TECHNICAL REPORT ISO/TR 21275 First edition 2017-02 Rubber — Comprehensive review of the composition and nature of process fumes in the rubber industry Caoutchouc — Examen exhaustif de la composition et de la nature des fumées de process dans l’industrie du caoutchouc Reference number ISO/TR 21275:2017(E) © ISO 2017 ISO/TR 21275:2017(E) COPYRIGHT PROTECTED DOCUMENT © ISO 2017, Published in Switzerland All rights reserved Unless otherwise specified, no part o f this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission Permission can be requested from either ISO at the address below or ISO’s member body in the country o f the requester ISO copyright o ffice Ch de Blandonnet • CP 401 CH-1214 Vernier, Geneva, Switzerland Tel +41 22 749 01 11 Fax +41 22 749 09 47 copyright@iso.org www.iso.org ii © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) Contents Page Foreword v Introduction vi Scope Normative references Terms and definitions Overview of the rubber industry 4.1 General 4.2 Rubber component production processes 11 4.4 Rubber chemicals and additives 12 f 13 13 f 13 14 4.5.4 Metal oxides 14 14 ff f 15 Definition o f rubber fumes 15 Nature and composition of rubber fumes 16 6.1 General 16 f f 16 17 f f 6.3.1 General 17 f 17 18 Generic rub b er typ es M echanis tic chemis try o Generality S ul ur- accelerated cure sys tems Peroxide- b as ed cure sys tems O ther vulcanizing sys tems E elevated temp erature o n rub b ery p o lymers and rub b er additives 6.2 Key co mp o nents o 6.3 Trap p ing and analys is o 6.4 ect o umes and their o rigin rub b er umes C haracterizatio n s tudies carried o ut in 6.3 C haracterizatio n s tudies carried o ut under lab o rato ry co nditio ns acto ry enviro nments C hanges in rub b er techno lo gy that have influenced the nature and co mp o s itio n o f 6.4.1 6.4.2 6.4.4 6.4.5 rub b er 6.3 rub b er rub b er vulcanizatio n f 19 General 19 Overall trend in rubber workers’ exposure to total rubber fumes 19 19 Nitrosamines 19 Silane coupling agents and resorcinol steel cord coating agent 19 fumes and imp roved the p ro tectio n o wo rkers in the indus try Po lyaro matic hydro carb o ns Factors affecting the variability of rubber fumes 19 General 19 20 f f f f f ff f f 20 f ff f f 21 Review of literature on the composition and nature of rubber process fumes 22 8.1 Comprehensive literature search 22 8.1.1 General 22 f f f 22 f 32 f f 36 f f f 38 40 8.2 Other sources of information 41 8.2.1 General 41 f 42 8.2.3 Chemical abstracts results 42 8.2.4 General POLLUAB and NTSI database results 43 7.1 7.2 I nfluence o the rub b er co mp o und 7.3 I nfluence o di erent manu acturing p ro ces s es o n rub b er o rmulatio n o n the co mp o s itio n o 7.4 I nfluence o di erent p ro ces s ing temp eratures o n the co mp o s itio n o 8.1 Rub b er umes data o b tained 8.1 Rub b er umes data o b tained by lab o rato ry s tudies 8.1 Res earch o n s amp ling and analys is techniques 8.1 I nfluence o 8.1 Wo rk carried o ut at Rap Techno lo gy Ltd 8.2 S earch s trategy © ISO 2017 – All rights reserved ro m rub b er umes rub b er umes umes acto ry atmo s p heres o r rub b er rub b er additives o n the co mp o s itio n o umes rub b er umes o r external datab as es iii ISO/TR 21275:2017(E) S earch o f indus try- relevant p ub licatio ns , government p ub licatio ns and 8.2 relevant websites 43 44 10 Conclusions 45 Annex A (informative) Abbreviated terms 47 Bibliography 49 iv S u m m a r y o f t h e f i n d i n g o f t h e l i t e r a t u r e r e v i e w © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies) The work o f preparing International Standards is normally carried out through ISO technical committees Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters o f electrotechnical standardization The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part In particular, the different approval criteria needed for the di fferent types o f ISO documents should be noted This document was dra fted in accordance with the editorial rules of the ISO/IEC Directives, Part (see www.iso org/directives) Attention is drawn to the possibility that some o f the elements o f this document may be the subject o f patent rights ISO shall not be held responsible for identi fying any or all such patent rights Details o f any patent rights identified during the development o f the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso org/patents) Any trade name used in this document is in formation given for the convenience o f users and does not constitute an endorsement For an explanation on the meaning o f ISO specific terms and expressions related to formity assessment, as well as information about ISO’s adherence to the World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT) see the following URL: www.iso org/iso/foreword.html This document was prepared by Technical Committee ISO/TC 45, Rubber and rubber products © ISO 2017 – All rights reserved v ISO/TR 21275:2017(E) Introduction Fumes emitted during the rubber manu facturing processes were the topic o f many studies This comprehensive study was undertaken to compile and review published data with respect to rubber fume emissions in the workplace This review has provided a comprehensive bank of technical data for dissemination and further debate It has assessed literature regarding the chemical composition of rubber fumes in manufacturing