January 2000 version

SECTION 4:
Material Preservatives
For all product types considered as material preservatives, the overview provides information on: Existing methods for efficacy testing Evaluation of the methods by industry (CEFIC) The above information is organised as following: An introductory part A table which provides: Standard (reference number) Date of issue Title Evaluation of standards by industry (CEFIC) Note on the evaluation of the standards by CEFIC As described under the chapter Overview Approach, CEFIC provided the Secretariat with the evaluations of the efficacy standards for the following material preservatives: Paint Film Preservation Adhesives Preservation Plastics Preservation Leather Preservation Textile Preservation Metal Working Fluid Preservation

These evaluations included nine criteria. However, due to lack of space, only those evaluation criteria which are particularly relevant to EU efficacy requirements have been included, i.e.: Degree of reproducibility Capability of the method to predict field use levels Capability of the test to consistently rank products If a relevant standard biocide is identified. Comments on the general performance of the standard.

Evaluation of some standards was performed by 2 industry experts in the field.

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SECTION 4a

January 2000 version

SECTION 4a:
Paint Film Preservation Standards
Descriptions of use patterns for paint film preservatives Antimicrobial material preservatives are incorporated into paints and other coatings to prevent the deterioration or defacement of coating films. This is not simply a preservation for aesthetic reasons, but also a preservation of the film integrity. Hyphae of the fungus can extend into the paint film, and enzymes produced degrade the coating. The pests controlled are primarily fungi, mold and mildew which originate from airborne spores or from the soil. The ideal material preservative for this application is compatible with the product, cost effective, stable, safe, but also needs to be resistant to exposure to weather conditions (not leached) and ultra violet. Methods of efficacy testing for biocides used in paint film preservation The EPAS/EPFP database of efficacy tests included 11 Standard methods for paint preservatives: 5 ASTM standards, 2 BSI Standards, 1 AFNOR, 1 US Federal standard, 1 Irish standard and 1 Singaporian. The Secretariat has identified an Australian Standard. The ASTM standards were also referenced by Canada. However, not all these 13 standards describe methods for determining the efficacy performance of paint film preservatives. Specifically, there are 7 standards which evaluate the resistance or susceptibility of paint films to microorganisms mainly fungi and some algae: NF X41-520, ASTM D3273-94; ASTM D3456-86(1991)e1; BS 3900:1989; Federal test method 6271.1; IS 129; SS 345. Evaluation of methods for efficacy testing of biocides used in paint film preservation CEFIC has provided the Secretariat with the evaluation sheets for almost all these standards. The evaluation of each method was performed by at least 2 industry experts in the field. It should be mentioned that in some cases the industry evaluators appear to have a different opinion for specific features of a standard. When the views are not identical, it is indicated in the table below using a separate bullet for each different answer. According to CEFICs report Comments and Proposals Concerning Efficacy Data Requirements in the context of EU Biocides Directive (98/8/EC): After examination of the collected test methods on the EPAS/EPFP database, it is our opinion that there is no method which could be successfully used for comparative purposes. The main reasons for reaching this conclusion are that the limited test criteria (such as test species and substrate) do not reflect in-use or field performance. Further to this, results obtained with these standard methods are at best absolutely matrix specific and have low levels of reproducibility. In addition, there are no internal reference standard biocides. The American Standard Field Trial Method ASTM D 3456-81-1991 highlights the wide range of factors which affect the observed in-use performance of a biocide. Even this is matrix specific. It is also recognises that variations will occur from year to year. Field trials involving the matrix to be protected are supposed to be the ultimate test. In the table below a list of the 11 standards identified by CEFIC and Secretariat is given.

