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Biocides<br />

20<br />

INA STEPHAN<br />

RUDY PLARRE<br />

<str<strong>on</strong>g>Biodeteriorati<strong>on</strong></str<strong>on</strong>g>-<str<strong>on</strong>g>tests</str<strong>on</strong>g> <strong>on</strong><br />

<strong>wood</strong>/<strong>plastic</strong> <strong>composites</strong><br />

ABSTRACT<br />

The purpose of this article is to raise awareness about the<br />

possibilities for biodeteriorati<strong>on</strong> of <strong>wood</strong>/<strong>plastic</strong> <strong>composites</strong><br />

(WPCs). It will introduce the European standards (EN) and<br />

technical specificati<strong>on</strong>s (TS) with which the durability of<br />

WPCs against microorganisms and termites can be tested.<br />

INTRODUCTION TO WOOD/PLASTIC<br />

COMPOSITES (WPC)<br />

WPCs are blends of <strong>wood</strong> particles (or in some cases other<br />

cellulosic particles) into a thermo<strong>plastic</strong> matrix. Typically 50<br />

to 70 percent <strong>wood</strong> and 30 to 50 percent polymer are the<br />

ratio limits in which the materials are mixed. They can be<br />

used in outdoor applicati<strong>on</strong>s (e.g. decking, cladding, window<br />

/ door profiles, fences, playground equipment, footbridges,<br />

highway sound barriers, shutters, roofing shingles) as well<br />

as in indoor applicati<strong>on</strong>s (e.g. floors, panels, door frames,<br />

furniture, skirting boards, shelving,<br />

storage equipment).<br />

The predicti<strong>on</strong>s for the growth of<br />

the market are c<strong>on</strong>sistently high.<br />

The actual numbers for selected<br />

countries are quoted in table 1 (1).<br />

Plastic materials used in WPCs<br />

nowadays are mainly polyethylene<br />

(low, medium and high density PE),<br />

polyvinylchloride (PVC) and<br />

polypropylene (PP). In general<br />

<strong>plastic</strong>s used in WPC have to be<br />

suited to being processed at below 200° C in order not to<br />

damage the <strong>wood</strong> particles in the mixture (1).<br />

The slenderness of the <strong>wood</strong> particle defines the characteristics<br />

the <strong>wood</strong> has in a WPC. While <strong>wood</strong> flour (about 0.3 to<br />

0.4 mm diameter) acts as a filler in the WPC, <strong>wood</strong> fibres<br />

or shavings can add structural stiffness to the material (1).<br />

Besides <strong>wood</strong> and <strong>plastic</strong>, additives such as UV-stabilisers<br />

or absorbers and lubricants can be used as coupling agents.<br />

Furthermore, preservatives, e.g. fungicides, insecticides<br />

and/or algicides can be incorporated depending <strong>on</strong> the<br />

intended use of the product.<br />

ACCESSIBILITY OF WPC FOR ORGANISMS<br />

Microorganisms<br />

Wood is a natural, renewable resource. Therefore it is<br />

biodegradable by many organisms in nature. As a general<br />

rule it can be said that <strong>wood</strong> with a high natural durability<br />

is harvested from slow growing tree species, while <strong>wood</strong><br />

with low natural durability is harvested from fast growing<br />

tree species. C<strong>on</strong>sequently, <strong>wood</strong> with a low natural durability<br />

is more accessible <strong>on</strong> the market and cheaper. To delay the<br />

biodegradati<strong>on</strong> process of this <strong>wood</strong> by fungi several opti<strong>on</strong>s<br />

