Exploration of Management options for HBCD · 2011. 7. 1. · cooperation with industry and...

Swerea IVF Project report 10/11

Exploration of Management options for HBCD Stefan Posner, Sandra Roos och Elisabeth Olsson

Swerea IVF AB Box 104 SE-431 22 Mölndal Sweden Telephone: +46 (0)31-706 60 00 Fax: +46 (0)31-27 61 30 www.swereaivf.se

Swerea IVF Project report 10/11

© Swerea IVF AB 2010

Swerea IVF is a leading Swedish industrial research institute with materials, processes and production systems within manufacturing and product development as key areas. Our aim is to create commercial advantages and strengthen the competitiveness and innovation capacity of our members and customers. Swerea IVF performs research and development work in close cooperation with industry and universities, nationally and internationally. Our highly qualified personnel (about 150 people) based in Mölndal and Stockholm work in the fields of:

• Working life, environment and energy • Industrial production methods • Materials and technology development • Polymers and textiles • Business development and efficiency (streamlining).

We work with applied solutions to real industrial needs. Our industry-experienced researchers and consultants are able to deliver the fast and robust results that companies require in order to secure their competitiveness on the market.

Swerea IVF is a member of the Swerea Group, which comprises the Swerea parent company and five research companies with materials science and engineering technology as core activities: Swerea IVF, Swerea KIMAB, Swerea MEFOS, Swerea SICOMP and Swerea SWECAST. Swerea is jointly owned by industry through associations of owners and the Swedish state through RISE Holding AB.

Swerea IVF Project-report 10/11

Table of contents

1 Introduction 5

1.1 Chemical characteristics of flame retardants 5

1.2 Reactive versus additive flame retardants 5

1.3 Halogenated flame retardants 5

1.4 The flame retardant market 6

1.5 Characteristics of HBCD 10

1.6 Composition of major stereoisomers of HBCD 10

1.7 Physico-Chemical properties 13

2 Current sources of emissions 15

2.1 Uses of HBCD 15

2.1.2 Other uses of HBCD 17

3 Emissions from production and use of HBCD 17

3.1 Production of HBCD 17

3.1.1 Releases to working environment 18

3.1.2 Releases to the environment 18

3.2 Micronising 18

3.2.1 Emissions from micronising plants 19

4 Unintentional emissions 19

5 Emissions from manufacturing processes of products that contain HBCD 19

5.1 Uses and formulation of HBCD in EPS 23

5.1.1 Emissions from manufacturing of flame retarded EPS 24

5.2 Uses and formulation of HBCD in XPS 24

5.2.1 Emissions from manufacturing of flame retarded XPS 25

5.3 Uses and formulation of HBCD in HIPS 25

5.3.1 Emissions from manufacturing of flame retarded HIPS 27

5.4 Uses and formulation of HBCD in textile back coatings 27

5.4.1 Formulation of polymer dispersion for textiles 27


5.4.2 Emissions from textile back coatings 28

6 Emissions from use of products containing HBCD 28

7 Emissions from waste containing HBCD 29

7.1 Introduction 29

7.2 Waste management of EPS end products 29

7.3 Possible emission sources from waste 30

8 Historic emissions 30

9 Management options 31

9.1 Overview of existing legislation in UN ECE region 31

9.1.1 Canada 31

9.1.2 European Union (EU) 31

9.1.3 Japan 32

9.1.5 Switzerland 32

9.1.6 United States 32

10 Substitution, alternatives and emission control techniques 32

10.1 Fire safety requirements 32

10.2 Significant physical and mechanical polymer properties 34

10.2.1 Mechanical properties 34

10.2.2 Physical properties 34

10.2.3 Health and environmental properties 34

10.2.4 Commercial viability 34

10.3 Approaches for HBCD substitution 35

10.3.1 Flame Retardant Substitution 35

10.3.2 Resin and Material Substitution 35

10.3.3 Product Redesign 35

10.4.1 Organophosphorus flame-retardants 36

10.4.2 Intumescent systems 37

10.4.3 Ammonium polyphosphate (APP) 38

10.4.4 Nitrogen based organic flame-retardants 38

10.4.5 Resin and Material Substitution to HBCD 39

10.5 Brominated flame retardants 40

10.5.1 Ethylene bis(tetrabromophthalimide (EBTPI) 40

10.5.2 Benzene, ethenyl-, aromatic-bromo derivatives (Mono-, di- and tri-bromostyrene) 41

10.5.3 Pentabromobenzyl acrylate 41

10.5.4 Decabromodiphenylethane (DBDPE) 41

10.5.5 Health and environmental aspects of brominated flame retardants 41


10.6 Possible management actions and cost implications 43

10.6.1 Global production and consumption of polystyrenes 43

10.6.2 Economic aspects on the EPS and XPS markets 45

10.6.3 The chemicals industry 47

10.6.4 Environmental and health concerns 48

10.6.5 Industrial initiatives 48

10.6.6 Market trends of halogen free flame retardants 48

10.6.7 Cost switchover considerations 49

10.6.8 Innovation and research 50

10.6.10 Third countries and international relations 50

10.7 Possible management options under the UN ECE protocol 51

11 References 52

Appendix 1 Submissions of information on HBCD from countries in the

UNECE region 54

Appendix 2 The EUROCLASS System 65

Appendix 3 UL 94 74

Appendix 4 An overview of fire requirements for textile applications 76

Appendix 5 CAplus search of current uses of different isomers to

HBCD 80

Appendix 6 Summery table of emissions and exposures of HBCD during the life cycle stages 82


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1 Introduction

1.1 Chemical characteristics of flame retardants

Flame retardants (FRs) represent a large group of chemicals that consist mainly of inorganic and organic compounds based on bromine, chlorine, phosphorus, nitrogen, boron, and metallic oxides and hydroxides. The fire safety of products can also be achieved by other means than flame retardant chemicals through materials design and barrier technologies (intumescent systems).

1.2 Reactive versus additive flame retardants

Chemical flame retardants are either additive or reactive. Reactive flame retardants are added during the polymerisation process and become an integral part of the polymer. The result is a modified polymer with flame retardant properties and different molecular structure compared to the original polymer molecule. Additive flame-retardants are incorporated into the polymer prior to, during, or more frequently after polymerisation. Additive flame-retardants are not chemically bonded to the polymer but only physically mixed into it. They may therefore, in contrast to reactive flame retardants, be released more easily from the polymer and thereby also discharged to the environment.

1.3 Halogenated flame retardants

Halogenated flame retardants are primarily based on chlorine and bromine. Typical halogenated flame retardants are halogenated paraffins, halogenated alicyclic and aromatic compounds and halogenated polymeric materials. Halogenated flame retardants also sometimes contain other heteroelements, such as phosphorus or nitrogen. When antimony trioxide is used, it is almost invariably as a synergist for halogenated flame retardants. As a synergist, the main advantage by the addition of antimony trioxide is to reduce the amount of halogenated flame retardants applied to the polymer.

The effectiveness of halogenated additives is due to their interference with the radical chain mechanism in the combustion process of the gas phase (Posner, 2006).

Chemically, they can be further divided into three classes:

• Aromatic, e.g tetrabromobisphenol A (TBBPA), polybrominated diphenyl ethers (PBDEs), and polybrominated biphenyls (PBBs).

• Aliphatic, e.g short chain chloroparaffins


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• Cycloaliphatic, e.g hexabromocyclododecanes (HBCD).

The highest amount of halogenated flame retardants is currently being used in the area of electronics in the manufacturing of circuit boards, casings for home and office electronics, including mobile phone equipment. The plastics industry is by far the largest user of flame retardants. A smaller proportion of world production of flame retardants goes to the textile and paper industries.

1.4 The flame retardant market

The aim of this chapter is to give a general overview about the international FR market. The differences between the different regions and their FR consumption will be listed in terms of volume and value.

In 2005 the total market for flame retardants in the United States, Europe and Asia was about 1.5 million metric tons and was valued at about 2.9 billion USD (see table 1). In 2008 this market has expanded to about 1.8 billion metric tons at about 4.2 billion USD. The market of FR is expected to grow at an average annual rate of about 3.7% on a volume bases over the 2007-2012 period (SRI Consulting 2008).


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Table 1 Global consumption of FRs in 1000 tons and their geographical distribution 2005 and 2008 (SRI Consulting 2005) (SRI Consulting 2008).

Category United States

Europe Japan Other Asia

incl. China (figures for

China in brackets)

Total volume

[1000 metric tons]

Value [million USD]

Year 2005 2008 2005 2008 2005 2008 2005 2008 2005 2008 2005 2008

Aluminium hydroxide (ATH)

315 345 235 280 47 49 48 61

(50)

645 735 424 559

Organo phosphorous FRs

65 72 95 83 30 32 14 22

(9)

205 208 645 838

Brominated FRs

66 64 56 45 50 56 139 246

(77)

311 410 930 1428

Antimony trioxide

33 33 22 20 17 18 44 70

(40)

115 141 523 697

Chlorinated FRs

33 33 35 40 5 5 10 53

(50)

82 131 146 291

Other FRs 51 75 47 61 11 14 14 44

(36)

123 194 197 424

TOTAL 564 622 489 529 160 173 269 495

(222)

1481 1819 2865 4236

Some other resources for example the BCC Research (2008) study states that the global market for flame retardant chemicals will grow to 6.1 billion USD in 2014,


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which means an annual growth rate of 7%. However this number was predicted before the recent financial crisis, the new expectations are lower, in annual average growth it is expected to be less than 4%. The influence of the crisis also shows that the general demand for FRs depends on the demand for the final products, which in the case of FRs means mainly the plastic market. Plastic Europe expects stagnation and slow growth on the polymer market, after the decline of 2008-2009 (PlasticsEurope, 2009). The questions that remains for further research is the slope of the sales in the coming period, the differences in the different polymer markets and the way they influence the future FR market.

Brominated flame retardants (BFR) account for about 23% of the world market, which may be regarded as a significant proportion of total world production of flame retardants (see Table 2). TBBPA and decaBDE are the most common brominated flame retardants on the global market, with about 230 000 metric tons and 73 000 metric tons respectively.

HBCD is the third most used brominated flame retardant and the global market demand in 2001 was 16 700 tons that had increased to 21 000 metric tons in 2008.

Table 1 World market in percentage of different categories of flame retardants (SRI Consulting, 2008).

FR type % of t. produced Worldwide % European FR Consum

ATH 40 53.0

Brominated FRs 23 8.6

Organophosphorus FRs 11 15.6

Antimony trioxide 8 3.8

Chlorinated FRs 7 7.6

Other 11 11.5

100 100

The European FR consumption has different indicators in terms of volumes compared to the global FR production. By volume, mineral based FRs (ATH and magnesium) compounds with 54% represent the largest group, followed by


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organophosphorus (16%), BFR (9%) and chlorinated compounds (8%). On a value basis, organophoshorus compounds are the largest group of FRs with 26%, followed by BFRs (20%), mineral based FRs (20%), antimony trioxide (9%) and chlorinated compounds (8%) (SRI Consulting, 2008).

The differences between the different regions’ FR consumption in volume are shown in figure 1. There are several reasons behind the regional differences. Asia (Japan, China and Other Asia) has the biggest demand for FRs, besides the expected growth rate of FRs, sales is also expected to be the highest in Asia (excluding Japan) (about 6-7%) compared to other regions. The growth in this region is due to the shift in production (electronic manufacturing) to these areas, especially to China, Thailand and Malaysia, Due to the so far lack of strong regulation on FRs almost half of Asia’s FR consumption still mainly consists of BFR.

Figure 1 Flame Retardant Consumption by Region in 2007 (SRI Consulting, 2008).

In the United States the current economic uncertainties are reflected on the FR market, which is expected to grow at 2-3% average annual rate through 2012. The major driving force for the US FR business is the existence of government regulations, in addition industry segments such as electronics have been self-regulating. They are aware of existing and pending international regulations, they wish to use FR systems that will be accepted worldwide (SRI Consulting, 2008).


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1.5 Characteristics of HBCD

The German company BASF used HBCD for the first time in their production of flame retarded polystyrene foams in the late 1980s. However, the substance has been on the world market since the 1960s. Hexabromocyclododecane was named Hexabromid with the CAS No 3194-55-6 when it was synthesized by BASF (KemI, 2009).

Commercially available hexabromocyclododecane (HBCD) is a white odourless non-volatile solid compound which is used as an additive flame retardant on its own, or in combination with other flame retardants.

Aliphatic brominated flame retardants, such as HBCD, are not used in large amounts on the market since they are thermally less stable than aromatic brominated flame retardants. They are hovewer more effective as flame retardants at lower temperatures than aromatic flame retardants (Tohka etl al. 2002)

Technical HBCD is often characterized as a mix of mainly three diastereomers, that are compounds that are identical except for the spatial disposition of the atoms, α -, β -, and γ -HBCD, and the final distribution of these diastereomers in technical HBCD varies with a range of about 70-95 % γ-HBCD and 5-30 % α- and β-HBCD (UNEP, 2009).

The correct stereochemistry of HBCD is still not known. Several contradicting HBCD structures have been published in the past (Heeb et .al. 2007). Technical HBCD is in reality a mix of several diastereomers and enantiomers, where the different diastereomers seldom have the same physical properties apart from enantiomers that have exactly the same physical properties.

There is ongoing research to isolate and characterize the stereochemistry of technical HBCD mixtures and assigned their relative configurations (Heeb et .al. 2007). This and other ongoing research will provide to a better understanding of the correct stereochemistry of HBCD that may support their fate and impact in several different environmental compartments.