53

SECTION 4a

January 2000 version

Table 4a: Paint Film Preservation Standards

Standard Date/ Issue Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

NF X41-520

1968

Test method for the resistance of paints to microorganisms and their protective capabilities

Standards for paint film preservation 2 No No No

ASTM D3273-94 ASTM D345686(1991)e1 ASTM D5590

1 1

1991

1991

Resistance to growth of mold on the 8 surface of interior coatings in an 1 environmental chamber 6/7 Standard practice for determining by exterior exposure tests the susceptibility of paint films to microbiological attack Test method for determining the resistance of paint films and related coatings to fungal defacement by accelerated four-week agar plate assay Method of test for paints Part G6: Assessment of resistance to fungal growth Part G6: Assessment of resistance to algal growth (draft) Mildew resistance of organic coating materials Emulsion paints. Appendix H. resistance to fungal growth

No

Yes

No (only in a single matrix) Yes

No

No

Test of mixed inoculation (spore/mycelium) Test of burying Test of exposure to a tropical chamber Test of ageing Test of radiation Test by spaying of dirty?? Ranking can be done only in a single matrix. High variability due to soil. Different substrates will give different results. Ranking is matrix specific and site specific) All factors which affect susceptibility of paint are mentioned Identified by the Secretariat

1994

BS 3900

1989

5/6

No Yes

No Yes

No

Designed to predict field performance but is absolutely matrix specific. Some degree of reproducibility

Federal test Method 6271.1 IS 129

1965

No

No

No

Matrix and substrate specific ie. filter paper. Use anyone of 3 test organisms Only two test species Filter paper only substrate. Matrix specific

1964

No

No

No

54

SECTION 4a

January 2000 version

Table 4a: Paint Film Preservation Standards (cont.)

Standard Date/ Issue
1990

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

SS 345

SISIR Specification for algae resistant emulsion paint for decorative purposes

No

No

No

Only 1 test algae. Matrix specific. No substrate. Species grow in algal medium in solution on paint film Evaluation of growth on surfaces. Not a performance test. Not a performance standard

ASTM 1 D3274-95 ASTM D392480(1991)e1 ASTM D4610-98

1

1995

1991

1998

BS 3909-C

Other standards Standard method for evaluating degree of surface disfigurement of paint film by fungal growth or soil and dirt accumulation Specification for Standard Environment for Conditioning and Testing Paint, Varnish, Lacquer, and Related Materials Guide for determining the presence of and removing microbial (fungal or algal) growth on paint and related coatings Specification for ingot lead radiation No evaluation sheet provided shielding algal evaluations

Not a performance standard

Apart CEFIC, Canada also refers to this method.

55

SECTION 4b

January 2000 version

SECTION 4b:
In-can Preservation Standards
Descriptions of use patterns for In-can preservatives According to the descriptions of the use patterns provided Karen McCullagh in the Document 2A of the 2nd meeting of OECD Biocides Steering Group in Paris February 1999: Emulsion paints are consisted of polyvinyl acetate which is produced commercially using emulsion polymerization techniques. In container, emulsifiers and protective colloids used in the polymerization process provide nutrients for microorganisms. If allowed to proliferate, the microorganisms cause physical changes in the latex emulsions including discolouration, odours, emulsion breakage, and slime build-up. Any of these can render the product unfit for further use. Manufacturers of latex use small amounts of antimicrobial agents before it is stored or shipped to prevent this. Adhesives in container contain a high water and surfactants concentration and therefore are susceptible to microbial attack. Biocides are therefore used to protect them.

Methods of efficacy testing for biocides used for in-can preservation and their evaluation The CEFIC list of efficacy tests included 5 standard methods for in-can preservatives. These are National standards mainly for emulsion paints. Additionally, CEFIC has provided the Secretariat with evaluation sheets of these standards. The evaluation of some standards was performed by 2 industry experts in the field. In some cases the industry evaluators appear to have a different opinion for specific features of a standard. When the views are not identical, the different views are indicated using a separate bullet for each different answer. According to CEFICs report Comments and Proposals concerning Efficacy Data Requirements in the context of EU Biocides Directive (98/8/EC): The existing few National standards for assessing the effectiveness of biocides for the in-can protection of paints are either limited to the determination of Minimum Inhibitory Concentrations in artificial matrices or do not give sufficient detail or guidance to carry out a properly controlled challenge test. No reference biocides are used nor are standard paint formulations recommended. thus comparisons between biocides are impossible. Reproducibility is low and the tests are not predictive of field performance. No data is given on the precision of the results obtained. In the table below a list of the 6 standards identified by CEFIC and Secretariat is given.

56

SECTION 4b

January 2000 version

Table 4b: In-can Preservation Standards

Target organisms Type of product Standard Date/ Issue Title
Reproducibility? Predict field use levels?