Table 1. Annual use in t<strong>on</strong>nes of WPC materials in selected<br />

countries.<br />

Ina<br />

Stephan<br />

Rudy<br />

Plarre<br />

are possible: a) use of biocides, b) use of modified <strong>wood</strong><br />

or <strong>wood</strong> with a high natural durability c) keeping the <strong>wood</strong><br />

moisture c<strong>on</strong>tent below 25 percent. In this c<strong>on</strong>text, the <strong>plastic</strong><br />

comp<strong>on</strong>ent of a WPC has the potential to envelope the dry<br />

<strong>wood</strong> particles and thus keep the moisture away from it.<br />

Nevertheless, <str<strong>on</strong>g>tests</str<strong>on</strong>g> in the field as well as in the laboratory<br />

dem<strong>on</strong>strated that while moisture uptake is delayed in WPCs,<br />

it cannot always be prevented (2).<br />

To induce <strong>wood</strong> decay and mass loss by microorganisms,<br />

the moisture c<strong>on</strong>tent of the <strong>wood</strong> fibre is critical. Below a<br />

level of 25 percent decay is usually not possible. Therefore,<br />

several authors have focused <strong>on</strong> the water uptake of different<br />

WPC materials (3, 4). While the water uptake over the whole<br />

of the product dimensi<strong>on</strong> might be below 25 percent it has<br />

to be c<strong>on</strong>sidered that the water is not homogenously distributed<br />

in the WPC material. It can be assumed that a) the <strong>plastic</strong><br />

comp<strong>on</strong>ent does not take up any significant amount of water<br />

and b) that there is a moisture gradient with higher levels<br />

of moisture in the outer layer, therefore allowing and favouring<br />

fungal attack in certain parts of the material. This would<br />

lead to the effect that the outer<br />

appearance and surface feel of a<br />

material can change under moist<br />

c<strong>on</strong>diti<strong>on</strong>s whereas the stability of<br />

a product is reduced by fungal<br />

decay at a slower rate, depending<br />

<strong>on</strong> its overall dimensi<strong>on</strong>s (5).<br />

Surface growth<br />

For many customers the surface<br />

appearance is often a reas<strong>on</strong> for<br />

deciding for or against a product.<br />

This is especially true where either large areas of the material<br />

are seen or the product is a c<strong>on</strong>spicuous locati<strong>on</strong>, e.g. with<br />

deckings for terraces. Algal growth and moulds living <strong>on</strong><br />

debris and moisture collecting <strong>on</strong> surfaces are a comm<strong>on</strong><br />

cause for complaints. Even though the WPC-material may<br />

not be metabolised by these organisms, they are known to<br />

build biofilms that could damage <strong>plastic</strong>s and additives by<br />

releasing e.g. organic acids. Research <strong>on</strong> such interacti<strong>on</strong>s<br />

with WPCs is still in its infancy. However, it is already evident<br />

that biofilms make surfaces slippery and decelerate drying<br />

of underlying material, thus enhancing fungal decay.<br />

Insect damage<br />

Several insect species can damage <strong>wood</strong> or <strong>wood</strong> c<strong>on</strong>taining<br />

materials. By far the most important insect group worldwide<br />

causing destructi<strong>on</strong> of <strong>wood</strong> are termites, especially soil<br />

inhabiting and dry <strong>wood</strong> termites (6). They are known to<br />

cause damage throughout the tropics, sub-tropics and temperate<br />

regi<strong>on</strong>s (7). Water is essential for termite survival, however,<br />

<strong>on</strong>ly few termite species demand a minimum moisture c<strong>on</strong>tent<br />

of the <strong>wood</strong> they attack, since they either utilise independent<br />

water sources in the soil or physiologically compensate low<br />

moisture c<strong>on</strong>tents by metabolic water producti<strong>on</strong>.<br />

Termites have a complex social organisati<strong>on</strong> with definite<br />

chimica oggi • Chemistry Today • vol 26 n 3 / May-June 2008


patterns when feeding in groups using all resources to the<br />

maximum (8). Although some preferences for certain <strong>wood</strong><br />

species may occur (9-11), all cellulose c<strong>on</strong>taining material can<br />

be used as food and energy sources. Termites, therefore, feed<br />

<strong>on</strong> any <strong>wood</strong>en material.<br />

As termites, especially subterranean termites, search for<br />

food, they may penetrate and damage many n<strong>on</strong>cellulose<br />

materials as well, including <strong>plastic</strong>s, even if these do not<br />

serve as food source and can not be digested (12). The<br />

sharp mouth parts of worker termites can abrade or break<br />

apart virtually any material and the high<br />

reproductive rate in termites instantly replaces<br />

workers with blunt mandibles.<br />

It is therefore not surprising that most <strong>plastic</strong>s<br />

failed in <str<strong>on</strong>g>tests</str<strong>on</strong>g> for resistance to termites (13-<br />

