Editado por Luiz Henrique Capparelli Mattoso, Alcides Leão e Elisabete Frollini

MAGALHÃES, W. L. E.

SOUZA, M. F. de

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L.H.C. Mattoso, E. Frollini and A. Leão (ed.)                Natural Polymers and Composites IVSOLID WOOD TREATED BY PLASMA JETWashington L.E. Magalhães; Milton F.de SouzaInstituto de Física de São Carlos - CePOFAbstractCold plasmas were produced by electric glow discharges in a gas medium at reducedpressure and low frequency. A new technique called plasma jet was used to improve the depositionrate on solid wood. The treatment caused the solid softwood surface to become hydrophobic. Thewater contact angle was used to evaluate surface hydrophobicity. Although the surface plasmatreatment resulted in water repellence, permeability to water vapor remained. The ability of theplasma jet technique to coat the surface of wood orifices was investigated using a mixture oftetraethyl orthosilicate vapor (TEOS) and oxygen (O2).Keywords: solid wood, glow discharge, plasma polymerization, hydrophobic surfaceIntroductionSolid wood is a natural polymer composite that can be subjected to a wide variety oftreatments to render it suitable for specific technical applications. The greatest disadvantage of solidwood, however, is its hygroscopicity. Moist wood is vulnerable to attack by fungi and termites andloses its dimensional stability. The most widely used treatments for solid wood are impregnation [1-2] and coating with paints and varnishes [3-4]. A promising future technique for solid wood surfacecoating is a plasma treatment with a glow discharge. Chen Hy and Zavarin [5] treated solid woodwith radio frequency plasma and studied the permeability along the grain. Cho and Sjöblom [6] usedseveral gases (CH4, C2F4, hexamethyldisiloxane, O2, acrylic acid) to control the hydrophobicity ofsolid wood surfaces and to improve paint adhesion. Denes et al. [7] have also usedhexamethyldisiloxane-plasmas to produce water repellent surfaces. Recently, Denes and Young [8]have studied the improvement of solid wood weathering resistance through plasma treatment.Although these authors worked with high frequency plasma, they did not investigate the ability of theplasma technique to deposit inside wood capillaries.Two different techniques – known as capacitive coupled plasma and plasma jet – were testedin this study. Both these techniques appear promising in view of the low vacuum level, lowfrequency power supply required, the lack of pollutants, and the use of industrial chemicals.The study reported on here involves the modification of moisture absorption and waterrepellence of solid wood surfaces through the deposition of plasma-polymer films of 1-butene andTEOS vapor, using a homemade reactor operated at 60 Hz, 200 kHz and a plasma jet. Using lowenergetic plasmas, the deposited film can be polymer-like with a less crosslinked structure.Experimental ProcedureThe gases were supplied by Air Liquid do Brasil and the tetra ethyl orthosilicate (TEOS)from DATIQUIM Produtos Químicos Ltda (Brasil). The rest of the chemicals were supplied byAldrich Chemical Company Inc.Two substrates were used: B270 1-cm thick optic glasses and flat grained solid Pinuscaribaea hondurensis softwood.The glasses were immersed for 1 hour in a sulfuric acid / hydrogen peroxide 70/30 volumesolution, after which they were washed with pure water and dried with dry nitrogen. Having becomeclean and hydrophilic after the above treatment, these glasses were used as substrate for the plasmatreatments.Defect-free pine (Pinus caribaea hondurensis) was sawed into blocks with a 2.0x2.0x1.0 cmnominal size in the radial, tangential and longitudinal directions, respectively. Flat-grained boardswith a nominal dimension of 0.5x2.0x2.0 cm were sawed and sanded with 220-grit sandpaper. Theblocks and boards were oven-dried at 100oC for 24 hr, plasma treated, and then used for waterW.L.E. Magalhães; M.F.de Souza       Natural Polymers and Composites IVabsorption measurements in a controlled environment. After being plasma treated, the boards wereused for contact angle measurements along the