SILICON CARBIDE 1. Exposure Data Relative molecular mass: 40.097 Synonyms: Carbon silicide; carborundum, a 1.1 Chemical and physical commercial name for silicon carbide abra- sives, is sometimes used as a common name properties for silicon carbide dust; silicon monocarbide 1.1.1 Nomenclature Trade names: Annanox, Betarundum, Carbofrax, Carbogran, Carbolon, Crystar, (a) Silicon carbide fibres Crystolon, Densic, DU-A, Ekasic, Green densic, Halsik, Hexoloy, Hitaceram, Ibiden, Chem. Abst. Serv. Reg. No.: 308076-74-6 Lonza, Norton, Polisher, Shinano Rundum, Chemical name: Synthetic fibres, silicon Sika, Silundum, Sixcy, Supersic, Tokawhisker, carbide Ultrafine (carbide) (CAMEO Chemicals, Synonyms: Ceramic fibres, silicon carbide; 2014) [this list is not intended to be exhaustive]. silicon carbide ceramic; silicon carbide ceramic synthetic fibres; silicon carbide 1.1.2 General description fibres; silicon carbide synthetic fibres Trade names: Dow X; Enhanced Nicalon; Silicon carbide appears in two different crys- Hi-Nicalon; Nicalon NP 1616; SCS 6; SM; talline forms: hexagonal α-silicon carbide is the Sigma; Sylramic; Textron SCS 6; Tokamax; main product, while cubic β-silicon carbide is Tokawhisker S200; Tyranno ZX (Chemical formed at lower temperatures (Føreland et al., Book, 2014). 2008). Silicon carbide occurs in several forms: as “non-fibrous,” as “polycrystalline fibres,” or as one (b) Non-fibrous silicon carbide of more than 150 different single-crystal modi- fications (or polytypes) of “whiskers” (Health Chem. Abst. Serv. Reg. No.: 409-21-2 Council of the Netherlands, 2012). A “whisker” EINECS: 206-991-8 is a type of single-crystal fibre, whereas a “fibre” Chemical name: Silicon carbide may be single- or polycrystalline, or non-crystal- line (ASTM, 2011). IUPAC systematic name: Silicon carbide Non-fibrous silicon carbide or the particulate Chemical formula: SiC (ACGIH, 2003) material – also called silicon carbide dust, silicon Molecular formula: carbide particles, or granular silicon carbide – Si+ C- has an average particle size of 1–20 μm. Exposure to silicon carbide dust can occur during the 243 IARC MONOGRAPHS – 111 manufacture or use of synthetic abrasive mate- Refractive index: 2.650 rials (Health Council of the Netherlands, 2012). Oxidation: Occurs above 700 °C Silicon carbide fibres – also known as silicon Sublimes and then decomposes: 2700 °C carbide continuous fibres or silicon carbide Solubility: Insoluble in water, alcohol, and acid; ceramic fibres, which are mostly polycrystalline soluble in molten alkalis (sodium hydroxide materials (ASTM, 2011) – are unwanted by-prod- or potassium hydroxide) and molten iron ucts of silicon carbide particle production and are considered to be pollutants (Bye et al., 1985; Reactivity: Chemical reactions do not take Dufresne et al., 1987a, b; Bégin et al., 1989; place at ordinary temperatures Scansetti et al., 1992; Dufresne et al., 1993, 1995; Appearance: Variable, exceedingly hard, green Dion et al., 2005; Gunnæs et al., 2005; Skogstad to bluish-black, iridescent, sharp crystals et al., 2006; Føreland et al., 2008; Bye et al., 2009; Odour: None Føreland et al., 2013). The length and diameter of Conversion factor: 1 mg/m3 = 0.5990 ppm at these fibres are variable, but fulfil the definition 20 °C. of WHO fibres (particles > 5 μm with a width of < 3 μm and an aspect ratio of > 3) (Rödelsperger (a) Chemical properties & Brückel, 2006). Fibrous silicon carbide may exist as whiskers Silicon carbide is a crystalline material, the or continuous fibres (Bye et al., 1985). Silicon colour of which is determined by the level of carbide whiskers often have a diameter < 5 μm impurities. Pure silicon carbide is colourless and a length > 20 μm and are thus respirable and transparent. The green to black colour of fibres similar to amphibole asbestos. Silicon the industrial product results from impurities, carbide whiskers are single-crystal structures mostly iron. The green specimen is a somewhat that are cylindrical in shape (ACGIH, 2003). purer, slightly harder, but more friable form Silicon carbide fibres are unwanted by-prod- (Wright, 2006). ucts from the Acheson