Flame retardants for electrical equipment

Introduction Accurate figures are difficult to obtain but it has been estimated that fires kill up to 100,000 people annually worldwide, with more than 4000 in the European Union (EU). It is also estimated that 10% of fires are attributed to electrical faults, due to mains wiring in buildings and in electrical equipment, with these fires accounting for 19% of injuries. Flame retardants are used very effectively to prevent fires, reduce their seriousness and also to delay onset to allow people more time to evacuate. US research has shown that flame retardants can give as much as 15 times longer to escape than plastics without flame retardants. Since they were introduced, 1000s of lives have been saved and so there is no doubt about their value. Figures for the UK estimate that 3000 lives were saved between 1988 and 2000 as a direct result of using flame retardants. Why are flame retardants used? Flame retardants are used as additives to plastics in a wide variety of electrical equipment. Many types of plastics burn very easily and it has been estimated that the plastics in a typical TV set are equivalent to 6 litres of petrol, not something consumers want in their living rooms! However, only around 12% of plastics contain flame retardants. Some types are inherently resistant to fire, such as rigid PVC, and so do not need flame retardant additives. Some equipment is not at risk such as battery powered products like mobile phones because of the low voltages used, and therefore flame retarded plastics are not needed. Mobile phone battery chargers however do need to have flame retardants as they are powered at mains voltages and so arcing and high temperatures can occur if there is a defect. Equipment manufacturers use flame retardants mainly because they are required to by legislation. In the EU, the General Product Safety Directive and the Low Voltage Directive require products to be safe and this includes not creating a risk of fire to consumers or business users. Compliance with these directives is through many different mandatory Standards which are written for specific types of equipment. Fire safety is usually specified by standards from the Underwriters Laboratory (UL) referred to as UL94 which has various fire protection levels such as V0, 1, 2 or HB. IT and telecom equipment in the EU usually complies with UL94 V0 whereas consumer goods such as televisions need to meet UL94 HB which is a considerably lower level of protection than UL94 V0. Televisions and other consumer products in the USA must meet UL94 V0 which explains why TV fires in US are far less common than in Europe.

What types are available? (refer to glossary) There are well over 100 different types of flame retardants available including more than 70 brominated flame retardants. The main types and their characteristics are: Brominated flame retardants these account for 21% by weight (32% by value) of all flame retardants worldwide and are suitable for many types of plastic, and are the only types that can be used with HIPS and ABS. PBT is used for connectors and is also difficult to flame retard effectively without brominated compounds. This family includes reactive flame retardants that react with other ingredients in plastics to create brominated polymers which are very stable and do not leach out into the environment. Tetrabromobisphenol A (TBBP-A) is used in the largest quantities of the brominated flame retardants with 90% being used reactively in FR4 epoxy resin PCB laminates. Most of the remainder is used as an additive flame retardant in ABS where it has replaced octabromodiphenyl ether which is now banned in the EU and some US States. Brominated compounds together with some of the phosphorous based compounds are the most effective flame retardants and so can be used at the lowest concentrations. However, brominated flame retardants are under pressure from environmentalists. The reasons are complex; very few are harmful and a very small number are classified as toxic such as HBCDD. Many are persistent which means that if they escape into the environment, they remain there for a long time. Some have been found in womens breast milk and also in Polar Bears. This would not be a cause for concern if they are totally harmless but research on many chemicals is incomplete and so the possibility that they might have some toxicity cannot always be ruled out. Another concern where real harm does occur is due to uncontrolled recycling of electronic scrap in Asia and Africa. If these materials are recycled by modern, well-controlled processes no harmful by-products are produced. However, in Asia and Africa, backyard recycling is carried out to recover metals by burning on open fires. This creates very toxic brominated furans and dioxins which are carcinogens and so poison the local populations. Efforts to prevent these practices have so far been unsuccessful and so Environmental Groups are demanding that these materials are banned. This however would not completely solve this problem as burning all types of plastic produces toxic emissions, the most toxic being polycyclic aromatic hydrocarbons (PAH) which are also carcinogens. Also, the toxicity of fumes from burning organophosphorous flame retarded plastics is not known. Antimony oxide this is a synergistic flame retardant which is always used with either brominated flame retardants, chlorinated flame retardants or chlorinated polymers such as PVC. It is very effective at fairly low concentrations so that the amounts of brominated flame retardant used can be halved. Typically about 3% antimony oxide can replace about 10% of brominated flame retardant. Phosphorous based flame retardants these account for about 14% by weight of flame retardants used worldwide. These are increasingly

