Diamond, Carbon, Coke, Graphite

Home , Amorphous carbon, Carbon black, Coke (fuel), Graphite, Synthetic diamond

REACh Contribution to the ongoing consultation on Risk Assessment of Nanotechnologies – A1.a Submitted to DG SANCO by Dr. Harald Tillmanns PRO-Coaching GmbH

SUMMARY

The objective of the studies is to find a reliable and science based definition to distinguish between bulk C- materials and nano scaled C-materials. Even if both substances are formed from the same element C, they can be differentiated by chemical and/or physical properties e.g. like structural pattern and especially by their formation mechanism.

Objective is to separate and focus the obligation of evaluation on those substances which need to be studied on detail due to their intrinsic hazardous properties. Substances, even build up out of the same elements may significantly differ in there potential intrinsic properties and those which are proofed to be inert having no intrinsic hazardous properties.

To distinguish between bulk type materials and nano scaled materials is needed any way, because otherwise the results of the data evaluation can not be interpreted nor understood. Furthermore it will lead to a confusion, while the bulk C materials are showing no hazardous properties whereas the nano scaled C material might show certain hazardous properties. As tools can be used e.g. physical and /or chemical properties like x-ray pattern and/or the formation mechanism for the interpretation of the results of the evaluation. This study is focused on substances formed out of the element C manufactured in bulk form (minimal particle size 1 – 10 µm by technical milling) respectively in C nano scaled the particles (< 1 up to 100 (500) nm maximum by a frozen nucleation mechansm).

© Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 1 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns REACh Contribution to the ongoing consultation on Risk Assessment of Nanotechnologies – A1.a Submitted to DG SANCO by Dr. Harald Tillmanns PRO-Coaching GmbH . Due to the sufficient reliable differentiation by physical and/or chemical properties (e.g. like crystal / molecular structural orientation detectable by x-ray analysis) and/or formation mechanism they have to be evaluated and handled separately in respect to the obligations of the REACh regulations: • Synthetic bulk C materials (All forms of synthetic diamond / coke / carbon / charcoal / graphite) should be included in Annex V due to their intrinsic non hazardous properties, • Naturally occurring substances (e.g. like diamonds, carbon and graphite) are exempted already by the Annex V, whereas • Nano scaled C-materials have to be evaluated separate probably under the umbrella of carbon black due to their similarity in properties and formation mechanism. Remark: The EINECS # is not a suitable tool for separating and/or grouping substances, it is only a code saying that the substance is listed as an existing substance, regardsless of there properties. It can only be used like the CAS # for identification)

All studies reported here, where mainly focused on different substances formed by the element C.

For most types of initially nano C materials are below the threshold limit of 1 t/a in Europe and therefore not included in any obligations of REACh, The volumes > 1 t/a, covered by REACh obligations, are carbon-black and nano tubes of carbon and fullerene

Whether these tools are applicable for other substances needs further studies, but for some of them (e.g. TiO2) a frozen nucleation process in a solution is described in literature. © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 2 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns REACh Contribution to the ongoing consultation on Risk Assessment of Nanotechnologies – A1.a Submitted to DG SANCO by Dr. Harald Tillmanns PRO-Coaching GmbH

Conclusion

The different substances should be grouped, where possible, so that read-across principles can be used, following the scheme • carbon materials initially forming nano scaled particles (fullerene, C-nanotubes, carbon black, graphene foam) and • carbon material initially forming bulk scaled particles (diamond, carbon, coke, graphite) while being manufactured or naturally formed have different structural orientation (by x-ray) ------The bulk scaled carbon materials could be separated further in • mono-constituent substance - synthetic processed materials (diamond / coke- (petroleum / coaltar / coaltarpitch) / coke calcined / charcoal / carbon / graphite) and • mono- or multi constituent substance - naturally sourced materials (diamond / carbon (e.g. coke coal / anthracite / charcoal ?) / natural graphite) All bulk C – substances can be differentiated e.g. by x-ray analysis from the nano-scaled C-substances as well as by there formation mechanism and the intrinsic properties. ------A grouping of C substances by a C – nano C substances manufacturer is published and separates between diamond / graphite / fullerene and nano tubes - see next table.

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Several types of carbon from the point of view of a C-nano tube manufacturer

Diamond, a transparent mineral Chemical bonds between atoms are strong, and the tetrahedral symmetry is that of a dense and isotropic material. It is an electrical insulator, and the best refractory and thermal conductor known.

