and properties of the copper naphthenate present in the wood after 12 years of exposure. The formation of solid cuprous oxide occurred regardless of pre- or post-steaming conditioning.
H M Barnes, D P Kamdem, M H Freeman
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
Copper binding capacity of modified wood flour
1992 - IRG/WP 92-3709
Wood flour was modified by reaction with oxidising agents and CCA preservative. The copper chromium and arsenic were removed from the CCA treated wood flour by an acid leaching procedure. The modified wood flours were allowed to react with copper acetate solution and the level of copper fixation achieved was determined. The modified wood flours had greater affinity for copper ions present in solution than unmodified wood flour.
N C Milowych, W B Banks, J A Cornfield
Literature survey on the permanence and distribution of salt-type wood preservatives
1969 - IRG/WP III 1B
The objective of this survey is generally to review some of the more important published work dealing with the distribution and permanence of salt-type waterborne wood preservatives in treated timber. The survey is limited to the major chrome-containing formulations and the classification system proposed by Becker (1964) has been adopted throughout. CK - chromium, copper (copper, chrome); CKA - chromium, copper, arsenic (copper, chrome, arsenate); CKB - chromium, copper, boron (copper, chrome, boron); CFK - chromium, fluorine, copper (copper, chrome, fluorine); CFA - chromium, fluorine, arsenic (fluor, chrome, arsenate); CF - chromium, fluorine (fluor, chrome). The literature compilation covers the performance of these preservatives assessed from laboratory tests, field tests and practical experience; their application and distribution in the treated wood; and their influence on materials such as glues, paints or metals and the wood itself. It is not the purpose of this survey to draw conclusions regarding the relative merits of the various formulations, the choice of a formulation in a given situation depending upon many factors outside the terms of reference of this review, and not all of a technical nature. In general, there is insufficient directly comparable data for a definitive assessment and in the few comparisons available special factors frequently apply.
EPR investigations of interactions between ammoniacal Cu(II) octanoate and wood
1996 - IRG/WP 96-30110
Ammoniacal solutions of copper(II) octanoate [ C u . h l f . 2 . r h l f.(O2CC7H15)4], interactions of these solutions with wood and wood components, and leaching of copper(II) octanoate from impregnated wood samples, have been studied by electron paramagnetic resonance (EPR) method. It is still not clear if in the Cu(II) octanoate - water - ammonia system, Cu(II) remains in a (copper(II) octanoate - ammonia) complex. The majority of leached Cu(II) with distilled water and a solution simulating acid precipitations was washed out in the first five hours of leaching procedure (up to 35% of initial Cu(II)). Time dependence studies of interactions of ammoniacal Cu(II) octanoate with wood, cellulose and brown rotted lignin showed, that the fastest and most significant was the reaction with lignin. Cu(II) is immobilised also on cellulose. A significant contribution of ammonia evaporation to the fixation mechanism of the preservative was observed as well.
F Dagarin, M Petric, F Pohleven, M Sentjurc
Leaching of copper, chromium and arsenic from CCA-treated slash pine heartwood
1994 - IRG/WP 94-50020
Drying green slash pine with any of three high temperature drying schedules produced a product in which both the sapwood and the heartwood could be penetrated with CCA using a modified Bethell treatment schedule. Required H3 retentions were achieved in both sapwood and heartwood, from 200 litres per m³ charge uptake. Post-treatment fixation/drying was accomplished by three different regimes, including an accelerated fixation. Although acceptable preservative penetration and retention was achieved in the heartwood, arsenic fixation (as determined by both AWPA procedure E11-87 and U.S. EPA TCLP procedure) was inferior to that attained in the sapwood. TCLP leachates from 1 cm³ heartwood blocks contained up to 4.5 mg/l arsenic, very close to the maximum value (5.0 mg/l) currently permitted in Australia for arsenic waste disposal. Though there are clear advantages in achieving heartwood penetration, caution must be exercised to ensure that this step does not compromise the accepability of the product. No process modification could be accepted if it introduced possibilities of exceeding safe disposal limits for sawdust and offcuts, or building site contamination.
M J Kennedy, G Palmer
The course of fixation of Cu-Cr-As wood preservatives
1972 - IRG/WP 307
Copper-chrome-arsenic (CCA) preservatives in contact with wood result in an instant extensive increase of pH, because of ion-exchange and adsorption reactions with the wood. During precipitation of the active elements the pH continuously increases but reaches a maximum, when all chrome is consumed. Some of the early reaction products are unstable and slowly convert via dissolution into stable compounds. The conversion proceeds by proton liberating as well as proton consuming reactions. The pH therefore alternatively decreases and increases until the reactions cease after several months. The final equilibrium fixation products are: ion-exchange fixation of Cu to the wood CrAsO4, Cu(OH)CuAsO4 and Cr(OH)3. The chrome fixation is 2nd order with respect to hexavalent chrome in the liquid phase, four regions with distinct chrome fixation rate constants were found. A hypothesis is given for the mechanism of fixation.