CEFIC Evaluation
Ranking of products Standard biocide identified? Comments

Fungi Soil microorganis ms Bacteria

Paints

NF X41520

1968

Paints (emulsion)

SABS 1102

Microorganisms Paints (emulsion)

ASTM D25714-97

Standards for efficacy testing of In-can preservatives 2 No No No Test method for the resistance of paints to microorganisms and their protective capabilities 1987 Bacterial efficacy of No method evaluation sheet provided biocides used in waterbased emulsion paints No 1997 Test method for the Yes (for No 7 resistance of emulsion one 1 (see 2nd paints in the container to paint) bullet in attack by microorganisms comments No column)

Bacteria Yeast Fungi

Adhesives

ASTM D4783-97

1997

Test methods for resistance of adhesives preparations in container to attack by bacteria, yeast and fungi

Yes

No

No

Not suitable for bacteriostatic compounds Although this method purports to be able to assess performance of in-can paint preservatives it falls far short of procedures to carry this out. Indeed it states that no precision or bias can be attached to the test because it is.. Well written method which pays attention to In-can situations ie using mixed cultures derived from contaminated adhesives. However, the ...?? allowable means that direct comparisons of biocide efficacy ..??

57

SECTION 4b

January 2000 version

Table 4b: In-can Preservation Standards (cont.)

Target organisms Type of product Standard Date/ Issue Title
Reproducibility? Predict field use levels?

CEFIC Evaluation
Ranking of products Standard biocide identified? Comments

ASTM D 5588-97

1997

DIN 58 940 Part 5

1979

Other standards This test is identified by the Secretariat as relevant to In-can preservation but it is not Test method for a efficacy testing standard determination of the microbial condition of paint, paint raw materials and plant areas 7 No No No It can not be used to assess Method for the application related to efficacy determination of susceptibility of pathogenic bacteria to chemotherapeutic agents; determination of MIC by broth dilution method

58

SECTION 4c

January 2000 version

SECTION 4c:
Adhesive Preservation Standards
Methods of efficacy testing for biocides used for adhesive preservation The CEFIC list of efficacy tests included only 6 Standard methods related to adhesive preservation: 4 British standards from BSI and 2 American standards (ANSI and ASTM). However, only one of them (ASTM D4300) seems to be relevant to the efficacy testing of adhesive films against micro-organisms and specifically fungi. The other standards are mainly specification standards for adhesives mainly for installation of ceramic tiles, mosaics and for hanging wall coverings. Note that only one of the 4 BSI standards could be located on BSI web site. Additionally, the Secretariat has identified one standard from SAA relevant to a method for resistance of adhesive films to fungal growth. Regarding the efficacy testing of biocides used to protect the adhesives in container (in can) only one standard has been identified, i.e. ASTM D4783-89 and it is included in the table for In-can preservation. Evaluation of methods for efficacy testing of biocides used in adhesive preservation CEFIC has provided the Secretariat with evaluation sheets of these standards. The evaluation of some standards was performed by 2 industry experts in the field. Where the views are not identical, the different views are indicated in the table below using a separate bullet for each different answer. According to CEFICs report Comments and Proposals concerning Efficacy Data Requirements in the context of EU Biocides Directive (98/8/EC): After examination of the collected test methods on the EPAS/EPFP data base, it is our opinion that there is no standard method which could be successfully used for comparative purposes. The main reasons for reaching this conclusion are that differing adhesive types have differing application and therefore require different test methods. Most of these methods are based around simple agar diffusion techniques which at best indicate some level of antimicrobial activity in a given matrix. Limited test species are described with, in some cases, only one non-target fungus being the challenge. In just one case is a reference internal standard biocide mentioned however, as this compound is susceptible to hydrolysis in alkaline conditions, its performance will vary dramatically between matrices. Finally, one test method was so poor that it resulted in a paper being published which highlighted its shortcomings.