Graphite, a black and friable mineral I ts structure consists of layers stacked together, each formed of regular hexagons of carbon atoms. This structure is 1/3rd weaker than that of diamond, making graphite an anisotropic and virtually two-dimensional solid. The layers are connected together by weak forces, and slip easily over one another. It is a semi-metal within the layer, with little conductivity in the other direction.

Fullerene, or Buckminsterfullerene This molecule consists of 60 carbon atoms placed at the top of a regular polyhedron whose sides are hexagons or pentagons. Fullerene is electrophilic. It features high resistivity (approximately 1014 O/cm). Fullerene has a few applications, including microporous filters, sample supports for electronic microscopes, lubricants, etc.

Carbon nanotubes Carbon nanotubes are a closed pipe-shaped material consisting of crystallized carbon. The length of the nanotubes can reach several microns, while their diameter ranges from 1 nm to 60 nm. The nanotube is represented by a graphene sheet wrapped or coiled based on a reference axis and direction. The helix angle (helicity) is variable, ranging from 0° to 30°. Nanotubes are closed by distortion of the hexagons, and by the introduction of pentagons in the nanotube structure. There are several types of nanotubes. Nanotubes are structured into single walls (Single Wall Nano Tubes, SWNTs) or multi walls (Multi Wall Nano Tubes, MWNTs). The tubes nest within one another, with the distance between the walls close to the distance between two graphite planes (0.34 nm). Both structures are the result of different synthesis conditions.

Reference: http://www.arkema.com/sites/group/en/products/spotlight/nanotubes1.page

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In the past I send already several contributions on the discussion of carbon respectively graphite bulk materials and the differences in structure of bulk C-substances and the significant different structure e.g. of nano-scaled C-materials like e.g. fullerens / nanotubes / graphene / graphene foam and others. (see up dated attachement)

Crystal structures of the different allotropes of carbon. (Left to right) Three-dimensional diamond and graphite (3D); two-dimensional graphene (2D); onedimensional nanotubes (1D); and zero-dimensional buckyballs (0D). (Adapted and reprinted with permission from66. © 2002 Prentice Hall.)

Reference: Hill, J. W., and Petrucci, R. H., General Chemistry, 3rd edition, Prentice Hall, NJ, (2002)

A more detailed table of structural orientation is given in the next diagram.

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Substance Isotropy %sp? Symmetry 3D Diamand : La = Lb = Lc sp3 tetrahedral 3D Glassy carbon / Carbon Foam sp2sp3 3D Graphite : La = Lb <> Lc sp2 regular hexagons La 2D Graphene : La = Lb sp2 regular hexagons 1D? Nanotubes : Lb <> La = Lc sp2 hexagons, (+pentagons) 0D Fullerene : La = Lb = Lc sp2 hexagons+pentagons

New investigations on further studies on the structure of the different types of C-materials showed that this can be proofed e.g. by x-ray analysis:

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• graphite is a stack of more or less perfect plane layers, 3 dimensional structred where the orientation in the direction La = Lb are the same and may only differ in there extension. The orientation in Lc is defined by the number of stacked layers and an average interlayer distance of 3,35 up to < 3,44 Angstroem. Which can be characterised by x-ray diffraction pattern. • carbon or amorphous respectively isotropic or glassy oriented carbons can be described also by a 3 dimensional structure with an average interlayer distance greater than 3,44 Angstreom. The perfect isotropic (-structure is called diamond. therefore all natural respectively synthetic carbons respectively graphite materials are located somewhere between a single crystal graphite structure and a diamond structure.

The structure of so called bulk carbons / graphite differ clearly and detectable by structural key data from so-called nanoscaled C-substances / molecules . Here a few e.g. • fullerene are isotropic ball like structure of single or multilayer structure with equal structure orientation La=Lb=Lc • nanotubes are anisotropic structure of concentric tubes with an orientation of La=Lc and a different orientation in Lb varying in the extension. • graphene and graphene foam exist of mono layer element with LA=Lb and Le=1

This demonstrates that bulk C – substances e.g. like diamond / carbon / coke / charcoal / graphite and nano scaled C – substances e.g. like grapheme / fullerene / C – nanotubes (both single and multi walled) / and carbon black have defined different structural orientation and formation mechanism explained on detail in the following diagrams. © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 7 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns REACh Contribution to the ongoing consultation on Risk Assessment of Nanotechnologies – A1.a Submitted to DG SANCO by Dr. Harald Tillmanns PRO-Coaching GmbH