1.6 Composition of major stereoisomers of HBCD

General data for all HBCD isomers:

Molecular summary formula: C12H18Br6 Molecular Weight: 641.7 g/mol IUPAC name: hexabromocyclododecane


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Table 3 Summary table of the composition of major stereoisomers of HBCD (European Union 2008), (CAplus)1..

CAS registry number

Chemical name Other names Common trade names Chemical structure

3194-55-6

Cyclododecane, 1,2,5,6,9,10-hexabromo-

1,2,5,6,9,10-Hexabromo-cyclododecane

Bromkal 73-6D FR 1206 FR 1206HT Pyroguard SR 104 SR 104 YM 88A

25637-99-4

Hexabromododecane (HBCD), cyclododecane, hexabromo-

Bromkal 73-6CD Nikkafainon CG 1 Pyroguard F 800 Pyroguard SR 103 Pyroguard SR 103A Pyrovatex 3887

Great Lakes CD-75P™ Great Lakes CD-75 Great Lakes D75XF Great Lakes D75PC (compacted) (Dead Sea Bromine Group Ground FR 1206 ILM Dead Sea Bromine Group Standard FR 1206 I-LM Dead Sea Bromine Group Compacted FR 1206 I-CM)c FR-1206 HBCD ILM HBCD IHM

1 Caplus is the largest chemical bibliographical database in the world today, edited and published by American Chemical Society. http://www.cas.org/expertise/cascontent/caplus/index.html

Br

Br

Br

Br

Br

Br

Br

Br

Br

Br

Br

Br


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CAS registry number

Chemical name Other names Common trade names Chemical structure

134237-50-6

α -Hexabromocyclo dodecane

(1R,2R,5S,6R,9R,10S)-rel-,2,5,6,9,10-hexabromocyclo dodecane

Br

Br

Br

Br

Br

Br

134237-51-7

β -Hexabromocyclo dodecane

(1R,2R,5R,6S,9R,10S)-rel-,2,5,6,9,10-hexabromocyclo dodecane

Br

Br

Br

Br

Br

Br

134237-52-8

γ -Hexabromocyclo dodecane

(1R,2R,5R,6S,9S,10R)-rel-,2,5,6,9,10-hexabromocyclo dodecane

Br

Br

Br

Br

Br

Br


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1.7 Physico-Chemical properties

Table 4 Summary of physico- chemical properties (ECHA, 2008)(Tema-Nord 2008).

Property Value

Physical state at 20 C and 101.3 KPa White odorless solid

Melting / freezing point Ranges from approximately:

172-184 °C to 201-205 °C

190 °C , as an average value, is used as input data in EUSES.

179-181 °C α-HBCD

170-172 °C β-HBCD

207-209 °C γ-HBCD

Boiling point Decomposes at >190 °C

Relative density 2.38 g/cm3

2.24 g/cm3

Vapour pressure 6.3·10-5 Pa (21 °C)

Surface tension --

Water solubility (20 OC)

65,6 µg/l (technical product of HBCD, sum of α-

β- and γ- HBCD in fresh water)

46,3 µg/l (technical product of HBCD, sum of α-

β- and γ- HBCD in salt water)

48.8 µg/l α-HBCD

34.3 µg/l α-HBCD (salt water)

14.7 µg/l β-HBCD

10.2 µg/l β-HBCD (salt water)

2.1 µg/l γ-HBCD 1,76 µg/l γ-HBCD (salt water)

Partition coefficient n-octanol/water (log value)

Log Kow = 5.62 (technical product)

5.07 ± 0.09 α-HBCD

5.12 ± 0.09, β-HBCD 5.47 ± 0.10 γ-HBCD


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Property Value

Flash point Not applicable

Flammability Not applicable-flame retardant!

Explosive properties Not applicable

Self-ignition temperature --

Oxidising properties Not applicable

Granulometry --

Stability in organic solvents and identity of relevant degradation products

--

Dissociation constant --

Viscosity --

Auto flammability Decomposes at >190 °C

Reactivity towards container material

--

Thermal stability --


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2 Current sources of emissions

2.1 Uses of HBCD The main downstream uses of HBCD are in the polymer and textile industries. HBCD can be used on its own or in combination with other flame retardants e.g. antimony trioxide and decabromodiphenyl ether. HBCD is used in four principal product types, which are: Expandable Polystyrene (EPS)

Extruded Polystyrene (XPS)

High Impact Polystyrene (HIPS)

Polymer dispersion for textiles

According to industry information, the main use (90 %) of HBCD is in polystyrene (PS). The predominant use of PS is in rigid insulation panels/boards for building construction (EPS and XPS). About 2 % of the total use of HBCD is in “high impact polystyrene” (HIPS). Examples of end-products containing HBCD are given in table 5 below (European Union, 2008).


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Table 5 Use patterns of HBCD (IOM Consulting 2008).

Material Use/Function End-products (Examples)

EPS Insulation • Construction, insulation boards, (packaging material)

• Packaging material (minor use and not in food packaging)

• Insulation boards (against cold or warm) of transport vehicles e.g. lorries and caravans

• Insulation boards in building constructions e.g. houses walls, cellars and indoor ceilings and “inverted roof” (outdoor)

• Insulation boards against frost heaves of road and railway embankments

XPS Insulation • Construction, insulation boards

• Insulation boards (against cold or warm) of transport vehicles e.g. lorries and caravans

• Insulation boards in building constructions e.g. houses walls, cellars and indoor ceilings and “inverted roof” (outdoor)

• Insulation boards against frost heaves of road and railway embankments

HIPS Electrical and electronic parts

• Electric housings for VCR • Electrical and electronic

equipment e.g. distribution boxes for electrical lines

• Video cassette housings Polymer dispersion on cotton or cotton/synthetic blends

Textile coating agent

• Upholstery fabric • Bed mattress ticking • Flat and pile upholstered

furniture (residential and commercial furniture)

• Upholstery seatings in


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Material Use/Function End-products (Examples)

transportation • Draperies, and wall coverings • Interior textiles e.g. roller

blinds • Automobile interior textiles

2.1.2 Other uses of HBCD

Some other uses have been reported, For example, the use of HBCD in polypropylene (PP), adhesives, latex binders and unsaturated polyester has been reported in the USA. A minor use of HBCD in polypropylene (PP) is reported by industry. HBCD can be used in adhesives and coatings and in SAN resins (styrene-acrylonitrile copolymer). It may also be used in PVC (wires, cables and textile coatings) (Posner 2006).

An extensive literature search has been carried out in CAplus[1] of uses and occurrence of HBCD isomers, see appendix 4.

3 Emissions from production and use of HBCD

HBCD is used industrially in the life cycle steps: production, formulation and industrial use with the aim to increase the flame resistance of different end-products. Products are used both professionally and by consumers, have a relatively long service life and are disposed of by different means through incineration, recycling, put on landfill or left in the environment. (KemI, 2009).

3.1 Production of HBCD

The production of HBCD is a batch-process. Elementary bromine is added to cyclododecatriene in the presence of a solvent. The process temperature is 20 to 70°C, and the reaction takes place in closed systems. The suspension obtained is filtered, the solvent is removed with water, and the product is dried, stored in a silo and packed. According to one producer, production and transportation of the

[1] Caplus is the largest chemical bibliographical database in the world today, edited and published by American Chemical Society. http://www.cas.org/expertise/cascontent/caplus/index.html


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material to silo and the packaging are done in a closed system. The product is delivered as powder or pellets.

The production method as described in general terms as follows:

• Loading of raw materials

• Bromination

• Filtering

• Drying

• Storage in silo

• Packaging

3.1.1 Releases to working environment During production of HBCD, there is potential for exposure to HBCD during packing, compaction (to form granules), when process operators have to enter the centrifuge or dryers, and, to a lesser extent, during handling of packaged HBCD in the warehouse.

3.1.2 Releases to the environment Available site-specific information on the annual release of HBCD to air and wastewater indicate emissions of HBCD into waste water and adjacent STP. (ECHA, 2008).

3.2 Micronising

The HBCD particles in some applications (e.g. for use in textile back-coating) need to be very small. Therefore some quantities of HBCD are micronised in a grinding process.


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3.2.1 Emissions from micronising plants

Based on the information given by the largest microniser in EU, only emissions to air were indentified and emissions to water and land involved in micronising were negligible (ECHA 2008).

4 Unintentional emissions

Since HBCD decomposes already at temperatures shortly above 190°C it is not likely that emissions of HBCD occur at elevated temperatures during incineration processes and may therefore not be of any concern under controlled incineration processes.

During incineration of products that contain PBDEs the formation of dioxins and dibenzfurans is a big problem. This is not the case for HBCD. However only a few studies under controlled incineration conditions are published.They show that very low amounts of dioxins and dibenzofurans are formed during incineration. (Brenner , 1993) .

5 Emissions from manufacturing processes of products that contain HBCD

As a consequence of low vapour pressure of HBCD, emissions to air at elevated temperatures are the most likely source of emissions or of particle bounded as dust. Since HBCD decomposes already at temperatures shortly above 190°C it is not likely that emissions of HBCD occur at elevated temperatures during incineration processes (Stenbeck et al, 2001).


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Table 6 Potential emission sources of HBCD for various products over its life cycle (Stenbeck et al 2001) ,(IOM Consulting 2008),(KemI 2006).

Products Manufacturing Service of life

Recycling Land fill

Controlled incineration

XPS and EPS insulation boards

E E E E O

EPS packaging

Not relevant E E E O

Textile back coatings

E E Not relevant

E O

E = Emissions cannot be excluded O= Emissions are not likely to occur Not relevant = Emissions are not an issue

There are estimated emission data provided from the HBCD Industry Users Group in 2006, see table 8 that the total emissions from insulation boards and back coated textiles are the dominant emissions sources for HBCD.( IOM 2006). In absolute volumes the use of HBCD is by far much larger for insulation boards than it is for textiles. Emissions from insulation boards may be correlated to their regional consumption, since insulations boards are bulky products that are not transported over long distances and most likely manufactured for the market where it is used (KemI, 2006). This correlation is not so clear for textiles back coatings, because of the import from other regions.


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Table 7 The estimated releases of HBCD to the environment from different use categories in EU based on consumption figures for 2006 supplied by the HBCD Industry Users Group. The data for textiles use estimates for 2007(IOM 2008).

Use Category Consumption (Tonnes/year)

Releases (kg/year)

Air Wastewater

Surface water

Total Diffuse Point

Insulation boards

11 160 654,9 350 623 1627,9 542 1085,9

Electronic devices

210 6,3 5 1,3 12,6 12,6 0

Textile coating 210 1,52 1197,5 299,4 1498,42 28,9 1469,4

Total 11 580 662,72 1552,5 923,7 3138,92 583,5 2555,3

Since a textile back coating may contain approximately 25% HBCD which corresponds to approximately a load of 7 to 9 % on the back coated fabric (70 to 90 kg HBCD per ton of fabric), the consumption of 210 tonnes HBCD, as mentioned in table 8, would only last for 2300 to 3000 kg of back coated fabrics in Europe, which sounds unlikely for the whole back coated textile consumption in EU.

For instance automotive fabrics, where HBCD is used, the import share to EU in 2008 was € 49 billion2 where each car contains approximately 30 kg of back coated fabrics. Without any accurate trade data in total it is likely that a substantial part of textiles consumed in EU, and possibly treated with HBCD, are manufactured outside EU but used within EU. Since some of these textiles are washed during service of life it is likely that point sources of HBCD applied outside EU do occur which is indicated in table 8 where elevated emissions are identified to waste water from textile service of life.

2 http://ec.europa.eu/enterprise/sectors/automotive/index_en.htm


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Table 8 The estimated releases of HBCD to the environment from manufacture and different uses of HBCD based on consumption figures for 2006 supplied by the HBCD Industry Users Group. The data for textile coating use estimates for 2007(IOM 2008).

Total HBCD emissions from

Air (kg/year)

Wastewater (kg/year)

Surface water (kg/year)

All compartments (kg/year)

Sources

Diffuse Point

Manufacturing processes

Manufacture of HBCD

2 0,73 0 2,73 x

Micronising of HBCD

0,28 0 0 0,28 x

Total 3,01

Use of HBCD in formulations

EPS and HIPS formulation

30,4 75 330 435,4 x

XPS formulation 13,5 84 10 107,5 x

Formulation of polymer dispersion for Textiles

1,4 44 11 56,4 x

Total 599,3

Professional uses

Industrial use of EPS

159 128 31 318 x

Installation of insulation boards

236 0 236 472 X

Industrial use of XPS

146 63 16 225 x

Industrial use of HIPS

6,3 5 1,3 12,6 X

Textile coating 0,12 1130 283 1413 x

Total 2440,6

Releases during service life of products

Insulation boards

70 0 0 70 X

Textiles during service life

0 21,4 5,4 26,8 X

From washing of Textiles

0 2,1 0 2,1 X

Total 98,9

Total 665 1553 925 3142 584 2559


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5.1 Uses and formulation of HBCD in EPS

Expandable polystyrene (EPS) is produced in a batch process, i.e. discontinuously, by suspension polymerization of styrene in water. Styrene is dispersed in water in the form of small droplets. Prior to combining the water with the organic phase, additives are introduced. Typically these include suspension agents, free-radical forming initiators and HBCD flame-retardant. HBCD-powder, most often delivered in paper bags with a plastic liner, with typically a content of 25 kg, is suspended at low temperatures in styrene prior to the addition of the water phase.