59

SECTION 4c

January 2000 version

Table 4c: Adhesive Preservation Standards

Standard Date/ Issue
1972

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

ANSI A136.1

1 American National Standard for Organic Adhesives for installation of ceramic tile. Methods of Testing materials for Resistance to Fungal Growth. Part 10: Resistance of Adhesives and Glues to Fungal Growth. Standard test methods for ability of adhesive films to support or resist the growth of fungi

AS 1157.10

1979

ASTM D4300-97

1997

BS 3046

1981

BS 5350

1987

Specification for adhesives for hanging flexible wallcoverings Methods of test for adhesives Part D1: Laboratory ageing conditions for testing bonded joints

No No Other species are in field also important, No (other therefore, no production of the field use level. species as No Aspergillus niger in studies mentioned. Aspergillus are also important Identified by the Secretariat. This standard is under revision (Revision draft DR 98439 CP). It describes procedures for determining the resistance of water-resistant and water-sensitive adhesives and glues to fungal growth which may have an adverse effect on appearance. Any changes in physical properties or performance of the products are not assessed. This standard provides a laboratory test which is intended to provide severe, standardised assessment of fungal resistance under laboratory conditions. It does not include testing in the field. No No (not for No In the standard is mentioned that activity of 8 humid certain biocides may not be demonstrated by 4/5 condition. these test methods as a result of irreversible Matrix reaction with some of the medium specific constituents (e.g. quarternary ammonium compounds are inactivated by agar). Bacteria are not mentioned; they are also important in the ??? of liquid adhesives 3 Yes No Yes Different adhesives need different biocides. Standard biocide could hydrolyse giving varying results 1 No No No No practical method

60

SECTION 4c

January 2000 version

Table 4c: Adhesive Preservation Standards (cont.)

Standard Date/ Issue
1990

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

ISO 9142

BS 5385

1976

BS 5980

1980

Adhesives - Guide to the Method identified by the Secretariat. It seems to be identical with the BS 5350. However, the latter selection of standard standard was not possible to be identified in BSIs web site. laboratory ageing conditions for testing bonded joints Only refers to BS 5380 Code of practice for wall tiling Part 1: Internal ceramic wall tiling and mosaics Part 2: External ceramic wall tiling and mosaics Specification for adhesives Only Aspergillus niger for use with ceramic tiles and mosaics

61

SECTION 4d

January 2000 version

SECTION 4d:
Plastics Preservation Standards

Methods of efficacy testing for biocides used for plastics preservation The CEFIC list of efficacy tests included 10 standard methods related to plastics preservation which are mainly AFNOR and ASTM standards. However, most of these methods assess the inherent resistance of the polymer formulation to microorganisms (bacteria, fungi and algae) and do not specifically relate to the influence of preservatives in plastics performance. Only one standard (ASTM E1428-91) is evaluating the performance of antimicrobials in/on polymeric solids against staining by Streptoverticillium reticulum (bacteria). Evaluation of methods for efficacy testing of biocides used in plastics preservation CEFIC has provided the Secretariat with the evaluation sheets of the above standards. According to CEFICs report Comments and Proposals concerning Efficacy Data Requirements in the context of EU Biocides Directive (98/8/EC): National Standards exist for assessing the inferent biodegradability/resistance of plastics and any fungi toxic activities using well defined methodologies. However, reproducibility is low as the assessment is carried out by a visual rating on the amount of microbial growth on a sample or the zone of inhibition around a preserved sample. The interpretation of the data in the latter case is difficult and different plastic formulations, even within the same basic polymer, cannot be compared using these methods. No reference materials are recommended and the methods are not predictive of field performance because of their design. No data for the precision of these tests are given.

62

SECTION 4d

January 2000 version

Table 4d: Plastics Preservation Standards

Standard Date/ Issue
1961/08

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

AFNOR: NF X41513 AFNOR: NF ISO 846

1997/08

AS 1157.11

1999

AFNOR: NF X41515 ASTM G21-96

3/62

1996

Protection of the plastic materials - Part 1: Test method of resistance of constituents to microorganisms Determination of the behaviour under the action of fungi and bacteria. Evaluation by visual examination or by measure of mass variations or physical characteristics Methods of testing materials for resistance to fungal growth - Resistance of rubbers and plastics to surface fungal growth Protection of the plastic materials - Part 3: Test method of the resistance of materials and apparatus to microorganisms Standard practice for determining resistance of synthetic polymeric materials to fungi

5/6

No

No

Yes (MgCl2)

7/8

No

No

Yes (MgCl2)

Only bacteria and fungi used; also some yeasts can cause problems

Identified by the Secretariat

5/6

No

No

No

Standard not specified

Evaluation sheets not provided

63

SECTION 4d

January 2000 version

Table 4d: Plastics Preservation Standards (cont.)