Bulk carbon / graphite > 1 -10µm Nano - C < 1 – 100 nm (initial particle size) Diamond Solid carbon Graphite Carbon black Nano-C Graphene: Natural (Natural ?) Natural Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic

Solid state Liquid phase Solid state Only by gas- / vapour- phase Only by gas- / process or solid state process out nucleation process. vapour- phase out of graphite process out of of pre-oriented catalytic at ultra high Hydrocarbons by solid carbon by Only gas- / vapour- phase catalytic metal surface -pressure, heat treatment heat treatment metal surface nucleation nucleation -temperature

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Glassy carbon Macro-, Carbon black Nanotubes, Single layer, Carbon foam Micro- Fullerene, graphene foam (solid shapes) granular (Single walled, (agglomerate of Isotropic coke or Multi walled) single layers) Regular coke single Nano-C others Needle coke crystal, Particle size limitations based on technical manufacturing processes A mechanical down sizing of The mechanism to form nano scaled C bulk C materials by materials is basically different . technical means of grinding and Nano C-particles, in an initially size range of milling is only possible down to < 1 to 100 nm are only formed by nucleation. minimal 1 to 10 µm Particles up to 500 nm are formed by agglomeration

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Glassy carbon Macro-, Carbon black Nanotubes, Single layer, Carbon foam Micro- Fullerene, graphene foam (solid shapes) granular (Single walled, (agglomerate of Isotropic coke or Multi walled) single layers) Regular coke single Nano-C others Needle coke crystal, Proposal for including in Annex V or substance grouping according to REACh Bulk carbon and graphite substances are or should be The nano scaled C substances don’t have a tetrahedral (diamond–sp2) included in Annex V. due to the fact that they structural hexagonal / rhombohedral (graphite-sp3) structure. orientation (e.g. x-ray diffraction) are different nd they Nano scaled C substances can be differentiated from bulk-C (diamond / have no intrinsic hazardous properties as proofed by carbon / graphite) by there structural orientation (e.g. x-ray known medical applications and biocompatibility pattern). Any assumed hazardous properties are nano size related

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Glassy carbon Macro-, Carbon black Nanotubes, Single layer, Carbon foam Micro- Fullerene, graphene foam (solid shapes) granular (Single walled, (agglomerate of Isotropic coke or Multi walled) single layers) Regular coke single Nano-C others Needle coke crystal, Proposal for including in Annex V or substance grouping according to REACh Bulk carbon and graphite substances should be included Nano scaled C substances can be differentiated from bulk-C . in Annex V Any assumed hazardous properties are nano size or molecular structure related. Natural graphite is a mineral and exempted - Annex V Might be grouped, according to the principle of sameness with carbon black. Synthetic bulk-carbon / -graphite should be exempted QSAR (carbon black / nano-C) might be applied. and has to be added to - Annex V equivalent to coke This needs further investigations

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Spectral data, crystalline structures (e.g. detectable by X-ray diffraction as well as different formation mechanism are applicable as identifiers according to RIP 3.10

RIP 3.10 Guidance on substances identification -- UVCB 4.2.3 Substances of defined chemical composition and other main identifiers Some substances (e.g. inorganic minerals) which can be identified by their chemical composition need to be specified by additional identifiers to get their own substance identification. These substances can be either mono-constituent substances or multi-constituent substances, but need, in addition to the substance identification parameters described in the previous chapters, other main identifiers to record the substance identity unequivocally.

4.2.3.2 Identifiers These substances are identified and named according to the rules for mono- constituent substances (see Chapter 4.2.2) or multi-constituent substances (see Chapter 4.2.3). The other specific main identification parameters to be added depend on the substance. Examples of other main identifiers can be elemental composition with spectral data, the crystalline structure as revealed by X-ray diffraction (XRD), Infra Red absorption peaks, swelling index, cation exchange capacity or other physical and chemical properties. © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 12 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns REACh Contribution to the ongoing consultation on Risk Assessment of Nanotechnologies – A1.a Submitted to DG SANCO by Dr. Harald Tillmanns PRO-Coaching GmbH

Modelle zum Aufbau von C-Nanomaterial aus Graphene-Elementen und deren mögliche Verwandschaft zu Ruißen