Normally the bags are emptied into an intermediate storage container from where the HBCD is transported via pipes and a weighing station prior the addition to the styrene. In the reactor, styrene forms the disperse phase as small monomer droplets in the continuous water phase. Final droplet size (0.01 to 0.5 mm) is determined by the ratio of disperse to continuous phase (typically 50:50) and by stirrer speed. The suspension agents prevent coalescence.

Within the monomer droplets (bulk), polymerization occurs while the reactor content is heated up and held at its reaction temperature between 65 °C to 140 °C. During this free-radical polymerization an expansion agent (e.g. pentane) is added to the reactor under pressure, where it is absorbed in the polymer droplets. In the final EPS beads, HBCD is incorporated as an integral and encapsulated component within the polymer matrix with uniform concentration throughout the bead.

After complete conversion of the styrene monomer to EPS-beads, the reactor is cooled down and the beads are separated from the water by centrifugation. The decanted water, which could contain dissolved and dispersed HBCD, is reused and exchanged on an annual basis or less frequently. The EPS beads are dried, and thereafter classified into various size fractions and surface coated. These different grades are packed in bins, bags, or transported in bulk trucks to the EPS-converters.

The maximum concentration of HBCD in EPS beads is assumed to be 0.7 % (w/w).

EPS foam is produced from EPS beads via pre-expansion of the beads with dry saturated steam, drying with warm air and shaping in shape moulds or in a continuous moulding machine. First, the raw material beads are pre-expanded in loose form with the help of dry saturated steam in pre-expanders. The raw materials are transported via pipes or tubes from the packaging containers to these stirred vessels. After expansion the beads are partly dried in fluid bed driers with warm air.


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The beads are subsequently stored in large permeable silos to “mature” for several hours up to 24 hours. During this stage the beads dry further and reach equilibrium with the ambient atmosphere around them. In the third phase the beads are transported/blown, via pipes/tubes into block or shape moulds or in a continuous moulding machine in which the product gets its shape. The foam can then be further formed by cutting, sawing or other machine operations.

5.1.1 Emissions from manufacturing of flame retarded EPS

There is only scarce actual emission data available from EPS producing industry.

The estimated releases of HBCD for manufacturing of EPS to the environment are based on consumption figures for 2006 supplied by the HBCD Industry Users Group. The emission estimates shown in Table 8 are based largely on site specific information, applying the largest emission factor from actual sites to the use quantity not covered by the specific information. They are taken from the risk assessment report (European Commission, 2008) and are based on the tonnages used in the period 2000-2004 in the EU15. Emissions may occur when HBCD is added as powder from 25 kg paper bags to the styrene reactor. With the basis of physic-chemical data of HBCD from table 4, emissions to air are possible in the production if the polymerization from styrene to polystyrene occurs at temperatures above 130 °C.

5.2 Uses and formulation of HBCD in XPS

At the production of XPS-material the formulation stage can take place either at a separate site or at the same site as the following stage of industrial use.

The HBCD is supplied either in powder or in low-dust granulated form in either 25 kg bags or in 1 ton supersacks or “big bags”. The supersacks are emptied into hoppers designed to minimize dust emissions. The HBCD is then carried to the point of mixing with screw or air driven metering equipment. The compounded polystyrene is extruded and cut into granules, and packaged. The extrudate is either air-cooled or cooled by running in a water bath. According to industry information the masterbatch can contain approx. 40 % (w/w) of HBCD.

The manufacture of XPS materials is carried out in the following way:

• The polystyrene, the additives such as processing aids, flame retardant, dye and blowing agent are fed continuously to an extruder.


25

• The polymer is melted at 240°C; the blowing agent is mixed with the melted polymer and a “foamable gel” is formed.

• The gel is then cooled before it exits through an orifice called a die, where the blowing agent volatilizes, causing the plastic to assume a foam structure. The blowing agent is usually a volatile, chemically stable compound, and by its introduction into the molten polymer, it reduces the density of the product by the formation of a myriad of closed cells within its structure.

• The foam is then trimmed to desired shape. The boards are packed into shrink-wrapped bundles and pallated. The pallets are stored for curing around a week and are then ready for shipment.

• A remainder of about 25 % of the material is recycled to the extruder. This material is mainly “skin” from the surface, with higher density. The recycled material comes in contact with water.

It will be assumed for the calculations of exposure, as a realistic worst case, that the concentration of HBCD in XPS is 3 % (w/w).

5.2.1 Emissions from manufacturing of flame retarded XPS

The estimated releases of HBCD for manufacturing of XPS to the environment are based on consumption figures for 2006 supplied by the HBCD Industry Users Group. The emission estimates shown in Table 8 are based largely on site specific information, applying the largest emission factor from actual sites to the use quantity not covered by the specific information. They are taken from the risk assessment report (European Commission, 2008) and are based on the tonnages used in the period 2000-2004 in the EU15. There is only scarce actual emission data available from XPS producing industry. When there are closed processes there are no emissions to waste water. If there is no closed system for process water there is a potential possibility of enhanced levels of HBCD in waste waters from those particular plants. Since HBCD is added before melting of the polystyrene it is possible that HBCD decomposes to a certain degree since this decomposition already takes place at temperatures shortly above 190 °C.

However with the basis of physic-chemical data of HBCD from table 4, emissions to air are possible in the production sites as small XPS plastic HBCD- containing fragments or even in air at elevated temperatures.

5.3 Uses and formulation of HBCD in HIPS

High Impact Polystyrene (HIPS) is produced either in a batch or continuous polymerization process. The final raw material is homogenized and extruded into


26

HIPS pellets either strand- or face-out. These pellets are the starting material for the production of flame-retarded HIPS. Different flame retardant additives are used of which HBCD constitutes only a small part.

The HBCD powder, delivered in plastic bags, is filled in intermediate storage containers from where the HBCD is transported to a weighing station. HBCD and other ingredients required for the particular HIPS formulation are weighed and transported further to the feeding hopper of the extrusion equipment. In the feeding hopper all ingredients together with the HIPS pellets are metered in the extruder for further mixing, homogenization and granulation into pellets.

An alternative route for HIPS production is via an intermediate-compounding route. First a masterbatch of general-purpose polystyrene pellets and HBCD at a high concentration is prepared, followed by compounding this master batch with virgin HIPS material in a conversion step. The process of preparing the HBCD masterbatch is similar to that of the HIPS production but at a higher HBCD concentration.

After the molten mass at the end of the extruder is pressed through a plate with holes (die/plate), different granulation processes take place, for example:

• face cutting in air; a rotating knife directly after the plate cut the extruded“strands” into pellets cooled by air.

• under water face cutting; a rotating knife directly after the plate in a water bath cuts the extruded strands in pellets cooled by water.

• strand cutting; the molten strands are passed through a water bath to solidify and cool and are cut in a granulator.

After the granulation process the HIPS pellets are dried and packed, either in bulk silos/containers or 25 kg bags, ready for conversion into HIPS products. The HBCD masterbatch process normally uses the strand-cutting route.

HIPS materials can be converted into HIPS products using various extrusion techniques and injection moulding. HIPS products can also be manufactured via a compounding route, i.e. mixing virgin HIPS raw material with a HBCD masterbatch during the extrusion or injection moulding process.

The HBCD content is 1 - 3 % (w/w) or in other cases 5 or 7 %. It will be assumed for the calculations of exposure, as a realistic worst case, that HIPS contains 7 % HBCD (w/w). (European Union, 2008)


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5.3.1 Emissions from manufacturing of flame retarded HIPS

There is only scarse actual emission data available from HIPS producing industry. Most potential emissions from the manufacturing of flame retarded HIPS occurs at temperatures below the degradation temperatures of HBCD so no or very low emissions to air are expected. However potential emission sources of HBCD are expected in HBCD containing dust from the manufacturing process.

5.4 Uses and formulation of HBCD in textile back coatings

HBCD is formulated to polymer-based dispersions (e.g. acrylic or latex) of variable viscosity in the polymer industry. The dispersions are then processed in the textile finishing industry.

The HBCD particles used for textile back-coating need to be very small. Therefore micronising (see chapter 3.2) is performed before the formulation step.

5.4.1 Formulation of polymer dispersion for textiles

Textile formulators prepare flame retarded formulations, which are water-based dispersions and can contain a binder system and HBCD as well as up to 20 other ingredients. These flame retarded formulations, mostly custom tailored, are supplied as dispersion to back-coaters. In this scenario, formulation is carried out in an open batch system. HBCD is added to a dispersion containing water, a polymer e.g. synthetic latex, acrylates or PVC, thickener and dispersion agent.

The chemical preparation can also contain other brominated flame-retardants such as decabromodiphenyl ether. In addition, synergists such as antimony trioxide and antimony pentoxide could also be included in the end-product. According to industry information, the concentration of HBCD in the dispersion may range from 5 to 48 %. However, additional product information indicates that a likely concentration of HBCD in the coated layer may be about 25 % corresponding to 10 - 15 % in the final dilution of the dispersion. Water and solvents will leave the preparation when dried and concentrations of flame-retardants in the coating layer will be higher than in the preparation. Preparations with the highest concentration of HBCD are assumed to be diluted before use.

The water based dispersion used by the back coaters; both paste as well as foam, need to be stable (no precipitation and no viscosity change) and should not contain particles clogging the system. This is why the particle size of the solids is so important. Too fine particles act as thickener, where too course material will


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lead to a non-stable dispersion (precipitation) and an applied coated film with a non acceptable rough surface.

Applying a back-coating to textile can be carried out in the following ways:

1. as paste where a layer is “glued” to the textile and a scratch knife defines the final thickness depending on the flame retardant standard, the textile used and the flame retardant concentration in the dispersion or

2. as foam, where a foam layer is pressed on the textile through a rotating screen. Once applied the foam cells will break resulting in a thin coating film.

The coating is dried and fixated in an oven at temperatures between 140 till 180 °C, The formulated product is used on technical textile and furniture fabric, on cotton fabrics and cotton polyester blends. For the calculations of exposure, it will be assumed that the back coating layer of the finished textile contain 25 % HBCD (European Union, 2008).

5.4.2 Emissions from textile back coatings

Releases from Textile back coating in table 8 is estimated using site specific information, applying the largest emission factor from actual sites to the use quantity not covered by the specific information. These emissions estimates are based on the tonnage used in period 2000-2004 for EU 15 countries (IOM 2008).

HBCD is added to a dispersion containing water, a polymer e.g. synthetic latex, acrylates or PVC, thickener and dispersion agent. If residues of these pastes are rejected from the process, potential emissions of HBCD is expected in surface or waste water depending on the actual plant facilities.

Since the manufacturing processes of flame retarded textile back coatings operate during curing between 140°C to 180°C, in context with physico-chemical data according to table 4, low or moderate emissions of HBCD to air are expected from textile back coating processes, (European Commission, BREF Polymers, 2007).

6 Emissions from use of products containing HBCD

HBCD is applied as an additive into the polymer matrix and is therefore not chemically bounded to the matrix. Therefore HBCD can migrate from the matrix depending on temperature, humidity and the internal molecular structure the


29

polymer matrix. There are probably diffuse emissions that dominate during service of life for consumer end products.

Diffuse emissions from insulating boards of XPS/EPS are likely to occur both in contact with rain with emissions to surface waters and through direct exposure of sun light into the atmosphere (Stenbeck et al, 2001).

Textile back coatings are common in interior textiles in buildings and transportation. When these textiles are exposed to washing they may release emissions of HBCD through waste water that ends up in STPs (Stenbeck et al, 2001).

7 Emissions from waste containing HBCD

7.1 Introduction

Increasing environmental awareness is deeply affecting end-of life management systems for wastes containing BFR. There are in short three ways to recycle products

• Recycle the product itself • Recycle materials in products • Recycle the energy content of the product

Mechanical processing and recycling may be accomplished with selective disassembly, shredding, magnetic and eddy current separation so as to generate metal-rich fractions. For many waste streams recycling routes may be blocked due to the presence of brominated flame retardants. For example the use of recycled ABS (acrylonitrile-butadiene-styrene) as a blend with PC (polycarbonate) is not possible to recycle, because the BFR causes the PC to depolymerise resulting in a poor quality of recyclate. Also, there is a large interest from the bromine industry to recover bromine from waste streams that contain brominated flame retardants by means of thermal treatment. (Tange et.al,2001)

7.2 Waste management of EPS end products

EPS has an estimated service of life of approximately 30 years which would make it rather difficult to collect and recycle used EPS with a profitable business. Some EPS can be recycled and used for the manufacture of bricks where the polystyrene is gasified and leaves a cavity in the center of the brick.


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Fragmanted EPS may be remelted and reused for insulation, drainage and soil treatment. It can also be remelted to new granulates to reduce the volumes of raw material, which would be beneficial for new EPS production of end products.

Since EPS end products are not particularly labelled, it is very hard to distinguish between HBCD flame retarded EPS and EPS without any content of HBCD. With no labelling there are at higher risk diffuse emissions of HBCD than for controlled waste streams of EPS identified with their content of HBCD (KemI 2006).

7.3 Possible emission sources from waste

Recycled products that contain HBCD are potential emission sources in the same way as virgin products.

Recycling materials include fragmentation of materials where there is a risk of potential emissions through HBCD containing particles or dust from the fragmentated recycled material.

Since HBCD decomposes already at temperatures shortly above 190°C it is not likely that emissions of HBCD occur at elevated temperatures during incineration processes and may therefore not be of any concern under controlled incineration processes.