from a comprehensive range of processes It has been postulated that fume emissions from rubber compound vulcanization can be considered a single chemical entity, cited as posing a carcinogenic risk to human health Although many studies have tried to characterize rubber fume emissions, there is no known concise study that provides a rational explanation for this conclusion This study has tested this postulation and provided an insight as to whether it is a sound conclusion The aim o f this project was to evaluate, on a basis o f sound scientific literature, whether it is scientifically robust to consider “rubber fumes” as a homogeneous entity from a chemical point o f view and, more importantly, in relation to measurement and control o f occupational exposure risk for the rubber industry as a whole An extensive literature review aimed at providing a compilation of literature related to rubber fume not on the toxicological or epidemiological aspects emissions, this study has concentrated on the chemical compositional aspects o f rubber fumes only and In addition, although rubber dust and rubber fumes are being considered by the EU for a potential incorporation in the scope o f the Carcinogens Directive, this study has only considered rubber fumes This document provides detailed in formation on the study carried out, the results obtained from the literature reviews and the conclusions drawn from this information This document comprises two main parts; the first provides a general overview o f the key areas o f rubber technology and the second provides an extensive review o f in-house and external literature on the composition and nature of rubber process fumes Natural rubber (NR) has been known to the civilized world since about 1493 when early European explorers found natives o f Haiti playing with balls made from the exudates o f a tree called “cau-uchu” The term “rubber” was coined much later by the English chemist J.B Priestly for its ability to erase lead pencil marks The French scientist De La Condamine first introduced NR to Europe in 1736 and published his observations on the material in 1745 Industrial application o f rubber only occurred a fter Charles Goodyear in 1841 discovered the process termed “vulcanization”, which converted the rubber to a more stable and use ful material, that paved the way for the growth o f the modern industry Synthetic rubbers were first produced in Germany in the 1930s, and during the Second World War when the supply o f natural rubber was interrupted, methods were developed for the bulk production o f synthetic rubbers Styrene butadiene rubber (SBR) was one o f the first synthetic rubbers to be developed and manu factured in high volume in the 1940s, mainly for the production o f tyres and in an attempt to match the properties o f natural rubber Since that time, many di fferent synthetic rubbers have been developed to allow the use o f rubber in a very wide variety o f environments and applications Over the years, the importance o f rubber to modern li fe has constantly increased This is not always immediately apparent because rubber components are o ften not colour ful, eye catching or are used in applications where they are not readily visible Natural and synthetic rubber compounds are used in a highly diverse range o f rubber products which are manu factured throughout the world for various sectors o f industry and for a variety o f end users, including, but not exclusively, automotive, aerospace, medical/pharmaceutical, defence, commercial, general industrial and others O f the sectors where rubber is used, the automotive industry is o f particular importance since tyre and tyre products account for approximately 60 % o f the synthetic rubber and ~75 % o f the natural rubber used today vi © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) Table provides an overview of the diverse range of rubber components made from general f f but helps highlight the diverse areas and products in which rubber is used manu ac tu ri ng pro ce s s e s and d ipp e d late x te ch nolo g y T he l i s t o comp onents i s b y no me an s exh aus tive Table — Range of rubber components Tyre s p a s s en ger c a rs , tr ucks , rac i ng veh icle s , c ycle s , o ff-ro ad tyre s , i n ner tub e s , c u r i ng C o nve yor/ s te el cord conve yo r b elti n g , rep a i r mater i a l bladders Transmission belting Industrial hoses Automotive products co nve yor b elti n g , s c rap ers , m i n - water ho s e s , h igh-p re s s u re ho s e s , weld i ng ho s e s , hyd rau l ic ho s e s , s p i l ho s e s , offshore hoses, oil hoses, chemical hoses co ol a nt ho s e s , ho s e s , General mouldings/ Sheeting for i n g co nveyors , V-b elts , fl at b elts , s ynch ronou s b elts fuel fuel ho s e s , s e a l s a nd ga s ke ts , a nti-vib ration mo u nts , hyd rau l ic i nj e c tors , ti m i ng b elts , wi ndow a nd or ch a n nel l i n g , tra n s m i s s io n and engine components, wiper blades, exhaust hangers mo u lde d s e a l s a nd ga s ke ts , a nti-vibration p ro duc ts , flo or cover i ngs , s he e ti n g , tub e r i ngs , ro o fi ng l ayers , s ub s o i l water s he e ti n g , ro l ler co ver i ngs , p ro te c tion l i n i n gs , mou lde d m ic ro - cel lu l a r p ro duc ts , comp o s ite pro fi le s , r ub b er i z e d fab r ic, m ic ro - cel lu l a r r ub b ers/pro fi