A comparative study of CCA type C and B treated poles in service
1993 - IRG/WP 93-50001-05
CCA K33 type B and C treated utility poles, 9 pieces of each treatment type, were analyzed for preservative retention after 11 years in use. Borings were taking 1 m above and 0.3 m below the ground line. Also total amount of copper, chromium and arsenic was determined in soil surrounding the poles. The solubility of these active components in soil was monitored by using different leaching procedures. Remarkable losses of Cu, Cr and As were found in both type of poles, particulary As from type B poles. Exact figures could not be given because of missing original preservation data. In comparison to the natural background high As and Cu contents were found in soil. CCA type B poles emitted As up to 760 mg/kg (oven dried soil) which is least 760 times higher than the natural background (0.4-1.0 mg/kg). The average value of As emitted by C type poles was 92 mg/kg. The amount of copper varied from 10 to 50 fold to the background but no essential differenceswere noticed among the two groups. Type C poles emitted more Cr but the average figures were lower than that with As and Cu. The solubility of As, Cu and Cr, as a very important factor, was investigated by preparing series of leaching tests. Only slight differences were found between EPA (US Environmental Protection Agency) and water leaching tests. In both leaching tests As was the most soluble element and 1.2-1.1 mg/l of As in the soil connected to B type poles was in soluble form. The figures were much lower with the case of C type poles and were 0.16-0.26 g/l respectively. Additional tests also proved that lower pH values decreased the solubilily of As. The effect was even stronger with adding ferrous sulphate. On the contrary increases pH resulted higher solubility.
A J Nurmi
Fixation of chromated copper arsenate (CCA) wood preservative in Australian hardwoods: A comparison of three Eucalyptus species
1996 - IRG/WP 96-30107
New environmental guidelines for the management of CCA treatment plants were released in Australia in 1995. This has stimulated interest in techniques for controlling or accelerating the fixation of CCA in freshly treated timber products. The ability to understand, then effectively control and/or accelerate fixation of CCA in treated timber products can be an economic, technical and environmental advantage. Data available on fixation of CCA in timber commodities however, is mainly on softwood not hardwood species. In this paper, the rate of fixation of CCA Type C Oxide in poles of three species of Australian Eucalyptus was monitored over a six week period following treatment. These results will assist in the design of adequate drip pad and undercover storage area for pole treaters in South East Queensland.
Leaching Characteristics of Copper in Copper Treated Wood
2003 - IRG/WP 03-30316
The leaching characteristics of copper in copper treated bamboo and other wood species such as slash pine and poplar has been conducted in this paper according to AWPA M11-87 standard, the result indicates that: --Copper fixation rate of salts from organic acids such as citrate and oxalate and malate is less than other non-organic acid formulations. --Copper fixation rate of oven-dried bamboo samples is less than air-dried bamboo samples for all formulations containing copper. --Copper fixation rate of bamboo treated with ACQ containing dimethyl didecyl ammonium chloride (DDAC) is higher than other type of ACQ formulation containing benzalkonium chloride. Copper fixation rate of ammonia-based ACQ-B treated bamboo is higher than amine-based ACQ-D while in the same retention level. --Copper fixation rate in some formulations containing phosphate is higher than non-phosphate ones.
Mingliang Jiang, Junliang Liu, Daochun Qin, Yamei Wang, Zehui Jiang
Determination of fixation properties by bioassays - A proposal for the assessment of safety indexes in wood protection
1990 - IRG/WP 3566
In the determination of environmental effects of chemicals tests with fishes, daphnia and algae have proved to be practicable. With respect to wood protection such bioassays are suitable to control effects of treated timber against aquatic organisms. By using the fish-acute-toxicity-test the development of a laboratory test method is described for the checking of the fixation rate of a copper-chromium wood preservative. By this the importance of the observation of a proper fixation period is demonstrated for the use of treated wood in water contact. Estimating ecotoxicological effects of leachable compounds using sensitive bioindicators allows a differentiated determination of environmental risks of impregnated timber. The comparison with the toxic effects of the compounds of a wood preservative are a first step in the assessment of safety indexes in wood protection.