grain.The film growth rates were calculated after measuring the film thickness on 1-mm thick glasssubstrate using a Tyle Step Hudson stylus profilometer.Static advancing water contact angle measurements were taken at room temperature by thesessile drop method, using optical microscopy (MM Optics, Inc. Brazil) and digitizing the imagetaken by a CCD (LG Honeywell) camera. The photographs were enlarged on a computer screen,providing a clear picture of the contact between the droplet and the substrate surface. About 9contact angle measurements were measured on different parts of one wood sample for each reportedaveraged value of the angle in the parallel and perpendicular directions of the wood surface grains.The standard deviation of the contact angle was less than 2 degrees for glass substrates and less than8 degrees for wood substrates.SEM (scanning electron microscopy) micrographs and Si mappings were made using a Zeiss960 microscope equipped with an EDS Analytical Link QX 2000 analyzer.Before deposition of the plasma-polymerized film, the reactor chamber was evacuated to abase pressure of 9.33 Pa and flushed three times with argon. A glow discharge with Ar at 53.33 Pawas then applied for 15 min to clean the surfaces, after which the reactor was again evacuated to thebase pressure.The next step was the admission of the reactive gas, with the control valve adjusted to set thepressure in the chamber to 106.66 Pa before the glow discharge was switched on.TEOS was vaporized into the interior of the reactor using an appropriate apparatus withheating and Ar bubbling.The capacitive coupled plasma reactor is described elsewhere [9].To deposit the plasma jet, an ion beam was built (fig.1) and operated attached to the plasmachamber window. The plasma jet consists of a cylindrical aluminum tube into which the 1-butene gasis admitted at one end, while three metallic grids with three different electric potentials are mountedat the other end to generate and accelerate the plasma through the substrate. The first grid operates at260 VAC, 60 Hz, the second one at minus 5 KVDC, and the third at 15 KVAC, 60 Hz. Permanentring magnets are fixed around the external aluminum cylinder. Thus, the magnetic field(1,200 Gauss) is applied parallel to the cylinder’s axis. Electrons repelled from the cathodes areattracted to the anode but the magnetic field constrains the electrons to follow helical trajectories,increasing their path length and enhancing ionization efficiency.gasinletpermanent magnetplasmajetFigure 1. Diagram of the plasma jetSince film deposition by plasma jet does not depend on substrate thickness, this technique ishighly efficient to coat solid wood surfaces.W.L.E. Magalhães; M.F.de Souza       Natural Polymers and Composites IVResultsDeposition rateTable 1 shows the rate and uniformity of the film deposited on a common glass substrate withtwo thicknesses for different treatment conditions. Depending on the thickness of the substrate, thedistinct deposition rate observed for capacitive coupled plasma suggests a much lower depositionrate for the wood substrate. Deposition uniformity is the same for all treatments and can be improvedby modifying the homemade equipment to increase the gas flow symmetries. The deposition rate inthe capacitive coupled plasma with the 2-mm substrate on the cathode is twice that of the depositionrate using the plasma jet. Nonetheless, the plasma jet technique is useful in solid wood treatmentbecause surface roughness and porosity are readily covered, regardless of the substrate thickness.Table 1. Deposition rate and uniformity of the film60 HzDeposition rate(nm/min)on an anode on a cathode200 kHzon a cathodePlasma jet1 mm thick glass 1,6 1,3 64 242 mm thick glass - - 48 24Uniformity (%) - - 10% 10%MorphologyFigure 2 shows the morphology of the longitudinal tracheid cell wall before and after 1-butene-plasma treatment. Figures 2A, B, and C show, respectively, the external cell wall of untreatedwood, wood treated by capacitive coupled plasma, and wood treated by plasma jet. Figures 2D, E,and F show the internal cell wall of untreated wood, capacitive plasma-treated