le s , wi re a nd c ab le j acke ts a nd i n s u l ation s , gl a s s sealants, pump impellors, roof membranes, pond liners, rail mounts, bridge Medical/ Pharmaceutical products Clothing Food contact products b e a ri n gs , m i l ita r y veh icle track p ad s s u rgic a l glo ve s , me d ic a l tub i n g , M D I va l ve ga s ke ts , c athe ters , d i a l ys i s p ro duc ts , s u rgic a l i mp l a nts , pro s the s e s , co ntracep tive s , s o o thers , b ab y fe e d i ng te ats a nd breast caps, blood transfusion tubing and valves, medical and antistatic sheeting and membranes, masks and respirators boots/footwear, protective suits, household gloves, industrial gloves, footwear/ boot heels and soling, cellular rubber soles, wet suits, diving suits, coated fabrics, sports footwear and clothing fo o d tra n s p o r tation (e g conve yer b el ts , ho s e s a nd tub i ng) , fo o d h a nd l i ng (glove s) , pip e a nd m ach i ner y co mp onents (s e a l s , ga s ke ts , fle xib le co n ne c tors a nd d i aph ragm/ butter fl y va l ve s) , pu mpi ng s ys tem comp onents ( p ro gre s s i ve c avity Potable water products Miscellaneous products pumps stators, diaphragm pumps), plate heat exchanger gaskets, seals/gaskets for cans, bottles and closures pipe seals and gaskets, hoses, linings of pumps and valves, tap washers, membra ne s i n p ip e s a nd fi lters , co ati n gs on pro ce s s p l a nt, ta n k l i n i ngs adhesives, rubberized asphalt, high vacuum and radiation components, carpet b acki n g , l ate x th re ad , s e a l a nts a nd c au l ki n g , toys It is important that the reader of this document concludes that the rubber material used to make any p ar tic u lar pro duc t i s no t a s i ngle entity but i s a comple x comp ou nde d materi a l re ferre d to as a “comp ou nd” or “ formu lation”, wh ich may contai n a la rge nu mb er o f e s s entia l chem ic a l i ngre d ients T he s e i ngre d ients wi l l i nclude the b as e rubb er p olymer(s) , rei n forci ng a nd non-rei n forci ng p ar tic u late fi l lers , pro ce s s oi l s , vu lc an i z i ng agents , pro te c tive agents , pro ce s s aid s , e tc (a l l o f wh ich are avai lab le i n many typ e s a nd grade s from many s upp l iers and c an b e i nclude d at d i fferent level s) T he comp a ny or i nd ividua l who de s ign s a r ubb er cho o s e from a nd as s uch, many formu l ation for formu lation s a s p e c i fic pro duc t s a vas t nu mb er o f i ngre d ients to are there fore p o s s ible for a s p e c i fic r ubb er pro duc t T he pro ce s s i ng route b y wh ich the maj ority o f rub b er comp onents are ma nu fac ture d i nclude s m i xi ng the i ngre d ients to ge ther i n a control le d man ner to pro duce a rubb er “comp ou nd” or “m i x”, s hapi ng o f the m i xe d comp ou nd to give the de s i re d s hap e or form, then “vu lc an i z i ng” (a l s o known as “cro s s l i n ki ng” and “c uri ng” ) the comp ound to conver t it to a cond ition where it s p ermanent prop er tie s and s hap e T he typ e o f rubb er materi a l s and manu fac tu ri ng pro ce s s e s u s e d wi l l dep end up on the i nd ividua l pro duc t a nd a re de s c rib e d i n th i s c u ment M any o f the manu fac tu ri ng pro ce s s e s i nvolve generati ng he at i n the rubb er comp ound where vol ati le s p e cie s s uch a s “ fume s ” c an b e rele a s e d T he la rge d ivers ity i n b o th the rubb er formu lation s from it avai lab le a nd the ma nu fac tu ri ng pro ce s s e s u s e d c an there fore p o tenti a l ly give ri s e to a h igh ly d ivers e range o f s p e c ie s evolve d © ISO 2017 – All rights reserved vii ISO/TR 21275:2017(E) I n order to a s s i s t the re ader to unders ta nd the term i nolo g y as s o c iate d with the r ub b er te ch nolo g y i n th i s c u ment, a glo s s a r y o f term s i s i nclude d i n viii Annex A © ISO 2017 – All rights reserved TECHNICAL REPORT ISO/TR 21275:2017(E) Rubber — Comprehensive review of the composition and nature of process fumes in the rubber industry Scope This document, based on 95 publications, gives an overview of what is the composition of the fumes f f are a complex and variable mix of chemicals which have a wide range of possible sources and origins, including chemicals generated from the chemical reactions occurring in the rubber compounds during processing and curing Some of these chemical substances can be hazardous, others are not This f f f chemicals to which the operators in the factories producing rubber articles can be exposed to, allowing em itte d du ri ng the rubb er ma nu ac turi ng pro ce s s e s T he re s u lts ob tai ne d fi rm that rubb er c u ment demon s trate s the ne e d ume s or I nternationa l Standard s to qua l i y a nd qua nti y the h a z a rdou s the identi fic ation and m itigation o f p o tenti a l he a lth ri s ks Normative references There are no normative references in this document Terms and definitions For the pu r p o s e s o f th i s c u ment, the fol lowi ng term s and defi n ition s apply ISO and IEC maintain terminological databases for use in standardization at the following addresses: — IEC Electropedia: available at http://www.electropedia org/ — ISO Online browsing platform: available at http://www.iso org/obp 3.1 accelerator compounding ingredient used in small amounts with a vulcanizing agent to increase the speed of vu lc an i z ation a