Brominated Flame Retardants

2.2 Use in Manufactured Goods

2.2.1 Printed Circuit Boards
2.2.2 Housing of Electric and Electronic Equipment
2.2.3 Other Components of Electric and Electronic Appliances and Machines
2.2.4 Lighting
2.2.5 Wiring and Power Distribution
2.2.6 Textiles
2.2.7 Building Materials
2.2.8 Paints and Fillers
2.2.9 Transportation
2.2.10 Other Uses
2.2.11 Summary
2.3 Unintended uses as contaminant

2.2.1  Printed Circuit Boards

Printed circuit boards are assemblies consisting of a copper-foiled laminate on which small electric and electronic components, encapsulated in plastic and metal, are mounted. Both laminates and plastic for encapsulation are flame retarded, usually with brominated flame retardants.

Laminates

There are two main groups of laminates - with and without reinforcement /32 /. Flexible laminates without reinforcement represent a smaller material volume than the reinforced types. Flexible laminates are most often made of polyester or polyimid /32/. Some types are flame retarded with brominated flame retardants, but no detailed information have been available.

The reinforced laminates consist usually of either glass fibre reinforced epoxy (FR4), or cellulose paper reinforced phenolic resin (FR2), but a range of different laminates are used (FR3, FR5, CEM1, BT Epoxy, etc.).

FR4 is by far the most used laminate. The laminate typically contains about 15% TPPBA. The TBBPA content of the most used 1.6 mm FR4 laminate can approximately be estimated at 0.42 kg per m2 /33 /.

In industrial and office electronics, e.g. computers and electronics for telecommunication, the printed circuit boards are generally based on FR4 or a similar type of laminate.

By the early 1990'es European type FR2 laminates were flame retarded with TBBPA whereas Asian type FR2 laminates were flame retarded with PeBDE /32,34/. For both types the content of a typical FR2 laminate has been estimated at 0.036 kg/m2 /32/. Of recent years it seems there has been a shift away from PeBDE, and today most Asian FR2 laminates seem to be flame retarded with TBBPA (/35/ among others). In phenolic resins TBBPA is used as an additive flame retardant contrary to the reactive use in epoxy based FR4 laminates /8/. As a rough estimate it will be assumed that PBDEs still cover 30% of the FR2 laminates in consumer electronics other that TV-sets.

Traditionally printed circuit boards for TV sets and home electronic appliances have been based on FR2 /32/, but within the high-priced market segment there has been a trend towards printed circuit boards based on FR4. However, FR2 still seems to be the dominant laminate for home electronics. It will be assumed that all TV-sets contain TBBPA based FR2 (nearly all TV-sets on the Danish market is European produced).

Electronic components

Plastic encapsulation of electronic components on the board is predominantly made of epoxy resin with TBBPA /33/. Of the top ten component groups by volume, seven of the groups contain TBBPA. According to Legarth, 1996 /33/ these groups are plastic/paper capacitors, microprocessors, bipolar power transistors, IGBT power modules, ASICs, and metal oxide varistors. None of the top ten groups contains other brominated flame retardants.

The concentration of TBBPA in the plastic encapsulations is relatively low. The plastic encapsulation of an integrated circuit (chip) is reported to contain approx. 20-30% epoxy with approx. 2% TBBPA incorporated /53/.

The total content of TBBPA in encapsulated components will vary by type and an average content can only be estimated with high uncertainty. Hedemalm et al. have estimated an average value of 90 g/m2 /32/. It will roughly be estimated that the total use of flame retardants in electronic component will be within ± 50% of this value.

PBDEs and PBBs may also be present in electronic components. Analyses of PBDEs and PBBs in electronic components from 42 scrapped circuit boards assemblies in 1996 showed the presence of PBBs in the fraction 'carbon-metal resistors' and 'tantalum capacitors' and PBDEs in 'microchips' and 'capacitors' /36 /. It was only possible to extract a few percentages of the total halogen content, and the results cannot be used for an estimation of the content of the substances in the component. As the circuit boards were derived from disposed electronics, the content will represent use patterns ten years ago.

To take a possible content of PBDEs into account it will be estimated that the boards contain <10 g/m2 PBDE.

Other plastic parts

Brominated flame retardants may also be present in small plastic parts on the printed circuit board. In the above mentioned fractionation of assembled printed circuit boards, no TBBPA, PBBs or PBDEs were found in the fractions 'connection tools' and 'plastic part' (4.5% of total weight). To take a possible content into account it will be assumed that in total <4 tonnes may be present in other parts.

Production in Denmark

There is no production of laminate for printed circuit boards in Denmark.

The production of printed circuit boards, is assessed in section 2.1.4. There is both import and export of printed circuit boards. The total TBBPA content of printed circuit boards produced in Denmark in 1997 is estimated at 100-160 tonnes.

There is a net export of printed circuit boards i.e. the consumption of printed circuit boards for production of electronics in Denmark is smaller than the production of the boards.

There is in Denmark a production of consumer electronics (TV sets, radios, etc.), medical and laboratory equipment, radio- and telecommunication equipment and control and process equipment. A detailed investigation of the production is not covered by the present assessment, but the use of brominated flame retardants in produced products can roughly be estimated from a few assumptions. From the trade statistics the total supply of printed circuit boards for Danish production of electronic products can be estimated at 470 tonnes (using weight/value ratio of export for calculating the weight of the production). FR2 printed circuit boards are assumed to account for 15% of the supply, whereas FR4 is assumed to account for 80%.

Considering these assumptions, the total consumption of TBBPA with printed circuit boards for production of electronics is estimated at 55-82 tonnes in 1997.

Import/export

Approximately 90% of the electronic products produced in Denmark is exported, and similarly about 90% of the consumption is imported.

Consumption in Denmark

The consumption of brominated flame retardants in printed circuit boards in electric and electronic appliances appear from table 2.5. The total consumption is estimated to be 100-180 tonnes. The estimate is based on information on consumption of EE equipment and a rough estimate of the average content of printed circuit board in each type of equipment derived from Hedemalm et al. /32/. The detailed estimate is included in appendix 6.

The major contribution groups are office machines, control and process equipment, medical and laboratory equipment, radio and telecommunication equipment and consumer electronics.

Table 2.5
Consumption of brominated flame retardants with printed circuit board assemblies 1)

As an alternative estimation method the total content of printed circuit boards could be calculated from estimates of the average content of printed circuit boards in each group of products. This approach has been used by Legarth (1996) for printed circuit boards in EEE waste /33/. Within the range of uncertainty it would give nearly the same result. Legarth estimates the total content of printed circuit board in EEE waste in 1995 to be 3,000-5,500 tonnes, and translates this into approx. 144 tonnes TBBPA. The estimate of Hedemalm et al., using the same average content of printed circuit boards as used here, gave an estimate of 183 tonnes TBBPA in 1995 (Swedish figures divided by 1.83). Both estimates were based on the same amount of EEE waste.

Trends

The consumption of TBBPA with printed circuit boards and electronic components is increasing as a consequence of the increase in the consumption of electronic products.

For consumer electronics in which halogen-free alternatives are available on the market, the increase in the consumption of the products will to some extent be counteracted by a shift to halogen-free laminates, but the halogen-free laminates seem only to account for a minor part of the global market.

Waste from manufacturing

During the production of printed circuit boards a substantial part of the laminates is cut off and ends up in solid waste. Considering information from producers it is estimated that 15-25% of the laminates - corresponding to 15-25 tonnes TBBPA - is disposed of with solid waste.

During assembling of the circuit boards with components a few percentages of the laminates are removed by drilling, etc. This waste is assumed to be included in the 15-25% waste from production of the circuit boards.

A minor part of the products will be defective and disposed of with waste. This contribution to waste is considered negligible.

Emission from uses

Emission of brominated flame retardants from products in service is discussed in detail in section 1.4, and a total emission from al uses is roughly estimated.

From epoxy based laminates in which TBBPA is used as reactive flame retardant the emission during service is considered negligible although small amounts of unreacted TBBPA may be emitted.

By contrast the emission from paper-phenolic laminates, in which the flame retardants are used as additives, may be significant as the circuit boards heat up during operation. No profound studies of emission of TBBPA from phenolic-paper laminates exist.

Recycling and waste disposal

Printed circuit boards are ultimately either combusted during recycling of the metals or disposed of to landfills or incineration. Recycling of electronics is discussed in detail in section 3.1.1.

Substitution

Halogen-free alternatives are available for both epoxy and paper-phenolic laminates (see section 7.2.1).

