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Deca-BDE and Alternatives in Electrical and Electronic Equipment
Executive Summary
Overall evaluation
This study has not identified any application of Deca-BDE in electrical and electronic equipment for which substitution is not possible, from the scientific or technical point of view. For all EEE materials and components presently using Deca-BDE, technically acceptable alternatives are available on the market. The widespread use of alternatives, and availability of EEE components without Deca-BDE, is indicated by the fact that a large number of the world's major manufacturers of EEE have phased out the use of Deca-BDE in their products.
The study
The study summarises information on the use of Deca-BDE and its alternatives in electrical and electronic equipment. The information was obtained mainly from the literature and from public information available on web-sites of manufacturers, trade organisations, institutions, etc. Due to the fact that the study is part of the scientific documentation supporting a case before the Court of Justice of the European Communities, the documentary emphasis was laid on published information. Only limited additional information was obtained by personal communication with companies and trade organisations.
It was beyond the scope of this study to undertake an environmental and health assessment of Deca-BDE and selected alternatives, or to compare any negative environmental or health impacts caused by substitution with the environmental and health benefits of the substitution. These aspects are covered by a separate environmental and health assessment initiated concurrently by the Danish EPA.
Applications of Deca-BDE
The global market demand for Deca-BDE in 2001 was about 56,100 tonnes. The market demand in Europe was 7,600 tonnes, considerably lower than the demand in the Americas and Asia. A significant part of the volume is used in electrical and electronic equipment (EEE).
The main EEE application has traditionally been enclosures made of High Impact Polystyrene (HIPS), especially for TV-sets, but also for printers, scanners, fax machines, etc. Other EEE applications are connectors, switches, and other internal parts made of engineering plastics like thermoplastic polyesters (PBT/PET) and nylon (PA), and wires and communication cables made of polyolefins (PP and PE).
As part of the European Commission's RoHS stakeholder consultation, the manufacturers of brominated flame retardants have specifically pointed at difficulties in the substitution of Deca-BDE in the plastics HIPS, ABS, and PBT, citing the lack of cost-effective alternative flame retardants that can provide good flame retardancy and good mechanical properties.
Alternatives to Deca-BDE
Table 1 lists 25 selected flame retardants, and shows the types of plastic in which each may be used. The list is not considered comprehensive. Only flame retardants that can be used to obtain plastics meeting the UL 94 vertical flame test, V-0 have been included. V-0 grade is typically required for plastic parts in connectors, switches, and other components in contact with current-bearing metal parts of EEE. In the USA, V-0 grade plastics are also required for TV-set enclosures, whereas the European standard has less strict requirements.
Two brominated flame retardants – bis(pentabromophenyl) ethane and ethylene bis(tetrabromophthalimide) – have application spectra very close to the spectrum for Deca-BDE, and they have been produced and marketed as general purpose alternatives to Deca-BDE by the same companies that produce Deca-BDE. For most applications the two compounds have superior technical properties (except for colour) compared to Deca-BDE, but the two substances are more expensive than Deca-BDE.
The flame retardants in Table 1 can all be used to reach a high level of flame retardancy, but some of the flame retardants may, for some applications, fail to be a viable substitute for Deca-BDE for other technical reasons. In particular, the application of some of the non-halogenated alternatives may significantly change the properties of the flame-retarded plastics. The list may be considered a gross list; more information on the specific alternatives is provided in Chapter 3 of this report.
Enclosures
Enclosures for TV-sets are typically made of HIPS, ABS, or copolymers like PC/ABS, PPE/HIPS and PPE/PS. The addition of PC or PPE makes the resins themselves less flammable, and the flammability requirements can then be met using less efficient and/or smaller quantities of flame retardants. Personal computer monitors are mainly made from ABS and PC/ABS because these plastics have higher impact strength and are less susceptible to cracking than HIPS. In the USA, enclosures for TV-sets have traditionally been made from HIPS with Deca-BDE, and this application has accounted for around 80% of the use of Deca-BDE in the USA. In Europe, due to the lower flame-retardancy requirements for TV-set enclosures, HIPS without flame retardants has been used, in particular for the lower-price market segment for TV-sets. In response to fire statistics indicating significantly more fires in European produced TV-sets than in American ones, the major European producers today use a higher level of flame-retardancy than required by the European standard. The materials of choice are copolymers with non-halogen organo-phosphorous flame retardants. The discussion of alternatives is exemplified by the case of enclosures for TV-sets, as most information is available on this product group, and the observations are equally applicable to enclosures for other equipment.