nd/or en hance the phys ic a l prop er tie s o f the vu lc an i z ate [SOURCE: ISO 1382:2012, 2.5] 3.2 activator compounding ingredient used in small proportions to increase the effectiveness of an accelerator [SOURCE: ISO 1382:2012, 2.6] 3.3 ageing exposure of a material to an environment for a period of time [SOURCE: ISO 1382:2012, 2.13] 3.4 ageing irreversible change of material properties during exposure to an environment for a period of time [SOURCE: ISO 1382:2012, 2.14] © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) 3.5 antidegradant compounding ingredient used to retard deterioration by ageing Note to entry: Antidegradant is a generic term for certain additives such as antioxidants, antiozonants, waxes and other protective materials [SOURCE: ISO 1382:2012, 2.21] 3.6 antioxidant compounding ingredient used to retard deterioration caused by oxidation [SOURCE: ISO 1382:2012, 2.24] 3.7 autoclave pressurized vessel used for vulcanizing rubber in a vapour or gas [SOURCE: ISO 1382:2012, 2.33] 3.8 benzene C6 H6 simplest member o f the aromatic series o f hydrocarbons Note to entry: It is colourless liquid with a b.p o f 80 °C and is used in the manu facture o f many organic compounds 3.9 blank piece o f rubber compound o f suitable shape and volume to fill the mould [SOURCE: ISO 1382:2012, 2.44] 3.10 bonding agent substance, usually in liquid form, coated onto another material and used to produce a good bond between the material and rubber [SOURCE: ISO 1382:2012, 2.54, modified — Note to entry has been deleted.] 3.11 butadiene CH CHCHCH buta-1,3-diene gas used in the manu facture o f polybutadiene rubber and as one o f the copolymers in the manu facture o f styrene-butadiene and nitrile rubbers 3.12 calender machine with two or more essentially parallel rolls, operating at selected sur face speeds, nips and temperatures, for such operations as sheeting, laminating, skim coating (topping) and friction coating of a product to a controlled thickness and/or controlled surface characteristics [SOURCE: ISO 1382:2012, 2.65] © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) industry contributed to this document by providing in formation on around 800 chemicals, and one o f the conclusions was that the industry had improved the way that it was working over the years by substituting chemicals that caused concern with safer ones, or eliminating the chemicals altogether 8.1.6 Work carried out at Rapra Technology Ltd A considerable amount o f the fundamental scientific work that has been carried out on the nature and composition o f rubber vulcanization fumes has been conducted by Rapra Technology These studies, which began in the 1970s and carried on through into the late 1990s were led by Dr Bryan Willoughby The results that were obtained and the understanding of the chemical relationships that resulted enabled the composition of rubber fumes from a given rubber compound to be predicted with a high degree o f accuracy One o f the principal approaches that were taken was to carry out a series o f over 40 vulcanization experiments, using industrially relevant formulations, in a specially designed apparatus [the Gas Trans fer Mould (GTM)] using a “pool” o f 75 ingredients and studying the species that were given o ff in the fumes by inter facing the GTM with a GC-MS More than 150 di fferent chemical species were detected and these enabled ingredient/process conditions/emission relationships to be identified, for example: — a list o f all the formulations which yield a single emission and those that yield more than a certain amount o f a specific emission, the common ingredients in such lists o f formulations; — a list o f all the formulations which use a specific ingredient; and the common emissions from such a list of formulations; — the overall effect of the formulation, the curing temperature and the temperature of the rubber at the time o f analysis The complexity o f industrial rubber mixes meant that the relationship between the ingredients and the emissions obtained was not necessarily simple For example, an individual component o f rubber fumes may have more than one source in a formulation The work at Rapra did reveal certain key trends however For example, three distinct sources of volatile emissions were recognized: — volatile ingredients, e.g antioxidants and plasticizers; — volatile impurities of ingredients, e.g residual monomers and manufacturing impurities; — volatile by-products o f chemical reactions, e.g vulcanization and antioxidant reactions Among the in formation provided by this in-depth paper[7] are sections on the origin o f specific individual compounds, such as carbon disulfide, and a table which lists the potential origins o f over 40 volatiles species which can be detected in rubber fumes The results of the Rapra Vulcanization Project, and a description o f the predictive rubber fumes so ftware that resulted from it, have also been presented in a Rapra publication.