Standard Date/ Issue
1990

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

ASTM G2276(1990)

Standard practice for determining resistance of plastics to bacteria

No

No

No

ASTM G29-96

1996

Standard practice for determining algal resistance of plastics films

No

No

ASTM E1428-91

BS 2848 N/ref. 9108 CSTM

1973

No No No Test method for evaluating 2 the performance of antimicrobials in or on polymeric solids against staining by Streptoverticillium reticulum (A Pink Stain Organism) Flexible insulating sleeving Is this standard relevant to efficacy testing of plastics preservation?? for electrical purposes Methode d'valuation de la resistance des revtements plastiques en faade vis vis des microorganismes

This method assesses the inherent resistance of the polymer formulation and does not specifically relate to the influence of preservatives. The method on its own admission has a low order of reproducibility and does not recommend reference substrates. Method not specifically designed to use antimicrobial agents Only 1 alga is used which is not representative of the range of algae which could ?? plastic products. No descriptive how to incorporate biocides into plastic It can not predict field use levels

64

SECTION 4d

January 2000 version

Table 4d: Plastics Preservation Standards (cont.)

Standard Date/ Issue
1997/06

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

ISO 846

Plastics - Determination of 2 behaviour under the action of fungi and bacteria Evaluation by visual examination or measurement of change in mass or physical properties.

No

No

No

The test cannot be used for comparative testing of biocides across the range of plastics nor are the species used suitable as deteriogens of all plastics.

65

SECTION 4e

January 2000 version

SECTION 4e:
Leather Preservation Standards
Descriptions of use patterns for leather preservatives According to the descriptions of the use patterns provided Karen McCullagh in the Document 2A of the 2nd meeting of OECD Biocides Steering Group in Paris February 1999: Leather tanning is the conversion of animal skin collagen fibers into a thermally stable, hydrolytically sound non-putrescible material. Leather manufacturing is a labour intensive industry. The process can involve up to 20 different steps including wet operations and dry operations. Different types of tanning include: Chrome tanning (most common)- 4-6 hour process using trivalent chromium Vegetable tanning (sole tanning)- 12-48 hour process using vegetable extract Combination tanning - chrome/vegetable rarely used Aluminum/zirconium/iron/resin/styrene/syntan tanning - rare and expensive

Microorganisms are encountered throughout the leather manufacturing industry. Raw hides, skins, pelts arrive at the tannery with pre-existing problems such as bacterial infections. Microorganisms may be introduced into the tanning process through the raw material and process chemicals (bacteria and fungi). Microorganisms are found in the tanned leather (fungi predominate). Biocides are added primarily during the wet operations of tanning operation to control bacteria and fungi. Most of the fungicides are added as emulsifiable additives, while bactericide because of their water solubility are added directly. Evaluation of methods for efficacy testing of biocides used for leather preservation The EPAS/EPFP database included 4 standard methods related to leather preservation which are mainly standards from trade associations and concern fungi . CEFIC has provided the Secretariat with the evaluation sheets of the above standards. Additionally, the Secretariat identified 1 more recent Australian Standard relevant to persistence of leather and wet blue hides to fungal growth. According to CEFICs report Comments and Proposals concerning Efficacy Data Requirements in the context of EU Biocides Directive (98/8/EC): After examination of methods taken from the database, it is our opinion that we do no yet have a method that could be used for comparative purposes. The main reasons for this are as follows: 1. It is essential for any test used to compare one product with another, to have a high degree of reproducibility. In our opinion the degree of reproducibility in most cases examined here is poor. 2. Performance depends on the part of the leather you test, e.g. butt or neck areas (due to variable/differing biocide uptake) 3. There is little effective use of an internal reference standard. The use of an effective internal standard could offset the problems of poor reproducibility, provided there was total agreement on the standard chosen, a position history shows is difficult to achieve. The majority of the methods assessed could be used to determine if a product will perform well as a biocide, with those from the Trade organisations and LASRA of particular interest. The table below provides information on 5 standards identified by CEFIC and Secretariat. 66