process and are morpho- Although silicon carbide has a very simple logically heterogeneous, whereas silicon carbide chemical formula, it can exist as numerous whiskers are intentionally produced and have different structures (polytypes) (Shaffer, 1969). homogeneous morphology. Skogstad et al. (2006) These structures are composed of a single basic reported the close resemblance of the morphology unit, a tetrahedral (SiC or CSi ) layer, with 4 4 and size distribution of silicon carbide whiskers different stacking arrangements for silicon and to those of the Norwegian airborne industrial carbon atoms (Kordina & Saddow, 2006; Oliveros by-product fibres used by Stanton & Layard et al., 2013). The distance between the carbon (1978), Stanton et al. (1981) and Johnson et al. and silicon atom is 0.189 nm, and the distance (1992) to carry out in-vivo and in-vitro tests. between the carbon atoms is 0.308 nm (Fig. 1.1; Kordina & Saddow, 2006). 1.1.3 Chemical and physical properties The polytypes are represented by a number showing how many tetrahedra are stacked along From ASTM (1998), ACGIH (2003), Health a specific direction in the unit cell and by a Council of the Netherlands (2012), Chemical letter for the crystal symmetry: cubic (C) and Book (2014) hexagonal (H) (Fig. 1.2). The polytypes of silicon carbide are defined by the stacking order of the Density (specific gravity): 3.22 g/mL at 25 °C double layers of silicon and carbon atoms. The Crystalline form: Hexagonal or cubic polytypes 3C-, 4H-, and 6H-silicon carbide are 244 Silicon carbide Fig. 1.1 Silicon carbide tetrahedron formed by covalently bonded carbon and silicon C C 1.89Å Si Si 3. 0 8 Å The characteristic tetrahedron building block of all silicon carbide crystals. Four carbon atoms are covalently bonded with a silicon atom in the centre. Two types exist. One is rotated 180 ° around the c-axis with respect to the other, as shown. From Kordina & Saddow (2006). Reproduced with permission from Saddow SE and Agarwal A, Advances in Silicon Carbide Processing and Applications, Norwood, MA: Artech House, Inc., 2003. © 2003 by Artech House, Inc. Fig. 1.2 Atomic stacking for silicon carbide polytypes The three most common polytypes in silicon carbide viewed in the [1120] plane. From left to right: 4H-silicon carbide, 6H-silicon carbide, and 3C-silicon carbide; k and h denote crystal symmetry points that are cubic and hexagonal, respectively. From Kordina & Saddow (2006). Reproduced with permission from Saddow, Stephen E, and Agarwal, Anant, Advances in Silicon Carbide Processing and Applications, Norwood, MA: Artech House, Inc., 2003. © 2003 by Artech House, Inc. 245 IARC MONOGRAPHS – 111 the most frequent. The simplest cubic structure (b) Physical properties is referred to as β-silicon carbide, whereas the The physical parameters of fibres (density, hexagonal structure is referred to as α-silicon length, and diameter) as well as their aerody- carbide (Gunnæs et al., 2005). All polytypes have namic behaviour are important factors that affect equal proportions of silicon and carbon atoms their respirability, deposition, and clearance in but, because the stacking sequences between the the respiratory tract (Cheng et al., 1995). planes differ, their electronic and optical prop- (i) By-product fibres from the Acheson process erties differ (Kordina & Saddow, 2006; Wright, and cleavage fragments 2006). Silicon carbide is very stable, but can never- The generation of fibres as a by-product theless react violently when heated with a mixture has been demonstrated during the industrial of potassium dichromate and lead chromate. production of silicon carbide in a Norwegian Chemical reactions between silicon carbide plant (Bye et al., 1985). Characterization of the and oxygen as well as a variety of compounds airborne fibres from the furnace department in (e.g. sodium silicate, calcium, and magnesium the silicon carbide industry showed that more oxides) are possible at relatively high tempera- than 93% of fibres consisted of silicon carbide tures. Indeed, silicon carbide undergoes active fibres which were divided into eight categories or passive oxidation depending on