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For all other types of nanoscale C-substances comparable differentiations in the orientation can be described and proofed by x-ray measurement. Considering the differences which can be detected by X-ray measurement leads clearly to the result that all types of nanoscaled C-substances can and have to be evaluated as independent, individual substance. Newer results show that typical structural characteristics of nanosclcd C-substances are found in low concentrations in carbon black. Further structural investigations (e.g. X-ray have to proof where nanoscaled C-substance may grouped with carbon black. A further indication that nanoscaled C-substances have to separated in the grouping from graphite respectively from carbon are: • bulk type carbon and graphite substances are formed in a liquid or solid phase thermal decomposition process and can be mechanically reduced by mechanical means in grain size down to min. 1 to 10 µm • C - nanoscaled substances are formed by a frozen nucleation process in respectively out of the gas or vapour phase or on a catalytically initiated nucleation process building defined molecular structure ”molecules” of a similar atom orientation. Freezing the nucleation means stopping the growth of particles by quenching . C nano scaled substances including single - and multi walled nanotubes and fullerens vary in their molecular weights and in their particle size from < 1nm up to max 100 nm. Larger sized particles ( up to ~ 500 nm) are generally formed by are agglomeration of initially formed nanoscaled particles of < 100 nm.

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Therefore based on x-ray structure studies a grouping of defined nanoscaled C-substances with bulk type carbon respectively graphite is not based on natural science facts. Bulk and nanoscaled C substances do not meet the demands of REACh definitions of an acceptable sameness. Both types of C-materials and have to be evaluated and handled separately as individual substances according the REACh regulation..

The differents of X-ray pattern and diffraction to distinguish between typically bulk C – substances and nano scaled substances are demonstrated in the next two diagrams

Probably it is acceptable to group the nano scaled C-substances with carbon-black

Whether a comparable differentiation in structural and/ molecular characterisation for other materials e.g. TIO2 is applicable has to be investigated.

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Naturally occurring graphite Synthetic graphite

Amorphous carbon (poor graphitizing)

Ref.: Dr. H. Tillmanns, Ph. Thesis, 1970 –1975, Dissertation (1975) E. Fitzer, Funk, F. Rozploch 4th London Int. Carbon & Graphite Conf. (1974)

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(a) (b) (c)

(d)

Ref.: (a) SWNT bundles (b) MWNT’s (c) Fullerene C60

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ATTACHMENT

D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH

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SUMMARY

REGULATION (EC) No 1907/2006 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL Article 2 Application

7. The following shall be exempted from Titles II (REGISTRATION OF SUBSTANCES) , V (DOWNSTREAM USERS) and VI (EVALUATION):

(a) substances included in Annex IV, as sufficient information is known about these substances that they are considered to cause minimum risk because of their known intrinsic, none hazardous properties;

(b) substances covered by Annex V, as registration is deemed inappropriate or unnecessary for these substances and their exemption from these Titles does not prejudice the objectives of this Regulation; ------Substance Name CAS# EINECS# Considered bulk forms of Carbon materials (defined i.e. X-ray pattern and the formation mechanism in liquid phase / solid state) Diamond *) 7782-40-3 231-953-2 Graphite 7782-42-5 231-955-3 Carbon 7440-44-0 231-153-3 Coke (coal) **) 65996-77-2 266-010-4 Coke (petroleum), calcined 64743-05-1 265-210-9 Considered nano forms of Carbon materials (defined i.e. X-ray pattern and the formation mechanism frozen nucleation) Carbon black 1333-86-4 215-609-9 Carbon nano materials as such i.e. Fullerene, Nanotubes, Graphene foam 99685-96-8 (Fullerene) n.a. *) Diamond as such is not considered here on detail. **) Including i.e. Charcoal, Lignite Coke

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Proposal for a schematic classification of carbon materials according to the crystal structure and initially manufuctered particle size (bulk scaled / nano scaled) and the mechanism of formation

Proposal for a schematic classification of carbon materials

Manufactured Inital C-Group (structure) Name CAS# EINECS# Annex Particle Size Synthetic Diamond (sp3) Diamond 7782-40-3 231-953-2 carbon material, Intermediate C (sp3 - sp2) Coke (petroleum), calcined64743-05-1 265-210-9 IV mono constituent Intermediate C (sp3 - sp2) Carbon 7440-44-0 231-153-3 substance Graphite (sp2) Graphite 7782-42-5 231-955-3 Initial bulk carbon material Natural Diamond (sp3) Diamond 7782-40-3 231-953-2 IV carbon material Intermediate C (sp3 - sp2) Coke (coal) *) 65996-77-2 266-010-4 IV mono- or multi- 3 2 Carbon constituent Intermediate C (sp - sp ) 2 substance Graphite (sp ) Graphite *) 7782-42-5 231-955-3 IV Carbon material

Initial Carbon black (sp3 - sp2) Carbon black 1333-86-4 215-609-9 ? nano scaled carbon material i.e. Fullerene, Nanotubes Fullerene 99685-96-8 n.a. ?