During incineration of products that contain PBDEs the formation of brominated dioxins and dibenzofurans is a big problem. This is not the case for HBCD. However only a few studies under controlled incineration conditions are published but they show that very low amounts of dioxins and dibenzofurans are formed during incineration.( Brenner, 1993)

Uncontrolled incineration may result in potential emissions of incineration residues of unknown chemical composition, which of course may pose risks for health and environment at local compartments. If the uncontrolled incineration process is done at temperatures below 200°C there is a possibility that HBCD containing particles are emitted from the incineration source under uncontrolled conditions.

8 Historic emissions As metioned earlier in this report the German company BASF used HBCD for the first time in their production of flame retarded polystyrene foams in the late 1980s. However, the substance has been on the world market since the 1960s. (KemI, 2009). Since there is no historic data available of HBCD production over


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these decades in context to market data of HBCD containing products there is no possibility to assess historic emissions of HBCD.

9 Management options

9.1 Overview of existing legislation in UN ECE region

The flame retardant market is affected by regulation in two countervailing ways. On the one hand, the international regional and national fire safety and flammability regulations are becoming stricter. On the other hand, there are changes in the regulations due to new studies according to which certain chemical species are deemed to have deleterious effects on the environment and on human health. Countries with current regulation, ongoing risk assessments or other legal information on HBCD are listed below. Information from a current review based on a questionnaire from each country in the UN ECE region is listed in annex 1.

9.1.1 Canada

In Canada a risk assessment of HBCD a final draft will be published in 20103.

9.1.2 European Union (EU)

REACH (Registration, Evaluation, Authorization and restriction of Chemical substances) legislation, which will require the registration of more than 140.000 currently marketed chemicals, including all commercial FRs in use. It is expected that some BFRs will face restrictions under REACH for example HBCD, which is categorized as a substance of very high concern (SVHC) because of PBT properties. The REACH registration of FRs will make more environmental and toxicological information available, for high volume products (>1000 tons/year) by the end of 2010.

The RoHS (Restriciton of certain Hazardous Substances in electric and electronic equipment) restricts the use of four heavy metals and polybrominated biphenyls (PBBs) and polybrominated diphenylethers (PBDEs including decaBDE) in the manufacture of various types of electronic and electrical equipment. The RoHS directive is currently under revision (“recast”) and could possibly include further substance bans in the future (e.g. additive TBBPA). There is an ongoing review in EU of the RoHS directive where HBCD is proposed to be included.

3 Personal communication, Greg Hammond Environment Canada (2010)


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The WEEE (Waste Electrical and Electronic Equipment) Directive in the EU which requires the separation of plastics containing BFRs prior to recycling. However, in practice a manual separation of these materials rarely happens.

9.1.3 Japan

In Japan, HBCD was designated as the Type I Monitoring Chemical Substances because of its persistence and high bioaccumulation under the Act on the Evaluation of Chemical Substances and Regulation of Their Manufacture, etc. (commonly referred to as the Chemical Substances Control Law: "CSCL").

9.1.4 Norway

Norway has completed their national assessment and has included HBCD in its national action plan for Brominated Flame Retardants. A proposal of a national regulation with ban on use of HBCD in products is under consideration.

9.1.5 Switzerland

Switzerland has not yet regulated HBCD nor do we have reduction measures in place.

9.1.6 United States

The US Environmental Protection Agency (US EPA) has launched a review of HBCD that should be finalized in 2012 (BSEF 2009).

10 Substitution, alternatives and emission control techniques

10.1 Fire safety requirements

Together with the increasing use of easily flammable materials and products tightened legislation and tougher fire safety requirements are the major drivers for the use of flame retardants. Generally, laws demand a common basic safety level for products like electronic equipment, building products or furniture. Technical standards for these product groups define safe products. For fire safety, this is commonly done by reference to the classification of materials or products by certain fire tests, again defined in standard documents.

The manufacturer of a product has the choice of achieving the required fire safety level by using non-combustible materials like metals, adapting the design of the product or adding flame retardants to otherwise flammable materials like common


33

polymers or textiles. There are a large number of national and international fire test standards, often specific for certain application areas and representing different fire or ignition scenarios. In Europe, major efforts have been ongoing to harmonize fire safety standards in the construction and transport sector (railways)4.The EU Construction Products Directive specifies hygiene, health and environment as one of 6 essential requirements to be specified in harmonized product standards. This essential requirement recognises national legislation relating to dangerous substances, which could be emitted or released from construction products into indoor air, soil, surface or ground water or which may have an environmental impact. National restrictions shall be listed in the product standards, and standards for thermal insulation products shall contain such a list. HBCD appears on the indicative list of dangerous substances issued by the EU Commission. The directive applies to product properties when installed in a building, i.e. not the manufacturing or demolition or disposal phases.

The flammability of a material or product is not a material property alone, but depends to a large extent on factors like the ignition source (e.g. small or large flame, glowing wire, radiant panel), the shape and orientation of the specimen (e.g. horizontal or vertical) and the “heat environment”. Therefore, materials will sometimes perform differently in different fire tests and a simple ranking is not always possible. If flame retardants are added to improve the flammability behaviour of a material, just enough flame retardants are dosed to achieve the necessary performance. Typical dosages are 5% to 20%, but even concentrations up to more than 50% are necessary for the less effective inorganic flame retardants like aluminium trihydroxide (ATH). These high filling levels lead to detrimental effects on the desired polymer properties which need to be limited. Also, the flame retardant has to match the polymer in terms of physical properties and processibility, e.g. the flame retardant has to remain stable under the processing conditions (temperatures) of the polymer. Therefore, there is no “one size fits all” for flame retardants, but they have be matched to the target material.

However, certain measurable properties can be postulated for a desirable flame retardant system:

• The flame retardant should commence thermal activity in the temperature range of the thermal decomposition of the polymer

• The flame retardant should not generate any toxic gases beyond those produced by the degrading polymer itself and should not increase the smoke density of the burning polymer

4 For further reading concerning the vast diversity of fire test standards and regulatory variations from one country to another, see annex 1,2 and 3.


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10.2 Significant physical and mechanical polymer properties

Besides the preferred fire functionalities, flame retardants incorporated in the polymer may deteriorate the properties to the polymer which may limit its suitability to be used for certain applications. As many properties as possible of flame retardants need to be defined and understood as regards their functional characteristics before and during use. There are some important characteristics that need to be fulfilled in a satisfactory way in order to provide a marketable flame retarded material. These significant properties include: 10.2.1 Mechanical properties

• Not significantly alter the mechanical properties of the host polymer

• Be easy to incorporate into the host polymer

• Be compatible with the host polymer

• Should be stable under processing and service of life conditions

10.2.2 Physical properties

• Be resistant towards ageing and hydrolysis

• Not cause corrosion

• Should not bleed or bloom

• Should be stable under processing and service of life conditions

10.2.2.1 Depending on the application

• Be colourless or at least have non-discolouring properties

• Have good light stability

10.2.3 Health and environmental properties

• Not have harmful health effects

• Not have harmful environmental properties

10.2.4 Commercial viability

• Be commercially available and cost efficient


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10.3 Approaches for HBCD substitution

10.3.1 Flame Retardant Substitution

This approach involves identifying a drop-in chemical substitute for HBCD. The drop-in chemical would ideally be cost and performance comparable to HBCD. It is the simplest approach because it typically does not require changes to the polymer material or to the design of the product. This change could be implemented by the polymer processor or compounder (Morose 2006).

10.3.2 Resin and Material Substitution

This approach involves changing the resin system, while also changing the chemical used as the flame retardant. This is a more complex approach than simple flame retardant substitution because it has a greater effect on overall product cost and performance. This change could be implemented by the polymer processor/compounder or the end-product manufacturer (Morose 2006).

10.3.3 Product Redesign

This approach involves changes to the actual product design to minimize or eliminate the need for flame retardant chemicals. Examples of product redesign include using fire barrier material, as well as separating or reducing the source of heat from the product. This change could be implemented by the end-product manufacturer (Morose 2006). Essentially product redesign for insulated building constructions are combinations of flame inherent and embedded flammable materials (panels), e.g non flame retarded EPS, in such a way that the whole construction may withstand fire in a satisfactory way according to current fire standards and fire regulations.

Figure 2: An example of a fire protected insulated wall sandwich construction

If EPS is applied in constructions as described in figure 1 above, it is important that there is no open exposedsurroundings or to any ignition sources. These kind of important issues need to be considered carefully during the design of such constructions.

10.4 Chemical flame retardant substitutions to HBCD

10.4.1 Organophosphorus flame

This large group of organophosphorus flame retardants include triphenyl, isopropyl – and t-butylsubstitutthese, phosphates with larger substitution carbon chains (therefore less volatile) are commercially available.

Aryl phosphates are used as flame retardants for phthalate plasticised PVC, HIPS and styrenics. Triaryl phosphates are more efficient flame retardants than the alkylated triaryl phosphates. However, the alkylated triaryl phoshates were shown to be more efficient plasticizers than triaryl phosphates.

The three common commercial aryl phosphates HIPS and other styrenics are triphenylphosphate, resorcinol bis (biphenyl)phosphate and diphosphate (Posner 200

Figure 3 Chemical structure of phenylenetetraphenyl diphosphate

.

Figure 4 Chemical structure of

Swerea IVF Project

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If EPS is applied in constructions as described in figure 1 above, it is important open exposed surface of non flame retarded EPS exposed to the

ignition sources. These kind of important issues need to be d carefully during the design of such constructions.

Chemical flame retardant substitutions to HBCD

Organophosphorus flame-retardants

This large group of organophosphorus flame retardants include triphenyl, butylsubstituted triaryl and cresyl phosphates. In addition to

these, phosphates with larger substitution carbon chains (therefore less volatile) are commercially available.

Aryl phosphates are used as flame retardants for phthalate plasticised PVC, HIPS Triaryl phosphates are more efficient flame retardants than the

alkylated triaryl phosphates. However, the alkylated triaryl phoshates were shown to be more efficient plasticizers than triaryl phosphates.

ree common commercial aryl phosphates used as alternatives to BFRs in HIPS and other styrenics are triphenylphosphate, resorcinol bis (biphenyl)phosphate and 1-methylethylidene)di-4,1-phenylenetetraphenyl

(Posner 2006)..

Chemical structure of 1-Methylethylidene)di-4,1-nylenetetraphenyl diphosphate

Chemical structure of resorcinol bis (biphenyl)phosphate.


If EPS is applied in constructions as described in figure 1 above, it is important surface of non flame retarded EPS exposed to the

ignition sources. These kind of important issues need to be

Chemical flame retardant substitutions to HBCD

This large group of organophosphorus flame retardants include triphenyl, ed triaryl and cresyl phosphates. In addition to

these, phosphates with larger substitution carbon chains (therefore less volatile)

Aryl phosphates are used as flame retardants for phthalate plasticised PVC, HIPS Triaryl phosphates are more efficient flame retardants than the

alkylated triaryl phosphates. However, the alkylated triaryl phoshates were shown

as alternatives to BFRs in

phenylenetetraphenyl

resorcinol bis (biphenyl)phosphate.


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Figure 5 Chemical structure of triphenylphosphate.

10.4.2 Intumescent systems

Intumescent (or swelling) systems have existed since the 1940s, principally in paints. Several intumescent systems linked to textile applications have been on the market for about 20 years, and have successfully shown their great potential. Intumescent systems include use of expandable graphite impregnated foams, surface treatments and barrier technologies of polymer materials.

Almost all intumescent systems consist of three basic components

• a dehydrating component, such as APP

• a charring component, such as pentaerythritol (PER)

• a gas source, often a nitrogen component such as melamine

INCIDENT RADIANT HEAT

INTUMESCENT COATING

Cha

r la

yer

Figure 6 Mechanisms for intumescent systems.


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The main function of APP is to catalyse the dehydration reaction of other components in the intumescent system. It has been shown that in spite of the fact that APP functions as a catalyst it has been used in rather large concentrations partly due to its participation in the formation of a char structure. In polyolefin polymers it has been shown that melamine and PER act as synergists to APP. Other intumescent systems have been applied in polymers such as expandable graphite, silica based, and metal hydroxide compounds, some of them incorporated as nanocomposites. Recent research describes extended nanoparticles of clay as promising char-forming fillers for good fire protection. These applications are however still on a research level and await commercial introduction. (Posner 2006). Irrespective of the detailed mechanisms that operate for specific intumescent systems the following characteristics are always present: The formation of a thick char layer, high carbon concentration, high viscosity of pyrolyzing melt and low penetration capability for propagation of heat, which together make intumescent systems efficient to reduce flammability and the exposure of fume gases (Posner 2006).

10.4.3 Ammonium polyphosphate (APP)

APP is mainly used as an dehydrating acid source in intumescent systems, which was described in more detail in chapter 10.4.2. APP alone as a flame retardant has been found effective in polyamides and polyolefins if combined with suitable synergists.

10.4.4 Nitrogen based organic flame-retardants

One common example of nitrogen based flame retardants is melamine, which is also a common constituent in intumescent systems. Nitrogen containing polymers have been found to be synergetic with phosphorus compounds, e.g. melamine polyphosphate is typically used in combination with phosphorus-based compounds. Similar to ATH, melamine polyphosphate undergoes endothermic decomposition but at a higher temperature (350°C). It retards combustion when the released phosphoric acid coats and therefore forms a char around the polymer, thus reducing the amount of oxygen present at the combustion source. Melamine polyphosphate dissociates in water to form melamine cations and phosphate anions.


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Figure 7 Chemical structure of melamine polyphosphate.