the ambient based on their morphology. In addition, less oxygen potential. Passive oxidation occurs under than 2% of the fibres constituted silicon carbide conditions of high partial pressure of oxygen, fragments probably resulting from the cleavage producing a protective layer of silicon dioxide on of non-fibrous silicon carbide crystals and corre- the surface: sponding to WHO fibres; these fragments were 2SiC (s) + 3O (g) → 2SiO (s) + 2CO (g) mostly found during sorting operations. In the 2 2 [where s = solid and g = gaseous] processing department, 25% of fibres consisted Accordingly, silicon carbide crystals take the of silicon carbide fibres and 57% of cleavage form of a rainbow-like cluster caused by the layer fragments. The geometric mean (GM) length of of silicon dioxide produced by passive oxidation, all fibres > 5 µm was 9.5 µm (range, 5–900 µm) which is determined primarily by the nature and and the GM diameter of all fibres was 0.39 µm concentration of impurities. (range, 0.07–2.90 µm); 33% of the fibres had a Active oxidation takes place under condi- diameter between 0.07 and 0.25 µm, and 15% tions of low partial pressure (30 Pa) of oxygen corresponded to Stanton fibres (length, 8 µm; at 1400 °C and gaseous oxidation products are diameter ≤ 0.25 µm) (Skogstad et al., 2006). The formed: occurrence of silicon carbide fibres was also SiC (s) + O (g) → SiO (g) + CO (g) confirmed in a Canadian silicon-carbide prod- 2 SiC (s) + 2SiO (s) → 3SiO (g) + CO (g) uction factory (Dufresne et al., 1987b; Dion et al., 2 [where s = solid and g = gaseous] 2005). Fresh surfaces of silicon carbide are thus Silicon carbide cleavage fragments are elon- exposed to the oxidizing atmosphere (Wright, gated particles produced by the splintering of 2006), and can be covered largely by silicon larger crystals during the grinding and classifying dioxide film or islets, heterogeneously distributed of silicon carbide. They can be distinguished from at the surface (Dufresne et al., 1987b; Boudard fibrous particles, such as asbestos, glass fibres, et al., 2014). and whiskers, by their irregular shape. Typically they fulfil the WHO criteria for respirable fibres. Even granular or powdered silicon carbide may 246 Silicon carbide Table 1.1 Typical parameters of three characterized types of silicon carbide whisker Type Fibre (total/μg) Percentage of fibres with length Percentage of fibres with > 5 μm diameter < 0.3 μm and length > 8.0 μm SiC-W 1 7.6 × 106 31.0 3.8 SiC-W 2 1.61 × 105 93.7 6.9 SiC-W 3 1.05 × 107 30.8 10.8 SiC-W, silicon carbide whisker Adapted from Johnson et al. (1992), by permission of John Wiley & Sons contain traces of cleavage fragments that fulfil are released during the machining of ceramic the definition of WHO fibres (Rödelsperger & and metal matrix composites (Beaumont, 1991). Brückel, 2006). (iii) Polycrystalline silicon carbide fibres (ii) Synthetic silicon carbide whiskers Polycrystalline silicon carbide fibres (diam- Exposure to silicon carbide whiskers may eter, generally < 2 µm; length, generally ≤ 30 µm) occur during the manufacture of the whiskers or can also be manufactured for commercial during the production, machining, and finishing purposes by various methods (i.e. polymer pyrol- of composite materials (Beaumont, 1991). ysis, chemical vapour deposition, or sintering) Silicon carbide whiskers have diameters of a (Wright, 2006). few micrometres (average, 0.5 µm) and lengths of up to 5 cm (average, 10 µm) and occur mostly 1.2 Sampling and analytical as hair- or ribbon-like crystals (Wright, 2006). methods Because whiskers are single crystals, they frac- ture across and not along the long dimension. The sampling and analytical methods for They meet the dimensional criteria for a fibre silicon carbide fibres are very similar to those (length:diameter (aspect) ratio, > 3) (Beaumont, for asbestos and man-made mineral fibres. Bulk 1991) but can exceed an aspect ratio of 10:1 samples are prepared and ground in an agate (Rödelsperger & Brückel, 2006). Several types mortar to produce fine particles, and further of silicon carbide whisker exist, some of which processed using a mesh or gravimetric