9th International Conference on Wood & Biofiber Plastic Composites ~

Improved Durability and Moisture Sorption Characteristics of Extruded Wood-Plastic Composites Made from Chemically Modified Wood
B.K. Segerholm, R.M. Rowell, P Larsson-Brelid, M.E.P Wlinder, . . M. Westin, and G. Alfredsen

Abstract
Extruded wood thermoplastic composites are primarily used today in applications such as decking and joinery replacing traditional preservative-treated lumber. In such environments, moisture sorption combined with an increase in temperature will induce movements in the wood component and polymer matrix giving rise to macroscopic dimensional changes and distortion, i.e., warping, cupping, and bowing of the composite boards as well as microscopic wood particle-polymer interfacial debonding. Moisture sorption (diffusion/capillary penetration) in the composite also makes the wood component more susceptible to attack by microorganisms. With the introduction of a modified wood component, which is less hygroscopic, problems with moisture sorption can be minimized or entirely avoided. The object of this research is to study the moisture sorption behavior of acetylated and heattreated wood particles in thermoplastic composites with relationship to micro-morphology and durability to attack by fungi.

Segerholm: Ph.D. Student, Building Materials, KTH, Royal Institute of Technology, Stockholm, Sweden Rowell: Professor, Department of Biological Systems Engineering, University of Wisconsin, and Pioneering Scientist, USDA Forest Products Laboratory, Madison, Wisconsin, USA Brelid: Research Scientist, SP Technical Research Institute of Sweden, Bors, Sweden Wlinder: Assistant Professor, Department of Civil & Architectural Engineering, Building Materials, KTH, Royal Institute of Technology, and Research Scientist, SP Technical Research Institute of Sweden, Stockholm, Sweden Westin: SP Technical Research Institute of Sweden, Stockholm, Sweden Alfredsen: Norwegian Forest Research Institute, s, Norway

Introduction
Wood-plastic composites (WPCs) are a combination of a hydrophil wood component, e.g., wood residuals originating from sawdust, shavings, chips, flakes, etc., and a hydrophobe (thermoplastic) matrix. This combination brings both positive and negative properties of each component to the composite. The wood component brings the positive properties of flexibility, strength, stiffness, and low cost but also brings the negative properties of moisture sensitivity, dimensional instability, susceptibility to attack by microorganisms, an avenue for wicking moisture, and susceptibility to ultraviolet (UV) energy degradation. The

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thermoplastic brings the positive properties of thermoformability, moisture resistance, UV energy protection, and the ability to encapsulate the wood component but also brings the negative properties of swelling and creep under load due to heat. The optimum technology is to form a wood-thermoplastic composite that combines the best of both materials and minimizes the negative aspects of both phases. While non-modified wood components bring some negative characteristics to the composite, it is possible to modify the wood component to minimize these negative factors. Wood can be chemically modified by acetylation which greatly reduces its moisture sorption and swelling characteristics without reducing its strength (Larsson-Brelid and Simonson 1999). Wood can also be heated to reduce its moisture sorption and swelling characteristics but strength is reduced. It is also well documented that if a wood-thermoplastic composite is able to sorb moisture, it will degrade in the presence of microorganisms (Morris and Cooper 1998). If, however, moisture levels can be kept at a satisfactory low level, the composite will not degrade in the presence of microorganisms (Ibach and Clemmons 2006). When interested in the micromorphology of these types of material, it is often hard to use conventional cutting techniques such as a microtome or razorblade without having artifacts on the specimen surface from the technique itself. In this study, specimens for micromorphology studies have been prepared with a UV laser technique. The technique for specimen preparation of wood has been described in general by Seltman (1995) and Stehr et al. (1998). The objective of this research was to study the moisture sorption and micromorphological effects of moisture of wood particle/thermoplastic composites that have been made using modified wood particles with greatly reduced moisture sorption properties and test their resistance to degradation by microorganisms in fungal box tests.

particles in a two-step process. First 190-mm-long blocks were fed into a disk flaker (Bezner) and processed into thin veneer strands. In the second step, the veneer strands were fed into a dry grinding knife-mill (Condux) and chopped into fine particles. The particles were characterized by standard sieve analysis (Fig. 1). The thermoplastic matrix used was polypropylene (PP) (Moplen HF 500N).