Electronic components with flame retarded halogen-free plastic encapsulates have been introduced, but at present only for a very limited number of components.

2.2.2 Housing of Electric and Electronic Equipment

Housing of electric and electronic equipment - in particular TV sets and computer monitors - has traditionally accounted for a significant part of the consumption of PBDEs.

Base polymer

Housing or enclosures for computer monitors and other appliances is predominantly made from high-impact polystyrene (HIPS), ABS-polycarbonate blends or ABS based flame retardant compounds /11/, but polypropylene (PP), polycarbonate (PC) and blends of polyphenylene ether (PPE) and styrene/butadiene polymer may be used as well.

In the early nineties, HIPS represented 30% of the global DeBDE consumption, and ABS accounted for around 95% of the total OcBDE supplied in the EU.

During recent years PBDEs in housing have to a large extent been replaced by other brominated or halogen-free flame retardants. A detailed survey of flame retardants in housing of EE appliances on the Danish market is complicated by the fact that there is no general use pattern. The housing of identical products may contain different base polymers and flame retardants. To make exact estimates it is thus necessary to know the content of a large number of different products.

It has not been possible to obtain detailed information on the material content of imported products. The estimates for the major applications, TV-sets and office machines - will therefore be based on German test data. The fire safety of electronic products is regulated by the same standards in Germany and Denmark (see section 6.2.1), and it is assumed that the material content of the same brand on the two markets in general is the same.

Consumer electronics

Back panels - and to some extent the front cabinet - of TV sets are usually made of flame retarded materials. In the USA and Japan brominated flame retardants are still used in back panels and front cabinet (USA) of TV sets, but in TV sets purchased in Europe the front cabinet does not contain flame retardants, and there is a trend away from the use of halogenated additives in back panels /37/. Based on the monitoring of the German magazine Stiftung Warentest it has been shown that the percentage of tested TV set enclosures that contained halogenated flame retardants decreased from 68% in 1994 to 8% in 1997 as shown in figure 2.3 /37 /. It should be noted that the different tests do not cover the same market segment; some of the test e.g. only include 17'' TV sets. However, the trend seems to be clear. The absence of BFRs in European TV sets and the possible effect on the flammability of the TV sets have been discussed in /37/.

Figure 2.3
Percentage of tested TV set enclosures containing halogenated flame retardants according to the journal articles (from /37/)

Most other consumer electronics - radios, videos, etc. - are considered not to contain brominated flame retardants in the housing /32,51/.

There are, however, some exceptions. At least some video camcorders on the Danish market are known to contain TBBPA in the housing.

Office machines

The housing of office machines - computers, printers, copying machines, fax machines, etc. - is made of flame retarded plastic. PBDEs have traditionally been used for flame retardancy, but during the last years TBBPA and non-halogen flame retardants have substituted for the PBDEs.

Test results of electronic products on the German market show that out of more than 150 computer monitors, notebooks (portable computers) and printers tested in 1997/98, none contained PBDEs or PBBs (the source of information is confidential). A part of the analyses is represented in table 2.6. Of the bromine containing products 72% contained TBBPA. The remaining 28% contained other not identified brominated flame retardants.

Table 2.6
Test results on brominated flame retardants in plastic parts of electronic products sold in Germany

There is a marked trend from 1997 to 1998 towards bromine-free monitor housings, especially for the more expensive 17'' monitor. It is moreover notable that there is a significant difference between the more expensive 17'' monitors - presumably for the office market - and monitors of PCs for the consumer market. Of the 17'' monitors only 1 out of 14 contained brominated flame retardants, whereas more than half of the "home-PC" monitors contained bromine. For the office market it is more usual to buy monitors with the TCO-label, controlled by the Swedish Confederation of Professional Employees (see section 6.4). The TCO-label, assigned for more than 350 monitors (Oct. 98), requires that organically bound bromine is not present in parts >25 g. The significant difference between the two monitor groups could be an effect of the labelling.

For the printers, there is a significant difference between laser and inkjet printers that may reflect the different heat generation of the two printer types. All laser printer housings contain brominated flame retardants, mainly TBBPA.

Four out of 14 notebooks contained brominated flame retardants in the housing. In one out of 13 notebooks the housing of the power supply also contained brominated flame retardants. The result indicates that the power supply of other electronics in general may not contain brominated flame retardants.

It has not been possible to obtain detailed information on copying machines. Leading companies on the market state that PBDEs are not used in machines anymore, but do not have statements on other types of brominated flame retardants. In the absence of specific information it will be assumed that the housing of copying machines like laser printers contain brominated flame retardants and that the flame retardants will be predominantly TBBPA. The Nordic Swan and the German Blue Angel require that copying machines do not contain PBBs or PBDEs in plastic parts >50 g, but there are no requirements concerning other brominated flame retardants (see section 5.4).

Fax machines are assumed to follow the same pattern as laser printers.

Some old keyboards may contain brominated flame retardants, but new keyboards do not contain these flame retardants /38/.

As to the information received from Danish producers, the housing of telephones and mobile telephones should in general not contain brominated flame retardants.

BFRs are known to be present in the housing of some modems used for Internet communication.

Medical and laboratory equipment

The consumption volume of BFRs in housing of medical and laboratory equipment may potentially be significant, but the product group is even more diverse than consumer and office electronics. Brominated flame retardants are not used any more in the housing of Danish manufactured medical and laboratory instruments, but they were, however, formerly used.

Domestic appliances

Brominated flame retardants may be present in the housing of small home appliances. According to Swedish experience, coffee machines do generally not contain brominated flame retardants in the housing /38 /, but minor plastic parts in contact with live parts of the machine will contain flame retardants (see next section). According to the assessment from APME (see table 1.7) flame retardants should only be used in inner parts of domestic appliances.

There are no specific requirements regarding housing of heat generating appliances like hair dryers and coffee machines, but the inner parts in contact with live parts may be larger in this type of appliances.

Western European consumption

The W. European consumption of BFRs for ABS and HIPS which traditionally have been used for housing of electronic equipment was in 1998 8,500 tonnes representing about 10% of the total BFR consumption (see table 1.6). This indicates that BFRs are still widely used for housing of European produced electronics.

Content of flame retardants    In previous analyses of brominated flame retardants in EEE waste in Denmark it has been assumed that the PBDE content in housing was around 18%. The test results in table 2.7 indicate that the content of brominated flame retardants in the housing is significantly lower. In table 2.7 the recommended loading for computer housing plastics (UL94 V-0 HIPS) from one manufacturer of brominated flame retardants is shown. TBBPA is not as effective as DeBDE, and higher loading is necessary to meet the V-0 requirements.

Table 2.7
Recommended loadings for UL94 V-0 (1,6mm) HIPS /39 /

From the same producer, the recommended loading of TBBPA for V-0 ABS is 20-26%. It is known from other sources that ABS for housing contains about 23% TBBPA.

The recommended loadings indicate that the applied loading of the tested appliances in table 2.6 may be too low for V-0 rating or the analyses underestimate the actual content. In the absence of more specific information it will be assumed that the test results reflect the actual content of the housing of the appliances.

Production in Denmark

Around 3-6 tonnes TBBPA are contained in ABS used for production of housing for electronics in Denmark. The ABS is imported both as plastic compounds and sheets. The casing is predominantly used for electronics for telecommunication that is exported.

Consumption

The total consumption of brominated flame retardants with housing of electric and electronic equipment in Denmark is shown in table 2.8. The total con-sumption is estimated at 80-130 tonnes.

Table 2.8
Consumption of brominated flame retardants with housing for electric and electronic equipment in Denmark 1997

Trends in consumption

Housing is the field of application where the most pronounced changes in the use of brominated flame retardants have been taking place.

In Danish production in the order of hundred tonnes of brominated flame retardants were used for housing until a few years ago.

In previous studies on waste of electric and electronic equipment (EEE waste) in Denmark it has been assumed that DeBDE accounted for approximately 100% of the flame retardants in housing. Estimates on the total content of PBDEs in EEE waste in Denmark (1995) have varied from 157 to 1,220 tonnes (see section 3.1.1).

At the early nineties DeBDE and OcBDE were the most used flame retardants for housing. Today these compounds have to a very large extent been replaced by TBBPA, other brominated flame retardants or non-halogen flame retardants in housing of electronic appliances on the N. European market.

Several factors have contributed to the development: Working environment considerations (e.g. Denmark), legislation concerning furan/dioxin formation (Germany), ecolabels, consumer awareness, and environmental policy of companies.

