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◉ Introduction of Halogen
Fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), referred to as halogen. Since astatine is a radioactive element, it hardly exists in the product, and the first four elements exist in the form of organic compounds in the product, especially in the polymer material. So people often say halogen just refers to: fluorine, chlorine, bromine and iodine. Halogens are widely used in flame retardants (PBB, PBDE, TBBP-A, PCB, hexabromododecane, tribromophenol, short-chain chlorinated paraffins), refrigerants, solvents, organic chemical raw materials, pesticides, pesticides, bleaching agent, wool degreasing, etc. Most of the halogen compounds used in industry are organohalogen compounds. Many organohalogen compounds are listed as chemicals harmful to humans and the environment. They are prohibited or restricted in use and are key pollutants controlled by countries around the world.
◉ What Products Contain Halogens?
(1) Flame Retardant
Halogen compounds are widely used in various plastic additives, such as polybrominated biphenyls (PBB), polybrominated diphenyl ethers (PBDE), tetrabromobisphenol A (TBBP-A), polychlorobenzene (PCB), hexabromocyclododecane (HBCCD), tribromophenol, short-chain chlorinated paraffin (SCCP), etc. can be added to PVC, PU, polyester and epoxy resin to be used as flame retardants; difluorodichloromethane can be added to ABS, PS, It is used as a foaming agent in PVC, PU, EVA, PE and PP; chlorinated paraffin can also be used as a plasticizer for plastic materials.
Flame retardant (Flame Retardant) is a class of additives that can prevent the ignition of flammable materials or inhibit the spread of flames. The 1970s and 1980s were the golden age for the development of flame retardants in the world, especially in European and American countries. Because during this period, the United States promulgated some flame retardant regulations, which provided a huge boost to the flame retardant market. Halogen-based flame retardants (mainly brominated flame retardants) have the advantages of high efficiency, low dosage, high performance, and low price, and the addition of halogen-based flame retardants has little effect on the inherent physical and mechanical properties of the flame-retardant substrate. Therefore, its development is quite rapid, with an annual growth rate of up to 20%. However, the use of halogenated flame retardants also has a disadvantage: in the event of a fire, the incomplete combustion of halogenated flame retardants will produce a large amount of carcinogens, and at the same time, a large amount of smoke and toxic corrosive gases will be generated, thus hindering fire fighting and personnel. Evacuate, corrode instruments and equipment.
Therefore, many countries have formulated relevant laws and regulations to control the use of halogenated flame retardants. For example, the most well-known EU RoHS Directive (Directive on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Products, 2002/95/EC) restricts the use of two types of brominated flame retardants such as polybrominated biphenyls and polybrominated diphenyl ethers, and other RoHS-related regulations formulated by countries and regions also restrict the use of these two brominated flame retardants. In addition, EU 2003/11/EC also proposes to limit the use of pentabromodiphenyl ether and octabromodiphenyl ether, and 2002/45/EC also proposes restriction requirements for short-chain chlorinated paraffins. Restrictions on the use of medium-chain chlorinated paraffins, hexabromocyclododecane and tetrabromobisphenol-A are also proposed in the draft Norwegian PoHS regulation (Restriction of Certain Hazardous Chemical Substances in Consumer Products). In the United States, several states also banned the use of PentaBDE, OctaBDE and DecaBDE in products in early 2006.
(2) Polyvinyl Chloride (PVC)
Polyvinyl chloride (PVC) is one of the most common plastics on the market at present. It has the advantages of good flame retardancy, high acid and alkali corrosion resistance, good mechanical strength and electrical insulation, so it is widely used in wire sheaths, plates and pipes. , shoe soles, toys, doors and windows, stationery and other industries. But its heat resistance is poor, the softening point is 80 ℃, it begins to decompose and discolor at 130 ℃, and the acid gas hydrogen chloride (HCl) is precipitated. Once burned, other toxic substances, such as dioxins, will be released. Direct incineration or landfill disposal after disposal will also cause pollution to soil and water sources. The raw material for the production of polyvinyl chloride, vinyl chloride monomer, is also a carcinogen, and its residue in the finished PVC will also pose risks to the health of subsequent producers and users. In addition, additives such as lead, cadmium and phthalates are used in many PVC products to increase the performance of the product, and these substances are considered harmful.