SECTION 4e

January 2000 version

Table 4e: Leather Preservation Standards

Standard Date/ Issue Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

ALCA, L1

ASTM D457686(1991)e1 Australian std 1157.1 Australian std 1157.6

1991

Determination of the resistance of chrome tanned leather to the growth of fungi. Test Method for Mold Growth Resistance of Blue Stock (Leather)

2/3

No

No

No

Inoculation not exactly prescribed

2/3

No

No

Yes (but not specified)

1998

1998

BLC

1985

Methods of testing materials for resistance to fungal growth. General principles of testing pt. 1/2 Methods of testing materials for resistance to fungal growth. Persistence of leather and wet blue hides to fungal growth Practical evaluation of fungicides

No

No

No

it is mentioned in the standard that this method may not suitable to evaluate fungicides that are inactivated by proteins. This includes alkyldimethyl-benzyl ammonium chlorides. Only inocubated with Aspergillus

Identified by Secretariat

4/5

No

No

No

Not a standard. Incubation until growth can be visually seen

67

SECTION 4f

January 2000 version

SECTION 4f:
Textile Preservation Standards
Methods for efficacy testing of biocides used for textile preservation The EPAS/EPFP database and evaluation sheets included 9 standard methods related to textile preservation which are mainly AFNOR and BSI standards. The Canadian Index of Pest Management Regulatory Agency Referenced Efficacy Protocols For Antimicrobial and Insecticide Pesticides, includes 2 efficacy protocols relevant to textile preservation and Germany proposed 3 DIN standards. Additionally, the Secretariat identified 3 more recent Australian Standards relevant to textile resistance to fungal growth. All of the above protocols are included in the table below. Evaluation of methods for efficacy testing of biocides used for textile preservation According to CEFICs report Comments and Proposals concerning Efficacy Data Requirements in the context of EU Biocides Directive (98/8/EC ): After examination of methods taken from the database, it is our opinion that we do no yet have a method that could be used for comparative purposes. The main reasons for this are as follows: 1. It is essential for any test used to compare one product with another, to have a high degree of reproducibility. In our opinion the degree of reproducibility in most cases examined here is poor. 2. There is little effective use of an internal reference standard. The use of an effective internal standard could offset the problems of poor reproducibility, provided there was total agreement on the standard chosen, a position history shows is difficult to achieve. The majority of the methods assessed could be used to determine if a product will perform well as a biocide, with those from the Trade organisations and LASRA of particular interest.

68

SECTION 4f

January 2000 version

Table 4f: Textile Preservation Standards

Standard Date/ Issue
1992

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

BS6085

Determination of the resistance of textiles to microbiological deterioration Determination of breaking strength and elongation of woven fabrics Preservatives and treatments for textiles - parts 1 and 2 Performance requirements for textile preservative treatments mildew resistance of organic coatings A rapid method for assessing the efficacy of biocides applied to textiles Test of cellulosic textiles to microorganisms (natural or artificial). Mixed inoculation method (spores/mycelium) Test of cellulosic textiles to microorganisms (natural or artificial). - Burying method Test of cellulosic textiles to microorganisms (natural or artificial). - Exposure in a tropical chamber Textile preservation. Test method of resistance to microorganisms of the stringing and the cables in natural fibre, marine use. Methods of testing materials for resistance to growth -Resistance of textiles to fungal growth

2/3

Yes

No

No

5 different tests (Agar plate, soil ???, saturated atmosphere..) Very complex test method No standard biocide identified

BS2576 BS12087 UK Reference 68-141/1 WIRA NF X 41-600

1986 1981 1990

Not evaluation sheets provided Not evaluation sheets provided

1985 03/71

No

No

No

Yes (No statistics)

Yes

Yes

Not fixing products or those which have no affinity to wool Not very accurate Required a dynamometer and could become more complex.

NF X 41-601 NF X 41-602

03/71 07/76

Not evaluation sheets provided 1 No No No Required an oven with tropical atmosphere.