The reason for the substitution of PBDEs on the German market is partly the German Dioxin Ordinance (see section 5.3) that specifies the maximum allowable quantities of specified chlorinated or brominated dioxins and furans that can be present in products marketed in Germany. The dioxins and furans may be present as contaminants or be formed during intrusion, moulding or recycling of plastics containing PBDEs /10/. The levels of brominated dioxins and furans formed in the manufacture of plastics at temperatures of 150-300ŗ C have been reported to be several orders of magnitude higher when DeBDE or OcBDE were present compared to the levels when TBBPA or bis-tetrabromophthalimide were present /10/.

Other brominated flame retardants have been designed to preclude the possible formation of brominated dioxins or furans and ensure compliance with the German Dioxin Ordinance. As an example ethylene bis-tetrabromophthalimide is marketed as a substitute for DeBDE in ABS and HIPS with reference to the German Dioxin Ordinance.

The requirements regarding brominated flame retardants of four of the most accepted and widespread ecolabels in N. Europe are described in section 5.4. With a few exceptions the Nordic Swan and the German Blue Angel only require that the housing of electronic products do not contain PBBs or PBDE, and there are no requirements regarding minor plastic parts and printed circuit boards. The most restrict requirements are stipulated by the TCO label (more than an ecolabel) that requires no organically bound bromine in parts >25 g.

Emission during production

Emission to air and waste water during production is treated jointly for all production processes in sections 1.4 and 3.4.

Emission during use

Emission during use is discussed in section 1.4. It should be noted that TBBPA is used as an additive in housing, and emission of TBBPA from computer monitors is presumably of much higher significance than emission from the printed circuit board of the computer.

Recycling and waste disposal

Housing of EE equipment is disposed of to landfills or incineration. Recycling of electronics is discussed in detail in section 3.1.1 and waste disposal in section 3.2. The plastic containing flame retardants are not recycled.

Substitution

Substitutes for brominated flame retardants are available for all kinds of housing, see section 7.2.3.

2.2.3  Other Components of Electric and Electronic Appliances and Machines

Brominated flame retardants may be present in a number of other components of electric and electronic appliances and machines:

The conceptual boundary between switches and other gear used in appliances and machines and similar components used for wiring and power distribution - included in section 2.2.5 - is not fixed, but lined up in the aim of distinguishing between short-term and long-term applications.

The sources of information that the consumption estimates will be based on do not use this distinction, and there will be some uncertainty as to the allocation of the consumption on this section and section 2.2.5.

Parts of relays, switches, pumps, etc.

Switches, relay parts, pump parts, etc. and other internal component of appliances and machines can broadly be distinguished from the housings - included in the previous section - by the used base polymers.

The main base polymer options for production of the internal components are thermoplastic polyesters (PBT, PET), polyamides (PA, nylons), polycarbonate (PC), polyphenylene sulphide (PPS) and liquid crystal polymers (LCP).

Part of relays, switches, pumps etc. are often made of PET/PBT and PA.

It has not been possible to obtain specific information on the BFR content of all these parts, and the estimates will be based on the following more general information on the consumption of BFRs with the plastic types of relevance.

DeBDE has been widely used for PET/PBT, PA and these plastics represented 20% and 15% respectively, of the total global consumption of DeBDE in 1992. This corresponds to approximately 10% of the total consumption of brominated flame retardants.

PET/PBT and PA is cf. table 1.6 estimated to account for 10% and 5%, respectively, of the total Western European consumption of brominated flame retardants in 1998 corresponding to 8,500 tonnes.

As a rough estimate the consumption in Denmark with these plastics in end-product should be of the magnitude 50-120 tonnes BFRs (cf. the estimate in section ). Parts made of these plastics will be included in this section, but are as well used for wiring and industrial automation (section 2.2.5) and in transportation (section 2.2.9).

The total consumption of flame retarded plastics used for production of ''Electrical equipment material" in W. Europe was 35,000 tonnes in 1995 of which 54% were flame retarded with BFRs (see table 1.7). The group includes circuit breakers, switches, etc., but not internal parts of appliances and machines. These applications will thus be included in section 2.2.5. The total content of brominated flame retardants in the products consumed in Denmark can roughly be estimated at 30-40 tonnes. For the estimate it is assumed that Denmark accounts for 1.5% of the W. European consumption and that the BFR content is 12-15%.

The consumption of BFRs with these plastic materials for production of EEE parts in Denmark was in 1997 around 35 tonnes. BFRs have to a large extent been replaced by other flame retardants in PA and PC used in Danish production, but they are present in imported products. According to the market analysis og IAL consultants /18/ it is mainly in the Northern European countries that the BFRs are replaced in polyamides.

Considering the present information it will be estimated that a total of 20-40 tonnes BFRs are used for these applications.

The flame retardants used will cf. section 1.3 be TBBPA and derivatives, PBBs, PBDEs and other BFRs.

Cables

Cables within electronics often contain brominated flame retardants to comply with the strict fire safety requirements of the internal parts of electronic equipment. Information has only been obtained from one major producer. The cables contain 5% bromine. The specific compound is considered confidential, but it is not PBDEs or PBBs. The 5% bromine content correspond to approximately 8% BFRs.

Moulding fillers

Flame retarded moulding fillers are used for sealing of electronics. The fillers are mostly based on epoxy or other thermoset resins. According to the Danish Product register about 1.5 tonnes DeBDE with moulding filler are annually used for production processes in Denmark. The fillers are predominantly used in professional electronics, but also electronics in battery chargers are known to contain flame retarded moulding filler.

Foam

Flame retarded PUR foam has been reported to be used in electric and electronic appliances and machines. According to manufactures BFR containing foams are not used for domestic refrigerators and freezers produced in Denmark. It has not been possible to identify specific uses, but it is assumed that there will be a small consumption with imported products.

Plastic insulation parts

Plastic parts in contact with live parts of all kind of electronic and electric equipment contain flame retardants. In heat generating appliances as hair dryers and irons, the inner parts in contact with live parts are relatively large.

Direct inquiries to agents of major producers of coffee machines, hair dryers, curling irons, electric irons, microwave ovens, and electric toasters have not revealed any specific information on the content of brominated flame retardants in these products. None of the producers have specifically stated that the product do not contain brominated flame retardants, but one producer have answered that their products do not contain PBDE and PBB.

Coffee machines do generally not contain brominated flame retardants in the housing /38/, but plastic parts in contact with live parts of the machine will contain flame retardants. In Hedemalm et al. (1995) /32/ it is roughly estimated that coffee machines contain 50 g flame retarded ABS per machine, corresponding to 10 g PBDE. With a consumption of about a half million coffee machines the total may amount to approximately 5 tonnes PBDE.

In the inventory from the APME shown in table 1.7 it is estimated that the consumption of flame retardant plastics for production of small and large domestic appliances in W. Europe was 3,000 and 11,000 tonnes, respectively. The share of brominated flame retardants is not stated, but if it is assumed that BFRs were used in 50% of the flame retarded plastics in a concentration of 15% it can be translated into about 1,000 tonnes BFRs. A part of this will be included in other groups of 18-50 this section.

The plastics used for these parts will be ABS, PP and PC among others. PP and PC accounted for 8% and 5% of the total European consumption of BFRs in 1998 (cf. table 1.6) corresponding to 8,000 tonnes.

Considering the present information it will be roughly estimated that other plastic parts account for a total consumption of tonnes flame retardants.

Production in Denmark

Approximately 35 tonnes brominated flame retardants were used in compounds of PBT/PET and PA for production of switches, relays, parts of electric machines, etc. in Denmark. Almost all was TBBPA, but PBBs and 'other flame retardants' both accounted for approximately 4 tonnes.

Table 2.9
Consumption of brominated flame retardants with other parts of electronic appliances and electric machine in Denmark 1997

Trend in consumption

In Denmark and Germany there has been a trend of substituting halogen-free flame retardants for BFRs in polyamides. For the other polymers the trend has been a replacement of PBDEs by TBBPA and other brominated flame retardants and an increase in the consumption due to a general increase in the consumption of EE equipment. For the total group the consumption is estimated to be stagnant, with two opposite-acting trends.   

The Nordic Swan and The German Blue Angel have at present ecolabels for coffee machines under development that expectedly will require that BFRs are not used at all in the machines. This reflect that small domestic appliances without BFRs are available on the market.