16). Nevertheless, differences exist between<br />

different <strong>plastic</strong>s and their susceptibility to<br />

termite attack. C<strong>on</strong>densati<strong>on</strong>-<strong>plastic</strong>s like<br />

polyesters appear more resistant than additi<strong>on</strong><strong>plastic</strong>s<br />

like polyethylene, polystyrene and<br />

polyurethane (13). However, it is not <strong>on</strong>ly the<br />

mechanical hardness of <strong>plastic</strong>s that characterises<br />

durability against termite attack, the surface<br />

structure is just as important. Smooth, even<br />

levelled surfaces, are more likely to prevent<br />

termite attack, but the smallest cracks and<br />

crevices or ruffled surfaces and edges provide<br />

immediate access for termite mandibles. The<br />

same holds true for WPCs. Once the surface<br />

is broken, destructi<strong>on</strong> is <strong>on</strong>ly a matter of time<br />

and termite populati<strong>on</strong> density, unless the<br />

material is protected by either an effective<br />

termiticide or a repellent that prevents c<strong>on</strong>tinuous<br />

feeding. Although it was shown that dry<strong>wood</strong><br />

termites are capable of attacking <strong>plastic</strong>s (13),<br />

it is c<strong>on</strong>sidered unlikely that this group of<br />

Wood/<strong>plastic</strong><br />

<strong>composites</strong> (WPC) are a<br />

fairly new category of<br />

materials <strong>on</strong> the market.<br />

The authors point out<br />

biological procedures to<br />

characterise and specify<br />

different WPC-materials.<br />

While moisture is<br />

essential for growths<br />

of algae and fungi,<br />

termites can also attack<br />

dry materials.<br />

Whether biocides<br />

are needed for<br />

protecti<strong>on</strong> of a materials<br />

depends<br />

<strong>on</strong> the envir<strong>on</strong>ment<br />

it will be exposed to<br />

during its use.<br />

termites would infest <strong>plastic</strong>s to establish col<strong>on</strong>ies as they do<br />

in pure <strong>wood</strong>en structures. For WPCs this still needs to be<br />

dem<strong>on</strong>strated.<br />

USE CLASSES FOR WOODEN MATERIALS<br />

Before deciding <strong>on</strong> measures to protect the WPC it is important<br />

to decide where the material has to perform and to what<br />

envir<strong>on</strong>ment it will be exposed. In the field of <strong>wood</strong> protecti<strong>on</strong>,<br />

the definiti<strong>on</strong> of use classes (former hazard<br />

classes) was found to be useful and could now<br />

also be applied to identify the intended use for<br />

WPC-materials (17, 18). These use classes<br />

cover the following general service situati<strong>on</strong>s:<br />

Use class 1 for interior and covered, use class<br />

2 for interior and not covered, use class 3 for<br />

exterior above ground, use class 4 for exterior<br />

in the ground or fresh water and use class 5<br />

for use in salt water. Some minor subdivisi<strong>on</strong>s<br />

in the use classes may occur.<br />

TESTING OF WPCS FOR BIOLOGICAL<br />

DURABILITY<br />

In Europe, CEN with its Technical Committee<br />

249, Working Group 13, has been working <strong>on</strong><br />

laboratory methods to characterise WPCs since<br />

2003. Chapter 8.6 of the technical specificati<strong>on</strong><br />

TS 15534-1released in 2006, “Resistance against<br />

biological agents” (19), deals with the different<br />

forms of microbiological decay (Annex C: termites,<br />

Annex D: <strong>wood</strong> destroying basidiomycetes,<br />

Annex E: soft rotting micro-fungi, Annex F:<br />

discolouring micro-fungi and algae).<br />

Biocides


Biocides<br />

22<br />

The test methods described in TC 15534-1 are intended to<br />

be used for the characterizati<strong>on</strong> and specificati<strong>on</strong> of WPCs.<br />