*) It might by suitable to identify the bulk, natural carbon material as mono-constiuent or as multi- constituents or as naturally occurring substances. in accordance with RIP 3.10 Figure 4.1 and section 4.2.3; containing inorganic constituents, i.e. like silca (quartz) or other minerals in excess over 20 %

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The objective of the comments is to support the experts in finding a reliable and practible conclusion in grouping and read-across approach for the different forms of solid carbon materials and to distinguish between bulk scaled and nano scaled substances in respect to include carbon & graphite (synthetic and natural) in Annex V and to register nano scaled carbons separately under the umbrella (sub grouping with) carbon black.

Conclusion The different substances should be grouped, where possible, so that read-across principles can be used, following the scheme • carbon materials initially forming nano scaled particles (fullerene, C-nanotubes, carbon black) and • carbon material initially forming bulk scaled particles (diamond, carbon, coke, graphite) while being manufactured or naturally occurring. ------The bulk scaled carbon materials could be separated further in • mono-constituent substance - synthetic processed materials (diamond / coke (petroleum) calcined / carbon / graphite) and • mono- or multi constituent substance - naturally sourced materials (diamond / coke (coal) / natural graphite) if the content of inorganic constituents, i.e. like silca (quartz) or other defined minerals exceed the impurity level or an individual evaluation of hazard properties of one of the constituent can not be neglected the substance can be classified as multi constituent substance. ------© Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 3 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH -

Sufficient information are known about all solid carbon containing substances that they are considered to cause minimum risk because of their intrinsic, non hazardous properties. Other forms of bulk carbon materials like “coke (petroleum) calcined”and “coke (coal)” and comparable forms show similar inherent inert properties like carbon and graphite. Therefore bulk carbon and graphite should be treated similar to coke and be exempted in Annex V. The only differences in carbon is the precursor (technical hydrocarbons i.e. like polymers and/or resins (cured and uncured) respectively natural forms of hydrocarbons i.e. like lignite / wood / nutshells). The precursor for graphite is a pre-oriented carbon or coke transferred only by high temperature treatment into more or less perfect layer structure of graphite

Reported hazardous properties are only related to the presents of mineral constituents i.e. like silica (quartz) in naturally occurring substances like natural graphite (exempted in Annex V) and are not reported for any form of synthetic bulk carbon and graphite materials as such.

• All forms of bulk carbon materials as such should be grouped and be listed in Annex V due to their inherent inert properties of solid bulk carbon materials. • Nano scaled structured C-substances can can be distinguished from the bulk form by crystal structure analysis (i.e. X-ray diffraction and there formation mechanism. All nano scaled forms of carbon needs to evaluated separately and might be handled as a separated sub-group of carbon black, due to the similarity in properties and formation mechanism. ------

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Initial particle size while formed

Bulk Carbon

Carbon black Diamond Carbon Nano Carbon Coke (coal) Coke (petroleum), calcined Graphite 0,1 1 10 100 1000 10000 100000 1000000

Initial particle size [nm] Dr. H. Ti

The structure of nano scaled carbons i.e. like fullerene and C-nanotubes including multilayer C-nano materials are still distinct molecules in a wide variety of molecular weight, better comparable to individual primal particles of carbon black powders and their principles of formation are similar (frozen nucleation i.e. in the gas or vapour- phase).