Emission during production    Emission to air and waste water during production is treated jointly for all production processes in section 1.4 and 3.4.

Emission during use

Emission during use is discussed in section 1.4. It should be noted that the brominated flame retardants are mostly used as an additives. Emission for other plastic parts of the equipment may be of same significance as the emission from the housing.

Recycling and waste disposal

Other plastic parts of EE equipment is ultimately disposed of to landfills or incineration. Recycling of electronics is discussed in detail in section 3.1.1 and waste disposal in section 3.2. The plastic containing flame retardants are not recycled.

Substitution

Substitutes for brominated flame retardants are available for PA and PC, but at present not for PBT/PET; see section 7.2.4 and 7.2.5.

2.2.4  Lighting

Brominated flame retardants may be present in lighting in:

Sockets

Sockets used for incandescent lamps may be made of ceramics, thermoplastics or Bakelite, a phenol based thermoset. Plastic sockets will often be made of flame retarded PBT. Some PBT sockets used for production in Denmark is known to contain 11-12% TBBPA, but it is not known whether this is general to all plastic sockets. Plastic sockets should according to a leading supplier account for about 90% of the Danish market of sockets. (Plastic sockets are by users often designated "Bakelite sockets").

Considering information from a leading importer and Danish producers of lighting, it is estimated that plastic sockets account for the major part of sockets in lamps sold in Denmark as well.

Plastic covers

Covers, shades and similar parts are to pass a glow-wire test at 650° C, if they are placed closer than 30 mm from any heated part of the lamps (see section 6.2.3). The covers may be made of flame retarded grades of PC, PMMA, HIPS or PA /11/. PA flame retarded with BFRs have previously been used by Danish producers, but today halogen-free grades are used. Often the producer of the end products do not know the specific flame retardants used is plastic parts supplied by sub-contractors. A screening of plastic parts used by a leading Danish producer revealed that bromine compounds were present in one out of 50 analysed parts. Considering the available information it is estimated that the consumption of BFRs with other plastic parts is relatively small and less than 3 tonnes. Both PBDE, TBBPA and other flame retardants may be used.

Compact fluorescent tubes

The basis of compact fluorescent tubes (energy-saving light bulbs) is often made of flame retardant plastics. It has not been possible to obtain specific information on the flame retardants in the basis, but it is most probable BFRs.

Switches

Switches is most probably made of flame retardant plastics. The switches of lighting usually only weigh a few grammes and the total amount of flame retarded plastic will be small compared to the sockets.

Other parts

Other lamp parts as capacitors for fluorescent tubes of electronic parts may contain brominated flame retardants. It has not been possible to identify any uses, but according to the information obtained the capacitors do not contain BFRs.

It will roughly be estimated that the total content of BFRs in switches and other parts of lighting sold in Denmark in 1997 was below 4 tonnes.

Production

Lighting is produced in Denmark by several manufacturers. The BFR containing semi-manufactures for the production is mainly imported, and there is a limited knowledge regarding BFRs in the products.

Consumption

The total consumption of brominated flame retardants with lighting in Denmark 1997 is estimated at 4-14 as shown in table 2.10.

Table 2.10
Consumption of brominated flame retardants with lighting parts in Denmark 1997

Trend in consumption

In Danish production of lighting there has been a trend of substitution BFRs for other flame retardants in plastic cover parts.

Emission during use

Emission during use is discussed in section 1.4. The brominated flame retardants are predominantly used as additives. In lighting the plastic parts, especially sockets, heat up during operation and the emission may be significant.

Recycling and waste disposal

Plastic parts of lighting is ultimately disposed of to landfills or incineration. Waste disposal of lighting is included in section 3.2. The consumption of BFRs with lighting is estimated to be stagnant and the amount disposed of is roughly estimated to equal the current consumption.

2.2.5  Wiring and Power Distribution

To comply with the fire safety standards most plastic parts of wiring in houses and within other power distribution systems contain flame retardants or are based on polymers, notably PVC, with inherent flame retardancy.

Brominated flame retardants are used as well as chlorinated, phosphorus and inorganic flame retardants.

The main applications of brominated flame retardants are:

Sockets, mounting boxes and other components used for wiring in houses often contain brominated flame retardants. According to information from a major Danish producer 10-30% of all plastic parts will contain brominated flame retardants. Traditionally PBDEs have been used for these applications, but in products on the Danish market only TBBPA (in PET) and HBCD (in PS) have not been identified. PBDEs and other BFRs may be present in some imported products.

Both brominated and chlorinated flame retardants are used in rubber for insulation of flame retardant flexible cables. The main use of rubber insulated cables are temporary wiring at construction sites, but wiring of windmills also account for a significant volume. The cables have to comply with fire safety standards, be flexible and resistant to high mechanical wear.

Information on the flame retardants in rubber has been received for products from three major producers. Two producers were using PBBs and PBDE, one was using chlorinated compounds. Halogen-free products are available for smaller wires.

The brominated flame retardants are used in the rubber at loadings of about 6-7%. Based on rough estimates from a large foreign producer of cables containing PBBs and PBDEs, the total Danish consumption of each compound would be of the magnitude of 30 tonnes, if all rubber cables contained brominated flame retardants. They surely do not. From the producer in question only one third of the rubber cables contained brominated flame retardants, and chlorine containing cables have presumably a significant market share. There are, however, many companies represented on the Danish market, and an analysis of the whole market has not been possible.

On basis of the present information the total consumption of brominated flame retardants with rubber cables in Denmark in 1997 is roughly estimated at 1-5 tonnes PBDEs and 1-5 tonnes PBB.

In fire-resistant wires used for fire alarms, emergency lighting and other applications in which there are especially strict fire safety requirements, flame retardancy is usually obtained by layers of silicon compounds and glass woven fabric.

Brominated flame retardants may be used for other cables. Cable insulation is the major application for flame retarded polyethylene in W. Europe (cf. table 1.6). About 3,500 tonnes BFRs are used with PE in W. Europe, but it is not clear whether BFRs are actually used for cable insulation.

It has not been possible to identify any cables (except rubber cables) with brominated flame retardants on the Danish market, but as cables are imported from many countries it cannot be ruled out.

Contactors, relays, switch gear, starters, etc. used for power distribution and industrial automation are in general made from flame retarded PA, PC and PBT/PET. BFRs are the main flame retardants for these applications.

There is no Danish production of this equipment and it has been difficult to obtain specific information. The equipment is imported from many European countries and the group cover a wide range of different equipment. The Danish market for this equipment is of about the same value as the market for wiring parts.

As discussed in section 2.2.3 the W. European market volume for PET/PBT, PC and PA was about 12,500 tonnes in 1998. A significant part of this is estimated to be used for power distribution and industrial automation.

The total consumption of flame retarded plastics used for production of ''Electrical equipment material" in W. Europe was 35,000 tonnes in 1995 of which 54% were flame retarded with BFRs (see table 1.7). The group includes circuit breakers, switches, etc., but not internal parts of appliances and machines. If it is assumed that the plastics contain about 15% BFR the amount can be translated into about 3,000 tonnes.

Considering the available information it will roughly be estimated that 10-25 tonnes BFRs was used for these applications in Denmark in 1997.

Technical laminates based on for instance polyester, epoxy or phenolics in V-0 grades are used for a wide range of applications in electric equipment: bobbins, switchboard panels and partition walls, transformer insulation, etc. TBBPA is known to be used for technical laminates for these applications, but other flame retardants, for instance tetrabromophthalic anhydride, may be used as well. Most technical laminates used for transportation do not contain BFRs, but the fire safety requirements to the laminates used for electric equipment are stricter. The laminates are typically used for switchboard panels and similar applications and will be included in the estimates for contactors, relays, etc.

According to the literature BFRs may be used in capacitors. It has not been possible to identify BFR containing capacitors.

Consumption 

The total consumption of brominated flame retardants with equipment for wiring and power distribution in Denmark 1997 is estimated at 30-80 as shown in table 2.11.

Table 2.11
Consumption of brominated flame retardants with products for wiring and power distribution in Denmark 1997

Trend in consumption

In Denmark and Germany there has been a trend of substituting halogen-free flame retardants for BFRs in polyamides. For the other polymers the trend has been a replacement of PBDEs by TBBPA and other brominated flame retardants and an increase in the consumption due to a general increase in the consumption of EE equipment.

There is a wide range of cables marketed as halogen-free and a pronounced trend away from halogen-containing flame retardants. Of the equipment for power distribution and industrial automation it has only been possible to identify a contactor marketed as halogen-free. The other equipment is estimated to contain one or more BFR containing parts.

