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In focus: Sealing products and legal requirements Author: Dr Uwe Wallner, Head of Elastomer Compound Development, Packing Division Europe Naturally, seals and sealing materials have to meet the technical demands made on them. In addition, their components have to conform to relevant standards, regulations and laws. A series of articles in the SealingReport highlights recent changes to applicable regulations and describes their impact on sealing products. Polycyclic Aromatic Hydrocarbons (PAH) Carbon black and silicates are the main fillers used in elastomers. These substances are not generally classified as hazardous substances. However, due to the manufacturing processes involved carbon black may contain potentially carcinogenic polycyclic aromatic hydrocarbons (PAH). Therefore, the regulations of the U.S. Food and Drug Administration (FDA), for example, establish limits for carbon black content in elastomers coming into contact with food and completely exclude some types of carbon black. The first manufacturers of carbon black have started to produce carbon black with low PAH content and are specifying the PAH content of their products. The PAH content in the subsequent elastomeric assembly component can then be calculated by means of the carbon black content. Processing elastomer compounds requires the addition of – in some cases considerable amounts of – plasticizers, which are classified as mineral oil derivatives, fatty acid derivates, resins or synthetic products. From a toxicological perspective, the mineral oil plasticisers containing polycyclic 14 SealingReport · November 2011 PAH Structure Chemical formula CAS-No. GADSL EPA Naphthaline C10H8 91-20-3 • Acenaphthylene C 12 H 8 208-96-8 • Acenaphthene C 12 H 10 83-32-9 • Fluoren C 13 H 10 86-73-7 • Anthracene C 14 H 10 120-12-7 • Phenanthrene C 14 H 10 85-01-8 • Fluoranthene C 16 H 10 206-44-0 • Pyrene C 16 H 10 129-00-0 • Benz[a]anthracene C 18 H 12 56-55-3 • • Chrysene C 18 H 12 218-01-9 • • Benzo[b]fluoranthene Benz[e]acephenanthrylene C 20 H 12 205-99-2 • • Benzo[j]fluoranthene C 20 H 12 205-82-3 • Benzo[k]fluoranthene C 20 H 12 207-08-2 • • Benzo[a]pyrene C 20 H 12 50-32-8 • • Benzo[e]pyrene C 20 H 12 192-20-3 • Benzo[g,h,i]perylene C 22 H 12 191-42-2 • Indeno[1,2,3-cd] pyrene C 22 H 12 193-39-5 • Dibenzo[a,h] anthracene C 22 H 14 53-70-3 • • Table 1: Polycyclic Aromatic Hydrocarbons acc. to GADSL and EPA.
aromatic hydrocarbons (PAH) have attracted considerable attention as they are considered to be highly carcinogenic. Naphtenic or even aliphatic plasticisers, however, do not have the strong plasticising effects of the aromatic types which have come under criticism. Nevertheless, more and more specifications of elastomeric assembly components are now limiting the permissible PAH content. This is done based on the GADSL (Global Automotive Declarable Substance List) and the list published by the U.S. Environmental Protection Agency (EPA) of PAH in Table 1. Since January 2008 elastomeric assembly components have had to be tested for their PAH content if they are installed in equipment bearing the GS (= Tested Safety) mark. The testing procedures and limits by categories have been published in the ZEK document 01-08, “Testing and Evaluation of Polycyclic Aromatic Hydrocarbons (PAH) for Awarding of GS Marks”. For seals, the limits of category 3 – materials with foreseeable skin contact up to 30 s (short-term skin contact) or no skin contact – with nenzo[a]pyren < 20 mg/kg and total 16 PAH according to EPA < 200 mg/kg apply. For the automotive industry, limits of < 20 mg/ kg for each of the eight GADSL listed PAH apply. In some cases, however, customer requirements clearly exceed these limits. Parker has not been using plasticisers with carcinogenic potential for years. To confirm this, various materials containing carbon black and plasti- Compounds Substances Benzo[a]pyrene 8 PAK 16 PAK Requirement ZEK 01-08 GADSL GADSL ZEK 01-08 Category 3 Required < 20 mg/kg < 160 mg/kg < 200 mg/kg N3584-85 Actual < BG < BG 8,2 mg/kg N3512-90 Actual < BG < BG 1,6 mg/kg V9153-70 Actual < BG 0,2 mg/kg 2,7 mg/kg Table 2: Content of Polycyclic Aromatic Hydrocarbons in Parker-Prädifa Compounds (Detection Limit, Determination Limit = 0.1 mg/kg). cisers have been tested for their PAH content according to EPA and GADSL by an independent specialised laboratory of the DEKRA organisation. Some of the results are summarised in Table 2. The tests in Table 2 document that the PAH content of the compounds tested is clearly below the required limits. This shows that safe products can be manufactured and supplied through skilful selection of raw materials. SealingReport · November 2011 15
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