used as replacements for brominated flame retardants and can be equally effective in some types of polymer but are not suitable for HIPS or ABS. HIPS and ABS can however be replaced by other plastics such as ABS/PC which can use phosphorous compounds. Most are regarded as being non-hazardous although a few older types have been found to have some hazardous properties. However, most organophosphorous based flame retardants are relatively new and have not been thoroughly tested. In general they are less persistent in the environment than brominated flame retardants but more testing is required to determine whether they pose a risk to health or the environment. One constraint on the potential for replacing brominated compounds by phosphorous compounds is the limitations in worldwide production capacity, as this is far less than would be required to replace all brominated flame retardants. Chlorinated the main types are chlorinated paraffins. These are available as short chain, medium chain and long chain. Short chain are PBTs (persistent, bioaccumulate and toxic) and endocrine disruptors (cause sex changes in aquatic animals) and are already restricted in the EU. Medium chain have similar toxicity and the EU is planning to restrict this material. The risks from long chain chlorinated paraffins are as yet not known. The use of these flame retardants has declined significantly over recent years due to concerns over their toxicity. Their main use is as additives to PVC in which they provide both plasticising properties and flame retardancy. Metal hydroxides the most common of these is alumina trihydrate (ATH) which accounts for 43% by weight of all flame retardants worldwide and an even higher percentage in Europe (>50%). It can be used in many types of plastic and is one of the cheapest options. However to achieve UL94 V0 requires very high loadings so that plastics are more ATH than polymer with 60% ATH typically being used. High loadings of ATH, which is a white powder, can be detrimental to the plastics physical properties and colour. It is used in polyethylene wire insulation to give a material which emits very little smoke in fires and so is safe to use in enclosed environments such as in tunnels and in vehicles. Magnesium hydroxide is more expensive but it can be used at lower loadings. Others there are several other types of flame retardant used in smaller quantities which are suitable for certain types of plastic. These include melamine based compounds, borates and stannates.

How do flame retardants work? To understand how flame retardants work, it is necessary to consider what happens in a fire. Fires start when solid materials are exposed to heat. This causes decomposition to smaller molecules which include flammable gases. These gases mix with oxygen from the air and, if the temperature is high enough, they react very rapidly giving out more heat which continues the process. The chemical reactions between oxygen and flammable gases involve charged molecules called free-radicals H+ and OH- which are essential for the reaction with oxygen molecules.

Flame retardants function in several different ways depending on the type. The main types are: Halogenated flame retardants, when heated these emit Br- or Cl- as free radicals which scavenge the H+ and OH- free radicals and so effectively stop the chemical reactions that create the high temperatures that cause the fire to continue. Brominated flame retardants are more effective than chlorinated compounds and are even more effective when combined with antimony compounds which create volatile antimony bromides. Antimony oxide is not a flame retardant on its own and is always used with organohalogen compounds. It allows the quantity of brominated flame retardant to be halved and is also used in plasticised PVC. In fires, it releases antimony bromide or antimony chloride which are very effective free radical scavengers. Phosphorous flame retardants function in a completely different way. When subjected to heat, they react to form polymeric phosphates that form a hard glassy layer on the surface of the plastic. This inhibits access of oxygen to the combustible material and prevents flammable gases from being released. As a result, the plastic chars rather than burning. Metal hydroxides such as aluminium and magnesium hydroxides have several effects. When heated, they release large volumes of water vapour which inhibits oxygen access to the surface and dilutes any released flammable gases. Also, they decompose endothermically which means that they adsorb heat, thereby cooling the material. Nitrogen based flame retardants such as melamine compounds. The mechanism of fire retarding is not fully understood and probably is a combination of effects. Inert nitrogen is released and stable barrier layers of char are formed on material surfaces. Intumescent materials are chemicals that produce a bulky porous ceramic coating that covers the material surface preventing it from burning. These materials release large amounts of inert gases and a thick viscous liquid which together form a foam. This foam loses its organic constituents when hot to leave a hard ceramic foam coating. Others Boron compounds function in a similar way as phosphorous flame retardants, Zinc borate works by a variety of mechanisms and zinc and tin compounds are added to PVC to reduce smoke emission and increase the effectiveness of other types of flame retardant.