10.4.5 Resin and Material Substitution to HBCD

10.4.5.1 Phenolic Foam

Closed cell phenolic foam has been used in the building industry for various applications such as roofing, cavity board, external wall board, and floor insulation. Phenolic resins are used to bind glass fiber, mineral wool, or shredded waste to make insulation products. Glass fiber is the most commonly used material, accounting for 88% of all phenolic insulation products. Phenol and formaldehyde are the raw materials used to make the phenolic resin monomer. Formaldehyde is used as a raw material for making phenolic resins. Formaldehyde is listed by the International Agency for Research on Cancer (IARC) as a known human carcinogen (Morose 2006).

10.4.5.2 Other Insulation Materials

There are several other materials that may be used as alternatives for EPS and XPS for certain insulation applications in the building and construction industry. The four major categories of building insulation are:

Blankets (fiber batts or rolls)

Blanket insulation is usually made of fiber glass or rock wool and can be fitted between studs, joists, and beams. They are available in widths suited to standard spacings between wall studs or floor joists. Continuous rolls can be hand cut and trimmed to fit various spaces. The blankets are available with or without vapor retardant facings. Batts with special flame resistant facings, treated with chemical flame retardants or consistent of flame inhererent materials, are available where the insulation will be left exposed.


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Loose-fill

Loose-fill insulation is typically blown into place or spray-applied by special equipment. It can be used to fill existing wall cavities and for irregularly shaped areas. Materials used for blown-in or spray-applied insulation include rock wool, fiber glass, cellulose, or polyurethane foam. Loose-fill cellulose insulation is commonly manufactured from recycled newsprint, cardboard, or other forms of waste paper. The blown-in loose-fill insulation can provide additional resistance to air infiltration if the insulation is sufficiently dense. Loose-fill insulation can also be poured in place by using materials such as vermiculite or perlite. These materials are produced by expanding naturally occurring minerals in a furnace (Morose 2006).

10.4.5.3 Alternative construction techniques

When using alternative building insulation materials or EPS and XPS without FRs, the necessary flame protection is often provided by use of a thermal barrier. Thermal barriers are fire resistant coverings or coatings that separate the insulation material from the building interior. Thermal barriers can be used to increase the fire retardant performance for various types of insulation. Thermal barriers are subject to current building code requirements. Commonly used thermal barriers include: gypsum board, gypsum or cement plasters, perlite board, spray-applied cellulose, mineral fiber, or gypsum coatings, and select plywood’s.

Using thermal barriers it is possible to fulfil fire safety requirements in most of the uses in constructions and buildings with EPS and XPS without a FR. This has been reported to be an available alternative on the market by Norway, Sweden and Spain.

10.5 Brominated flame retardants There is a wide range of brominated flame retardants (BFr) other than PBDEs, HBCD and TBBPA and its derivatives where current production volumes for these BFRs are largely unknown as well as their uses.

10.5.1 Ethylene bis(tetrabromophthalimide (EBTPI)

Ethylene bis(tetrabromophthalimide) (EBTPI) is an additive flame retardant. It finds use in polyolefins, high-impact polystyrene (HIPS), thermoplastic polyesters (PBT, PET, etc.), polycarbonate and elastomers whose applications include electrical and electronics components, wire and cable insulation, switches, and connectors (SFT, 2009).


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10.5.2 Benzene, ethenyl-, aromatic-bromo derivatives (Mono-, di- and tri-bromostyrene)

These group of brominated reactive intermediates are used in styrenic polymers and engineering plastics. (SFT, 2009) (Troitzsch, 2008).

10.5.3 Pentabromobenzyl acrylate

Pentabromobenzyl acrylate is used in polybutyleneterephatalate, (PBT), Polyethylene terephthalate (PET), ABS plastics and polyamides (SFT, 2009) (Troitzsch, 2008).

10.5.4 Decabromodiphenylethane (DBDPE)

This additive brominated flame retardant is mainly used in HIPS. It can also be used in ABS, PC/ABS and HIPS/PPE polymers. DBDPE was introduced into the market as an alternative for DecaBDE in 1991. (SFT, 2009).

10.5.5 Health and environmental aspects of brominated flame retardants

Most brominated flame retardants have negative effects on the environment and human health. This is and has been described in several scientific studies over the past 10 years.

Some of them show a strong bioaccumulation in aquatic and terrestrial food chains, some are very persistent, and some show serious toxicological effects such as endocrine disruption. During the last decade scientists in an increasing number of reports have presented evidence of these negative effects caused by BFRs.

Also a number of BFRs (PBDE’s, hexabromocyclododecane (HBCD) and tetrabromobisphenol-A (TBBPA) in particular) can be found in increasing concentrations in the human food chain, human tissues and breast milk which is of serious concern for public health.


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Table 9 Summary table of fire requirements, commercial uses and alternatives for the use of HBCD ( Posner 2006) (Morose 2006).

Polymer materials

Fire requirement(s)

Applications Commercial chemicals halogen free flame retardant alternatives

Alternative polymer material, non flammable or containing halogen free flame retardants, product redesign

HIPS UL94 (V-2)

About the UL94 standards, see appendix 2

Note:

For UL94(V-O) there are no known viable FRs alternatives to HBCD for HIPS only.

Housings of electronic products.

Wiring parts

Arylphosphates such as:

Resorcinol bis (biphenyl phosphate)

1-Methylethylidene)di-4,1-phenylenetetraphenyl diphosphate

Polymeric biphenyl phosphate

Diphenyl cresyl phosphate

Triphenyl phosphate

Alloys of PPE/HIPS5 treated with halogen free flame retardants alternatives (as mentioned in the left column) manage UL94 (V-0).

EPS & XPS

Germany

DIN 4102B1

UK

BS 476

+

Several other national standards

Insulation of foundation

Ground deck parking deck etc

No alternatives

Phenolic foams Blankets (fiber batts or rolls) or as Loose fills that may contain rock wool, fiber glass, cellulose or polyurethane foam

EPS/XPS whitout flame retardants, together with alternative construction techniques,and thermal barriers

5 PPE/HIPS: alloy of polyphenylene ether and high impact polystyrene


43

Polymer materials

Fire requirement(s)

Applications Commercial chemicals halogen free flame retardant alternatives

Alternative polymer material, non flammable or containing halogen free flame retardants, product redesign


Several fire standards, see appendix 3

Protective clothing

Carpets

Curtains

Upholstered fabrics

Tents

Interior in public transportation

Other technical textiles

In tumescent systems that contain for instance

a dehydrating component, such as ammoniumpolyphosphate (APP)

a charring component, such as pentaerythritol (PER)

a gas source, often a nitrogen component such as melamine

10.6 Possible management actions and cost implications

As earlier mentioned HBCD is used in four principal product types, which are:

• Expandable Polystyrene (EPS)

• Extruded Polystyrene (XPS)

• High Impact Polystyrene (HIPS)

• Polymer dispersions for textiles

According to industry information, the main use (90 %) of HBCD is in polystyrene (PS) The predominant use of PS is in rigid insulation panels/boards for building construction (EPS and XPS). About 2 % of the total use of HBCD is in “high impact polystyrene” (HIPS). (European Union, 2008).

10.6.1 Global production and consumption of polystyrenes

In practice, three different types of polystyrene are distinguished. The transparent and brittle polymer is called general purpose polystyrene (GPPS), the white, non-shiny but relatively flexible, rubber modified polystyrene is called (high) impact


44

polystyrene (IPS or HIPS). Expandable or foam polystyrene (EPS) is the third group to distinguish here due to its different production techniques (European Commission 2007).

Global production and consumption of polystyrene (all grades) in 2008 were approximately 16 million metric tons. Global capacity utilization was 74% in 2008, slightly lower than in 2007. Polystyrene consumption is estimated to have increased by just over 1% in 2008, and is forecast to average growth of 3.5% per year from 2008 to 2013, slowing to 3.0% per year from 2013 to 2018. Average global utilization rates are expected to increase to the mid- to high-80s range by the end of the forecast period.

General purpose (GP) and high impact (HI) polystyrene together account for almost three fourths of total global polystyrene consumption. The largest end use for GPPS and HIPS is in packaging applications, followed by appliances, and electric/electronic uses. EPS is used mainly in packaging and construction applications, especially for building insulation. (SRI Consulting 20096)

6 http://www.sriconsulting.com/CEH/Public/Reports/694.3000/


45

Figure x World consumption of polystyrene (EPS, GP and HIPS together) by end use and regions (SRI Consulting 2009).

Since around 90% of the world market volume of HBCD is used for polystyrene applications, mainly as insulation blocks in construction industry, we could expect that around 10% of the total polystyrene market applies HBCD in their end products. It is however hard to assess the influence the expected global increased market volumes of polystyrene has to to current and future market volumes of HBCD over the next coming years.

10.6.2 Economic aspects on the EPS and XPS markets

Western Europe is the second largest region worldwide concerning the consumption of polystyrenes where the EPS production sites are mainly located in Germany (27%), Netherlands (13%) and France (12%) and the XPS production sites are mainly located in Germany (21%), Italy (16%) and Spain (11%). In general EPS is a fragmented sector with many plants, with so called direct and indirect production is geographically spread out across the EU. (SRI Consulting


46

2009). According to an EUMEPS7 study from 2003 and 2004, around 58% of all EPS on the European market contained HBCD in the early 2000th. (Posner, 2006)

Together with the increasing use of easily flammable materials and products such as polystyrene insulation boards, tightened legislation and tougher fire safety requirements are the major drivers for the use of flame retardants such as HBCD. As all other flame retarded products it is important to understand that flame retarded insulation boards of polystyrene, are explicitly ordered and customer tailor made due to their market specific fire safety requirement. Simultaneously insulations boards are bulky products that are not transported over long distances and most likely manufactured for the market where it is used (KemI, 2006). It is therefore required for markets like Germany to manufacture HBCD flame retarded insulation boards that exclusively pass certain German fire requirements for insulation boards used in buildings. The same fire requirements can be differently governed and implemented in different countries. Some regulations are more flexible, making it possible to achieve the same fire requirements by less use of fire retardants. In some internal markets the use of HBCD has been phased out, like in the Scandinavian countries. They apply the same harmonized product standards and classification for fire safety properties as other countries in EU. The national fire safety requirements are achieved by the building codes specifying the different uses of insulation products in buildings and construction, through the use of thermal barriers. In Scandinavian countries like Norway and Sweden buildings are constructed to prevent the spread of fire and additionally the buildings should not pose any health and/or environmental hazard to residents and the local environment. The specific fire safety requirements in the Scandinavian countries are specified for the different uses of insulation boards in buildings and not exclusively for insulation boards. The production of EPS for the internal market in Norway is not flame retarded. National fire requirements are fulfilled through alternative construction techniques. These different regulatory systems for fire safety in Germany and Scandinavia result in a much larger German consumption of HBCD than the consumption in Scandinavia.

Consequences for the elimination of HBCD through legislation will influence markets with a substantial production and use of HBCD flame retarded insulation boards. Markets that don´t require these flame retarded products due to other fire safety regulations and policies will be influenced to a lesser extent .

7 EUMEPS : European Manufacturers of expanded polystyrene


47

There are three main scenarios if such legislation will be in force

1- some production sites will switch over to production of alternative fire protected insulation board

2- or switch over to production of EPS/XPS insulation boards with no flame retardants

3- others will move the production of HBCD flame retarded insulation boards to regions with less stringent legislation.

It is very hard to assess which scenario would dominate various markets in a short term perspective, but in a long term perspective most production sites will likely switch over to an insulation board production that harmonize with current fire safety requirements and legislation.

10.6.3 The chemicals industry

Several manufacturers of flame retardant chemicals are part of a larger specialty chemicals companies. Flame retardants account only for a small share of their total business. For other companies such as Albemarle, ICL-IP and Chemtura Corporation, these products represent a much larger share of their business (SRI Consulting, 2008). HBCD can represent up to one third of the total share for this companies.

With regard to their product range, most producers focus on one or two families of flame retardants such as organophosphorus or nitrogen based compounds. The major BFR manufacturers (Albemarle, Chemtura Corporation and ICL-IP) are an exception to this rule. As a result of threats from government regulations and environmental pressure these companies acquired halogen-free flame retardant or plastics addictive businesses, formed alliances with other companies and started their own development activities for non halogenated compounds. Thus the main drivers have been government regulations and environmental pressures concerning halogenated flame retardants and the trend toward halogen free systems as well as low profitability, price pressures and overcapacity. These show that there is a tough competition on the global flame retardant market, especially in regions with more stringent regulation.

The previously indicated current international market situation is influenced by several factors. Flame retardant (FR) manufacturers and other important stakeholders of the FR industry are making their decisions by recognizing the relevant trends of the market. New regulations and public awareness of potentially hazardous flame retardants can have a considerable impact on the market, as well as the growth or decline in the end-use market


48

10.6.4 Environmental and health concerns

The ongoing risk assessments regarding brominated and chlorinated compounds have raised a high level of attention among environmental and consumer organizations. Several NGO8s are conducting campaigns against brominated compounds in construction industry and electronics, which raises public attention and creates pressure on the regulation regime on the FR manufacturers and on material suppliers and manufacturers.

10.6.5 Industrial initiatives

There are several industrial initiatives only to incorporate less hazardous and recyclable components. In case of the main HBCD uses in polystyrene insulation boards achievement of alternative flame retardants initiatives are not so clear. One important reason is that the bromine manufacture industry emphasizes that there are no viable commercial alternative non halogenated flame retardants to HBCD in EPS/XPS on the international market that could meet the current fire safety requirements in a satisfactory way. These written statements and reports are often non transparent or even confidential and are for that particular reason often hard to assess.