A number of other brominated flame retardants are available for use in HIPS. A review of price estimates has been compiled on the basis of information from a major supplier of HIPS compounds for the TV sector. The prices of the compounds (consisting of resin, flame retardants and other additives) based on brominated alternatives are 10-20% higher than similar HIPS with Deca-BDE. The prices of the copolymers with organo-phosphorous flame retardants (FRs) are about 60-70% higher than HIPS with Deca-BDE, corresponding to a price increase of the raw materials of an average TV-set with CRT technology (27.5-inch screen) of about 5 €. With typical total manufacturing costs of 300 € for the average CRT TV-set, the difference in raw material costs corresponds to about 2%. Any additional costs of research and development, and changes of moulds and other process equipment by the enclosure manufacturer, may be relatively small if substitution takes place coincidently with design changes and introduction of new products, e.g. TV-sets with LCD screens or plasma display panels.
The volume of flame retarded (also abbreviated as FR) plastic in enclosures of an average LCD panel TV-set, in which the back cover is typically flame retarded, is nearly the same as in an average CRT TV-set, because of the larger screen size of the LCD panel TV-sets. Therefore, the price estimate for FRs in CRT TV-sets may also be applied to the LCD panel TV-sets.
Deca-BDE has traditionally not been used in ABS because octa-BDE was superior in this resin. With the ban of octa-BDE, Deca-BDE may have taken over a part of this market, but other brominated flame retardants have superior technical properties in ABS, and have been marketed as the recommended octa-BDE alternatives for use with ABS.
Connectors, switches, etc.
Small plastic parts of electrical connectors, switches, etc. made of flame retarded thermoplastic polyesters (PBT/PET) or polyamide (PA) are present in almost all EE products. These two plastic groups account for about 60% of the consumption of plastics for electrical components of EEE. Deca-BDE, in turn, accounts for about 10% of the global consumption of flame retardants used in PBT/PET in EEE, and for about 6% of the global consumption of flame retardants used in polyamide in EEE. Contrary to the situation for the enclosures, replacement of these plastics by other types of plastic is generally not an option. As a general rule, in both PBT/PET and PA, Deca-BDE is a lower cost solution, but tends to be less acceptable in terms of compatibility and mechanical properties. The most widely used FRs in PBT/PET are brominated carbonate oligomers and brominated epoxy oligomers. Halogen-free FR alternatives have only recently been commercially available for PBT/PET. These are based on organic phosphinates. For PA in EEE, the most widely used FRs are halogenated – polybrominated styrenes, or brominated polystyrenes, which have a market share 10 times higher than the market share of Deca-BDE. A number of halogen-free FRs for PA have also been available for many years and are widely used. The halogen-free FRs are based on red phosphorous, melamine cyanurate, melamine polyphosphate, magnesium dihydroxide or organic phosphinates. For some applications they are economically competitive with the brominated flame retardants. It has not been possible to identify any applications of electrical connectors, switches, etc. for which Deca-BDE cannot be readily replaced by other brominated flame retardants or halogen-free flame retardants.
Wires and cables
Deca-BDE has been reported to be used for some types of wire and cable that are fabricated with insulation made of polyolefins (PE and PPP). Wires and cables belong to a very diverse product group, with a number of different plastics and rubber used for cable insulation, and employing a variety of flame retardants. It has not been possible to identify any recent quantification of the use of Deca-BDE and alternative flame retardants in cables of EEE. In any case, a number of both halogen-containing and halogen-free flame retardants are available for V-0 grade polyolefins.
Companies that have phased out Deca-BDE
A large number of companies in the EE sector specifically state that they have phased out Deca-BDE and other PBDEs in all of their products, among these, Dell, Hewlett-Packard Company (including Compaq), Sony, IBM, Ericsson, Apple, Matsushita (including Panasonic), Intel and B&O. Some of the main driving forces for these commitments have been eco-labels, customer requirements (e.g. “green procurement” initiatives) and preparedness for the RoHS Directive and other legislation. Some of the companies replaced Deca-BDE already in the 1990s. These companies have typically managed the phase-out of Deca-BDE by enforcing specifications prohibiting its use in the products and components supplied by sub-contactors, but they generally have not specified which flame retardants should be used as substitutes. The specific flame retardants used in products are generally considered confidential, but a typical replacement scheme seems to be the use of copolymers with halogen-free organo-phosphorous compounds for enclosures and other large parts, and the use of alternative brominated flame retardants for the small parts (<25 g) in connectors, switches, etc. In this manner, the products still meet the most strict criteria of eco-labels.