They are derived from existing test methods in the fields of<br />

<strong>wood</strong> protecti<strong>on</strong>, <strong>plastic</strong>s and coatings. The methods presented,<br />

although used for many years for biocide-treated or untreated<br />

material, were not primarily designed for WPCs. In the future<br />

it is likely that the test methods will need to be adapted to<br />

WPC materials and products.<br />

Laboratory <str<strong>on</strong>g>tests</str<strong>on</strong>g><br />

Accelerated testing in the laboratory can be helpful to rank<br />

resistance against fungal or algal growth of WPC-materials.<br />

TS 15534-1 lists a variety of <str<strong>on</strong>g>tests</str<strong>on</strong>g> (19). Problems associated<br />

with surface moulds <strong>on</strong> <strong>plastic</strong>s (20) and algae <strong>on</strong> coatings<br />

(21) are addressed in test standards which employ visual<br />

estimati<strong>on</strong>s to rate or rank the results. Both standards are<br />

regarded as being useful to estimate the susceptibility of<br />

WPC surfaces to support surface growth <strong>on</strong> WPC-materials.<br />

The following three standards and specificati<strong>on</strong>s (see below)<br />

were all originally developed for testing durability of <strong>wood</strong><br />

and <strong>wood</strong>-based products. While the termite-standard (22)<br />

requires the visual estimati<strong>on</strong> of results, the two methods for<br />

fungal decay determine the mass loss of <strong>wood</strong> in percent<br />

based <strong>on</strong> the original mass of <strong>wood</strong> in a WPC (23, 24). The<br />

appropriate way of prec<strong>on</strong>diti<strong>on</strong>ing (e.g. UV-irradiati<strong>on</strong>,<br />

artificial weathering, leaching) of WPCs before testing is<br />

still a much debated topic. For the simulati<strong>on</strong> of water uptake<br />

in practise (which might take some years in certain envir<strong>on</strong>ments<br />

before the material can be decayed) several standardised<br />

opti<strong>on</strong>s are menti<strong>on</strong>ed in TS 15534 (25-27).<br />

Field <str<strong>on</strong>g>tests</str<strong>on</strong>g> and the fungus cellar<br />

No field <str<strong>on</strong>g>tests</str<strong>on</strong>g> are menti<strong>on</strong>ed in TS 15534. Nevertheless, they<br />

should be c<strong>on</strong>sidered or recommended as a sec<strong>on</strong>d tier after<br />

laboratory <str<strong>on</strong>g>tests</str<strong>on</strong>g>. This is especially the case for the evaluati<strong>on</strong><br />

of resistance to termites, since, under field situati<strong>on</strong>s, WPCs<br />

may be either neglected as a source of food or attacked <strong>on</strong>ly<br />

to a minimum when there is a choice between several food<br />

sources including all sorts of natural, cellulose c<strong>on</strong>taining<br />

materials. For testing WPC-materials or products against<br />

microbial decay the test methods for preservative treated<br />

<strong>wood</strong> can be adopted with success (28). However, since field<br />

<str<strong>on</strong>g>tests</str<strong>on</strong>g> can take several years, methods for accelerated testing<br />

in soil (e.g. fungus cellar) should be c<strong>on</strong>sidered (29, 30).<br />

ENHANCING THE DURABILITY OF WPCS<br />

AGAINST ORGANISMS<br />

As menti<strong>on</strong>ed above, several steps can be c<strong>on</strong>sidered to<br />

improve the resistance of WPC to biological attack. These<br />

c<strong>on</strong>siderati<strong>on</strong>s will certainly also be driven by cost and<br />

intended lifespan. Wood waste from saw mills etc. is a cheap<br />

raw material to substitute <strong>plastic</strong>s with. Wood of fast growing<br />

species is easier to source and therefore cheaper than <strong>wood</strong><br />

from slow growing species. Also, <strong>wood</strong> modificati<strong>on</strong> processes<br />

exist (e.g. acetylati<strong>on</strong>) that improve the resistance against<br />