Preparation of Composites The control and modified wood component were dried to a moisture content (MC) of less than 1 percent and mixed with the PP and compounded on a counter-rotating twin-screw extruder at OFK Plast AB in Karlskoga, Sweden. The wood/thermoplastic ratio was 70:30 based on dry weight and pellets were produced. The pellets were then fed into a conical extruder located at Conenor Oy in Tampere, Finland, and extruded into square-shaped hollow profiles of control, acetylated, and heat-treated composites. UV Lasered Surfaces The preparation technique involving UV laser for preparing wood surfaces were introduced in the early 1990s by Seltman (1995). The physical artifacts from conventional cutting techniques (e.g., microtome or razor blade) are avoided by using this technique (Stehr et al. 1998). This technique has shown to be very valuable for specimen preparation for studies of the unaffected interior of wood-plastic composites (WPC) where the differences in properties between the polymer matrix and the reinforcing wood component are large. In this study a Lambda Physic Ltd 210 ICC excimer laser was used, operated at a wave length of 248 nm. Blocks were cut from the sides of the extruded hollow profiles in the direction of extrusion. From these blocks, thin plates with dimensions of 22 by 5 by 1.5 mm3 were detached by the UV laser.

Materials and Methods Materials The raw material used in this study was prepared from acetylated and unmodified boards of Scots pine (Pinus sylvestris L.) and from heat-treated Norway spruce (Picea abies L.). Acetylation was performed according to Rowell et al. (1986) in a pilot plant with a microwave heated reaction vessel of 0.67 m3. The degree of acetylation was about 20 percent expressed as wood acetyl content. The heat treatment was performed by Stora Enso according to the ThermoWood D procedure which has a peak temperature of 212C (ThermoWood Handbook 2003). All boards were ground into
100 Frequency (%) 80 60 40 20 0 18-35 35-60 mesh 60-120 120Unmodified pine Heat treated spruce Acetylated pine

Figure 1. ~ Results from sieve analysis.

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Test Methods Water Vapor Sorption Tests Two replicates of each profile were cut into specimens with the dimensions 25 by 10 by 2 mm3 leaving one (25 by 10 mm2) original outer surface of the extruded specimen unaltered. All of the other surfaces were then sealed with aluminum tape and dried in a desiccator with silica gel for 4 weeks prior to the test. The water vapor sorption test was carried out by placing the specimens in an enclosed chamber above a saturated ammonium chloride solution, giving the ambient air a relative humidity (RH) of approximately 80 percent at 22C. The specimens were weighed at certain time intervals until the equilibrium moisture content (EMC) was reached, and the climate was recorded by a temperature and humidity logger placed inside the chamber. After the test when the specimens reached EMC, they were ovendried at 105C overnight in order to determine the initial and final MC. SEM of UV Lasered Surfaces In order to determine the micromorphology of the WPCs, the UV laser cut specimens were analyzed using a scanning electron microscope (SEM), JSM5310LV (Jeol Ltd., Tokyo, Japan). The microscope was run in a low vacuum mode (LV-SEM) to enable scans to be done without sputtering the surface of the specimens. First reference SEM micrographs were achieved. This was followed by a soaking-drying cycle, (soaked in distilled water for 7 days, wiped dry, and weighed). After drying at 105C, the specimens were weighed again. After that the specimens were analyzed in the LV-SEM again. Pre-Aging of Specimens for Biological Testing Test specimens were cut out from the extruded profiles in such a way that the outer polypropylene (PP)rich surface was removed. Specimen size was 5 by 10 by 100 mm3. All of the specimens were leached for 2 weeks in de-ionized water (5:1 water to test sample volume ratio) with water exchange 10 times and then ovendried for 18 hours according to EN 84. All specimens were water soaked 14 days in de-ionized water. The specimens were directly inserted in the test soils after the water soak. Terrestrial Microcosms Test According to ENV 807 Three types of terrestrial microcosms (TMCs) were used according to an expanded version of European test standard ENV 807. The three soils types used in this study were: TMC 1 a compost soil which was a mixture of two-thirds soil with high activity of both tunnelling bacteria and soft rot and one-third Bors

municipal compost from a mix of household and garden waste; TMC 2 soil from Simlngsdalen test field, a sandy soil with dominating brown-rot decay (mainly caused by Leucogyrophana pinastri); and TMC 3 soil was from a mixed forest 50 percent of the soil was from the test field in Ingvallsbenning (with high activity of white-rot fungus: Asterostroma cervicolor) and 50 percent from a mixed forest soil from near s in Norway with similar pH and WHC. The specimens were buried three-quarters of their length in the soil. Specimens where removed after 24 and 40 weeks (or 32 weeks) after which mass loss were calculated. Identical test set-ups with three soils were used at SP in Bors, Sweden and Skogforsk in s, Norway.