NF X 41-603

07/76

Not evaluation sheets provided

AS 1157.21998

1998

Identified by the Secretariat

69

SECTION 4f

January 2000 version

Table 4f: Textile Preservation Standards (cont.)

Standard Date/ Issue
1999

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

AS 1157.31999 AS 1157.41999 Sweizerische Normen Vereinigung (SNV) Appendix A EPA Fungicides Evaluation DIN 53931 DIN 53933

1999

Methods of testing materials for resistance to growth - Resistance of cordage and yarns to fungal growth Methods of testing materials for resistance to growth - Resistance of coated fabrics and electronic boards to surface fungal growth

Identified by the Secretariat

Identified by the Secretariat

1975/12

Examination of the Antibacterial Effect of Impregnated Textiles by the Agar Diffusion Test Fabric Mildew Fungistatic Test Method

Referenced by Canada

1970/12

Referenced by Canada

1993/01 1992/04

DIN EN 918

1995/11

Referenced by Germany Testing of textiles. Determination of the resistance of textiles to mildew. Growth test Referenced by Germany Testing of textiles. Determination of the resistance of cellulose textiles against microorganisms (resistance to bacteria and fungi in soil). Identification of rotting retardant finishing Referenced by Germany Geotextiles and geotextile-related products. Dynamic perforation test (cone drop test)

70

SECTION 4g

January 2000 version

SECTION 4g:
Metal Working Fluid Preservation Standards
Descriptions of use patterns for metal working fluid preservatives
The following descriptions were provided by Karen McCullagh, PMRA, Canada

Description of sites and pest problem Metal removal operations such as cutting or grinding, or metal forming operations e.g., rolling into sheets or drawing into wire inherently generate heat which can damage machine tools. Metalworking fluids are sprayed on or poured over the points of contact between the metal stock being worked and the metalworking tool, to carry away the heat generated there. Metal working fluids are used in large quantities in all types of metal forming operations. The open nature of the systems provides many opportunities for microbiological contamination. Once contaminated metal working fluids offer a fertile growing medium. The effects of microorganisms on metal working fluids are numerous. Bacteria can deplete emulsifiers resulting in oil separation and loss of lubricating properties. Corrosion inhibitors are metabolised resulting in increased corrosion of the workpiece, tools and machine parts. Acid metabolites are excreted again resulting in corrosion as well as pH changes and odour production. Fungi growing the metal working fluids results in clumps attached to the surfaces of the reservoirs and troughs of the system. Eventually the clumps break loose and clog filters and orifices, foul machines and work pieces, and create odours in the plant. There are several ways in which microbes can be introduced into metalworking fluids. The working fluids are typically open to the air, permitting contamination by airborne spores. Dirt, inherent in industrial operations, can easily find its way into fluid systems, especially if fluid return lines consist of trenches cut in the concrete floor and covered with metal grates. When microbes begin to thrive in fluids, the white milky colour of a diluted soluble oil or semi-synthetic fluid will darken to a tan or brown colour. Different species in the mixed microbial populations which grow in working fluids will deplete the concentrations of fluid chemical components by using them as energy sources. The original ratio of chemicals in the freshlydiluted fluid can be exactly restored only by draining the fluid after it becomes unworkable, and replacing it with a fresh charge. Sufficient gas production in the course of metabolic processes will create noticeable levels of unpleasant odours. Especially prevalent is the rotten egg odour of sulfides, produced by anaerobic bacteria, when a fluid is agitated after a weekend or other shutdown. In addition to chemically degrading corrosioninhibiting chemicals in working fluids, microbial masses can attack and alter the surface finish of worked metal parts. Slime build-up in fluid transfer lines can impede or even prevent fluid flow. Filters used to remove metal chips, fines and sludge can be overgrown, or blinded, resulting in fluid-flow impairment. Evaluation of methods for efficacy testing of biocides used for metal fluid preservation The CEFIC list and evaluation sheets included 6 standard methods related to metal fluid preservation: 3 ASTM standards and 3 industry standards. Only one ASTM Standard (i.e. ASTM E 686-91) is also reference by Canada. CEFIC has provided the Secretariat with the evaluation sheets for some of the above standards.