decay compared to n<strong>on</strong>-modified <strong>wood</strong> (2). However, these<br />

processes have to be performed before the <strong>wood</strong> comes in<br />

c<strong>on</strong>tact with the <strong>plastic</strong> and therefore causes additi<strong>on</strong>al<br />

producti<strong>on</strong> costs. Today, zinc-borate is the major biocide<br />

used in WPCs against a wide range of organisms. It exhibits<br />

fungicidal properties against surface moulds (31) and <strong>wood</strong><br />

decaying fungi and it is termiticidal. It is also thermally stable<br />

and thus compatible with producti<strong>on</strong> process of WPC and<br />

acts a flame retardant for <strong>plastic</strong>s (3). Fungicides acting<br />

against surface moulds <strong>on</strong>ly, e.g. Thiabendazole or DCOITbased<br />

formulati<strong>on</strong>s, are also employed. Anti-algal properties<br />

<strong>on</strong> the surface of WPCs can be introduced into a WPC<br />

material e.g. by algicides such as Terbutryne.<br />

CONCLUSION<br />

Depending <strong>on</strong> the expected life time and type of exposure (see<br />

use classes above), WPCs can become overgrown by and/or<br />

attacked by microorganisms. Furthermore, termites are a hazard<br />

to WPCs in certain regi<strong>on</strong>s of the world. Even if termites <strong>on</strong>ly<br />

attack WPCs under natural field c<strong>on</strong>diti<strong>on</strong>s to a minimum, they<br />

can provide ports of entry for increased moisture and thus<br />

favour microbial decay. Depending <strong>on</strong> the intended use of a<br />

WPC material, its durability and performance should be tested.<br />

TS 15534 lists some tools in this respect. Field <str<strong>on</strong>g>tests</str<strong>on</strong>g> and fungus<br />

cellar <str<strong>on</strong>g>tests</str<strong>on</strong>g> should be c<strong>on</strong>sidered as further opti<strong>on</strong> to characterise<br />

the l<strong>on</strong>g-term stability of a WPC material or products. Further,<br />

tailored test protocols would be advisable to optimise product<br />

developments outside of a given standard.<br />

REFERENCES AND NOTES<br />

1. D. Vogt, M. Karus et al., nova-publicati<strong>on</strong>s, nova-Institut GmbH (2006).<br />

2. P. Larss<strong>on</strong>-Brelid, paper prepared for the 37th meeting of Int. Research<br />

Group <strong>on</strong> Wood Preservati<strong>on</strong>; Tromsoe, Norway, accessible under<br />

www.IRG-wp.org, IRG/WP 06-40338 (2006).<br />

3. W. Wang, J.J. Morrell, Forest Products Journal 54, pp. 209-212 (2004).<br />

4. C.M. Clem<strong>on</strong>s, R.E. Ibach, Forest Products Journal 54, pp. 50-57 (2004).<br />

5. J. Sim<strong>on</strong>sen, C.M. Freitag et al., Holzforschung 54, pp. 2005-2008<br />

(2004).<br />

6. N.E. Hickin, The Insect Factor in Wood Decay, Hutchins<strong>on</strong>, L<strong>on</strong>d<strong>on</strong> (1968).<br />

7. M.J. Pearce., Termites, CAB Internati<strong>on</strong>al (19997).<br />

8. T. Abe, D.E. Bignell et al., Termites: Evoluti<strong>on</strong>, Sociality, Symbioses, Ecology,<br />

Kluwer Academic Publishers (2000).<br />

9. S.S. Bampt<strong>on</strong>, D. Butterworth et al., Material und Organismen 1,<br />

pp. 185-199 (1965/66).<br />

10. D. Butterworth, D. Kay et al., Material und Organismen 1, pp. 257-269<br />

(1965/66).<br />

11. R. Mannesmann, Material und Organismus 8, pp. 107-120 (1973).<br />

12. R.H. Beal, J.K. Mauldin et al., United States Department of Agriculture<br />

Home and Garden Bulletin 64 (1986).<br />

13. G. Becker, Materialprüfung 5, pp. 218-232 (1963).<br />

14. D. Butterworth, D. Kay et al., Material und Organismen 1, pp. 241-255<br />

(1965/66).<br />

15. U. Unger, A. Unger, Plaste und Kautschuk 31, pp. 241-247 (1984).<br />

16. W. Unger, Holztechnologie 26, pp. 240-241 (1985).<br />

17. DIN EN 599-1:1997 Durability of <strong>wood</strong> and <strong>wood</strong>-based products -<br />

Performance of preventive <strong>wood</strong> preservatives as determined by biological<br />