Emission during production

Emission to air and waste water during production is treated jointly for all production processes in section 1.4 and 3.4.

Emission during use

Emission during use is discussed in section 1.4. The brominated flame retardants are mostly used as an additives. Emission from this equipment may be of significance.

Recycling and waste disposal

Other plastic parts of EE equipment is ultimately disposed of to landfills or incineration. Recycling of electronics is discussed in detail in section 3.1.1 and waste disposal in section 3.2. The plastic containing flame retardants are not recycled.

Substitution

Substitution of BFRs in plastics for this equipment is discussed in section 7.4.2 and 7.4.3.

2.2.6  Textiles

Based on international experience, the following types of applications of brominated flame retardants in textiles are possible:

Textiles and furniture used in transportation are covered below in section 2.2.9, but the used materials will in broad outline not be different.

Flame retardants are one of the major categories of chemicals used in textiles. Comprehensive reports dealing with textiles and the chemicals used in textiles have been issued by the Swedish National Chemicals Inspectorate and the Danish Environmental Protections Agency in 1997 /40,41/. The first report discusses the chemicals used for textiles, and the latter focuses on the life cycle of the base textiles. The Swedish report inform that perhaps only 10-20% of the textiles sold in Sweden are Swedish-made, and that for apparels (clothes) the percentage may be only half.

These two reports do not give detailed information on brominated flame retardants used for textiles, which reflects a low or negligible use of these chemicals in the respective domestic textile industries and textile after treating industries.

However, the relatively high share of imported textiles, after-treating made abroad and imported textile-containing products (mainly furniture), means that the use of BFRs for textiles used in Denmark cannot be ruled out.

The dominating flame retardant system for textiles based on bromine is hexabromocyclododecane (HBCD) and decabromodiphenyl ether (DeBDE) in conjunction with antimony trioxide /9,42/. Both DeBDE and HBCD are additive substances.

The use of brominated flame retardants for textiles within the EU, takes place mainly in the United Kingdom and Ireland, where there are strict requirements of flame retardancy treatment of upholstered furniture.

Protective clothing

No use of brominated flame retardants has been identified for civil purposes. In the past though it has been normal to use e.g. the bromine-antimony system for some types of protective clothing. The disadvantage of the bromine based flame retardant systems for clothing, is the lack of softness of the treated product.

The only known use of BFRs in textiles for clothing in Denmark is connected to ABC uniforms from 1984 (ABC: atomic, biologic, chemical), produced for the Danish Army. The used mixture consists of the antimony/decabromodiphenyl ether system in combination with inorganic phosphorus compounds. The ABC uniforms are designed to be worn for maximum 30 days and to stand one wash at 30°C. When a uniform has been used (e.g. in war zones), the clothing is used for training purposes in Denmark and through repeated laundering, most impregnation will be washed out. On the basis on information from the Danish Army round 4 tonnes decabromodiphenyl ether will be present in the stockpile.

Children's night-dress 

Within the UK and the USA, requirements regarding the flammability of children's night-dresses exist, and night-dresses fulfilling these requirements are also found on the Danish market. According to major producers of flame retardants for textiles, the use of organophosphates is absolutely dominant, and possibly no brominated compounds are used. The only possible use might occur in 100% polyester products, in which BRF represents a cheap solution, meeting the requirements.

Tents

Internationally, tents are one of the major textile end-products for brominated flame retardants. They are used for both military tents and civil tents especially 'party' tents. Apparently there are no such consumption in Denmark. According to the Danish military other solutions than bromine antimony systems are used, but some import of flame retarded tents may take place. The possible consumption is assumed to be low, most probably under 1 tonnes.

Carpets

No use of brominated flame retardants in Denmark has been identified. Demands regarding flame retardancy exist only within the contract market. The contract market is defined as products purchased to public or private institutions, business, e.g. for offices, industry, canteens, hospitals, and kindergartens. The absolutely predominant flame retardancy system is based on aluminium hydroxide combined with various fillers, incorporated in the back side layer.

DeBDE might to some extent be used for synthetic carpets, but it is unlikely that these products reach the Danish market in significant amounts, whereas existing requirements for flame retardancy are reached by cheaper alternatives. Still industry information and /3/ indicate that PBDEs or other BFRs might be present in flame retarded carpets based on cheaper synthetic fibres, where they are encapsulated within the polymer fibres.

Curtains

Flame retarded curtains are not normally used in Denmark. It is in textiles based on plastic that brominated flame retardants are most likely to be found, and the most likely products are blackout curtains, roller blinds and cinema screens. Bromine/antimony systems with PBDEs or HBCD are likely to be used. No actual consumption has been identified, but a small consumption is likely to occur.

Upholstered furniture

In Denmark, furniture used for the contract market are normally flame retarded. The flame retardant may be added to both the textile and the padding.

Among the main Danish textile finishers supplying the furniture industry, the general statement is that no brominated flame retardants are used.

The main entries to the Danish market of furniture with textile treated with brominated flame retardants are furniture for the 'contract market'. A normal practise among some suppliers of contract furniture is to sell products produced for the English civil market, as these fulfil the requirements stipulated by the British Standard, that are regarded as some of the most rigorous rules for fire protection of furniture.

Foam and stuffing for upholstered furniture

Seemingly, no Danish producer of various types of foam for furniture, cars, etc., uses brominated flame retardants. Chlorinated organophosphates (e.g. TCPP) and melamine are normally used for slap stock foam, but it must be expected that foreign produced foams may contain brominated flame retardants. The bromine analogue to TCPP has had a widespread use. Other used systems might be phosphorus derivatives used with penta-bromodiphenyl ether.

The expanded polystyrene stuffing in sack chairs, health mattresses, nurse cushions, etc., is normally flame retarded with between 0.5% and 1% hexabromocyclododecane. This may correspond to a yearly consumption of HBCD between 200 and 700 kg.

Production in Denmark

Seemingly no application of brominated flame retardants for textiles takes place in Denmark. This information is based on inquiries among the Danish industries and major foreign suppliers of brominated flame retardants for textiles.

Inquiries among Danish producers of slap-stock foams indicate that no brominated flame retardants are used in Danish production of foams.

Import/export

The main supply of brominated textiles to the Danish market is through import of furniture or textile for furniture. A major part of the upholstered furniture, produced for export to the UK, is made with textiles treated or produced in the UK. The major part of the import of flame retarded textiles is possibly exported as furniture, partly for the UK market, partly for the contract market.

Consumption in Denmark

The major Danish consumption of BFRs within the category "textiles" is related to furniture.

BFRs might be present in imported special curtains and related textile products made on plastic basis and in imported carpets made from synthetic fibres. No cases have been identified though.

The total consumption of brominated flame retardants with textiles in 1997 is estimated at 2-11 tonnes as shown in table 2.12.

Table 2.12
Consumption of brominated flame retardants with textiles in Denmark 1997

Trends in consumption

The future trends in consumption are very dependent on the specific fire regulations. At the level of the EU, negotiations on this issue are underway. These will be of essential importance to the future consumption of flame retardants for textiles, and may have consequences for the choice between different technical solutions (i.e. the use of brominated flame retardants).

Seemingly, aromatic BFRs are substituted by aliphatic BFRs (e.g. HBCD). Furthermore the general tendency is that BFRs are being substituted by halogen-free alternatives, including inherently flame retardant textiles.

Emissions during use

It is expected that emission to waste water from washing of furniture textiles in offices, etc., will be negligible.

It is assumed that the emission from textiles that are washed regularly will lead to emissions to waste water. This is relevant to protective clothing. It is assumed that on average half of the flame retardants will be washed out, before the products are discarded. Furthermore the consumption of protective clothing with BFRs for civil purposes has formerly been larger.

Hence the emission to waste water is expected to be <150 kg BFRs per year. Correspondingly it is expected that 150 kg BRF are disposed of with solid waste.

On average, round 50 kg DeBDE is likely to be released per year to the waste water from ABC uniforms through the washing processes (the used uniforms are put to training use, and are washed repeatedly in this connection).

Waste disposal

It assumed that a volume corresponding to the consumption are disposed of with solid waste.