Therefore fullerenes and other C-nano materials should not be grouped with graphite, but with carbon black. Ref.: http://de.wikipedia.org/wiki/Kohlenstoff and numerous links to all forms of carbon materials are available in wikipedia and citied literature Ref.: Numerous articles, MSDS and producer informations have been evaluated by Dr. H. Ti

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Overview of information in the submission Additional information submitted Substance Ref. Effect on Ref. Compliance ……. Remarks submitted see Ref. # Effects evaluation Value of endpoints references attached listed reported in Carbon-C 7.7 Water solubility IUCLID/ Not soluble In all C-related MSDS reporting: (CAS# 7440-44-0) QSAR Sw: 22mg/L (25 deg C) Insoluble / neclectable 1) MSDS’s 428.,49 mg/l (25 deg C, est) QSAR only very limited applicable Carbon-C 8.1 Skin irritation MSDS May cause mild irritation and

redness Carbon-C 8.2 Eye irritation May cause mild irritation and

redness Carbon-C 8.3 Skin sensitisation Expert Not anticipated to be sensitising

judgement Carbon-C 8.4 Mutagenicity OECD Not genotoxic Carbon-C 8.5 Acute toxicity OECD LD0 rat oral 8000-10000 mg/kg No acute toxic effect reported. bw (carbon black) Graphite is used as pharma-ceutical / 2) Lit. medical implant Carbon-C 8.6 Repeated dose Carbon is used as pharmaceutical / toxicity medical implant / 3) Lit Very high biocompatibility Carbon-C 8.9 Carcinogenicity) Carbon is not listed as carccinogen in MSDS IARC nor in IUCLID dataset nor in 4) IARC – no NTP, OSHA or ACGIH NTP – no Carbon-C 9.1 Aquatic toxicity Acute EC/LC50 > 1000 mg/l or A more detailled evaluation of testing Sw NOEC > 10 mg/l results shows no toxic effect but, only 5) Expert Contradictive to: physical / mechanical impact judgement see position 8.5 + 8.6 + 8.9.1 Carbon is used in drinking water *) see compliance of graphite treatment Carbon-C 9.2 Degradation No degradation in the environment Ancient carbon findings – unchanged Carbon-C 9.3 Fate and behaviour No impact on the environment Expert in the environment Ancient carbon findings – no impact 6) judgement Carbon-C 9.4 Effects on errestrial No impact on terrestical organisms organisms Ancient carbon findings in the ground

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Overview of information in the submission Additional information submitted Substance Ref Effect on Ref. Compliance ……. Remarks submitted see Ref. # Effects . evaluation Value of endpoints references attached listed reported in Graphite-C 7.7 Water solubility In all C-related MSDS reporting: MSDS’s (CAS# 7782-42-5) Insoluble / neclectable 1) Graphite-C 8.1 Skin irritation MSDS May cause mild irritation and Compliance shoul be the same as for

redness Differs from graphite carbon *) Graphite-C 8.2 Eye irritation May cause mild irritation and Compliance shoul be the same as for

redness Differs from graphite carbon *) Graphite-C 8.3 Skin sensitisation Expert not anticipated to be sensitising Graphite-C 8.4 Mutagenicity judgement not anticipated to be sensitising Graphite-C 8.5 Acute toxicity MSDS Dust is irritating to the No acute toxic effect reported. respiratory tract Graphite is used as pharma-ceutical / 2) Lit Inhalation medical implant Graphite-C 8.6 Repeated dose MSDS Prolonged inhalation of excessive Graphite is used as pharmaceutical / toxicity dust may produce pulmonary medical implant disorders, 3) Chronic inhalation exposure to Toxicity effect is related the quartz Lit.. natural graphite is associated content if natural geaphite not to **) with the development of graphit itself. pneumoconiosis Synthetic graphite no effect Graphite-C 8.9 Carcinogenicity MSDS *) IARC : Group 1 carcinogen, NTP Graphite is not listed in IARC nor in 4) MSDS suspect carcinogen IUCLID dataset nor in NTP, OSHA IARC – no or ACGIH **) NTP – no

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Overview of information in the submission Additional information submitted Substance Ref Effect on Ref. Compliance ……. Remarks submitted see Ref. # Effects . evaluation Value of endpoints references attached listed reported in Graphite-C 9.1 Aquatic toxicity Acute EC/LC50 > 1000 mg/l or A more detailled evaluation of testing Sw NOEC > 10 mg/l results shows no toxic effect but, only 0) Expert physical / mechanical impact judgement Contradictive to: Carbon is used in drinking water 5) see position 7.7 + 8.5 + 8.6 + 8.9.1 treatment Graphite-C 9.2 Degradation No degradation in the environment Ancient carbon findings - unchanged Graphite-C 9.3 Fate and behaviour No impact on the environment Expert in the environment Ancient carbon findings – no impact 6) judgement Graphite-C 9.4 Effects on terrestrial No impact on terrestical organisms organisms Ancient carbon findings in the ground Hazardous properties identified are *) possible related to content of quartz **) only related to quartz