The European markets trends due to regulation are recognizable in the American or the Asian market as well, especially in the area of electronics since most of the OEM9s are global companies. These manufacturers with significant exports follow regulatory developments throughout their market area. (SRI Consulting, 2008).

Therefore these companies will often utilize flame retardant formulations that meet the most stringent regulations of any region. These market trends for electronics are not that clear for the building and construction industry.

10.6.6 Market trends of halogen free flame retardants

It is important to point out that there has been a major price increase for all FR types in 2007 and 2008. This particularly applied to phosphorus compounds, due to increased cost for feedstock materials, transport and energy. These cost dynamics generate competition among FR manufacturers and stimulate the development of new FRs.

Inorganic FRs like aluminiumtrihydroxide (ATH) and magnesium hydroxide are growing fastest on the European and North American markets. Companies

8 NGO: non governmental organisation 9 OEM: Original Equipment Manufacturer


49

producing BFRs are acquiring smaller mineral companies, in order to suit the new regulations since there is a trend that they start to produce mineral based FRs. (SRI Consulting, 2008).

10.6.7 Cost switchover considerations

Two main types of costs have to be considered concerning the switch from brominated into non halogen free flame retardants. One of them is the switching cost, which is the cost of reformulation, in other words the cost of the development work or equipment change. Manufacturing and processing facilities may need to invest in new equipment in order to shift to alternative FRs. This cost is difficult to estimate, and usually contains the cost of those research and development endeavours which did not succeed finding an efficient FR alternative. This is a cost which is generated at the beginning of a product life cycle.

The other significant cost type is the operating cost which reflects the price of the FR (raw) material cost. In addition, daily operation costs may be different for the new process steps required to manufacture other flame retardant chemical. To ensure economic viability, flame retardants must be easy to process and cost-effective for what most of the time high-volume manufacturing conditions are necessary. The cost of manufacturing are heavily dependent on the costs of raw materials, but the degree of this dependency varies among the FRs.

As far as the influence of flame retardant treated products are concerned, prices of flame-retardants are either more expensive per kg chemical to meet fire standards or higher loads of flame retardants are required per unit polymer mass (or volume) to meet the fire safety standards, which will increase the raw material costs. This means that large price differences between flame retardants chemicals must not necessarily mean that this difference has any impact on relatively expensive end products. Polystyrene boards are relatively cheap products so additions of expensive flame retardants will influence their market price.

Expected changes in cost concerning the disposal stage are dependent on changing regulations. For example, the WEEE Directive requires the separation of plastics containing BFRs prior to recycling, which imposes an additional cost on the BFR containing products. However, in practice a manual separation of these materials rarely takes place in practice, thus there are no additional cost involved. This fact raises questions not only about the relevance of the regulation, but causes further social problems which occur in third world countries like India, China, Nigeria and Ghana (Greenpeace, 2009).


50

10.6.8 Innovation and research

With new regulation and strong market drivers for a phase out of hazardous flame retardant systems, the academic and industrial research on new flame retardants are highly promoted. Sophisticated R&D efforts are required for flame retardant producers since there are many factors for feasible flame retardants they have to consider.

10.6.9 Consumers and households

At this stage of the transition from BFR towards non halogenated flame retardants, it is very hard to forecast any price increase in final products caused by the transition. However other influencing aspects like inflation and exchange rate fluctuation can always change the price of final products.

What is expected is that due to the stricter regulations of FRs, not only consumers and households but also employees of FR manufacturing companies will have a safer environment.

10.6.10 Third countries and international relations

To fully understand the full scope of halogenated flame retardants in general and HBCD in particular, the whole chain of industrial operations related to FRs has to be considered. These operations seem to be scattered across all continents of the globe. Throughout the entire lifecycle of HBCD flame retarded products they may cause serious environmental pollution and put workers at risk of exposure when the products are produced or disposed of.

The first step in producing these products is the extraction of raw materials through mining and processing. Manufacturing locations, historically based in Europe and USA, have been shifting to, reflect more and more the quest for cheap labour such as South-East Asia, India and China, but also low-waged qualified workers in Central and Eastern Europe (Greenpeace, 2009).

In many locations, cheap labour comes hand-in-hand with poor environmental standards, leading to environmental contamination due to the use of hazardous chemicals in the production process. The other dangerous stage of the product life cycle in terms of toxicity of FRs is at the end of a product’s life.

While state-of-the-art waste facilities (smelters, recycling, landfills, incinerators) can be found in OECD (Organisation for Economic Cooperation and development) countries, a worldwide waste trade, often illicit, feeds Asian countries, primarily China and India, practising rudimentary recycling, or African countries such as Nigeria and Ghana where lots of waste is simply dumped (Greenpeace, 2009).


51

The EU Waste Electrical and Electronic Equipment (WEEE) Directive makes producers individually and financially responsible, as of August 2005, for taking their e-waste back when their products are discarded. According to Greenpeace International (2009) the WEEE Directive has been poorly implemented by half of the EU Member States – in this current state, it will not deliver the expected benefits in terms of design incentives. Illegal trade of electrical and electronic waste to non-EU countries continues to be widespread.

There are no similar data for waste construction material available but if waste routes are similar for building waste, we may assume similar problems to those for electronic waste.

10.7 Possible management options under the UN ECE protocol

On the background of the findings in this report, the most appropriate measure will be to list commercial HBCD in annex I to eliminate production and use of the commercial mixtures containing concentrations greater than 0.1 per cent by weight in the homogeneous material of a product, with no exemptions. Simultaneously to promote commercial use and development of alternative non- chemical flame retarded or inherent systems based on product redesign. Homogenous material is defined to be a material of uniform composition throughout that cannot be mechanically disjointed into different materials, meaning that the materials cannot, in principle, be separated by mechanical actions such as unscrewing, cutting, crushing, grinding and abrasive processes. Because of the potential of releases during recycling of building materials and electronic appliances parties must take appropriate measures to ensure that recycling processes of articles manufactured or in use by the implementation date, do not result in recovered material containing 0.1 % or more of commercial HBCD by weight in the homogenous material of a product.


52

11 References Brenner Karl S. ”Polystyrene/- and extruded polystyrene foam (XPS) –hexabromocyclododecane-blends under thermolytic stress PBDF&PBDD determination”, BASF AG (1993).

BSEF, Factsheet HBCD –hexabromocyclododecane” , (2009).

BSEF, ”VECAP – the volontary emissions control action programme – measurable achievments – annual progress report” (2009).

European Chemicals Agency (ECHA), “Dossier- hexabromocyclododecane”, 2008).

European Union, ”Risk assessment – hexabromocyclododecane – final approved report”, (2008), R044_0805_env_hh_final_ECB.doc.

Heeb et. al “Solid state confirmations and absolute configurations of (+) and (-) alfa, beta, abd gamma hexabromocyclododecanes (HBCDs)” Empa (2007).

IOM Consulting, ”Data on manufacture, import, export, uses and releases of HBCD as well as information on potential alternatives to its use”, ECHA_2008_SR04_HBCD_report_12_01_2009.doc. (2008).

European Commission JRC, Reference Document on Best Available Techniques in the Production of Polymers” (2007).

Greenpeace “Switching on to green electronics”, http://www.greenpeace.org/raw/content/international/press/reports/Switching-on-Green-Electronics.pdf, (2009)

Morf L.S, Buser A. M, Taverna R, Bader H-P, Sceidegger R, “Dynamic substance flow analysis as a valuable risk evaluation tool- a case study for brominated flame retardants as an example of potential endocrine disruptors”, Chimia 62 (2008).

Morose Gregory, “An overview of alternatives to tetrabromobisphenol A (TBBP-A) and hexabromocyclododecane (HBCD)”, University of Massachussets - Lowell Center for sustainable production, (2006).

PlasticsEurope, European Plastics Industry (EU 27), PlasticsEurope Market Research Group, Statistical Monitoring, (2009).

Posner Stefan, “Survey and technical assessment ofalternatives to TBBPA and HBCD” KemI PM 1/06, (2006).


53

SRI Consulting Fink, U., Hajduk, F., Wei, Y., Mori, H., “Flame Retardants”, SRI Consulting, 2005 Speialty Chemicals, (2008).

SRI Consulting Fink, U., Hajduk, F., Wei, Y., Mori, H., “Flame Retardants”, SRI Consulting, 2005 Speialty Chemicals, (2005).

Sternbeck John, Remberger Mikael, Kaj Lennart, Strömberg Katarina, Palm Anna, Brorström-Lunden Eva, ”HBCD i Sverige – screening av ett bromerat flamskyddsmedel”, IVL (2001).

Swedish Chemicals Agency (KemI), ”Proposal of harmonised classification and labelling – hexabromocyclodocecane”, (2009).

Swedish Chemicals Agency (KemI), “Hexabromocyclododecane (HBCD) och tetrabrombisphenol-A (TBBP-A)“ , Report 3/06 (2006).

Tange et. al.”Waste management of plastics containing brominated flame retardants”, DSBG Eurobrom, (2001).

Tema.Nord, “Hexabromocyclododecane as a possible POP”, Tema-Nord 2008:520 (2008).

Tohka Antti, Zevenhoven Ron, ”Brominated flame retardants – a nuisanse in thermal waste processing?”, Helsinki university of technology, (2002).

Troitzsch Jurgen, ”Commercially availible halogen free alternatives to halogen-containing flame retardant systems in polymers”, (2007).

UNEP – Stockholm convention of persistant organic pullutants “Proposal to list hexabromocyclododecane in Annex A to the convention” (2009).

UNEP - Stockholm convention of persistant organic pullutants , “Guidance of alternative flame retardants to pentabromodiphenylether (PentaBDE)“, UNEP/POPS/POPRC.4/INF/13, (2009).


54

Appendix 1 Submissions of information on HBCD from countries in the UNECE region

(Note! Most of the information received form stakeholders were requested to be held confidential. We have therefore chosen not to publish the information received from stakeholders in this report.)

UNECE

Countries

Answers in Questionnaire (1a-3b)

Production (1a ) and Restrictions (1b)

Uses (2a) and Restrictions (2b)

Articles placed on the market

(2c)

Recycling operations and shredding activities

(2d)

Releases

(3a)

Alternatives and technologies

(3b)

Comments

Belgium - - - - - - Refer to documentation under REACH.

Canada No production.

EPS

(2000; 10 -100 tonnes/year)

Insulation boards.

Typical loading of HBCD in XPS and EPS is 0.5 - 1% w/w. Polystyrene foam

no no no 1HBCD is currently being assessed by the Government of Canada. The draft screening assessment report, planned for publication in the summer of


55

UNECE

Countries


No restrictions.

HBCD is under national assessment1.

XPS

(2000; 100-1000 tonnes/year)

No restrictions.

HBCD is under national assessment1.

insulation applications include: external wall foam sheathing, roof applications (green roofs, cathedral ceilings, conventional), foundations and basements, below grade applications (geofoam light-weight fill/ soil stabilization, highway insulation).

2010, will provide a conclusion as to whether or not HBCD meets the virtual elimination criteria set out in subsection 77(4) of the Canadian Environmental Protection Act, 1999 (CEPA 1999).

Cyprus No No no no no no -

Croatia No EPS

(2005-2009; 10 - 72.2 tonnes/year)

Restrictions1

no no no no 1Governmental policy:

Since HBCD might become new POPs whose use and production will be restricted or banned in EU, Croatia will promptly accept it


56

UNECE

Countries


Czech Republic

No EPS (2009; 381 tonnes/year)

XPS (2009; 2,5 tonnes/year)

Restrictions1

- - - no 1REACH regulations in EU is in process

Denmark No No Some imported foams no no - -

Estonia No No no no no no -

Finland No EPS (2009; hundreds of tonnes)

no no no no -

Germany No Polystyrene (1999; ca. 500)

Textiles (1999; <2000)

Regulations1

Polystyrene (insulation) (1999; 170 000 tonnes/year)

yes2 - Mineral wool and foam glass are general available and used

1included on the list of substances added to a proposal to revise the RoHS (Restriction of Hazardous Substances) directive; ECHA decided to include HBCD to the list of Substances of Very High Concern (SVHC) for authorization


57

UNECE

Countries


2 incineration and deposition of halogene containing residues

Italy No

Regulations1

EPS for construction

Regulations2

no no no no 1HBCD is on the candidate list for listing in Annex XIV of REACH Regulation; if listed a production is allowed only if the producer obtains a specific authorization.

2HBCD is on the candidate list for listing in Annex XIV of REACH Regulation; an utilization is allowed only if the user obtains a specific authorization.

Norway No

Regulations1

EPS granulate for export

(2007; 4 tonnes/year)

No use for the internal market in production of EPS and textiles1,2

EE-articles, transport vehicles, building materials, textiles3

no yes Mineral wool, glass wool, fiber glass, EPS without FRs using thermal barriers

1A regulation of HBCD in our Product control act is under consideration. The proposal includes a ban on sales, production and use of HBCD in consumer products. Transport vehicles and export of EPS granulates containing EPS will


58

UNECE

Countries


not be affected by this regulation.

2There are no production of products containing HBCD for the internal market. EPS granulate with HBCD are still being produced, but are exported to EU for professional use. In Norway, HBCD has earlier been used in larger quantities in the production of furniture textiles. This use was voluntary phased out over a longer period and there is no known use in this sector today.

