Paul A. Cooper

Thermal and burning properties of wood flour- poly(vinyl chloride) composite

The present study deals with the effects of wood flour on thermal and burning properties of wood flour-poly(vinyl chloride) composites (WF-PVC) using thermogravimetric (TG), cone calorimetry (CONE), and pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS). TG tests show that an interaction occurred between wood flour and PVC during the thermal degradation of WF-PVC. Wood flour decreased the temperature of onset of decomposition of PVC. However, the char formation could be increased by adding wood flour to PVC. CONE test indicates that wood flour had positive effects on heat release and smoke emission of PVC. Comparing with PVC, WF-PVC reduced average heat release rate and the peak HRR by about 14 and 28%, respectively; smoke production rate was also decreased. The degradation mechanism was studied by Py–GC/MS. The results show that the volatile pyrolysis products of WF-PVC are very different from PVC. The yields of HCl and aromatic compounds decreased dramatically, and the aliphatic compounds increased by the incorporation of WF.

Copper stabilization in ACQ-D treated wood: retention, temperature and species effects

The rates of stabilization or fixation of copper in ACQ-treated wood were compared for different post treatment conditioning temperatures (22°C and 50°C), solution concentrations (0.4–2.3%) and wood species. In some species, sapwood/heartwood differences were evaluated. The rate and extent of copper stabilization were estimated from changes in concentration of expressed solution at different times after treatment. The quality of the stabilization reaction was evaluated based on leaching performance of the wood after conditioning. Copper stabilized much faster at lower ACQ retentions and when conditioned at 50°C compared to high retentions and stabilization at 22°C. High retention treatments held without drying at 22°C could require five weeks or more for the copper to stabilize in the wood. Generally species effects were minor for the species evaluated, except for Douglas-fir in which copper reacted more quickly than in other species.ZusammenfassungDer Grad der Stabilisierung oder Fixierung von Kupfer in ACQ-behandeltem Holz wurde verglichen für Wärme-Nachbehandlungen bei 22°C und 50°C für Tränkkonzentrationen zwischen 0,4% und 2,3% und für verschiedene Holzarten. Rate und Ausmaß der Kupferstabilisierung wurden abgeschätzt aus der Konzentrationsänderung der zu verschiedenen Zeiten ausgepressten Tränklösung nach der Behandlung. Die Güte der Stabilisierungsreaktion wurde abgeschätzt anhand des Auslaugverhaltens nach der Konditionierung. Kupfer stabilisierte sich viel schneller bei geringeren ACQ-Konzentrationen und Konditionieren bei 50°C im Vergleich zu hohen Rückhaltekonzentrationen und Wärmebehandlung bei 22°C. Bei hohen Rückhaltekonzentrationen ohne Trocknung bei 22°C kann es bis zu fünf Wochen oder noch länger dauern, bis das Kupfer sich im Holz stabilisiert. Allgemein war der Einfluss der untersuchten Holzarten gering außer bei Douglasie; hier reagierte das Kupfer viel schneller als in anderen Holzarten.

Rate and extent of adsorption of ACQ preservative components in wood

Abstract The adsorption of copper, [as Cu(II)], monoethanolamine (MEA) and didecyldimethyl ammonium chloride (DDAC) components of CuMEA and alkaline copper quaternary (ACQ) solutions impregnated into wood was followed by measuring the changes in solution concentrations in the wood over time. The rate and extent of copper and MEA adsorption were highly dependent on the solution strength and the conditioning temperature. Both copper and MEA were adsorbed by the wood structure with a rapid initial reaction, with higher relative amounts sorbed from lower concentration solutions. This was followed by a slower adsorption that still had not equilibrated after 7 weeks at 22°C. Generally, the adsorption pattern was similar for copper and MEA, suggesting that they were adsorbed as a copper MEA complex, with an MEA/copper molar ratio close to the theoretical maximum of 4. At a higher conditioning temperature of 50°C the reaction time was greatly reduced, with the adsorption after 1 week higher than after 7 weeks at 22°C, suggesting faster and more complete reaction at higher temperatures. DDAC was adsorbed more quickly and to a higher degree than Cu(II) for all treatment solutions and should be preferentially removed from such solutions, especially if empty-cell treatments are used. There appeared to be higher Cu adsorption from the higher concentration solutions of CuMEA than from corresponding ACQ solutions, likely due to DDAC competition with copper for the same reaction sites.

Stimulating growth and xylindein production of Chlorociboria aeruginascens in agar-based systems

Four isolates of Chlorociboria aeruginascens were tested for possible stimulatory effects when grown on malt agar media containing wood additives. The addition of any of the four types of test wood (Acer saccharum, Populus tremuloides, spalted P. tremuloides, and Ailanthus altissima), stimulated colony growth and xylindein production in C. aeruginascens. Addition of any amount of wood produced more growth than no wood additions, while ground wood produced more growth than chopped wood. Of the wood types tested, A. saccharum wood stimulated all four isolates, while spalted Populus tremuloides stimulated three of the four isolates. High glucose and sucrose amounts may be partially responsible for the greater stimulatory affect of some woods over others. The development of this simple and reliable method for growth and pigment stimulation of C. aeruginascens in laboratory conditions will allow for further development of this fungus for decorative and commercial use.