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0) General remarks No access to the references listed in the overview of information in the submission. No detailled crosscheck are possible. Contradictive statement of compliance, even if the values of endpointsare the same (see carbon & graphite)

1) Water solubility: Different forms of carbon materials are reported in all checked MSDS as insoluble or immiscible COLLOIDAL GRAPHITE: Solubility in Water IMMISCIBLE Ref.: http://www.setonresourcecenter.com/msds/docs/wcd00007/wcd0077c.htm <>/GRAPHITE GRADES :Solubility in Water INSOLUBLE Ref.: http://www.setonresourcecenter.com/dtSearch/dtisapi6.dll?cmd=getdoc&DocId=1297... Coke: SOLUBILITY IN WATER Not Soluble Ref.: MSDS Oxbow Calcining LLC Natural graphite: SOLUBILITY IN WATER Insoluble. Ref.: MSDS WEST SYSTEM® 423™ Graphite Powder.

2) Acute Toxicity: “This product (Coke) is nontoxic. The “nuisance dust” exposure values that are listed apply to any inert substance capable of producing airborne particulates. Excessive concentrations of calcined petroleum coke may reduce visibility, cause unpleasant deposits in the eye, ears, and nasal passages, or irritate the skin or mucous membranes by mechanical means. However, normal workplace exposure has not been determined to cause a significant health effect. Calcined petroleum coke, as with many petroleum products, may cause minor skin, eye, or lung irritation, but good hygienic practices can minimize these effects.” Ref.: www.oxbow.com/text/MSDS_COKE.pdf

3) Biocompatibility of carbon and graphite:. “Carbon Particles (CP) - Diamond Powder Particles (DPP) and Graphite Particles(GP) have been examined on molecular, macroscopic and clinical level. ……….. In vivo examinations with Carbon Particles (GP & GP) proved the biocompatibility with living organism ( the contact reaction with peritoneum) and these results indicate that only DPP (Remark: probably related to surface structure. Dr.H.Ti) is bioactive…. Ref.: http://www.science24.com/paper/905 The feasibilty of an organic mechanical attachment between cortical bone tissues and elemental carbon has been successfully demonstrated. Ref.: Elemental carbon as a biomaterial Jim Benson Journal of Biomedical Materials Research Volume 5, Issue 6 , Pages 41 – 47 © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 9 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH -

4) Carcinogenity: Carbon nor Graphite or high temperature annealed coke are not listed as carcinogen in the actual IARC Monographs Ref.: http://monographs.iarc.fr/ENG/Classification/index.php *) “Synthetic Graphite : None of the components present in this material at concentrations equal or greater than 0.1% is listed by IARC, NTP, OSHA or ACGIH as a carcinogen.” Ref.: http://www.timcal.com/SCOPI/Group/timcal/tim01cor.nsf/Timcal-frm-Download?readForm&lang=wo&aliasdoc=902020 „ Natural Graphite: Natural Graphite may contain impurities of 1 - 3 % crystalline silica (quartz, CAS 14808-60-7) which is listed by IARC as Group 1 carcinogen and by ACGIH as A2 (suspected human carcinogen).” Ref.: http://www.timcal.com/SCOPI/Group/timcal/tim01cor.nsf/Timcal-frm-Download?readForm&lang=wo&aliasdoc=902020

Natural Graphite - Carcinogenicity: For Silica, Crystalline: Content 0 – 4 % - Cristobalite (14464-46-1), quartz (14808-60-7), and tridymite (15468-32-3) are listed by NTP as known to be a human carcinogen. - NIOSH considers cristobalite, tridymite, quartz, and tripoli (1317-95-9) to be potential occupational carcinogens. ------\Cancer Lists\------NTP Carcinogen--- Ingredient Known Anticipated IARC Category ------Graphite (7782-42-5) No No None Quartz (14808-60-7) Yes No 1 Ref.: http://www.jtbaker.com/msds/englishhtml/g8122.htm “Calcined Petroleum Coke: Is product listed as Carcinogen or Potential Carcinogen by: NTP? No IARC? No OSHA? No” Ref.: www.oxbow.com/text/MSDS_COKE.pdf “Coke: None of the components present in this material at concentrations equal or greater than 0.1% are listed by IARC(Group 1,2A or 2B), NTP, OSHA or ACGIH as a carcinogen. Ref.: http://www.timcal.com/SCOPI/Group/timcal/tim01cor.nsf/Timcal-frm-Download?readForm&lang=wo&aliasdoc=902020