<str<strong>on</strong>g>tests</str<strong>on</strong>g> - Part 1: Specificati<strong>on</strong> according to hazard class (1997).<br />

18. American Wood-Preservers’ Associati<strong>on</strong> Standard, ASTM U1-07 2007 Use<br />

Catergory System: User Specificati<strong>on</strong> for treated <strong>wood</strong> (2007).<br />

19. CEN/TS 15534-1:2006 Wood Plastic Composites (WPC) - Part 1: Test<br />

methods for characterisati<strong>on</strong> of WPC materials and products (2006).<br />

20. ISO/FDIS 16869 “Plastics – Assessment of the effectiveness of fungistatic<br />

compounds in <strong>plastic</strong> formulati<strong>on</strong>s” (2008).<br />

21. EN 15458 “Paints and Varnishes - Laboratory method for testing the<br />

efficacy of film preservatives in a coating against algae” (2007).<br />

22. EN 117: 2005 “Wood preservatives - Determinati<strong>on</strong> of toxic values against<br />

European Reticulitermes species - (Laboratory method)“ (2005).<br />

23. ENV 12038:2002 “Durability of <strong>wood</strong> and <strong>wood</strong>-based products – <strong>wood</strong><br />

based panels - Methods for determining the resistance against <strong>wood</strong>destroying<br />

basidiomycetes” is suitable (2002).<br />

24. CEN/TS 15083-2:2005 “Durability of <strong>wood</strong> and <strong>wood</strong>-based products -<br />

Determinati<strong>on</strong> of the natural durability of solid <strong>wood</strong> against <strong>wood</strong>destroying<br />

fungi, test methods - Part 2: Soft rotting micro-fungi” (2005).<br />

25. DIN EN 927-6:2006 Paints and varnishes - Coating materials and coating<br />

systems for exterior <strong>wood</strong> - Part 6: Exposure of <strong>wood</strong> coatings to artificial<br />

weathering using fluorescent UV lamps and water (2006).<br />

26. DIN EN 321:2002 Wood-based panels - Determinati<strong>on</strong> of moisture<br />

resistance under cyclic test c<strong>on</strong>diti<strong>on</strong>s (2002).<br />

27. DIN EN 152-1:1989 Test methods for <strong>wood</strong> preservatives; laboratory<br />

method for determining the protective effectiveness of a preservative<br />

treatment against blue stain in service (1989).<br />

28. DIN EN 252:1990 Field test method for determining the relative protective<br />

effectiveness of a <strong>wood</strong> preservative in ground c<strong>on</strong>tact (1990).<br />

29. I. Stephan, M. Grinda et al., Internati<strong>on</strong>al Research Group <strong>on</strong> Wood<br />

Preservati<strong>on</strong> DocNo. IRG/WP 98 20149 (1998).<br />

30. J. van Acker, paper prepared for the 37th meeting of Int. Research Group<br />

<strong>on</strong> Wood Preservati<strong>on</strong>; Tromsoe, Norway 2006, accessible under<br />

www.IRG-wp.org, IRG/WP 06-20347 (2006).<br />

31. B.Daws<strong>on</strong>-Andoh, L. Matuna, Holz als Roh - und Werkstoff 65, pp. 331-<br />

334 (2007).<br />

INA STEPHAN, RUDY PLARRE<br />

BAM Federal Institute for Materials Research and Testing<br />

Unter den Eichen 87<br />

Berlin, 12205, Germany<br />

chimica oggi • Chemistry Today • vol 26 n 3 / May-June 2008

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