sedimen- have been well characterized, and their typical tation in water. This suspension is then filtered parameters are presented in Table 1.1. and mounted for observation using appropriate During the manufacture of discontinuously analytical devices. Air samples are obtained using reinforced composites, silicon carbide whiskers a vacuum pump equipped with a membrane are combined with metal or ceramic powders filter to obtain a representative air volume, and and formed into the desired shape. The metal the filters are then processed for the analytical composites can be extruded, forged, rolled, bent, methods. Biological specimens, such as lung and machined in a fashion similar to the base tissues, lymph nodes, sputum, and bronchoal- alloy. The ceramic composites can be machined veolar lavage fluid (BALF), are digested using on lathes, drill presses, and milling machines sodium hypochlorite or hydrogen peroxide or and finished by abrasive grinding in a manner a combination thereof, and the mineral compo- similar to that of common metals. Some whiskers nents are recovered on a filter for analysis. Tissue 247 IARC MONOGRAPHS – 111 samples can be ashed using a low-temperature is a transparent mineral that is as brilliant and plasma asher, and the ashed solutions are then almost as hard as diamond. Only synthetically filtered for further analysis. produced silicon carbide is used for commercial All the processed samples on the filters applications because natural moissanite is very can be analysed using a phase-contrast optical scarce (Wright, 2006). microscope (PCOM) to count the fibres The available information on history and according to WHO (1997) or National Institute production levels mostly concerns the Acheson for Occupational Safety and Health (NIOSH) production industry, involving mainly powdered method 7400 (NIOSH, 1994a). The sample- and granular silicon carbide particulates. Thus loaded filters can also be mounted on a stub and data on the history and production levels of analysed using scanning electron microscopy silicon carbide fibres and whiskers are limited. with an energy dispersive X-ray analyser (SEM- EDX) (Funahashi et al., 1984; Bye et al., 1985) 1.3.2 Production levels or mounted on a transmission electron micros- The world production capacity of silicon copy (TEM) grid and analysed using TEM-EDX carbide was 1 010 000 tonnes in 2013. Of these, the according to NIOSH method 7402 (NIOSH, Norwegian plants produced 8%, Japan produced 1994b). TEM allows analysis of the crystal 6%, Brazil produced approximately 4%, the structures and identification of the mineral USA and Canada produced 4%, and China was fibres using electron diffraction and comparing the world’s leading producer of abrasive silicon them with reference minerals (Bye et al., 1985). carbide, accounting for 45% of the production Powdered bulk samples can be analysed using capacity (Table 1.3). X-ray diffraction to observe the different crystal- Production and salient statistics for abra- line compounds, based on NIOSH method 9000 sive silicon carbide in the USA and Canada for (NIOSH, 1994c). To obtain the weight percentage 2013 are shown in Table 1.4. Silicon carbide was of silicon carbide or other amphiboles, standards produced by two companies at two plants in the for silicon carbide should be prepared. Selected USA, and bonded and coated abrasive prod- methods for the analysis of silicon carbide fibres ucts accounted for most abrasive uses of silicon in various matrices are presented in Table 1.2. carbide (USGS, 2014). [These data were not avail- able for other countries.] 