2.2.7   Building Materials

Within the building industry, brominated flame retardants are used in some specific synthetic materials. The main categories are

Insulation   

Insulating boards and sheets for buildings that potentially contain brominated flame retardants can be made of:

Insulation, EPS & XPS 

EPS and XPS are at large used for comparable purposes. Still, XPS is more durable and more expensive than EPS, and this does influence the actual application of the two materials. In Europe, both materials are normally flame retarded with hexabromocyclododecane (HBCD). In EPS between 0,5% and 1% is used, and in XPS between 1% and 2% is used.

The plain insulation panels have a wide use in construction. They are used for insulation of foundation, ground deck, parking deck, compact (flat) roof, roof terrace and roof gardens. They are furthermore used for soil insulation in connection with frost vulnerable constructions such as railways, road, other traffic areas, sport centres, water pipes and waste pipes.

Insulation panels made of EPS and XPS may be worked up and sheathed with various materials for special insulation panels for e.g. the construction industry and for transportation. This processing is called 'fabrication'.

In general, XPS materials used in Denmark are flame retarded today whereas EPS materials used in Denmark are only flame retarded when this is in explicit demand.

Due to the strict requirements regarding the flammability of building materials in Denmark, the plastic based insulation is normally only allowed when it is encapsulated in non-combustible and approved materials, and hence no flame retardants are required for the foam. The major exception from this is flat roof constructions on factory buildings where less strict requirements exist, and local fire authorities sometimes grant dispensation. This permits the use of typically EPS as an alternative to mineral wool. Considering information from suppliers it is estimated that as a maximum, five percent of the EPS used in construction in Denmark are flame retarded. This corresponds to 0.5 to 2.7 tonnes HBCD per year in EPS insulation.

The use of flame retarded XPS in construction in Denmark is possible only explained by the fact that all XPS are produced abroad, in countries where the fire regulations allow the use of flame retarded foams for insulation of buildings.

Furthermore, industry contacts explain the foreign use of flame retarded EPS and XPS panels for road construction and building with the fire risk during the construction phase. Fire risks may for instance be possible fire-raising at road constructions or sparks from welding on construction sites.

Insulation, PUR

Flame retarded rigid polyurethane is used for a number of different insulation purposes within construction. PUR is a thermoset plastic made through the reaction of an isocyanate and a polyol. PUR may be flame retarded with both additive and reactive brominated flame retardants. The dominant flame retardants for polyurethanes are brominated polyols, that is reactive flame retardant. If requirements are strict, other additives and reactives may be combined with the brominated polyol.

The predominant use of flame retarded rigid polyurethanes is with construction.

PUR foam has very good insulation characteristics and is widely used within the building sector for cold-storage plants, freezing rooms and cold stores, e.g. at supermarkets, processing rooms in the food industry, and refrigerating holds at ships and in containers. Minor consumption areas are faēade insulation, pre-insulated pipes, and joint filler foam.

In general these applications are always flame retarded, except the last three where the use of flame retardants depends on the actual application.

In a number of applications flame retardants, and hence also BFRs, are not used. These are home-refrigerators, plain district heating pipes (some indoor uses e.g. in factories may imply the use of BFRs).

PE pipe-insulation

Heat pipes and hot water pipes may be insulated with flexible self-extinguishing foam-tubes, made of PE foam. According to professionals, this PE pipe insulation is only used occasionally by smaller entrepreneurs and private persons for home-made installations in smaller dwelling houses, whereas professional entrepreneurs in Denmark almost solely choose mineral wool. PE foams may be flame retarded with HBCD, but also PBDEs may be used. Round 4-500 km PE tubes og 75-100 gram per meter is expected to correspond to 0.5 to 2.5 tonnes used per year.

Foils

Foils may be made of polyolefins (PE, PP, etc.) or PVC. For most applications, the PVC product does not contain any flame retardants. The polyolefins may be flame retarded with chlorinated and brominated paraffins, with PBDEs and other additive flame retardants, such as ethylene bis(tetra-bromo-phthal-imide), brominated polystyrene and TBBPA derivatives.

Foils are used for three main purposes:

In Denmark, only the first category is normally flame retarded due to formal regulation. Round 20% of the flat roofs in Denmark are roofed with alternatives to roofing felt. The major part - approximately 90% - of the roofing foils are made of PVC. Of the remaining part approximately 80 tonnes polyolefins are flame retarded with brominated flame retardants, corresponding to 1-4 tonnes brominated flame retardants, depending on the base polymer.

Foils used for damp proofing under roof and in walls would normally not be flame retarded in Denmark due to price competition.

Foils used for civil engineering are normally not affected by fire regulations, but according to industry information, up to 10-20% is possibly flame retarded.

Outer panels

Internationally, flame retarded panels are used for construction. Epoxy based TBBPA in glass fibre reinforced panels for construction and translucent panels with a combination of halogenated FR and phosphorus chemicals for building roofing are examples /11/, but Danish applications have not been identified. Small amounts of these types of building materials may be used in Denmark.

Other uses

Other materials than those mentioned above might be flame retarded, but have not been assessed. These might be wall linings, e.g. based on glass fibre with a flame retarded binder, special grips, handles, etc.

Also through-going installations between premises must be flame retarded. Hence it is known that PBDEs may be used for the outer coating of some through-going water pipes, and that some ventilating shafts also may be flame retarded. Today the self extinguishing polyphenylenesulfide polymer is often used for the latter purpose, and the consumption of BFRs for this purpose is most probably negligible.

Wooden panels may be impregnated with ammonium bromide to obtain a building material that passes the test as a class 1 covering material. Ammonium bromide does, however, fall outside the present definition of BFRs, while ammonium bromide is an inorganic substance.

Production in Denmark

All the substances used for the different productions - if any - are imported. This is e.g. polystyrene granulate for expanded polystyrene, polyolefins and isocyanates for polyurethanes, polyethylene for foils.

The domestic supply of EPS panels is almost solely produced in Denmark, and flame retarded panels are seldom requested. The production for export is mainly based on processed panels, and on flame retarded panels.

There is no production of XPS in Denmark.

An extensive production of polyurethane panels exists in Denmark. On the basis of information from the industry, it is estimated that 50-70% of the Danish production of expanded PUR is exported, and that the import covers round 20% of the home market. Import are mainly directed at smaller refrigerated rooms. The total supply to the Danish market corresponds to round 50% percent of the production, which is 80-120 tonnes. Hence the consumption corresponds to round 40-60 tonnes per year

No production of PE pipe insulation exists in Denmark.

Flame retarded foils are produced in Denmark, for both roofing and as damp courses. Both types of products are mainly exported, and the latter is apparently solely produced for export.

Consumption in Denmark

The total consumption of XPS insulation in Denmark amounts to round 35,000-45,000 m3. Of this it is assumed that 80% are flame retarded, and hence the consumption related to XPS corresponds to 11-29 tonnes HBCD.

The total consumption of brominated flame retardants with building materials in 1997 is estimated at 50-100 tonnes (see table 2.13).

Table 2.13
Consumption of brominated flame retardants with building materials in Denmark 1997

Trends in consumption

In general, the consumption within the building and construction sector is stable.

Waste generation during use

Generally, when a tender is given, the waste generation at the construction site is taken to be 10% /43 /. In practice, the average waste generation is expected to be lower, depending on the material and the application.

Based on information from the line of business it is estimated that 2-5% of the used EPS and XPS is cut off during mounting and disposed of with combustible building waste.

The loss during use is depending on the application. According to suppliers, the loss is normally low and here estimated to be 2% of the used volume.

For PE pipe insulation, foils and panels the waste generation during use is assumed on average to correspond to 5% of the used volume.

2.2.8   Paints and Fillers

Brominated flame retardants may be used in:

Paints   

As to flame retardancy paints can be divided into two groups:

Intumescent paints

There are two market segments of intumescent paints: Steel constructions in buildings and industry and off-shore constructions and ships.

When heated, intumescent paints are designed to swell (intumesce) into a thick, insulating char that protects the underlying material from fire by providing a physical barrier to heat and mass transfer. The paints are typically based on epoxy polymers and do not contain BFRs. The retardancy effect is obtained by the combination of a carbon source, a catalyst (e.g. ammonium polyphosphates), and a blowing agent (e.g. melamine). There is no production of intumescent paints in Denmark.

PBDEs may be used for marine and industry paints /7/. Marine paints used in Denmark are imported directly by the customer from abroad and no specific information on these paints have been available.

"Low flame spread" paints

"Low flame spread" paints are used for cabins and engine rooms on ships. According to Danish producers of paints, these paints do not contain BFRs.