(3) Ozone-depleting substances
Refrigerants, such as Freon, are used in some refrigeration equipment, such as refrigerators and air conditioners. Most of these refrigerants are composed of chlorofluorocarbons (CFCs), which are also halogen compounds. Many of these refrigerants are ozone-depleting substances (ODS) that damage the ozone layer. Another class of substances used as fire extinguishing agents in fire extinguishing systems or portable fire extinguishers, Halon, is also an ozone-depleting halogen compound. When ozone depleting substances are exposed to sunlight in the atmosphere, they decompose free radicals of halogens. These chemically active groups combine with ozone to deprive an oxygen atom in the ozone molecule, triggering a destructive chain reaction and depleting ozone, thereby reducing the concentration of ozone and creating an ozone hole.
Therefore, in order to reduce the destructive effect of such substances on the environment, many countries and regions have also formulated corresponding restriction requirements. In March 1985, government representatives of 21 countries signed the Vienna Convention on the Protection of the Ozone Layer in Vienna, the capital of Austria, marking the beginning of the international unified action to protect the ozone layer. In order to truly implement international control over the production and use of ODS such as CFCs. Subsequently, government representatives of 24 countries signed the "Montreal Protocol on Substances that Deplete the Ozone Layer" in Montreal, Canada in 1987, restricting the use of 5 chlorofluorocarbons and 3 halons, to require countries to take action to phase out These substances, strengthen research and develop alternatives. my country also signed this convention in 1991.
(4) Persistent Organic Pollutants (POPs)
Persistent organic pollutants are a class of organic chemicals that persist in the environment, have a long half-life, and can accumulate through the food chain and cause adverse effects on human health and the environment. Such substances have the hazards of high toxicity, persistence, accumulation and mobility. Therefore, in 2001, many countries in Stockholm, Sweden signed the "Stockholm Convention on Persistent Organic Pollutants". The Stockholm Convention decided to ban or restrict the use of 12 POPs, including 8 organochlorine pesticides (aldrin, chlordane, dieldrin, endrin, heptachlor, mirex, toxaphene, DDT), 2 industrial chemicals (HCB and PCBs) and two dioxin-like substances (PCDDs and PCDFs), all containing Halogen organic compounds have a great impact on the human body and the environment. The entry into force of this convention means that the use of these compounds will be completely banned, and the use of these compounds will be restricted worldwide until they are completely banned.
It is also worth noting that the Stockholm Convention also includes several other organohalogen compounds on the candidate list of the Convention: chlordecone (Chlordecone), hexahexahexanol (a-,b-,g-, HCH), perfluorooctanesulfonyl compounds (PFOS), pentachlorobenzene (Pentachlorobenzene), short-chain chlorinated paraffins (SCCP), hexabromobiphenyl (HxBB), pentabromodiphenyl ether (PentaBDE), octabromodi Phenyl ether (OctaBDE).
(5) Other halogen compounds
Polychlorinated biphenyls and polychlorinated terphenyls are two types of chemically stable substances that are difficult to decompose in nature. Because of its high residual in the environment, it has serious harm to the environment, especially the water body and the atmosphere can be polluted. In order to reduce its harm to the environment, the European Union requires restrictions on its use in 76/769/EEC (Restriction of Hazardous Substances Directive).
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Hazardous Substances |
Applications in Electronic Components and Materials |
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organochlorine compounds |
（PCB） |
Insulating oil, lubricating oil, plastic flame retardant, etc. |
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（PCN） |
Lubricants, coatings, etc. (polychlorinated naphthalene (PCN) products containing more than 3 chlorine atoms) |
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（CP） |
Used as outer frame (housing), printed circuit board with accessory products |
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（Mirex） |
Flame retardants, rust inhibitors, etc. for resins, rubbers, coatings, textiles, electrical products, etc. |
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（PVC） |
Power cables, connecting cables, plastic wires for product interconnection, adhesives, high-voltage plastic wires, wrapping of demagnetizing coils, insulating tapes |
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Other organochlorine compounds |
Flame retardants for plastics, plasticizers, flame retardants on printed circuit boards, etc. |
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Organobromine compounds |
（PBB） |
Flame Retardants for Plastics |
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（PBDE） |
Flame Retardants for Plastics |
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TBBP-A） |
Flame retardants for plastics (four plastics such as PS, ABS, PC/ABS, Mope are the most commonly used semiconductor packaging materials and substrates) |
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Other organobromine compounds |
Flame retardants for plastics, flame retardants on printed circuit boards, etc. |
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◉ Analysis of the Reasons for no Halogenation in the World
From Freon to POPs, from PVC to brominated flame retardants (BFR), the harm of organohalogen compounds to human body and natural ecological environment is an indisputable fact. Organic compounds containing halogens themselves are very toxic, and wastes containing such organic compounds will cause secondary pollution during the combustion process and produce highly toxic organic compounds such as dioxins. Dioxin is a general term for polychlorinated dibenzo-P-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Its toxicity is 130 times that of sodium cyanide and 900 times that of arsenic. It is called "the poison of the century", so it is necessary to limit the use of halogen-containing organics.