[69] In addition to these summary publications, a large number o f other papers and publications have been published by Willoughby and other workers at Rapra during the course o f their work in rubber fumes For example, in a paper entitled “Prediction o f On-site Per formance for Vulcanization Fumes” RWB Smith and BG Willoughby[70] described rubber fumes as being comprised of two distinct phases: a) visible portion, composed o f aerosols formed by the condensation o f hot vapours, which can be trapped onto filters providing that the sampling flow rate is high enough; b) invisible portion, composed of a complex mixture of species that remain in the gaseous phase The wide range of species present mean that either a range of adsorbents, or a range of liquid media for trapping by absorption have to be used to ensure that the data subsequently obtained by analysis is fully representative The paper goes on to describe work carried out using the GTM/GC-MS configuration to predict the range o f species that will be present in factory fumes as an aid to putting together trapping protocols for the gaseous species; the GC-MS analysis o f fumes collected on a single adsorbent (Tenax) in a rubber factory when the same rubber compound is being vulcanized; and analysis by GC-MS o f the aerosol 40 © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) frac tion rele as e d from ho t rubb er a fter vu lc an i z ation u s i ng a lab orator y s ampl i ng device O ther p ap ers o f i ntere s t i nclude: C ontrol at s ou rce Plastics and Rubber Industries [71] I n an e arl ier review b y Wi l loughb y, for data obtained on the composition of rubber fumes, recorded [1] u s i ng l ab orator y-b as e d e xp eri ments Vu lc an i z ation Fu me s , B G Wi l loughby, He a lth a nd S a fe ty i n the with the Rapra GT M/G C-M S combi nation, are provide d wh ich i l lu s trate how the pro ce s s i ng temp eratu re c an a ffe c t the typ e s o f hyd ro c a rb on s p e cie s de te c table i n fumes released from rubbers containing SBR, and the relative levels of these species These data are shown in Table 20 T a b l e — I n f l u e Extrusion (up to 110 °C) n c e o t e m p e r detected in rubber fumes a t u r e o n t h e Hydrocarbon compound in fumes µg/m 25–180 20–160 1–20 1–15 0–3 0–10 0–7 0–20 1–10 f c o n c e n t r a t i o n o f s p e c Vulcanization (at 145 °C to 165 °C) µg/m Benzene Toluene 10–1 200 6–800 2–180 2–90 ND 2–200 1–75 5–180 5–400 Styrene E thylb en z ene -Vi nylc yclo he xene I s op rop ylb en z ene D i-i s op rop ylb en z ene Dodecenes C yclo de c atr iene i f i c c h e m i c a l c o m p o u n d s Vulcanization (at 180 °C to 240 °C) µg/m 8–15 4–8 90–500 30–150 30–210 60–250 35–70 300–7 000 ND D = D e te c te d b ut no t qu a nti fie d ND = Not detected I n a rel atively e a rly Rapra p ap er, [2] M a i s ey de s c rib e d the work that had b e en c a rrie d on r ubb er fume s u s i ng the GT M/G C-M S combi nation a nd s p e ci fic a l ly rep or ts the re s u lts that have b e en ob tai ne d on the effect that changing the moulding temperature has on the amount of a particular reaction product (c arb on d i s u l fide) rele a s e d from a s u l fu r- c u re d E PDM r ub b er contai n i ng the accelerator T M T D Re s u lts showe d that i ncre as i ng the temp erature i n s tep s , the amou nt o f c a rb on d i s u l fide rele as e d from from ° C to 0 ° C a nd fi na l ly ° C , i ncre as e d , m mole to ,9 m mole a nd fi na l ly to , m mol T h i s work b y Rapra s a l s o shown that b y mo d i fyi ng the c ure s ys tem, no c arb on d i s u l fide i s l ib erate d The effect of temperature on the amount generated of a particular compound is also commented with respect to the amount of TDI liberated from a urethane adduct curing agent for NR compounds [3] The amount of free TDI found in the vulcanization fumes was found to reduce as the temperature was f ff ff f f a mixing mill and above a moulding press, showing the effect that different processes and processing conditions can have Another Rapra paper[4] included a brief table showing how the total amount of rubber fumes, determined as total weight loss, varies with vulcanization temperature re duce d rom 0 ° C to ° C D i — at 16 ° C , ,1 % — at 175 ° C , , % — at 19 ° C , ,75 % erent level s o re e T DI were a l s o ou nd or the s ame comp ound ab ove 8.2 Other sources of information 8.2.1 General The following databases were searched © ISO 2017 – All rights reserved 41 ISO/TR 21275:2017(E) a) Chemical Abstracts Service (CAS) , a division o f the American Chemical Society CAS is the most authoritative and comprehensive source for chemical information CAS databases, including CAS REGISTRYSM, the gold standard for substance in formation, are curated and qualitycontrolled by CAS scientists Combining these databases with advanced search and analysis technologies, CAS delivers the most complete, crosslinked, and e ffective digital in formation environment for scientific research and discovery The CA SEARCH®: Chemical Abstracts® database includes over 20 million citations to the worldwide literature o f chemistry and its applications from 1967 forward b) Pollution Abstracts (POLLUAB) POLLUAB is a bibliographic database from Cambridge Scientific Abstracts that contains in formation on air, land, marine, and freshwater pollution, their sources, and their control Sewage and wastewater on environmental information are included POLLUAB corresponds to the printed publication Pollution Abstracts This database contains more than 376 391 records, around 12 000 new records per year, and dates from 1970 to the present treatment are covered, as well as water management Both scientific research and government policies c) NTIS database Containing over million bibliographic