1.3 Production and use During 2009–12, the USA imported 72% of the silicon carbide demand mainly from China 1.3.1 History (58%), South Africa (17%), the Netherlands (7%), Silicon carbide was first created syntheti- Romania (7%), and others (11%) for crude prod- cally by Edward Acheson in 1891 by heating ucts, and China (44%), Brazil (24%), the Russian quartz sand and carbon in a large electric Federation (8%), Norway (7%), and others (17%) furnace. Acheson called the new compound for grains. About 5% of silicon carbide is recycled “carborundum”, which became a trademark (USGS, 2014). for a silicon carbide abrasive (Encyclopaedia Britannica, 2014). Subsequently, in 1905, silicon carbide was observed in its natural form by the chemist Henri Moissan, in a meteor crater located in Canyon Diablo, Arizona, USA. Moissanite, named in honour of its discoverer, 248 Silicon carbide Reference   Governa et al. (1997) Johnson et al. (1992), Governa et al. (1997), Yamato et al. (1998) Johnson et al. (1992) HSE (1995, 1988), Miller et al. (1999) WHO (1985), Miller et al. (1999), Rödelsperger & Brückel (2006) Cheng et al. (1995) Governa et al. (1997)   Akiyama et al. (2003, 2007) Bye et al. (1985), Skogstad et al. (2006) Bye et al. (1985) Scansetti et al. (1992), WHO (1997); Dion et al. (2005), Føreland et al. (2013) Dufresne et al. (1987a), NIOSH (2003), Dion et al. (2005), Bye et al. (2009) Føreland et al. (2013) Scansetti et al. (1992), NIOSH (1998) Bye et al. (2009), Føreland et al. (2013) Cheng et al. (1995) Plinke et al. (1992)   Hayashi & Kajita (1988), Dufresne et al. (1995) Funahashi et al. (1984), De Vuyst et al. (1986) Akiyama et al. (2003, 2007) Davis et al. (1996) Dufresne et al. (1992) ss median aerodynamic diameter; MRI, Midwest ng electron microscopy; TEM, transmission atrices Detection limit   NR NR NR 0.01 fibres/mL NR NR NR   NR NR NR 13 fibres/mm2 0.005 mg per sample 12 μg 0.06 mg NR NR   NR NR NR NR NR ose esters; MMAD, maffraction; SEM, scanni d methods of analysis of silicon carbide fibres in various m Sample preparationAssay method    Direct transfer to SEM-stubSEM-EDX Suspension filtration; mounting on SEM stubSEM-EDX Suspension filtration; mounting on TEM gridTEM-EDX Deposition of fibrous dusts onto filterPCOM Deposition of fibrous dusts onto filterSEM Powder (for density)Helium pycnometer Powder (for surface area)BET    Direct reading instrumentDust monitor Polycarbonate filter (25 mm, 0.4 μm pore)SEM-EDX MCE filter (25 mm, 0.3 μm pore)TEM-EDX-SAED MCE filter (25 mm, 0.8–1.2 μm pore)PCOM Sampling with nylon cyclone (or HD cyclone, or XRDaluminum cyclone); ashing with plasma asher; redeposition on silver membraneXRD MCE filter (37 mm, 5 μm pore) with cycloneGravimetry Aerosol generation by small scale particle disperserCascade impactor (MMAD) Heubach, MRI dustiness testerCascade impactor (dustiness)    Digestion with sodium hypochlorite, hydrogen TEM-EDXperoxide or low temperature ashing SEM-EDX Digestion and filtrationXRD  SEM  TEM-EDX Teller; EDX, energy dispersive X-ray analyser; HD, Higgins–Dewell; MCE, mixed cellulot reported; PCOM, phase-contrast optical microscopy; SAED, selected area electron diD, X-ray diffraction Table 1.2 Selecte Sample matrix Bulk samples               Air samples             Biological samples Human lung and bronchoalveolar lavage fluid Animal lung     BET, Brunauer–Emmett–Research Institute; NR, nelectron microscopy; XR 249 IARC MONOGRAPHS – 111 Table 1.3 World production capacity for Table 1.4 Production volume and salient silicon carbide in 2013 statistics for abrasive silicon carbide in the USA and Canada, 2013 Country Production capacity (tonnes) China 455 000 Salient statistic Amount (tonnes) Norway 80 000 Production, USA and Canada (crude) 35 000 Japan 60 000 Imports for consumption (USA) 108 000 Mexico 45 000 Exports (USA) 17 700 Brazil 43 000 Consumption, apparent (USA) 125 000 USA and Canada 42 600 Compiled by the Working Group with data from USGS (2014) Germany 36 000 Venezuela 30 000 carbon monoxide according to the following France 16 000 Argentina 5 000 overall reaction: India 5 000 SiO + 3C → SiC + 2CO (Føreland et al., 2008) 2 Other countries 190 000 The Acheson furnace is heated by a direct World total (rounded) 1 010 000 current passing through powdered graphite Compiled by the Working Group with data from USGS (2014) within the charge mixture (Fig. 1.4). The furnace is fired for 40–48 hours, during which temper- 1.3.3 Production methods atures in the core vary from > 1700 to 2700 °C, Silicon carbide is intentionally manufactured and is < 140 °C at the outer edge. Silicon carbide by several processes depending on the levels of develops as a cylindrical ingot around the core, purity, crystal