3There is no exact information on amounts of HBCD in imported products, as importers frequently are unaware that the imported textiles may contain HBCD. Known uses includes: EE-products, transport vehicles, building materials (cellular rubber, insulation materials -


59

UNECE

Countries


EPS/XPS, glue/ varnish/ joint fillers, surface laminate for wet areas, and other special products), textiles, granulate (only for professional use – export). There are no production inside Norway of products containing HBCD for the Norwegian market.

Slovenia no No no no no no -

Spain no HBCD is mainly used in EPS and XPS. Use of HBCD in packaging material is minor (is pending further information on amounts)

Restrictions2

Packaging material1 Pending

Further information

yes Mineral insulation materials

Encasing of EPS or XPS without HBCD into fireproof casings

1Directive 2002/91- Framework -complementary legal instrument to lay down more concrete actions on energy savings. Construction products requires construction works and their heating, cooling and ventilation installations to be designed and built in such a way that the amount of energy required in use will be low.


60

UNECE

Countries


Sweden No

Restrictions1,

2

EPS

(2008; 3,5 tonnes/year)

Use of HBCD in textiles was stopped in 1998

Restrictions1,2

Packaging material

Electrical equipement

Textiles

yes polystyrene (EPS and XPS) does not need to be flame-retarded to meet swedish fire protection requirements

1Nominated for consideration as a 2POP of global concern within Stockholm convention

In October 2008, the European Chemicals Agency (ECHA) Member States Committee agreed to include HBCD in the candidate list for Authorisation under the European chemicals legislation (REACH). In May 2009, HBCD was included in the ECHA recommendation list of priority substances to be subject to Authorisation under REACH. On 1st June 2009 ECHA’s recommendation list was sent to the Commission, which will take the final decision on which substances should be submitted to Authorisation at this stage. Two legal obligations result from the inclusion of a substance on the candidate list. These obligations


61

UNECE

Countries


are not linked only to the listed substance on its own or in preparations but also to its presence in articles. Firstly, any producer or importer of an article containing HBCD has to notify ECHA of the presence of HBCD by June 2011 (art. 7.2 of REACH). This obligation applies if the substance is present above 0.1% (w/w) and its quantities in the produced/imported articles are above 1 tonne in total per year per company. Furthermore, the inclusion of a substance in the candidate list involves a “duty to inform” (art.33 of REACH). In particular, EU and EEA suppliers of beads, insulation foams, textile and plastics containing HBCD must provide sufficient information, available to them, to their customers and on request to


62

UNECE

Countries


a consumer within 45 days of the receipt of this request. (Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH). )

Switzerland No

Restrictions1

EPS and XPS in thermal insulation, mainly in insulation boards for construction of buildings

HIPS in electrical and electronic equipment

Textiles; Polymer dispersions, mainly used in furniture, transportation and textile industries

no no no no 1HBCD is listed on the "Candidate List" as a substance to be included in Annex XIV of the EU-REACH regulation.


63

UNECE

Countries


Restrictions1

Netherlands 2005;

6000 tonnes/year 1

yes1 yes1 no no yes1 1 Refer to:

'-Data on the manufacture, import, export, uses and release of HBCDD as well as information on the potential alternatives to its use, IOM Consulting, supported by BRE, PFA and Entec under framework contract ECHA/2008/2 (specific contract: ECHA/2008/02/SR4/ECA.226)

'-Hexabromocyclododecane as a possible global POP, TemaNord 2008:520

USA yes1

polystyrene foam product manufacturing and textile and fabric finishing mills.1

no no no no 1In the 2006 IUR (Inventory Update Reporting), the total production and import volume reported for CAS No. 3194-55-6 was 10 million - <50 million pounds. Reported uses include as


64

UNECE

Countries


a flame retardant and reported product categories are fabrics, textiles and apparel, and rubber and plastic products. EPA IUR Data: http://www.epa.gov/oppt/iur/tools/data/index.html

Ukraine Pending for further information

Restrictions1

cellular polystyrene products

Restrictions1

Pending for further information

no no no 1May be considered within the state environmental policy and Ukraine's obligations as a Party of the corresponding international agreements


65

Appendix 2 The EUROCLASS System10

Many of the member countries of the European Union (EU) have adopted the harmonized Euroclass system of reaction to fire performance of building products. The background of the harmonization process lies on the Commission Decision 94/611/EC implementing Article 20 of Directive 89/106/EEC on construction products in the field of fire safety. The Euroclass decision includes a classification system for building products based on their reaction-to-fire performance. It additionally defines the test methods according to which construction products shall be categorised. In the Euroclass system, floor coverings and other surface linings are considered separately.

The purpose of harmonization is to facilitate the trade of building products between the member countries of the EU by removing trade barriers due to differences in test methods and classification systems. Previously, products had to be tested and classified according to national standards in each country in which they were launched to the market. In the new system, the Euroclass classification of a product is acknowledged in all member countries based on its performance in the harmonized fire tests.

The decision on the classification of the reaction to fire performance of construction products was published in February 2000. The Euroclass system requires including the test methods and classifications of the Euroclass decision in the legislation of the member countries. The required fire performance for various purposes of use of construction products are still decided nationally, but the requirements are expressed in terms of harmonized standards.

This section is organized as follows:

1. Test methods

o Non-combustibility test EN ISO 1182

o Gross calorific potential test EN ISO 1716

o Single Burning Item test EN 13823

o Ignitability test EN ISO 11925-2

o Radiant panel test EN ISO 9239-1

2. Classes and criteria

10

http://virtual.vtt.fi/virtual/innofirewood/stateoftheart/database/euroclass/euroclass.ht

ml


66

1. Test methods

The European classes of reaction to fire performance for construction products excluding floorings are based on four fire test methods: the non-combustibility test EN ISO 1182, the gross calorific potential test EN ISO 1716, the single burning item (SBI) test EN 13823, and the ignitability test EN ISO 11925-2. The same test methods, excluding the SBI test, are used for floorings with the addition of the radiant panel test EN ISO 9239-1. The details of specimen conditioning and substrate selection are given in EN 13238, and the harmonized procedure for the classification is described in EN 13501-1.

The first two test methods below are only applicable for non-combustible materials. Fire retardant wood products cannot reach these criteria.

1.1 Non-combustibility test EN ISO 1182

The purpose of the non-combustibility test EN ISO 1182 is to identify the products that will not, or significantly not, contribute to a fire. The test apparatus is shown in Figure 6a. A test specimen of cylindrical shape is inserted into a vertical tube furnace with a temperature of about 750 °C. Temperature changes due to the possible burning of the specimen are monitored with thermocouples. The flaming time of the specimen is visually observed. After the test, the mass loss of the specimen is determined.

The quantities used in the European classification are the temperature rise of the furnace (∆T), the mass loss of the specimen (∆m), and the time of sustained flaming of the specimen (tf).

1.2 Gross calorific potential test EN ISO 1716

The gross calorific potential test EN ISO 1716 determines the potential maximum total heat release of a product when burned completely. The test apparatus is shown in Figure 6b. A powdery test specimen is ignited in pressurized oxygen atmosphere inside a closed steel cylinder (calorimetric bomb) surrounded by water jacket. The temperature rise of water during burning is measured. The gross calorific potential is calculated on the basis of the temperature rise, specimen mass, and correction factors related to the specific test arrangement used.

The classification parameter of the method is the gross calorific potential (PCS) measured in MJ/kg or MJ/m2 depending on the features of the product and its components.

1.3 Single Burning Item test EN 13823

The SBI test is a relatively new fire test method developed specially for the Euroclass system. The test is based on a fire scenario of a single burning item, e.g. a wastebasket, located in a corner between two walls covered with the lining


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material to be tested. The SBI test is used for construction products excluding floorings.

The SBI test was developed by a group of European fire laboratories on the basis of the specifications defined by a group of European fire regulators. The development work included the design of a prototype, the installation of test facilities, the determination of the accuracy of the method, and the production of data needed to finalize the classification system.

SBI test specimens are installed on a specimen holder with two vertical wings made of non-combustible board. The specimen holder wings of sizes 1,0 m × 1,5 m and 0,5 m × 1,5 m form a right-angled corner configuration. The thermal exposure on the surface of the specimen is produced by a right-angled triangle-shaped propane gas burner placed at the bottom corner formed by the specimen wings. The heat output of the burner is 30 kW resulting in a maximum heat exposure of about 40 kW/m2 on an area of approximately 300 cm2. The burner simulates a single burning item. Combustion gases generated during a test are collected by a hood and drawn to an exhaust duct equipped with sensors to measure the temperature, light attenuation, O2 and CO2 mole fractions and flow-induced pressure difference in the duct. The test apparatus is shown schematically in Figure 6c, and a photograph of a test in Figure 6d.

The performance of the specimen is evaluated for an exposure period of 20 minutes. During the test, the heat release rate (HRR) is measured by using oxygen consumption calorimetry. The smoke production rate (SPR) is measured in the exhaust duct based on the attenuation of light. Falling of flaming droplets or particles is visually observed during the first 600 seconds of the heat exposure on the specimen. In addition, lateral flame spread is observed to determine whether the flame front reaches the outer edge of the larger specimen wing at any height between 500 and 1000 mm during the test.

The classification parameters of the SBI test are fire growth rate index (FIGRA), lateral flame spread (LFS), and total heat release (THR600s). Additional classification parameters are defined for smoke production as smoke growth rate index (SMOGRA) and total smoke production (TSP600s), and for flaming droplets and particles according to their occurrence during the first 600 seconds of the test.

The FIGRA and SMOGRA indices are calculated as follows:


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where HRRav is the heat release rate averaged over 30 seconds (in kW), SPRav is the smoke production rate averaged over 60 seconds (in m2/s), and t is the time elapsed after the beginning of the test (in s), i.e. the ignition of the burner. The units of FIGRA and SMOGRA are W/s and m2/s2, respectively. Constant coefficients are added to the definition of the parameters to obtain convenient ranges of numbers. Different heat release related threshold values for the FIGRA calculation are used in different classes to obtain FIGRA0,2MJ and FIGRA0,4MJ values. Also SMOGRA calculation includes certain smoke production related threshold values, common to all smoke production classes.

The THR600s and TSP600s values are calculated over the first 600 seconds of the test as follows:

where HRR(t) and SPR(t) are the heat release rate and smoke production rate as functions of time (in kW and m2/s, respectively), and ∆t is the data acquisition interval of the measurement (in s). The units of THR600s and TSP600s are MJ and m2, respectively.

1.4 Ignitability test EN ISO 11925-2

In the ignitability test EN ISO 11925-2, the specimen is subjected to direct impingement of a small flame. The test specimen of size 250 mm × 90 mm is attached vertically on a U shaped specimen holder. A propane gas flame with a height of 20 mm is brought into contact with the specimen at an angle of 45 °. The application point is either 40 mm above the bottom edge of the surface centerline (surface exposure) or at the centre of the width of the bottom edge (edge exposure). Filter paper is placed beneath the specimen holder to monitor the falling of flaming debris. The test apparatus is shown in Figure 6e.

Two different flame application times and test durations are used depending on the class of the product. For class E, the flame application time is 15 seconds, and the test is terminated 20 seconds after the removal of the flame. With a flame application time of 30 seconds for classes B, C and D, the maximum duration of the test is 60 seconds after the removal of the flame. The test is terminated earlier if no ignition is observed after the removal of the flame source, or the specimen ceases to burn (or glow), or the flame tip reaches the upper edge of the specimen.

The classification criteria are based on observations whether the flame spread (Fs) reaches 150 mm within a given time and whether the filter paper below the specimen ignites due to flaming debris. In addition, the occurrence and duration of flaming and glowing are observed.


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1.5 Radiant panel test EN ISO 9239-1

In the radiant panel test EN ISO 9239-1, a test specimen of size 1050 mm × 230 mm is placed horizontally below a gas-fired radiant panel inclined at 30 °. The specimen is exposed to a defined field of total heat flux, 11 kW/m2 at the hotter end close to the radiant panel, and decreasing to 1 kW/m2 at the other end farther away from the radiant panel. A pilot flame front from a line burner is applied to the hotter end in order to ignite the specimen. The test apparatus is presented in Figure 6f.

The progress of the flame front along the length of the specimen is recorded in terms of the time it takes to travel to various distances. The smoke development during the test is measured on the basis of light obscuration by smoke in the exhaust duct. The duration of the test is 30 minutes.

The classification criterion is the critical heat flux (CHF) defined as the radiant flux at which the flame extinguishes or the radiant flux after a test period of 30 minutes, whichever is lower. In other words, CHF is the flux corresponding to the furthest extent of spread of flame.


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Figure 6 The test apparatuses for the European classification: a) test for non-combustibility and b) test for gross calorific potential, c) SBI test, a schematic drawing, d) SBI test, photograph, e) test for ignitability of building products subjected to direct impingement of flame and f) test for floorings.


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2. Classes and criteria

In the Euroclass system, building products are divided to seven classes on the basis of their reaction-to-fire properties. The performance description and the fire scenario for each class are presented in Table 6 according to the main principles used in the development of the Euroclass system (not given in the final decision).

Table 6 includes some examples of typical building products used in walls and ceilings in each Euroclass. It is noted that certain materials containing only a very small amount of organic compounds are deemed to satisfy the requirements of class A1 without testing. Examples of such materials are concrete, steel, stone and ceramics.

The decision on the classification of the reaction to fire performance of construction products was made in February 2000. The test methods and classification criteria are presented in Table 7 for construction products excluding floorings and in Table 8 for floorings.

The highest possible European class for fire retardant wood products is class B.

Table 6 Indicative performance descriptions and fire scenarios for Euroclasses.