records, the NTIS Database is the preeminent resource for accessing the latest research sponsored by the United States and select foreign governments The database represents billions of dollars in research, which includes research reports, computer products, so ftware, video cassettes, audio cassettes and more The complete electronic file dates back to 1964 and most records include abstracts On average, NTIS adds over 30 000 new records per year to the database d) Other external databases In addition to the three external databases that were searched, other databases were considered, but not searched as they were not thought to be cost-e ffective ways o f obtaining in formation that was use ful to the project These were: — — — — toxcentre; embase; healsafe; chemsafe 8.2.2 Search strategy for external databases To ensure that this part o f the project was carried out in a cost-e ffective way, an interactive approach between the information scientists and the rubber consultants was taken This enabled a targeted initial search to be undertaken, the results o f which were then checked to ensure that the right type o f article was being found and then the search refined and another carried out In addition to controlling costs by ensuring that time on the database was used e fficiently, titles only were obtained initially and then those that were of interest selected for the purchase of the abstracts This procedure was carried out a number o f times to ensure the best chance o f finding articles o f relevance 8.2.3 Chemical abstracts results The search strategy for this database was refined many times to optimize its e ffectiveness A few hundred titles were obtained and examined, and full abstracts purchased for over 30 articles These abstracts, which were in English, showed that around 10 of the articles were in German, Chinese, Japanese or Russian 42 © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) 8.2.4 General POLLUAB and NTSI database results a) Both o f these databases were searched a number o f times to refine the strategy to ensure optimum results b) These databases were included in the searching activities undertaken for the project as it was thought that they may contain articles that addressed the composition and nature o f rubber process fumes However, the results obtained were only indirectly relevant, with most o f the focus being on emissions (e.g VOC and dust) to atmosphere from the rubber factories and the reporting o f the results o f studies which addressed occupational hygiene and genotoxicity issues 8.2.5 Search of industry-relevant publications, government publications and relevant websites The websites of prominent government agencies were accessed and searched for relevant information a) UK Government Health and Safety Executive (HSE) website (www.hse gov.uk) The following publications were among those that were found: A new practical guide to complying with COSHH in the rubber industry — Guidance HSE Books 1997 ISBN 7176 1372 Control of rubber fumes at extruders, calenders and vulcanizing operations — Guidance HSE Books 1994 ISBN 7176 0783 Maintenance, examination and testing of local exhaust ventilation HSG54 — (Second edition) 1998 ISBN 7176 1485 An introduction to local exhaust ventilation 1001 HSE Books HSG37 (Second edition) HSE — Books 1993 ISBN 7176 The selection, use and maintenance of respiratory protective equipment: A practical guide HSG53 (Second edition) HSE Books 1998 ISBN 7176 1537 Safe to breathe: Dust and fumes control in the rubber industry Leaflet IACL95 — HSE Books 1995 ISBN 7176 0979 0) Controlling airborne contaminants in the workplace Technical Guide TG7 British Occupational Hygiene Society 1987 ISBN 9059 2742 A small survey of exposure to rubber process dust, rubber fumes and N-nitrosamines, Research Report RR819, Prepared by the Health and Sa fety Laboratory for the Health and Sa fety Executive, 2010 b) The EU website and the Council of Europe website Both o f these websites were searched via the home page search box using appropriate keywords but no relevant documents could be found c) Other websites The World Wide Science website was searched using terms such as “rubber emissions” and “rubber umes” f Several relevant articles were found, but these had already been detected using the various database searches Other articles that were found included various UK government guidance documents on the control of rubber dust and rubber fumes d) Search of other sources (e.g trade and research associations) British Rubber Manu facturers Association (BRMA), later divided into the British Tyre Manu facturers Association (BTMA) and the British Rubber and Polyurethane Products Association (BRPPA) e) Other information sources © ISO 2017 – All rights reserved 43 ISO/TR 21275:2017(E) In addition to the databases and sources described above, other sources of information have been consulted, including the following: — Rapra Review Reports, e.g Health and Sa fety in the Rubber Industry by Naesinee Chaiear; — books, e.g Rubber Fumes — Ingredient/Emission Relationships (by Bryan Willoughby), Nitrosamines in Rubber (by B.G Willoughby and K.W Scott) and Air Monitoring in the Rubber and Plastics Industries (by B.G Willoughby); — government publications, e.g those published by the UK Health and Sa fety Executive; — in formation obtained during the managing o f research