Results and Discussion Water Vapor Sorption Tests Figure 2 shows MC as a function of time for the three different material combinations. The EMC was reached after about 100 days for the WPC with unmodified wood, after about 50 days for the WPC with acetylated wood, and after about 150 days for the WPC with heat-treated wood. The initial and final MC of the composites differed significantly. The final MC of the WPC with unmodified wood was 8.4 percent compared to the WPC with acetylated wood and heat-treated wood where the final MC was 3.8 percent and 6.4 percent, respectively, i.e., WPC with acetylated wood component have reduced EMC by 55 percent. SEM of UV Lasered Surfaces Reference SEM micrographs were achieved before the specimens were soaked in distilled water and

10 moisture content [%] 8 6 4 2 0 0 50 100 150 Time [days] 200 250 300
Unmodified pine heat treated spruce

Acetylated pine

Figure 2. ~ Sorption curves for thin veneers of WPCs from modified and unmodified wood at 80% RH and 22C.

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Table 1. ~ MC before and after water soaking of WPC specimens.

Initial MC in WPC 3.2 1.4 2.5 Final MC Final based on MC in wood WPC component 24.1 8.1 15.2 34.4 11.6 21.7

Material combination (30/70 w/w) PP/unmodified pine PP/acetylated pine PP/heat-treated spruce

- - - - - - - - - - (%) - - - - - - - - - -

Figure 4. ~ UV laser-cut WPCs from acetylated wood particles before (top) and after (bottom) one water soaking cycle.

Figure 3. ~ UV laser-cut control WPCs from unmodified wood particles before (top) and after (bottom) one water soaking cycle.

dried. Table 1 presents initial and final MC of the different material combinations. WPCs made using unmodified wood picked up about three times as much water as the WPC made using acetylated wood. The water uptake is also reduced for the WPC with heattreated wood. The wood component in the WPCs with modified wood did not reach 25 percent MC, above which the risk for decay is dramatically increased. The SEM micrographs achieved after cyclic aging by water soaking/drying was compared with the reference micrographs. It can be seen that the WPCs made

using unmodified wood is severely damaged (Fig. 3) as cracks are formed at the interface between the wood and the polymer matrix. In the case of WPCs made using acetylated wood, the formation of cracks was greatly reduced (Fig. 4). The WPCs made using heattreated wood performed in between WPCs with unmodified and WPCs with acetylated wood (Fig. 5), i.e., cracks were formed but far fewer than observed for the unmodified WPCs. It has been demonstrated that the crack formation caused by swelling and shrinkage of the wood component can be kept to a minimum by using a modified wood component. This reveals that the UV laser preparation technique in combination with SEM is a powerful tool when analyzing these types of material.

TMC Test According to ENV 807 The results shown in Figures 6 and 7 are from the three soil boxes at Skogforsk in s, Norway. Figure 6 shows the mass loss (ML) after 24 weeks of exposure, and Figure 7 shows the mass loss after 40 weeks of exposure. The ML for the pine controls were 36 percent in the compost soil, 33 percent in the Simlngsdalen soil, and 8 percent in the forest soil after 24 weeks of ex-

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ML %

40
35,5 33

Compost soil Simlngsdalen soil Forest soil

30

20

10

6 3,5 3 2,5 3 0,5 0,5 0,5

0 Pine control WPC control WPC HT WPC Ac

Figure 6. ~ Results after 24 weeks in TMC test at Skogforsk.

ML %

80 70 60

74,5

Compost soil
50,5

Simlngsdalen soil Forest soil

27

50 40 30 20
9,5

10

5,5 4,5

2,5

Figure 5. ~ UV laser-cut WPCs from heat-treated wood particles before (top) and after (bottom) one water soaking cycle.