Product chain and industry structure
Based on a description of the product chain of equipment containing Deca-BDE, the impact of a Deca-BDE ban on the different industrial sectors is briefly discussed. The impact is highly dependent on whether Deca-BDE is replaced with other brominated flame retardants with nearly the same properties as Deca-BDE, or whether it is replaced with halogen-free flame retardants, sometimes including changes of the resin as well. In the first case the impact is mainly implying the use of more expensive flame retardants. Any shift to halogen-free alternatives in EEE is, on the other hand, not driven by the introduction of a ban on Deca-BDE, but should rather be seen as part of a more general ongoing movement toward the use of halogen-free flame retardants driven by consumer demand, eco-labels, NGO actions, etc.
Table 1 Deca-BDE and selected alternative flame retardants for relevant V-0 grade plastics in EEE
Flame retardant |
Enclosures |
Connectors, etc |
Wires |
|
HIPS |
ABS |
PC/ABS |
PPE/HIPS |
PA |
PBT/PET |
PP |
PE |
Halogen-containing FRs |
|
|
|
|
|
|
|
|
Deca-BDE / ATO |
X |
X |
X |
X |
X |
X |
X |
X |
Ethane-1,2-bis(pentabromophenyl) / ATO |
X |
X |
X |
X |
X |
X |
X |
X |
Ethylene bis(tetrabromophthalimide) / ATO |
X |
X |
X |
X |
X |
X |
X |
X |
Brominated epoxy polymer / ATO |
X |
X |
X |
|
X |
X |
|
|
Tetrabromobisphenol-A (TBPPA)/ ATO |
X |
X |
|
|
|
|
|
|
TBBPA carbonate oligomer / ATO |
|
|
X |
X |
|
X |
|
|
TBBPA bis (2,3-dibromopropyl ether) / ATO |
X |
|
|
|
|
|
X |
|
Tetradecabromodiphenoxybenzene / ATO |
X |
|
|
|
X |
X |
|
X |
Tris(tribromophenoxy) triazine / ATO |
X |
X |
|
|
|
|
|
|
Bis(tribromophenoxy) ethane / ATO |
|
X |
|
|
|
|
|
|
Tris(bromopentyl) phosphate / ATO |
|
|
|
|
|
|
X |
|
Poly(pentabromobenzyl acrylate) / ATO |
|
|
|
|
X |
|
X |
|
Brominated polystyrene / ATO |
|
|
|
|
X |
X |
|
|
Poly(dibromostyrene) / ATO |
|
|
|
|
|
X |
|
|
Chloroparaffins / ATO |
|
|
|
|
|
|
X |
|
Dodecachlorododecahydro-
dimethanodibenzocyclooctene / ATO or other synergists |
|
|
|
|
X |
X |
|
|
Non-halogen organo-phosphorous FRs |
|
|
|
|
|
|
|
|
Resorcinol bis(diphenylphosphate) (RDP) |
|
|
X |
X |
|
|
|
|
Bisphenol A bis(diphenylphosphate) (BDP) |
|
|
X |
X |
|
|
|
|
Triphenyl phosphates (TPP) |
|
|
X |
X |
|
|
|
|
Other non-halogen FRs |
|
|
|
|
|
|
|
|
Intumescent FR systems based on phosphor and nitrogen compounds |
|
|
|
|
|
|
X |
X |
Red phosphorous |
|
|
|
|
X |
|
|
X |
Melamine cyanurate |
|
|
|
|
X |
|
X |
|
Melamine polyphosphate |
|
|
|
|
X |
|
|
|
Organic phosphinates |
|
|
|
|
X |
X |
|
|
Magnesium dihydroxide |
|
|
|
|
X |
|
X |
|
ATO: Antimony trioxide used as synergist
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Version 1.0 February 2007, © Danish Environmental Protection Agency
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