projects, e.g Rubber Breakdown Products Project conducted for the UK Food Standard Agency from 2002 to 2005 and the Rapra Rubber Fumes Project that ran during the 1980s S u m m a r y o f t h e f i n d i n g o f t h e l i t e r a t u r e r e v i e w This clause gives a summary o f the overall findings o f the literature search, with additional specific summaries of the results provided in Clauses and A substantial literature search has been undertaken This has enabled a wide range of articles and in formation sources to be consulted, including peer-reviewed papers in scientific journals, articles published in trade journals, books, best practice guides, research project results, and ference proceedings These articles have shown that information has been published in a number of geographical areas, in particular the US, the Far East, Russia and the EU These articles have shown that rubber fumes has a very complex chemical composition, both in terms o f the types o f chemical compounds present (usually over 30 for a typical rubber compound) and the physical forms (e.g gases, volatile compounds and aerosols) that these chemicals are in They have also shown how changes in rubber technology over the past 40 years will have altered the composition o f rubber fumes and will have increased the level o f protection for workers in the rubber industry The following salient points have been obtained from the articles and papers that have been obtained and examined a) The specific processing conditions (e.g the precise moulding temperature) will influence the levels and types o f species present in the curing fumes o f a particular rubber compound b) In the case o f certain “high-risk” species (e.g nitrosamines and polyaromatic hydrocarbons) it has been shown that their presence and actual levels in rubber fumes are very dependent on the starting ingredients present in the original compound c) Within a particular rubber factory, the types and overall levels o f species in the process fumes varies according to the type o f process being carried out, i.e mixing, extruding, moulding, storage, etc For example, in the general rubber goods sector the overall level of exposure to rubber fumes has been found to vary as shown below: Moulding > Extrusion > Milling d) Rubber process fumes comprise a wide range of chemical species with respect to molecular weight and polarity A number o f studies have reported over 30 di fferent species in the fumes from a particular rubber compound, and the extensive work carried out by Rapra Technology has shown that over 150 di fferent chemical species could be detected in the fumes generated by the vulcanization o f 40 di fferent compounds using a “pool” o f 75 compounding ingredients The species present in rubber fumes have been shown by a number o f workers to fall into one o f a wide range o f chemical groups: 1) aliphatic hydrocarbons — straight chain and cyclic; 2) aromatic hydrocarbons; 44 © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) 3) halogenated compounds; 4) i s o th io c yanate s; 5) ketones; 6) nitrosamines; 7) thiazoles; 8) a ldehyde s a nd a lcohol s; 9) esters and ethers; 10) amines and nitosamines; 11) sulfur compounds e) T he work c arrie d out b y Rapra Te ch nolo g y h as shown that there are th re e d i s ti nc t s ou rce s o f volatile emissions: 1) volatile ingredients, e.g antioxidants and plasticizers; 2) volatile impurities in ingredients, e.g residual monomers and manufacturing impurities; 3) volatile reaction and breakdown products of chemical reactions that occur during processing, e g vu lc an i z ation a nd antioxida nt ac tivity T he relative contribution o f the s e to any given s ample o f rubb er fu me s a re dep endent on the ingredients present in each rubber formulation contributing to the fumes present in a working atmosphere in a particular moment in time f) The wide range of species that can be detected in rubber process fumes (listed in point 4) i present i n a nu mb er o f phys ic a l d i fferent phys ic a l form s , for form s pre s ent with i n a rubb er g) e xample gas e s , vap ours a nd aero s ol s T he relative level s o f the s e var y accord i ng to the d i fferent are a s (e g m i xi ng , mou ld i ng , s torage, e tc ) fac tor y I n com mon with a l l te ch nolo gie s , r ubb er te ch nolo g y has evolve d over the ye ars and the ch ange s have had a direct effect on the composition of rubber fumes One of the main drivers for this change h as b e en he a lth and s a fe ty legi slation a nd th i s i s b el ieve d to have b enefitte d the he a lth o f the workers i n the i ndu s tr y b y re duc i ng thei r exp o s u re to p o tenti a l ly z ardou s s ub s tance s 10 Conclusions T he a i m o f th i s l iteratu re review wa s to eva luate, on a b a s i s o f s ou nd s c ienti fic l iteratu re, whe ther or no t it i s s cienti fic a l ly robu s t to s ider “rubb er fu me s ” a s a homo gene ou s entity from a chem ic a l p oi nt o f view, and more i mp or tantly i n relation to me a s u rement a nd control o f o cc up ationa l exp o s u re ri s k for the r ub b er i ndu s tr y a s a whole T he re s u lts that have b e en ob tai ne d by th i s comprehen s ive s tudy fi rm that rubb er fu me s a re a ver y complex m i x o f chem ica l s ub s tance s wh ich have a wide range o f p o s s ible s ou rce s a nd origi n s Authoritative