structure, particle size, and shape with radial layers growing from graphite in the required. inside (which can be recycled to the next furnace) to hexagonal α-silicon carbide (the highest grade (a) Acheson process material with a coarse crystalline structure, 98% The Acheson process is most frequently silicon carbide), cubic β-silicon carbide (metal- used for the production of silicon carbide by the lurgical grade, 90% silicon carbide), firesand (80% carbothermal reaction of a mixture of petroleum silicon carbide, recycled to the next furnace), the coke (carbon) and high purity crystalline silica crust (a condensation layer of silicon dioxide (quartz) in an open electrical resistance furnace and other oxide impurities), and finally partly (Gunnæs et al., 2005). A silicon carbide plant and unreacted material (sand and coke) on the can be divided into four different departments: outside (Saint-Gobain, 2014). material storage, preparation areas, the furnace After the heating cycle, the furnace is disas- department where the crude silicon carbide is sembled and the side walls are removed to allow produced, and the processing department where cooling (up to 2 weeks). A cross-sectional view the silicon carbide grits are manufactured, as of the resistor furnace after cooling is given in presented in Fig. 1.3 (Føreland et al., 2008). Fig. 1.5 (Indian Institute of Science, 2014). Sawdust is occasionally added to the mixture The outer layer of non-reacted mixture is to reduce its density, to facilitate the escape removed from the crude and returned to the mix of evolved gaseous carbon monoxide, and to area, exposing the core of green or black silicon improve the porosity of the furnace mix (Smith carbide crystals. The crude silicon carbide is et al., 1984; Føreland et al., 2008). Silica reacts transported to the sorting area where β-silicon with carbon to produce silicon carbide and carbide is removed from α-silicon carbide. The final α-silicon carbide product is an aggregate of 250 Silicon carbide Fig. 1.3 Flow diagram depicting production of silicon carbide by the Acheson process SiC, silicon carbide Reproduced from Føreland et al. (2008). Føreland S, Bye E, Bakke B, Eduard W, Exposure to fibres, crystalline silica, silicon carbide and sulfur dioxide in the Norwegian silicon carbide industry, Annals of Occupational Hygiene, 2008, volume 52, issue 5, pages 317–336, by permission of Oxford University Press 251 IARC MONOGRAPHS – 111 Fig. 1.4 The Acheson furnace and the crude silicon carbide product SiC, silicon carbide; CO, carbon monoxide Reproduced from Føreland (2012), with permission of the author iridescent crystals, due to a thin layer of silica when a blow of gas escapes the baking lump of from superficial oxidation of the carbide, which silicon dioxide–petroleum coke in the electric is transported to the processing department for furnace (Bégin et al., 1989). Different morphol- crushing, grounding, magnetic and chemical ogies of fibrous silicon carbide in this layer have treatments to remove impurities, and screening been observed by SEM and TEM (Gunnæs et al., into the size required for the end-use (Wright, 2005; Skogstad et al., 2006). The high concen- 2006; Føreland et al., 2008). Two different types tration of fibres during the handling of the raw of silicon carbide crystal may be obtained: green material is consistent with the fibres encountered silicon carbide is the purest material with > 99% in recycled material. Silicon carbide fibres have silicon carbide, while the black material contains not been observed in the final abrasive products, ~98% silicon carbide (Bye et al., 2009). but have been observed in products for refractory and metallurgical purposes (firesand) (Føreland Formation of silicon carbide fibres et al., 2008; Bye et al., 2009; Bruch et al., 2014). Silicon carbide fibres are formed during the In addition to silicon carbide fibres (including Acheson process in the intermediate region, whiskers), the production of silicon carbide where the partly reacted material is found (Bye generates many airborne contaminants including et al., 1985). The fibres are believed to be formed 252