Leaching and fixation characteristics of chrome-copper-fluoride-zinc (CCFZ) treated wood
1996 - IRG/WP 96-30096
The leaching characteristics of radiata pine sapwood blocks treated with CCFZ were evaluated by the AWPA standard leaching test. The rate of fixation of the preservative components in CCFZ treated radiata pine were also evaluated by quantitative analysis of solution expressed from the treated wood. Both leaching and fixation characteristics of CCFZ were compared with CCA-Type C treated wood samples. The permanence of CCFZ is excellent and comparable to that of CCA-Type C, and the rates of CCFZ fixation were similar to those found for CCA-Type C. These results suggest that CCFZ has a potential as alternative preservative for the replacement of CCA-Type C.
Gyu-Hyeok Kim, Jong-Bum Ra
Applications of the shower test. Part B: Results from CC and CCB treated wood: influence of fixation process
1993 - IRG/WP 93-50010
This report outlines the results of shower tests conducted on CC and CCB treated wood. The results indicate the fairly good fixation of chromium and the reasonable fixation of copper in CC and CCB formulations, as judged by the leaching limits within the Environmental Regulations. In general boron leaches to a higher extent than chromium and copper. The shower test has proven to be a useful quality control and research test. It determines reasonably accurately the leaching under simulated conditions and, admittedly from a limited number of tests, it can determine differences between various fixation cycles. Natural fixation, controlled climate room fixation and steam fixation were compared. Overall the sleam fixation process gave the lowest leaching figures although the selection of an appropriate fixation facility is a question for individual companies, taking into account capital, customer base, throughput etc.
W J Homan, H Militz
CCA modifications and their effect on soft rot in hardwoods. Part 2
1983 - IRG/WP 3244
The work outlined in this document is a continuation of that presented in Document No: IRG/WP/3201. The findings described in the previous paper are summarised below: a double treatment of CCB followed by arsenic (CCB+A) is more effective than a double treatment of boron followed by CCA (B+CCA) or a single treatment of CCA, CCB or CCAB in controlling soft-rot due to Chaetomium globosum in birch. CCB+A is as effective as the other formulations in controlling Coniophora puteana and Coriolus versicolor in birch and scots pine. CCB fails to copper tolerant basidiomycetes such as Coniophora puteana (F.P.R.L. 11E). A further investigation into the relative activities of CCA and CCB+A was carried out in a soil-bed using loss in strength and loss in weight as the criteria of decay. At the same time some aspects of the chemical nature of the formulations were examined in an attempt to explain the different performances of the treatments in birch. Amongst these tests, gross chemical analysis of the treated woodblocks and observation of the progressive fixation of the preservatives were the most significant.
S M Gray, D J Dickinson
Studies on the mobility of arsenic, copper and chromium in CCA-contaminated soil
1990 - IRG/WP 3571
CCA contaminated soils from six Swedish preservation plants were investigated primarily to study the mobility of arsenic but also that of copper and chromium in the soils. The soil samples represented average types with different amounts of clay, organic matter, arsenic, copper, chromium and different pH. The total soluble amounts of the elements were measured. The pH dependent solubility and the water-soluble fraction were investigated. The fixation capacity of arsenic by treatment with iron and aluminium salts and the toxicity of CCA contaminated soils to ryegrass were also investigated. There is strong evidence that when the soils are contaminated by CCA solution or leachate, a fraction of the arsenic, copper and chromium is precipitated as copper and chromium arsenates or as other salts in the soils. The solubility of arsenic, copper and chromium is pH dependent and the release of these elements increases both with decreasing and increasing pH, with the lowest release at between pH 6 to 7. The elements are released at a constant rate in equilibrium and in proportion to the precipitated arsenates. The water-soluble fraction of the elements are higher in sandy than in clay rich soils. The mobility decreases in the order As>>Cu>Cr. It is possible to fix the arsenic in sandy soils with Fe(II) salts and this is most effective at about pH 5. The growth of ryegrass decreases when the arsenic content in the soil solution exceeds 0.25 mg/L and its growth is totally inhibited when the arsenic content exceeds 1 mg/L.
Fixation of copper-chrome-arsenic treated timber: A comparison of leaching methodologies
1996 - IRG/WP 96-50075
Five packs of kiln dried radiata pine heartwood were treated with copper-chrome-arsenic preservative treated, utilising a modified Bethell treatment schedule. Two methods of determining the level of preservative fixation were compared. These included the diphenylcarbazide method and simulated rainfall testing. The fixation levels were generally higher for tests involving simulated rain leaching. Fixation of copper-chrome-arsenic determined by the diphenylcarbazide method was found to fluctuate with time. Localised surface concentrations of preservative, 'hot spots', were suggested as the cause. Simulated rainfall appeared to provide a more realistic assessment method for determining potential preservative leaching of multisalt preservatives.