wood, and plasma jet-treated wood, respectively. Figure 2A illustrates the wood before treatment, showing the randomcellulose microfibrillar orientation of the primary cell wall. The S3 layer of the lumen's internal wall,with the microfibril nearly normal to the fiber's axis, is depicted in the electron micrography of figure2D. Exposure of the wood to 1-butene plasma caused the morphologies of both the external andinternal cell wall surfaces to change to a rougher texture.The plasma jet-treated surface (fig. 2F) was rougher than that treated by capacitive coupledplasma (fig. 2E). The principal difference between capacitive and jet plasmas is that the plasma jetcoats exposed orifices and channels more effectively than the capacitive arrangement did.TEOS/O2 mixture was used as reactive gas in the plasma jet in order to deposit SiOx films onthe solid wood surface. The deposited film was characterized by Si EDX mapping.Figures 3 and 4 show SEM micrographs of solid wood surfaces exposed to the TEOS/O2plasma jet.Figure 3A illustrates the morphology of the SiOx deposited film, showing that the deposit isas rough as the woody substrate. However, the coating concealed the ultrastructure of the solid woodsurface. Figure 3B shows the Si mapping, revealing white dots spread over the entire surface, whichconfirms the complete coating of the wood surface.Figures 4A and 4B show, respectively, SEM micrographs and Si mapping of the surface ofthe 1.0-mm wide, 3.0-mm deep slit opened in the solid wood. These micrographs demonstrate thatthe plasma jet coated orifices which capacitively-coupled plasma was barely able to coat.FigureprimarplasmaAW.L.E. Magalhães; M.F.de Souza                 2. A: primary cell wall before treatment; By wall after plasma jet. D: S3 layer befor; F: S3 layer exposed to plasma jet. MagnificD B E C FNatural Polymers and Composites IV : primary wall exposed to capacitive plasma; C:e treatment; E: S3 layer exposed to capacitiveation: 10,000XFiguseconFiguA) SConambiabsosubst1-buwoodsurfavalueremadegreTablWA B18µmArdrEtaerprte csinee        e 3. Solid wood surface along the grain coated with SiOx by plasma jet. A) SEM usingary electrons and B) Si mapping of the same region. Magnification: 500X             plasmajetwoode 4.M, ctThnt tioate,Thne-ande a aloeds. 2. itho2Pl18µmAW.L.E. Magalhães; M.F.de Souza       N Surface of the slit opened in the solid woodand B) Si mapping of the same region anglee cross section perpendicular to the fibreair showed cell lumens with a diameten by capillarity. Water droplets were rea rendering it difficult to take an accurate reae softwood surface treated by plasma filmplasma deposition. Table 2 shows the con common glass under different conditions.long and across the grain, rendering it hydng and across the grain were attributed to hydrophilic after plasma treatment, althContact angle on wood and glass surfaces uAlong the grainut treatment Absorbs the waterdroplet00 kHz 115°60 Hz 115°asma jet 117°Batural Polymers and Composites IV and exposed to TEOS/O2 plasma jet.s of untreated solid softwood exposed to ther of approximately 40 µm, facilitating waterdily absorbed into the structure of the woodding of contact angle values. deposition presented a distinct behaviour aftertact angle of water droplets on plasma-treated The plasma treatment affected the entire woodrophobic. The dissimilar surface contact angle uneven surface roughness. The glass substrateough the contact angle increased by over 55nder different plasma conditions.Cross section GlassAbsorbs the waterdropletSmall126° 75°140° 76°132° 80°Since the plasma jet penetrates solid wood orifices more efficiently than does thecapacitively-coupled plasma, new experiments with 1-butene as precursor were conducted toevaluate water vapor exclusion. Wooden blocks and boards were used as substrates, with the crosssection and the flat-grained surface, respectively, exposed to the plasma jet. Each wood surface wasexposed to the plasma twice owing to the plasma jet’s small (2 cm) diameter. Only the two largestsurfaces of the wood samples were directed coated by the plasma jet; the other four faces