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Table 7 Classes of reaction to fire performance for construction products excluding floorings. The abbreviations of classification parameters are explained in the text.


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Table 8 Classes of reaction to fire performance for floorings. The abbreviations of classification parameters are explained in the text.


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Appendix 3 UL 94 Test for flammability of plastic materials for parts in devices and appliances. One of the most important tests for polymers is the UL 94 flammability test. It contains procedures for testing materials in horizontal position (UL 94 HB) and in vertical position (UL 94 V-0, V-1 and V-2). UL94 is described in detail below.

UL94(V-0 to V2)

1. The test speciemen is hanged vertically above a piece of cotton fabric where a gas flame is applied to the bottom edge.

2. The gas flame is immediately withdrawn after 10 seconds where the afterflame time (t1) is registered

3. The procedure above is repeated to register the second afterflame time (t2) 4. This procedure,1 to 3, is repeated 5 times. 5. The afterglow time for the second repetition (t3) is registered.

The sum of the after flame is calculated of the material/application. Due to the result of this sum after flame and afterglow in context to ignition of the holder clamp, the material is classified accordingly. The holding cotton fabric must also not be ignited by flames and drippings from the material/application.

Table A2-1 The different fire regulatory classes of UL94.

UL94 class Criteria 1 [sec]

t2 + t3 [sec]

Sum afterflame [sec]

V-0 t1 + t2 < 50 < 30 See criteria 1

V-1 t1 > 30

t2 > 30

< 60 < 250

V-2 51 < t1 + t2<55 V-0 or V-1 251 to 255

UL94 (V-5A)

A rod shaped specimen is placed vertically and an attempt is made to ignite the specimen five times for 5 seconds. It must not continue to burn or glow for more than 60 seconds after the burner has been removed. The material must not drip.


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UL94(V-5B)

Sheets of the same thickness are tested in a horizontal position. The flame is applied to the centre of the specimen. Classification is done in V-5B if the specimen exhibits burn through hole, other criteria as for UL94 (V-5A).

Materials classified for UL94 (V-5A) or UL94 (V-5B) shall also comply with the requirements for materials classified for V-0, V-1 and V-2.

UL94(HB)

A test where 3 specimen of the cabinet material are placed in an angle of 45 degrees and ignited if possible with a burner. In order to be classified HB the burning rate must not exceed 40 mm/min over a 75 mm span for specimen thicker than 3 to 13 mm and 75 mm/min for specimen thinner than 3 mm. In each case the specimen must cease burning before the 100 mm reference mark.

UL94 (HF1 and HF2)

These regulations are for foamed products. In this method 2 sets of 5 specimen stored under different conditions are tested; an attempt is made to ignite the test specimen with a fishtail burner. The flame is kept under the specimen for 60 seconds. The following conditions must be met

1. Only one specimen must burn more than 2 seconds 2. No specimen must burn more than 10 seconds 3. No specimen must glow for more than 30 seconds 4. No specimen must burn or glow at a distance of 60 mm from the ignition

point 5. For HF-1 no drops must ignite the underlying surface 6. For HF-2 the underlying surface is allowed to be ignited

If a set of 5 specimen does not comply with the requirements because of one of the following situations, another set of 5 specimen subjected to the same conditions shall be tested.

1. A single specimen flames more than 10 seconds or 2. 2 specimens flame for more than 2 seconds but less than 10 seconds or 3. 1 specimen flames more than 2 seconds but less than 10 seconds, and a

second specimen flames more than 10 seconds or 4. 1 specimen does not comply with the additional criteria.

All specimens from this second set shall comply with the requirements in order for the foamed plastic material in that thickness and density to be classified HF-1 or HF-2.


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Appendix 4 An overview of fire requirements for textile applications Some examples of fire requirements and corresponding building standards based on the Flammable Fabrics Act (FFA) in the United States, which was adopted by the US Congress as long ago as 1953, the UK Furniture and Furnishings Fire Safety Regulations and the fire–safety requirements from 1988 still in force, and some important standards of other European countries and international transport organisations

Table A3-1 Some important fire regulations for textile applications.

Product type

Type of fire source

Example of risk

Standard or equivalent

Seating Smouldering cigarette

Smoking in furniture

Testing according to EN 1021-1. National requirements in several EU Member States

Seating

Smouldering cigarette

Smoking in furniture

Testing according to UFAC (The Upholstered Furniture Action

Council)

Voluntary industry requirements, followed by many

manufacturers in the US

Seating

Ignition with small gas flame

Carelessness with open fire

Testing according to EN 1021-2. National requirements in some EU Member States.Requirements for low flammability in purchasing for example for hotels

Seating

Etc.

Ignition with burning wood


Testing according to BS 5852, fire source 5. Requirements for consumer environment for upholstery materials for furniture, mattresses and cushions in the UK.Medium risk level for public environment in the UK according to BS 7176

Seating


Carelessness with open fire/arson

Testing according to BS 5852, fire source 7. High and very high risk level for public environment in the UK according to BS 7176


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Product type

Type of fire source

Example of risk


Seating, ships

Smouldering cigarette and small gas flame


Testing according to IMO Resolution A.652 (16): 1989.Requirement for low flammability

Seating, trains



Testing according to BS 5852, fire source 7.Requirement for seats in X2000 trains

Seating, trains

Ignition with burning paper

Carelessness with open fire / arson

Testing according to UIC 564-2, app. 13.

Used by Central European train companies

Seating, airplanes

Ignition with oil burner

Fire on board

Testing according to FAA 23.853.

Requirement for self-extinguishing is applied by most airlines

Mattresses, beds

Ignition with cigarette

Smoking in bed

Testing according to EN 597-1.

Requirement for low flammability in several European countries

Mattresses, beds

Ignition with cigarette

Smoking in bed

Code of Federal Regulations (CFR)

Testing according to 16 CFR part 1632 (USA) General requirements for low flammability in the USA

Mattresses, etc. ships

Smouldering cigarette and small gas flame

Smoking Carelessness with open fire

Testing according to IMO Resolution A.688 (17):1991. Requirements for low flammability


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Product type

Type of fire source

Example of risk


Mattresses, beds



Testing according to BS 6807, fire source 5. Medium risk level for public environment in the UK according to BS 7177

Mattresses, beds



Testing according to BS 6807, fire source 7. High and very high-risk level for public environment in the UK according to BS 7177.

Mattresses, beds

Ignition with gas burner

Carelessness with open fire / arson

Testing according to California Technical Bulletin 603. Requirement for limited heat and smoke generation from 2005. Other states are expected to follow suit.

Curtains and drapes

Gas flame + heat radiator


Testing according to EN 1101, EN 1102 and EN 13772 and classification according to EN 13773. These standards are expected to gradually replace existing national standards.

Curtains and drapes

Large gas flame


NFPA (National Fire Protection Association)

NFPA 701 (USA). Requirement for self-extinguishing

Curtains and drapes, ships

Gas flame Carelessness with open fire

Testing according to IMO res. A.471 (XII), 1981 Requirement for self-extinguishing products.

Interior materials in cars

Gas flame


Testing according to ISO 3795 and equivalent. Requirement for limited rate of flame spread is specified in FMVSS 302 (USA), Directive 95/28/EC and by individual car manufacturers.


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Table A3-2 EU standards covering personal protective clothing.

Type of risk Example of risk Corresponding EU standard

Small flames

All activity in the vicinity of Flames

EN 533

Larger flames and convective

Heat

Proximity to small fires EN 531 level B1

Radiated heat Proximity to ovens EN 531 level C1

Heat and flames Fire-fighting EN 469

Drops of molten metal Welding and cutting work with oxygen

EN 470-1

Splashes of molten metal Foundry, smelting plant EN 531 level D1 and E1

Table A3-3 Classification of textile fabrics according to the FFA (the Flammable Fabrics Act).

Class Time for spreading of flame

Class 1 Normal flammability 4 seconds or more

Class 2 Intermediate flammability Between 4 and 7 seconds before fabric ignites

Class 3 Rapid and intense burning Less than 4 seconds. Dangerous and flammable.

Unsuitable for clothing.


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Appendix 5 CAplus search of current uses of different isomers to HBCD A search in the chemical bibliographical database CAplus[1] was performed which included scientific articles, patents and books published between 1975 and January 2010. Of the 24 identified isomers of HBCD, only 19 substances were documented at all:

1. CAS 134237-50-6 2. CAS 134237-51-7 3. CAS 134237-52-8 4. CAS 138257-17-7 5. CAS 138257-18-8 6. CAS 138257-19-9 7. CAS 169102-57-2 8. CAS 25637-99-4 9. CAS 3194-55-6 10. CAS 673456-49-0 11. CAS 676552-82-2 12. CAS 678970-15-5 13. CAS 678970-16-6 14. CAS 678970-17-7 15. CAS 870247-98-6 16. CAS 870248-00-3 17. CAS 878049-04-8 18. CAS 878049-05-9 19. CAS 878049-08-2

3 of the isomers of HBCD had more than 20 bibliographical hits:

• CAS RN 25637-99-4 (“commercial mix”), 484 of 585 hits • CAS RN 3194-55-6 (1,2,5,6,9,10-Hexabromocyclododecane), 90 of 585

hits • CAS RN 134237-50-6 (α – HBCD), 23 of 585 hits[2]

Use of α-, β- and γ-HBCD

[1] Caplus is the largest chemical bibliographical database in the world today, edited and published by American Chemical Society. http://www.cas.org/expertise/cascontent/caplus/index.html [2] The other candidate substances β-HBCD and γ-HBCD did only occur in the same articles as α – HBCD.


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For α-, β- and γ-HBCD (CAS RN 134237-50-6, 134237-51-7 and134237-52-8), the literature sources found in CAplus, treated mainly HBCD as a pollutant. In case use in a specific material or application was mentioned, either the commercial mix (CAS RN 25637-99-4) or 1,2,5,6,9,10-Hexabromocyclododecane (CAS RN 3194-55-6) was also mentioned in the same document. No literature sources treating alternative chemicals or materials to substitute α-, β- and γ-HBCD were found.

Use of 1,2,5,6,9,10-Hexabromocyclododecane

In the literature sources found in CAplus, the most common material mentioned together with 1,2,5,6,9,10-Hexabromocyclododecane (CAS RN 3194-55-6) is polyester, with only half as many hits on polystyrene. Polyamides, epoxy and rubber are other commonly mentioned materials.

The occurring areas of application are household furnishings, construction materials and electrical appliances. Only one document treated the subject of alternative chemicals or materials to substitute HBCD.

Use of HBCD (commercial mix)

In over half of the literature sources found in CAplus, the use of HBCD (commercial mix) in polystyrene or polymers in general was described. Other commonly occurring materials in the literature review are fibrous materials, polyester, polyamide, epoxy and different types of rubber. The function as fire retardant was mentioned over 300 times and the function as plasticiser was mentioned 3 times.

The five most commonly occurring areas of application are construction materials, electrical appliances, household furnishings, paper and packaging and air filtering. Many documents treated the subject of alternative chemicals or materials to substitute HBCD.

Use of other HBCD isomers

No materials or areas of application were mentioned for the other isomers.


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Appendix 6 Summery table of emissions and exposures of HBCD during the life cycle stages

Data from ECHA_2008_2_SR04_HBCD_report_12_01_2009, “Data on manufacture, import, export, uses and realesse of HBCD as well as information on potential alternatives to its use”.

Note; values varies are taken from two or more sources

Life cycle stages vis-à-vis emissions of HBCD

Production Grinding / ”micronising”

Formulation Industrial use

Professional and private use

Service of life

Disposal

HBCD production

Working environment (mg/m3)

0.18 / 1.23 11

1.43 / 22.71

Environment

• Air (kg/year)

2 0.28

• Waste water (kg/year)

0.73 0

• Surface water (kg/year)

0 0

EPS


0.16 / 1.8912 0.05 / 0.1213

0.33 / 1.181

Inhalable unlikely >

0.1

Insignificant Exposure appr. 0.1

11 Mean values of respirable / inhalable HBCD 12 Mean values of respirable / inhalable HBCD, during the mixing 13 Mean values of respirable / inhalable HBCD during the extruding


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Service of life

Disposal

Environment No data

• Air (kg/year)

19.5-30.4 102 - 159 182 - 236 54


48-75 82.2 - 128 0 0


212-330 20.4 – 31 182 - 236 0

XPS


0.16 / 1.892 0.05 / 0.123

0.02 / 0.04 Inhalable unlikely >

0.1

Insignificant Exposure appr. 0.1

Environment No data

• Air (kg/year)

11.4 - 13.5 23.6 - 118 182 - 236 54


71.2 - 84 26.4 – 32 0 0


8.6 - 10 6.6 - 8.3 182 - 236 0

HIPS


0.16 / 1.892 0.05 / 0.123

Assumed same as for EPS

Lower than during

production

Low Low

Environment Assumed low

• Air (kg/year)

19.5-30.4 6.3 Negligible No data


48-75 5.0 Negligible Low


212-330 1.3 Negligible No data


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Service of life

Disposal



0.09 / 0.2314 0.12 / 1.3515

Assumed inhalation

0.5

0.3 - 9

Environment

• Air (kg/year)

1.4 - 6.8 0.12-0.64 No data 0 / 016 0 / 06


44 - 220 5.6 - 1130 No data 107 / 10.56 21.4 / 2.16


11 - 55 1.4 – 283 No data 27 / 06 5.4 / 06

14 Mean values of respirable / inhalable HBCD, for laboratory workers 15 Mean values of respirable / inhalable HBCD, for production workers 16 Wearing / washing the textile

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