S Walley, P R S Cobham, P Vinden
A comparison of the leaching resistance of diammine-copper complexes and copper carbonate precipitated in wood
1997 - IRG/WP 97-30158
Previous studies have shown that during treatment of wood with ammoniacal copper solutions, both simple copper precipitates and diammine-copper complexes are formed. The objective of the present study is to determine the relative importance of both forms of copper, on such aspects as preservative leachability and biological performance. In the current experiment, the leachability of copper carbonate precipitated in wood is compared with that of diammine-copper complexes. The results confirmed that both forms of copper resisted leaching by distilled water. However, when exposed to the more aggressive leaching conditions using the sodium citrate buffered solution, the diammine-copper complexes were significantly more ressistant to removal from the wood. Further studies are planned to examine the diammine-copper complexes present in the wood as well as the efficacy of these complexes against wood decay fungi.
Xiao Jiang, J N R Ruddick
Determination of ethanolamine in impregnated wood
2000 - IRG/WP 00-20198
Leaching of copper based preservatives from wood is usually prevented by adding chromium compounds to copper containing formulations. It seems that suitable substitutes for chromium fixation agents may be amines. In this paper, we report our results on interactions between copper(II) octanoate and ethanolamine (C2H7NO, 2-aminoethanole) with wood or its components. A part of ethanolamine from a wood preservative chemically reacts with wood and does not evaporate from it. This can be seen from retentions and from the changes of FTIR spectra of treated wood. We assume that ethanolamine mainly reacts with hemicelluloses and lignin complex. The unevaporated part of ethanolamine is even higher (for 2%) in the presence of copper(II) octanoate. We think that this difference originates from ethanolamine, which is complexed to copper(II) octanoate. Ethanolamine in wood can be easily determined with the indicator bromphenol blue in ethanol/acetic acid aqueous solution. Wood with ethanolamine turns blue while wood without ethanolamine remains yellow.
M Humar, M Petric
Copper naphthenate-treated Southern Pine pole stubs in field exposure: - Part 1: Gradient & biodeterioration analysis 12 years after treatment
2000 - IRG/WP 00-30242
Naphthenates have been used for the preservation of timber and cellulose since their original identification in Russia in the early 1880's as part of a series of petroleum characterizations. Later work in the development of copper naphthenate as a heavy-duty preservative for poles led to the development of various treating cycles similar to other oil-borne systems. Recent work concerning the post treatment steam conditioning of copper naphthenate treated southern pine has determined that some amorphous copper naphthenate is converted to a crystalline cuprous oxide. In small laboratory tests, this was later determined to be less efficacious than copper naphthenate. This paper reviews the performance of actual pole-diameter stubs placed in a high hazard location containing both termites and potential for early decay attack. Various treating cycles were used to treat the pole stubs in this test including various post-treatment conditioning methods.
H M Barnes, M H Freeman
Applications of the shower test. Part A: Results from CCA type C treated wood: influence of fixation process
1993 - IRG/WP 93-50009
This report outlines the results of shower tests conducted on CCA type C treated wood. The results indicate the inherent good fixation of CCA type C, as judged by the leaching limits within the Environmental Regulations. The shower test has proven to be a useful quality control and research test. It determines reasonably accurately the leaching under simulated conditions and, admittedly from a limited number of tests, it can determine differences between various fixation cycles. Natural fixation, controlled climate room fixation and steam fixation were compared. Overall the steam fixation process gave the lowest leaching figures although the selection of an appropriate fixation facility is a question for individual companies, taking into account capital, customer base, throughput etc.
W J Homan, H Militz, D A Lewis
Incomplete fixation of chromium in the pre-treated wood with a solution of copper and arsenic compounds
1995 - IRG/WP 95-50052
Ponderosa pine wood thin sections were treated with a combination of chromium, copper, and arsenic chemicals. The wood sections was analyzed by electron spin resonance spectrometry (ESR) and X-ray photoelectron spectrometry (XPS) to elucidate the mechanism of fixation of the chromated-copper preservatives. The wood subjected to the two-step treatment with copper and arsenic followed by chromium exhibited a strong Cr(V) ESR signal. However both Cr(III) and weak Cr(V) signals were observed in wood subjected to the one-step treatment containing chromium, copper, and arsenic. XPS spectra also supported the Cr(V) formation in the former treatment. The further chromium reduction from Cr(V) to Cr(III) for samples treated in two steps did not proceed very well during the fixation period of 3 months. Copper arsenate formed in the wood could disturb the interaction of chromium with the wood. These results indicate that re-treatment of wood with chromium containing preservatives may result in incomplete fixation of chromium.
J N R Ruddick, K Yamamoto, F G Herring, P C Wong, K A R Mitchell
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.