Prediction of long-term leaching potential of preservative-treated wood by diffusion modeling

Abstract An approach to modeling leaching and leaching impacts of preservative components from treated wood is presented based on three simple laboratory determinations: the amount of preservative component available for leaching (Le), equilibrium dissociation of preservative into free water in wood (Di) and diffusion coefficients for component leaching in different wood directions (D). In this study, the following inorganic wood preservative systems were investigated: chromated copper arsenate (CCA), the copper component of copper azole (CA) and alkaline copper quaternary (ACQ), and boron in disodium octaborate tetrahydrate (DOT). Aggressive leaching of finely ground wood showed that amounts of preservative compounds available for leaching were highest for borates, followed by copper in copper amine systems and arsenic in CCA, copper in CCA and chromium in CCA. The equilibrium dissociation or solubility of components in free water in the wood was much higher for borates and copper amine, followed by copper and arsenic in CCA and chromium in CCA. Use of the applicable diffusion coefficient (D) and Di or Le values in a diffusion model allows the prediction of total amount leached and emission or flux rate at different times of exposure for products with different dimensions and geometries. The approach was tested and generally validated through application of the model to results of laboratory water spray leaching of full-size lumber samples. The approach explains the rapid leaching of boron compounds (large diffusion coefficient and high initial dissociated concentration) compared to other preservative components and predicts that ACQ will have higher initial leaching rates compared to CCA and CA, but the latter preservatives will continue to leach copper at a measurable rate for a much longer time. The practical implications and limitations of the approach are discussed.

Effect of climatic variables on chromated copper arsenate (CCA) leaching during above-ground exposure

Abstract Until recently, most research on the leaching of preservatives from treated wood was conducted in the laboratory. Although these studies have contributed to the understanding of leaching, the data generated under controlled conditions often do not apply to leaching during natural exposure and weathering. In addition, little is known about the effects of climatic variables and long-term emission rates. This paper examines leaching of chromated copper arsenate (CCA) from lumber exposed above ground to 685 mm of precipitationduring 351 days of natural weathering. Stepwise multiple regression analysis revealed relationships between leaching and a number of treatment and climatic variables, including: species of wood, initial preservative loading, amount of precipitation, average air temperature, average light intensity, pH and duration of rain event. Regression models explained approximately 30% of the variation in chromium and arsenic leaching and 44% of the variation in copper leaching.

PEG bulking of wood cell walls as affected by moisture content and nature of solvent

Movement of polyethylene glycol (PEG) 1000 from wood cell lumens into adjacent cell walls was studied for different cell wall moisture contents (MCs) and PEG solvents; relative amounts of PEG that penetrated into the cell walls were estimated by Raman microscopy. It was shown that samples treated with PEG from chloroform solution adsorb less PEG than samples treated with PEG-water solution even in the case of samples with open cell wall structure near fibre saturation point MC. Reconditioning of PEG-chloroform treated samples at high relative humidities enhanced PEG bulking of cell walls, but not to the maximum amounts observed with PEG-water treatments. Raman microscopy was a useful tool for estimating relative PEG amounts in the cell walls.

Application of a CCA-treated wood waste decontamination process to other copper-based preservative-treated wood after disposal

Chromated copper arsenate (CCA)-treated wood was widely used until 2004 for residential and industrial applications. Since 2004, CCA was replaced by alternative copper preservatives such as alkaline copper quaternary (ACQ), copper azole (CA) and micronized copper quaternary (MCQ), for residential applications due to health concerns. Treated wood waste disposal is becoming an issue. Previous studies identified a chemical process for decontaminating CCA-treated wood waste based on sulfuric acid leaching. The potential application of this process to wood treated with the copper-based preservatives (alkaline copper quaternary (ACQ), copper azole (CA) and micronized copper quaternary (MCQ)) is investigated here. Three consecutive leaching steps with 0.1 M sulfuric acid at 75°C for 2 h were successful for all the types of treated wood and achieved more than 98% copper solubilisation. The different acidic leachates produced were successively treated by coagulation using ferric chloride and precipitation (pH=7) using sodium hydroxide. Between 94 and 99% of copper in leachates could be recovered by electrodeposition after 90 min using 2 A electrical current. Thus, the process previously developed for CCA-treated wood waste decontamination could be efficiently applied for CA-, ACQ- or MCQ-treated wood.

Demonstration of the efficiency and robustness of an acid leaching process to remove metals from various CCA-treated wood samples.

In recent years, an efficient and economically attractive leaching process has been developed to remove metals from copper-based treated wood wastes. This study explored the applicability of this leaching process using chromated copper arsenate (CCA) treated wood samples with different initial metal loading and elapsed time between wood preservation treatment and remediation. The sulfuric acid leaching process resulted in the solubilization of more than 87% of the As, 70% of the Cr, and 76% of the Cu from CCA-chips and in the solubilization of more than 96% of the As, 78% of the Cr and 91% of the Cu from CCA-sawdust. The results showed that the performance of this leaching process might be influenced by the initial metal loading of the treated wood wastes and the elapsed time between preservation treatment and remediation. The effluents generated during the leaching steps were treated by precipitation-coagulation to satisfy the regulations for effluent discharge in municipal sewers. Precipitation using ferric chloride and sodium hydroxide was highly efficient, removing more than 99% of the As, Cr, and Cu. It appears that this leaching process can be successfully applied to remove metals from different CCA-treated wood samples and then from the effluents.

Penetration of poly(ethylene glycol) into wood cell walls of red pine

Abstract Penetration of poly(ethylene glycol) (PEG) with a wide range of molecular weights into cell walls of red pine wood was investigated. The study included bulking measurements and visualization of diffusion of brominated PEG by scanning transmission electron microscopy coupled to an energy-dispersive X-ray analyzer (STEM-EDXA) and a time-of-flight secondary ion mass spectrometer (ToF-SIMS). Both bulking and visualization techniques were in agreement, showing that all molecular weights of the polymer (PEG 1000, PEG 8000, and PEG 20000) are capable of penetrating cell walls. ToF-SIMS was more sensitive than STEM-EDXA, allowing visualization of lower amounts of brominated PEG. A trend to higher concentrations of PEG in the middle lamellae was observed.