weretreated indirectly.The treated and untreated samples were cyclically exposed to a humid and dry environmentand their weight monitored at regular intervals. Figure 5 shows graphs of the water vapor absorptionof the 1-butene treated and untreated solid wood. Although the plasma jet treatment providedefficient protection from liquid water, it proved ineffective against water vapor (humidity).00 00 120 240 360 480 600 720 840 9600510152025  untreated 1-butene plasma jetmoisture content (% dry wood base)time (hours)00 120 240 360 480 600 72005101520 untreated wood 1-butene plasma jetmoisture content (% dry wood base)time (hours)Figure 5. Change in moisture content of Caribbean pine finished with 1-butene plasma jet coat andexposed to alternating cycles of 95 and 22 percent relative humidity at room temperature, comparedwith untreated wood. Left: boards with nominal dimensions of 0.5 (R) x2.0 (T) x2.0 (L) cm. Right:blocks with nominal dimensions of 2.0 (R) x2.0 (T) x0.5 (L) cm.The plasma jet penetrated inside the 1-mm slits but barely coated shadow areas, as illustratedin figure 6.                    plasmajetwoodsupportFigure 6 right. B) SAvery difflongitudinpowder ashield tha18µmAW.L.E. Magalhães; M.F.de Souza       Nat- A) Micrograph of the area not directly expoi mapping of the same region of A); white dlthough the plasma jet easily penetrates 1-mmicult. Figures 7 and 8 show that, when tal cell axis, internal coating of the cell wall nd debris adhered to the surface after the wt prevented the capillaries from being coatedBural Polymers and Composites IVsed to the TEOS/O2 plasma jet, see diagram atots correspond to Si deposition. size slits, deposition inside the cell lumen ishe jet’s incidence was not aligned with thewas very difficult to achieve. Moreover, woodood was sanded and machined, serving as a.Figujet ccontiFiguTEOcell wConwoodto counsuinadeAckinstit18µmW.L.E. Magalhães; M.F.de Souza       Nat        re 7. A) Micrograph of a wood surface slanted inoat, showing uncoated orifices. B) Si mapping nuous.       re 8. A) Micrograph of the longitudinal cut in thS/O2 plasma jet coating. B) Si mapping of the samall efficiently.clusionsA thin solid film deposited by 1-butene-cold p surface became hydrophobic after the plasma treat wood surfaces than capacitive coupled plasmccessful in preventing water vapor absorption aquate to coat wood capillaries.nowledgmentFinancial support for this work was provideution.18µmAural Polymers and Composites IV relation to the cell axis after TEOof the same region of A). The fe cell lumen, showing internal cee region as A). The treatment didlasma successfully coated solid soatment. Plasma jet treatment is ma treatment. The plasma-depositnd desorption because the technd by FAPESP, a Brazilian reseaBS/O2 plasmailm was notA Bll walls after not coat theftwood. Theore effectiveed film wasique provedrch fundingW.L.E. Magalhães; M.F.de Souza       Natural Polymers and Composites IVReferences[1] R. M. Rowell. Wood preservation and stabilization by chemical modification of the woodsubstance. Chemical aspects of Wood technology, Swedish Forest Products ResearchLaboratory, STFI Series No 772, 32-49, Stokholm, 1982.[2] W. L. E. Magalhães. Master thesis, University of São Paulo, Instituto de Física de São Carlos,1998.[3] F. Probst; M. P. Laborie; A. Pizzi; X. Deglise. Holzforschung, 51, 1997, 459.[4] R. S. Williams; M. T. Knaebe; W. C. F. Feist. Finishes for exterior wood. Selection,application, and maintenance, USDA, Forest Service, F P L, Madison, WI., 1996.[5] Hy Chen; E. Zavarin. J. Wood Chem. Technol., 10(3), 1990, 387.[6] D.L. Cho; and E. Sjöblom. J. Appl. Polymer Symp., 46, 1990, 461.[7] A. R. Denes; M. A. Tshabalala; R. Rowell; R. A. Young. Holzforschung, 53(3), 1999, 318.[8] A. R. Denes; R. A. Young. Holzforschung, 53(6), 1999, 632-640.[9] Magalhães, W. L. E.; de Souza, M. F. Solid softwood coated with plasma-polymer for waterrepellence. Surface & Coatings Technology, 2002.

Solid wood treated by plasma jet.

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Solid wood treated by plasma jet.

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