Joint fillers

Flame retardant joint fillers may contain brominated flame retardants. According to information from the line of business, flame retardant joint fillers will most often be of the intumescent type and contain nitrogen and phosphorus flame retardants.

An exception is joint filler foam of PUR that is included in section 2.2.7.

Fire proofing of wood

Flame retarded wood panels are used as an alternative to cement based panels in construction where there are requirements. As well brominated as other flame retardants are used for fireproofing of wood.

Consumption 

Brominated flame retardants are not classified dangerous, and there are no requirements on registering of the compounds in the Danish Product Register. However, if they are constituent parts of products containing dangerous substances, information on the flame retardants will be included in the record of the product. Paint, fillers and wood impregnation will usually contain classified substances and thus be registered.

According to the Danish Product Register 0.3 tonnes decabromodiphenyl ether (DeBDE) is annually used with paints. Empirically the registered quantities may be higher than the actual consumption and represent the consumption pattern some years ago. By the Product Register it has been confirmed that the products are still in use, but the information on the application areas is confidential. The use of brominated flame retardants in paints has not been identified in this survey, but it is assumed to be used for ships or construction works.

The registered consumption of brominated flame retardants with fillers and similar products was negligible, and it is estimated that the consumption with filler, etc. in 1997 was <0.2 tonne.

The registered consumption of brominated flame retardants with wood impregnation is considered confidential, but it is estimated that 0.5-1.2 tonnes other brominated flame retardants was used for this application in 1997.

In total 0.6-1.7 tonnes brominated flame retardants were used for these applications in Denmark 1997 (see table 2.14).

Table 2.14
Consumption of brominated flame retardants with paint, wood impregnation and fillers in Denmark 1997

Trend

There is no information on the trend in consumption.

Waste disposal

Brominated flame retardants in fireproofed wood is assumed to be disposed of with combustible building materials. The life span of building materials is in general more than 20 years, and the present quantities disposed of are assumed to be only 20-40% of today consumption.

The brominated flame retardants in paints are assumed to be disposed of with ships scrapped abroad or with construction steel for recycling.

2.2.9  Transportation

Transportation is together with electrical and electronic equipment probably one of the most important areas for the consumption of flame retardants.

Historically, brominated flame retardants have had very extensive use in transportation, mainly because of the combined demand for flame retarded, low-weight solutions.

Cars, trucks and busses

The following information is based on literature, communication with car manufacturers, and communication with sub-suppliers for the car-manufacturing industry. Inquiries have been sent out to a number of car manufacturers, but only few replies have been received.

The received replies indicate that the manufacturers in general have only limited knowledge on the used flame retardants in products from sub-suppliers. The explanation is often that attention up to now has mainly been placed on the technical capabilities of the products.

Meanwhile, the replies also indicate an increasing attention to the health and environmental related aspects, and hence attention also to brominated flame retardants. Some car manufacturers state that the use of brominated flame retardants has been phased out everywhere except in electronic devices.

Brominated flame retardants may be used in both interior and motor parts. The legal requirements regarding the flammability of the interior materials are normally more than met by the producers, partly explained by the fact, that the security of the driver and the passengers is a selling argument. Special requirements exist for busses and mini busses with more than 9 passenger seats. In general, though, it should be expected that the materials used for trucks and busses are similar to those used in cars.

In fact, the variation of the used flame retardants is seemingly wider between different producers than between different types of motor vehicles.

The available information makes it probable that regional differences in the choice of BFRs exist. The information does not support assumptions on differences in the used volumes, except that it is assumed that 20% of the European produced cars are produced without BFRs, where substitution by alternatives is possible.

The use of brominated flame retardants in cars is mainly connected to interior textiles and the electrical system, but also in a number of plastic parts flame retardants are found. According to information from producers, suppliers and /11/, flame retardants are often used in cars in the following parts:

Textiles:

Plastics:

Electrical/electronic parts:

Textiles, in cars, etc.

The interior textiles are most often with flame retardants in the back coating.

In European produced cars, the interior textiles are, with some exceptions, flame retarded with HBCD. The exception is cars containing alternative flame retardants, or textiles with inherent flame resistant characteristics. Though, there may exist variations within the European producers, and hence the use of other flame retardants cannot be ruled out.

From two producers from the Far East and the USA respectively, information has been received that the textiles in the cars are flame retarded with PBDE. A producer in the Far East states that up to 250 g PBDEs are used per passenger car, mainly in interior textiles.

When seat cushions are flame retarded, the chlorinated compound TCPP are normally used in Europe.

It is estimated, on basis of /44 / and information from the line of business, that an average passenger car implies the use of around 20 to 25 m2 interior textile, and around 10 m2 technical textiles.

For a European produced car the corresponding consumption of BFRs for textiles is estimated to be 0.1 to 0.3 kg per car, mainly constituted of HBCD. PBDEs may also be used though.

For other cars, the corresponding consumption of brominated flame retardants is assumed to be equivalent, though it is assumed, the used flame retardants mainly are PBDE.

It is assumed that the consumption per lorry and per commercial vehicle is comparable, and that the consumption per bus is described by scaling up these figures with a factor 5.

Plastics, in cars, etc.

A smaller number of specific components may, according to information from the line of business, be flame retarded. Furthermore, some of the typical polymers used for these plastic parts are often flame retarded with BFRs. In total, the typical consumption of plastics in a passenger car sum up to 125 kg /45 /. Flame retarded plastics will, however, only make out a small part of this. Numerous polymers may be used. Examples are PUR foams, solid PUR, PC, ABS, PP, PA, PC/ABS, PMMA, PVC and modified PPO /11/. Some of these are halogen or sulphur based polymers and hence inherent flame retardant, others may be flame retarded with BFRs as well as with halogen-free alternatives, and others are normally only flame retarded with BFRs.

On this basis it is estimated that up to 0.075 kg brominated flame retardants may be used per car in plastics, independently of the production region. The used BFRs are both PBDEs, TBBPA derivatives and other BFRs cf. the analysis of the W. European market for flame retardants discussed in section 1.3 . Many producers have internally banned the use of PBDEs, but it is presumed mostly to be the case for Northern European producers.

It is assumed that these figures may be scaled up in the same way as above.

Electronics/electrical system in cars, etc.

It is here assumed that the used volumes of BFRs in the electrical and electronic systems are alike in all cars.

It is assumed that a standard car contain approximately 500 cm2 printed circuit board, 300 g switches, sockets, etc., 100 g shieldings and encapsulations (polyolefins, thermoplastics and other), corresponding to 0.04-0.1 kg BFRs, shared on TBBPA and derivatives, PBDEs and other BFRs. It is assumed that these figures will be independent of the production region.

Trains

Trains are together with aircraft characterised by strict requirements regarding the flammability of the used materials. Especially the requirements on the textiles are more rigorous than requirements on textiles used elsewhere. The requirements are elevated, if the trains are to be used in tunnel-connections. Hence the requirements for new trains in Denmark have been tightened up since the opening of the Great Belt connection.

The main supply of trains in 1997 was to the subway of Copenhagen, and new inter-regional and inter-city trains. The supply was 42 train sets in 1997.

The total tonnage of trains is only a few percentages of the tonnage of cars, lorries and busses.

Materials used for Danish trains are regulated by a standard developed by the European Railway Companies (see section 6.2.8). To pass the prescribed tests, the use of BFRs may come into consideration. In general, requirements are put forward to all materials; rubber connections in inter-connection gangways, all interior materials, cellular plastics and rubber materials, rigid thermoplastics, electric cables, etc. (see section 6.2.8).

BFRs are - in general - not used in the interior textiles and seat cushions in Danish trains. The textiles for seats and flooring and the seat foam are delivered from manufacturers that have phased out the use of brominated flame retardants.

Inorganic, bromine containing flame retardants are used in interior panels. These inorganic substances do though fall outside the definition of BFRs used in this report (BFRs are here defined as flame retardants containing organic combined bromine).

BFRs are thought present in some of the used plastics. In a Danish Intercity train (IC3), the following combustible materials are used: round 5.5 tonnes PVC, round 1.5 tonnes rubber, round 2 tonnes polyester plastics and round 7 tonnes phenol plastics /45/.

PVC is mainly used for electrical cables in the train. It is assumed that these cables do not contain BFRs.

The rubber are mainly used for front and rear parts, gangway connections, mouldings for doors and windows and vibration dampers. The used rubbers are mainly neoprene rubber and EPDM. It has not been possible to obtain information about the used flame retardants. Most probably a chlorinated or a brominated FR is used. If a BRF is used, TBBPA derivatives, PBDEs or PBBs are possible. Furthermore only rubbers in contact with the interior plus the front and rear parts, are expected to be flame retarded. It is estimated that these components correspond to 400-700 kg rubber, and possibly to max. 50 kg BFRs in rubbers per train set.