Flame retardant selection and design implications Most equipment is designed without considering which type of flame retardant will be incorporated and in most products, manufacturers are unaware of which ones are used. Equipment is designed by selecting various parts which are available in certain types of plastic and which meet the required regulations. However, it is possible to design equipment which complies with fire regulations and national safety standards with little or no fire retardant and some manufacturers are adopting these ideas to minimise the use of additives. The flammability of plastics varies considerably with some types being highly flammable and there are others that will not sustain a fire. This is

related to the amount of oxygen from the air that the plastic needs to burn and is referred to as the Limiting Oxygen Index or LOI. Air contains 21% oxygen and any plastic with a LOI value less than 21 will burn. The lower the LOI value, the more flammable the plastic. The table below gives some examples: Plastic type Acrylic Polypropylene (PP) Polyethylene (PE) Polystyrene (PS) Polycarbonate (PC) Polyphenylene sulphone (PPS) Polyvinyl chloride (PVC) Polytetrafluoroethylene (PTFE) LOI 17 17 17 18 26 34 45 >95

Plastics with LOI values below 21 may need flame retardants to meet safety standards. However, plastics with higher values may also require flame retardants if they contain flammable additives that lower their LOI. For example, rigid PVC does not require flame retardants but plasticised PVC, used for cable insulation will require flame retarding additives, and antimony oxide is often used. This is because the additives themselves are flammable materials. The types of plastics with high LOI may either not require flame retardant additives or require smaller amounts than plastics with low LOI values. This can be helpful to maintain the physical properties of the plastic such as strength and colour. Most high LOI plastics are more expensive than low LOI plastics, the exception being PVC. PVC is however under pressure from environmental groups because toxic dioxins and furans are produced when PVC is burned using unsuitable and uncontrolled recycling which is, unfortunately, fairly common in some parts of Asia and Africa. Various fluorinated polymers are used as alternative wire and cable insulation as these do not require flame retardant additives and they are more flexible and can be used at higher temperatures than the other alternatives to PVC (flame retarded PE is a common choice). When fluorinated polymers burn however, they emit highly toxic gases. Design options One of the largest uses of flame retardants is in the enclosures of equipment. When these are adjacent to high voltage components, safety standards specify that these must not support combustion and so most of the plastics used for enclosures need to contain flame retardant additives. However, changing the design of equipment can avoid the need to use flame retardants. Some manufacturers now use metal enclosures as these do not require flame retardants and also these are easier to recycle at end of life. If an inner metal enclosure is used, a decorative outer plastic enclosure will not require flame retardants if this is not at risk from fire. This combination can be used where the appearance is important.

2008 Premier Farnell plc. Permission is granted for reproduction in whole, or in part, provided Premier Farnell is credited. Written in collaboration with ERA Technology Ltd (www.era.co.uk/rfa)

Glossary ABS Acetonitrile Butadiene styrene HIPS High impact polystyrene PAH Polycyclic aromatic hydrocarbons PC Polycarbonate PE Polyethylene PP Polypropylene PPS Polyphenylene sulphone TBBPA Tetrabromobisphenol A HBCDD - Hexabromocyclododecane PBT Polbutyl terephthalate or Persistent, Bioaccumulative and Toxic. ATH Alumina tri-hydrate