In fact, the "halogen-free" process in developed countries has already begun, and the proportion of halogen-containing flame retardants used is very small, replaced by inorganic flame retardants. For related enterprises in China, following the international trend of "halogen-free", the production of "halogen-free" products can not only effectively improve the competitiveness of the enterprise itself, play a role in increasing the added value of products, but also make products meet the needs of the international market. The way to go!
◉ Control Regulations
The EU's 2002/95/EC (RoHS Directive), 76/769/EEC, 2003/11/EC, as well as the Norwegian PoHS and the relevant laws of the US states all impose restrictions on certain specific halogen compounds.
(1) EU 2011/65/EU - Restricted use of bromine-containing flame retardants (PBB≤1000mg/kg, PBDE≤1000mg/kg)
(2) The global "Montreal Protocol" - restricts the use of 5 kinds of chlorofluorocarbons (CFCs) and 3 kinds of halons (Halon)
(3) 151 countries and organizations "Stockholm Convention" - restricted use of organochlorine pesticides, hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzo-p-dioxins (PCDDs) Benzofurans (PCDFs).
(4) Regulations for IEC printed board materials IEC61249-2-21 - Requirements for reinforced substrates, composite and non-composite halogen-free rings in printed circuit board and other interconnect assembly materials, flammability (vertical fire test) copper clad laminates Medium used in oxygen-electronic glass fiber reinforced laminates: chlorine (Cl) ≤900mg/kg, bromine (Br) ≤900mg/kg, total halogen (Cl+Br) ≤1500mg/kg.
(5) JPCA-ES-01-1999 formulated by Japan Electronic Circuit Industry Association (JPCA) defines the definition and standard of "halogen-free", which requires that the total amount of Br elements in printed circuit boards (PCBs) shall not exceed 900 ppm , the total Cl element must not exceed 900 ppm. The standard was revised in 2003, adding a new requirement that the total amount of both elements Br and Cl must not exceed 1,500 ppm.
(6) The International Electronic Industry Connection Association (IPC) has also formulated the IPC-4101B standard, which puts forward corresponding requirements for rigid multilayer printed circuit board substrates, stipulating that the total amount of Br elements used shall not exceed 900 ppm, and the total amount of Cl elements shall not exceed 900 ppm. Must not exceed 900 ppm, Br and Cl combined must not exceed 1500 ppm
◉ Testing Method
(1) Rapid detection of halogen XRF
(2) Chemical testing of halogen elements
(3) Chemical testing of specific halogen organic compounds
(4) Halogen whole machine verification
(5) Analysis of PVC composition
◉ Main Inspection Content
Heavy metal detection, halogen detection, UV detection, pentachlorophenol detection, lead content detection, phthalate detection, dimethyl fumarate detection, azo detection, perfluorooctane sulfonic acid/PFOA detection, formaldehyde, Benzene, TVOC, radon detection, aflatoxin detection, plasticizer detection, pesticide residue detection, food additive content detection, ELV detection and atomization detection, volatile organic compound detection, polycyclic aromatic hydrocarbon detection, fluorescent agent detection, ROHS/ REACH/SVHC/POSH/WEEE/testing, solid waste hazardous waste detection, solid waste, liquid waste, etc.
◉ Compliance Service
As a professional third-party testing technology service provider, Jiayu Testing boasts qualifications such as CMA, CNAS, CPSC, and CCC. Additionally, we have obtained laboratory accreditation from multiple authoritative certification bodies both domestically and internationally. Our laboratory is constructed and managed in strict accordance with standards, equipped with advanced instruments and equipment, and staffed by a skilled and professional technical team. We possess extensive industry service experience and robust testing technical capabilities, are proficient in various regulatory standards, and assist enterprises in actively responding to regulatory requirements. We help enterprises achieve hazardous substance risk control and effectively enhance product compliance. Welcome to contact us. Jiayu Testing's consultation hotline is: 400-9269-886!
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