examples in the literature that illustrate this situation are cited in this document, for example where monitoring of rubber fumes has taken place at sites where rubber products are manufactured, I n add ition to the la rge nge o f chem ic a l s p e c ie s th at c an b e pre s ent i n r ubb er shown that the phys ic a l form fume s , th i s s tudy s (i e ga s e s , vap ou rs or aero s ol) that the s e s p e c ie s exi s t i n the fac tor y envi ron ment c an b e i n fluence d b y the typ e o f pro ce s s b ei ng c a rrie d out and the pro ce s s temp erature T h i s review fi rm s that the typ e o f pro ce s s (e g mou ld i ng , c a lenderi ng , e tc ) and the pro ce s s i ng temp eratu re c an a l s o i n fluence the re ac tion s that ta ke pl ace i n a r ubb er comp ou nd a nd, hence, the © ISO 2017 – All rights reserved 45 ISO/TR 21275:2017(E) types o f species that can be emitted, in addition to the proportion o f the rubber compound which falls within the “volatile fraction” and so has the potential to be emitted as process fumes The studies that have been carried out and included in this document have therefore shown that, even when the detailed composition o f a rubber compound being processed is known, it is di fficult to compile a predictive list o f those species that are likely to be present in its process fumes It is di fficult to provide this comprehensive assessment, as there are many variables that influence the composition o f rubber fumes, and that is why methods that have been developed for the measurement o f rubber fumes have targeted a particular fraction o f the fumes (e.g the “visible portion” in the case o f the HSE’s MDHS Method 47) for quantification and have not attempted to carry out a more detailed analysis o f what that fraction is actually comprised o f Based on the in formation derived from this study into rubber fumes and that o f our own research into the subject, it is our considered opinion that the fumes emitted from rubber should not be considered as a single chemical entity, but as a highly complex mixture o f chemical species which varies depending upon the composition o f the rubber compound, the processes by which it is manu factured and the temperatures to which it is exposed during those processes It has been highlighted that rubber products are made from rubber formulations which can be very complex in the type, range and levels o f the ingredients contained within them As a result it is possible to produce an almost many number o f rubber formulations for a given application or product, which in turn will add to the diversity o f the possible volatile chemical species evolved during their manu facture Although the rubber industry is now over 100 years old, research and development work still continues, with objectives constantly under revision to meet current and projected needs and new legislation Existing rubbers continue to be modified, new process methods developed, new additives adopted and novel products designed As a result of these and changes due to legislation, such as the EU Directive 2005/69 (replacement of PAH-rich aromatic extender oils), and reduction in the use of nitrosamine forming additives over more recent years, the composition o f rubber fumes has changed and is likely to continue to change as further progress is made in the rubber industry These changes have resulted in improvements in the protection o f workers in the rubber industry, as have other technological changes, such as the movement away from open mill mixing to the use o f internal mixers, which has reduced their overall exposure to rubber fumes by around % per annum since the 1970s 46 © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) Annex A (informative) Abbreviated terms ACM AEM AU BR CIIR CM CO CPE CR CSM EACM EAM ECO EPDM ETER EU EVA FKM FPM FVMQ HNBR MBT MBTS NR PAH PVMQ ac r yl ic rubb ers e thylene - ac r yl ic terp olymer p olye s ter typ e p olyu re tha ne r ub b ers rubber based on butadiene ch lorobutyl rubb er ch lori nate d p olye thylene epich lorohyd ri n homop olymer ch lori nate d p olye thylene chloroprene rubber ch loro s u l fonate d p olye thylene e thylene - ac r yl ic terp olymer e thylene -vi nyl ace tate epich lorohyd ri n cop olymer with e thylene oxide e thylene -prop ylene ter p olymer epich lorohyd ri n terp olymers p olye ther u re thane e thylene -vi nyl ace tate fluoro ca rb on r ubb er fluoro ca rb on r ubb er fluoro vi nyl me thyl s i l icone hyd ro genate d n itri le r ubb er mercaptobenzothiazole d ib en z th i a z yld i s u l fide natural rubber p olyc ycl ic aromatic hyd ro c arb on phenyl vi nyl me thyl s i l icone © ISO 2017 – All rights reserved 47 ISO/TR 21275:2017(E) SMR TBBS TETD TBZDT TMTD TMQ VMQ ZDBC 48 Standa rd M a lays i an Rubb er N-tert-B utyl-2 -b en z o th i a z ole s u l fonam ide te trae thyl th iu m d i s u l fide te trab en z yl th iu m d i s u l fide te tra me thyl th iu m d i s u l fide p olymeric , ,4 -tri me thyl-1 , - d i hyd ro qu i nol i ne vi nyl me thyl s i l icone z i nc d ibutyl d ith io c arb amate © ISO 2017 – All rights reserved ISO/TR 21275:2017(E) Bibliography [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] Willoughby B.G Chapter on Health and Sa fety In: Developments in Rubber Technology — 4, (Whel an A., & L ee K.S eds.) 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