71

SECTION 4g

January 2000 version

According to CEFICs report Comments and Proposals concerning Efficacy Data Requirements in the context of EU Biocides Directive (98/8/EC): A number of relatively simple methods are available. However, the majority of these are laboratory-based methods and are severely limited in their ability to predict the field use-levels of biocides. This is due to the inability of laboratory tests to fully reproduce the important plant variables that can markedly influence overall biocide efficacy, e.g. machine characteristics, the metal being worked, changing fluid characteristics on use, contamination with the most relevant microorganisms. Tests based on field trials may be capable of predicting field use levels, but the recommendations are only relevant for the plant conditions tested and cannot be extrapolated to the other field situations. Despite the above comments, certain methods can be used to rank biocides, but this ranking will only be relevant to the fluid/conditions tested. Different fluids and operating conditions will lead to different rankings. No statistical limits were provided (or could be defined) for the methods assessed. Caution must therefore be applied in the interpretation of any ranking obtained using these methods. No standard biocides were identified in the methods assessed. In summary, it would appear that certain of these methods could be adapted to demonstrate the basic ability of a biocidal product to control the microbial contamination of a (defined) fluid. However, a universal, statistically validated test for all fluids with the ability to rank biocides in support of comparative assessment does not exist. Furthermore, the development of such a test is likely to be technically difficult, resource intensive and stands little change of final success. The table following provides information on the 6 standards identified by CEFIC.

72

SECTION 4g

January 2000 version

Table 4g: Metal Working Fluid Preservation Standards

Standard Date/ Issue
1991

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

ASTM E 686-91

Method for the evaluation of Antimicrobial Agents in Aqueous Metal Working Fluids

Not defined

No

Yes/No

No

ASTM E 979-91

1991

Test Method for the evaluation of Antimicrobial Agents as Preservatives for Invert Emulsions and other Water Containing Hydraulic Fluids
Test Method for Evaluating the Bacteria Resistance of Water-Dilutable Metalworking Fluids

Not defined

No

Yes/No

No

ASTM D394692(1997)

1997

Not defined

No (see comment 5)

Yes/No

No

Ranking depends on the definition of fluid/condition inoculum. Ranking is possible only if testing the same matrix and the same inoculum. Standard biocide: method suggests any biocide may serve as a positive control based on experience Ranking: Yes, if a standard fluid is used. No, if different products are tested Different to establish if test refers to use a single defined test emulsion or there is an option to use various emulsions Field use level: It is intended to allow the prediction of the level of biocide concentration needed for in-use control but highlights also some of the reasons why this is difficult. Ranking capacity of the test depends on the level of system definition (fluid/conditions/inoculum). Thus, the test can rank products using a defined system. If the system changes ranking may change.

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SECTION 4g

January 2000 version

Table 4g: Metal Working Fluid Preservation Standards (cont.)

Standard Date/ Issue
1990

Title
Reproducibility? Predict field use levels? Ranking of products

CEFIC Evaluation
Standard biocide identified? Comments

MOD 91-70 issue

Cutting fluid, soluble, biostable joint service designation ZX-9

Not defined

Yes Yes/No (field test component) No (lab tests)

No

IBRG (draft MWF)

1993

RENAULT D551721

1987

A Standardized Screening Method for Determining the Bioresistance of and Evaluating Biocides in Aqueous Metal Working Fluids Evaluation of the Biostability of Aqueous Metal Working Fluids

Not defined

No

Yes/No

No

Method states that is not for biocides but for nobiocide containing fluids but in practice however can be used for all biocides. This test is not intended to assess biocidal efficacy but can be adapted to be useful. Reproducibility: practical experience has shown that there are too many factors beyond experimental control e.g. soxhlet performance; ??role of pumb/tubing; ?? The prediction of field use levels and ranking are system specific. The answer is yes for a defined system. However, if the system parameters change (fluid/conditions/inoculum/machine0 then use level and ranking can change. Complexicity due to inoculum preparation method Highly defined test parameters but no indication of reproducibility. Ranking will only work if all the test conditions/fluids are identical. Method is for testing brostable products, not specifically biocides or biocide containing products.

Not indicated

No

Yes/No

No

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