The polyester plastics are used for instrument boards, casing for technical installations, passenger seats, the front part of trains, etc. BFRs are used in some of these materials. It is assumed that the consumption of BFRs may be 1 to 20 kg in polyester plastics per train.

BFRs are present in the electrical and electronic systems of the trains. It is assumed that 5 to 25 kg BFRs are used per train for the electrical and electronic systems.

This may correspond to max. 95 kg BFRs per train. But the estimate must be characterised as uncertain.

Aircraft

Strict international standards are dominating, and they secure that all aircraft fulfils the same requirements, and hence that comparable materials and flame retardants are used.

The tonnage of the yearly ‘consumption’ of aircraft are diminutive compared to the tonnage of passenger cars.

Halogen based systems (chlorinated or brominated such as TBBPA) combined with other additives (Sb2O3) are among the most widely used fire retardants for structural composite organic matrices such as epoxies. For furnishings and interiors, both thermoplastic and thermoset polymers (mainly phenolics) are used /11/. Everything onboard an air-plane, down to the ice cube container, is seemingly flame retarded.

Due to suppliers of textile and seat cushions, the use of brominated flame retardants in interior textiles and padding has been phased out in air craft. The reason should be an unwanted high level of aggressive fumes and soot formation in case of fire. The BFRs are active in the gas-phase by release of bromine, and therefore the fume evolution is closely related to the action of the brominated flame retardant (see section 1.1).

It is assumed that max. 5 tonnes BFRs are used yearly for aircraft including hot-air balloons, etc.

Ships 

The use of BFRs in ships has not been studied thoroughly, and the following description is mainly based on information from suppliers and fire-experts. It is expected that ships do not make out a significant area for the application of brominated flame retardants.

The use of brominated flame retardants in ships has been influenced by some of the present big disasters at sea, e.g. the loss of the Scandinavian Star. Hence halogen-free materials in passenger ships have seemingly become a selling parameter.

It can not be derived from the existing fire regulations, which types of flame retardants may be used predominantly. Brominated flame retardants may for instance be combined with other non-halogenated FRs, achieving good technical properties, and at the same time, in case of fire, avoid development of seriously elevated levels of hydrogen bromide. Furthermore some of the requirements may be fulfilled by selection of less flammable materials.

Textiles for ships belong to the category 'contract textiles' (see section 2.2.6), and it is expected that brominated flame retardants are present in some of the used textiles.

BFRs may be used in interior plastics, but seemingly the use is limited.

The electrical systems will contain BFRs.

Inorganic, bromine containing flame retardants may be used in phenol based and wood based panels in ships, but other flame retardants and solutions are also used.

In general, refrigerating holds on ships are insulated with a bromine containing PUR foam. The normally used compounds are reactive brominated polyols. The consumption of polyurethane for refrigerating holds on ships are included under the consumption described under section 2.2.7.

It is assumed that the consumption of BFRs for ships is max. 10 tonnes yearly.

Production in Denmark

Approximately 600 busses, lorries and special cars, and round 2,000 passenger cars were produced in 1997. In 1997, 41 train-set were produced in Denmark.

Import/export

The significant volume of cars, commercial vehicles, busses and lorries is imported to Denmark. Based on information on registration of new motor vehicles in Denmark, the supply to the Danish market may be described as follows. The supply of passenger cars and commercial vehicles imported from Europe was round 83,000 vehicles. The corresponding supply from other regions was round 99,000 vehicles. The supply of busses and lorries was round 7,000 and 930 from Europe and other regions, respectively /46 /.

Consumption

The total consumption of brominated flame retardants with transportation in 1997 is estimated at 30-90 tonnes (see table 2.15).

Table 2.15
Consumption of brominated flame retardants with transportation in Denmark 1997

Trends in consumption

The future trends in Europe will be dependent on the development of harmonised regulation. This applies especially to the railway sector, where EU-harmonisations are underway.

In the car industry, the trend is more depending on consumer pressure and volunteer based initiatives from the industry. But this will also be very depending on the development of formalised national positions in relation to the general development of harmonised fire regulations within various sectors in the EU.

Within textiles used for transport, the trend is seemingly that PBDEs are substituted by HBCD, and that BFRs are substituted by phosphorous based flame retardants and inherently less flammable textiles.

Major commercial actors within the vehicle producing sector are investigating or supporting the development of halogen-free electrical and electronic components.

In connection with purchase of new train material, the national railway company (DSB) is aiming at avoiding halogenated substances

Emissions during use

The emissions during use are assumed to correspond to the emissions described in the above sections on the single categories of components (textiles, plastics, electronics, etc.). However, the environment (temperature, light, etc.) in and around vehicles and other means of transportation may be rather harsh to the components, and hence elevated emissions may exist.

2.2.10  Other Uses

Brominated flame retardants may be used with a few products not covered by the sections above:

Flame retardant sprays

There are a number of spray can products available on the Danish market for after-treatment of textiles, e.g. seats in passenger cars. It has not been possible to gain access to information on the used substances, but a supplier to the American market (USA) has informed that ammonium bromide is used in their products. Ammonium bromide falls outside the definition of BFRs used in this report. It is assumed that corresponding substances are used in spray cans for after-treatment of textiles sold in Denmark.

Packaging
Expanded polystyrene (EPS) is widespread used as packaging for fragile equipment. It has in the literature been reported that EPS packaging for electronic equipment may contain HBCD as flame retardant. As to the information received from the Danish packaging industry, HBCD is not used for EPS packaging in Denmark, but it may be present in imported products. The total turnover of BFRs with packaging is estimated to quite limited and below one tonne per year.

Film and video tape

Flame retarded grades of polypropylene (PP) are according to IAL Consultants /18/ used for production of film and video tapes. It has not been possible to obtain specific information on the flame retardants used, but it may be brominated flame retardants.

It is roughly estimated that the total consumption of BFRs with other uses is <3 tonnes per year.

2.2.11  Summary

The present information on the consumption of brominated flame retardants with end products in Denmark 1997 is summarised in table 2.16. The results are further discussed in chapter 4.

Table 2.16
Consumption of brominated flame retardants with end products in Denmark 1997

2.3 Unintended Uses as Contaminant

Brominated flame retardants may be present in products as unintended contaminants originating from:

Biogenic formation
PBDEs or TBBPA are not reported to occur naturally /6,8/. A number of brominated compounds that are structurally similar to the PBDEs have been found in a number of marine species; especially marine sponges /3/. The compounds identified have the diphenyl ether structure, but contain one or more groups not present in the PBDEs. No information on natural occurrence of other brominated flame retardants has been found. A review of natural organobromines, sponsored by the bromine industry, is at present being prepared /47 /.

Contamination

PBDEs are present in food, especially fish. The daily intake in the Nordic countries has been roughly estimated at 0.2-0.7 µg/day /48 /. The intake from fish is assumed to represent 50% of the total intake. As the Danish intake of fish is considerably lower than the intake in the other Nordic countries, the daily intake in Denmark will be in the lower end of the estimate above. With a population of 5.3 million and an assumed daily intake of 0.2-0.4 µg/day, the total intake in Denmark can be estimated at 0.4-0.8 kg/year. PBDEs in food products will ultimately be released to waste water.

There has not been identified data from the Nordic countries on the concentration of TBBPA and other flame retardants (except PBDEs) in fish and other food. Two out of 19 fish and shellfish samples from Japan contained TBBPA at a concentration of 0.8 and 4.6 µg TBBPA /kg wet weight, respectively (ref. in /8/). In two other studies in Japan TBBPA was not detected in 210 fish samples (limit of determination 1 µg/kg wet weight) (ref. in /8/). For comparison the above mentioned PBDE intake from fish was calculated from an upper range of PBDEs in Baltic herring of 528 µg/kg fat which can be converted to about 37 µg/kg wet weight (medium fat content, 7%) /48/. The available data indicate that the TBBPA intake with fish may be considerably lower that the PBDE intake.

In a substance flow perspective the flow of TBBPA and other flame retardants with food products is estimated to be insignificant. This may not be true in other perspectives.

Recycling of materials

There is no recycling of flame retarded plastics from discarded products (see section 3.1), and flame retardants do not unintendedly end up in new products.