0,5 0,5 0,5

0 Pine control WPC control WPC HT WPC Ac

Figure 7. ~ Results after 40 weeks in TMC test at Skogforsk.

posure and 74 percent, 50 percent, and 27 percent, respectively, after 40 weeks of exposure. There was no ML for the pure PP specimens. The WPC controls had a corrected ML of 7 percent in the compost soil, 6 percent in the Simlngsdalen soil, and 3.5 percent in the compost soil after 40 weeks of exposure, and 9.5 percent, 5.5 percent, and 4.5 percent, respectively, after 40 weeks of exposure. ML for the WPCs are based on wood dry mass. There was fungal decay of the WPC controls in all soil types revealed by microscopic analysis. The ML of the WPCs with heat-treated spruce was 2.5 to 30 percent both after 24 and 40 weeks of exposure; the WPCs with acetylated pine was very low around 0.5 percent after both 24 and 40 weeks of exposure. No decay could be detected by microscopic analysis for the WPC specimens with a modified wood component, although there might have been some very slight decay in the WPCs containing heat-treated spruce based on its ML values (2.5% to 3%), but that could not be verified by microscopy. Table 2 presents the results of the TMC tests after 32 weeks of exposure at SP in Bors, Sweden. The ML of the pine controls are interpolated values from 24 and 40 weeks of exposure. The results from the WPC speci-

mens are from 32 weeks of exposure (because there were only eight replicate test specimens in each soil compared with 18 for pine controls). Results from the setup at SP showed similar results as the setup at Skogforsk and a slightly lower ML for all of the WPC specimens. Again a slight fungal decay was found in the WPC controls from all of the soils, and no decay was detected for the WPC specimens with a modified wood component.

Conclusions The use of modified wood elements in extruded PP composites substantially decreased moisture sorption of the final products. The UV laser technique has been shown to be a very powerful tool for preparing surfaces of WPCs for micromorphological studies without adding physical artifacts due to the preparation technique itself. WPCs made using acetylated wood greatly reduced the crack formation at the wood-plastic interface due to a soaking and drying cycle; heat-treated WPCs showed a few cracks but performed much better than the untreated WPCs. Furthermore this supports the

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Table 2. ~ Results after 32 weeks in TMC test at SP.

Corrected mass loss (%) after ENV 807 test Test material type Wood material Wood control Pure PP WPC control WPC HT WPC Ac Pine control None Unmodified pine Heat-treated spruce Acetylated pine % wood content 100 0 70 70 70 Other -100% PP 30% PP 30% PP 30% PP Compost soil Total mass 55 0 7 1 0 Wood mass 55 -10 2 0 Siml.dalen soil Total mass 42 0 5 1 0 Wood mass 42 -7 2 0 Forest soil Total mass 18 0 3 1 0 Wood mass 18 -5 2 0

theory that a modified wood component will enhance the long-term performance of WPC products. WPC controls were all decayed whereas none of the WPCs with modified wood showed decay, although there was a slight weight loss (2.5% to 3%) of the composites with heat-treated wood.

Acknowledgment VINNOVA (The Swedish Governmental Agency for Innovation Systems) within the framework of the Green Materials program and BiMaC (Biofibre Materials Centre) are greatly acknowledged. Literature Cited
Ibach, R.E. and C.M. Clemons. 2006. The effect of acetylated wood flour or coupling agent on moisture, UV, and biological resistance of extruded wood-fiber plastic composites. In: Proc., Wood Protection 2006. Forest Products Society, Madison, WI.

Larsson Brelid, P. and R. Simonson. 1999. Acetylation of solid wood using microwave heating. Part 2. Experiments in laboratory scale. Holz als Roh- und Werkstoff. 57: 383-389. Morris, P.I. and P. Cooper. 1998. Recycled plastic/wood lumber attached by fungi. Forest Prod. J. 48(1): 86-88. Rowell, R.M., A.-M. Tilman, and R. Simonson. 1986. A simplified procedure for the acetylation of hardwood and softwood flakes for flakeboard production. J. of Wood Chemistry and Techn. 6(3): 427-448. Seltman, J. 1995. Freilegen der Holzstruktur durch UV-Bestrahlung. Holz als Roh- und Werkstoff. 53: 225-228. Stehr, M., J. Seltman, and I. Johansson. 1998. UV laser ablation An improved method of sample preparation for microscopy. Holzforschung. 52: 1-6. ThermoWood Handbook. 2003. www.thermowood.fi (200706-12).

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