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5) Aquatic Toxicity: “Arsenic Removal from Drinking Water by Coagulation/Filtrationand Lime Softening Plants” Flocculatio:. Flocculation of alum hydroxide and various contaminants, including arsenic, occurs during this treatment process. During late summer, powdered activated carbon (PAC) ma ybe added for taste and odor control. Ref http://www.epa.gov/nrmrl/pubs/600r0006360/0r Chapter 4 : Removal of Organics and Inorganics by Activated Carbon Ref.: Chemistry of Water Treatment / Samuel Denton Faust , Osman M. Aly / CRC PRESS 1998

6) Degradation / Fate and behaviour in the environment / Effects on terrestrial organisms Historical, ancient findings of carbon materials i.e. like fire places or burned / carbonized wood show no degradation, no effect on the environment are observed, no impact on terrestial organisms could be detected. Ref.: Expert judgment

7) Meanwhile have additional investigations proofed that bulk C-materials and nano-scaled materials can be distinguished by their formation mechanism and by spectrographic and X-ray analysis (see attachment – SANCO consultation)

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Allotropes of carbon material

Main Allotropes Element Examples Subgroup of Allotropes

Diamond (sp3) bulk sized C (sp3) (i.e.natural / synthetic)

(i.e. glassy carbon / charcoal / bulk sized C (sp3 - sp2) activated carbon /coke (i.e. natural / amorphous C (sp3 - sp2) synthetic) and others) Carbon material C-molecules (sp2 - sp3(?)) 3 2 (i.e.carbon black / soot / fullerene / nano scaled C (sp - sp ) C-nanotubes and others

Graphit (sp2) bulk sized C (sp2) (i.e.natural / synthetic)

Three atomic bonds can be destinguished • Diamond (sp3) *) • Graphite (sp2), with dislocated electrons • Organic triple-bonds (sp1) **)

*) Diamond as such are not considered here **) (sp1) bonds are not of any significant for solid carbon materials and not considered here.

Two initially manufuctered of carbon materials according to particle size can be destinguished • Bulk scaled carbon materials • Nano scaled carbon materials © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 12 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH -

Structural aspects bulk carbon materials

All solid carbon materials described here are close to exclusively structured by (sp3) and (sp2) bonds.

A second major structural aspect to destinguish betwenn different carbon structure are the proportion of (sp3) and (sp2), the hights of the stacks without relevant defects and the avaraged basal layer distance, besides of the initially formed particle size while being produced..

The wide range of bulk carbon materials ( isotropic carbon i.e. glassy carbon, over amorphous carbon i.e. carbon char, coke, synthetic industrial baked carbon and highly anisotropic carbon like graphite,) can be desribed by percentage of by (sp3) and (sp2), a basal layer structure characterized by stackhights of basal layers and the avaraged distance of basal layers.

All bulk carbon materials are characterized by a three dimensional structure initially formed as coarse grained substance. The different allotropes are formed by a variation in the percentage of by (sp3) and (sp2) bonds, but all of them show no hazardous properties, proofed by the pharmaceutical and medical applications due to the fact that thes have a very high biocompatibility. The basal layer stackhights varies from 4-10 for isotropic materials like glassy carbon up to serveral hundred layers i.e. graphite (natural and synthetic). The avaraged basal layer distance varies from upto sereval times of a 0,335 nm for isotropic materials down to 0,335 nm for graphite.

Highly isotropic carbon material like tetraedric amorphous carbon can be defined as such bulk carbon materials containing more than 70 % (sp3) bonds.

The evaluation of properties of bulk carbon materials has to be restricted to the properties of the bulk carbon substance as such. Hazardous properties derived from other substances being a constituent or an impurity of the sysnthetic or natural carbon substance have to elavuated in separate risk assement restricted to this constituent i.e like silica/quartz in natural graphite.

Graphite Amorphous Carbon © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 13 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH - Image Ref.: http://de.wikipedia.org/wiki/Kohlenstoff

Physcal Properties of C-Material f(structure)

] 1,E+18

m Diamond O

µ 1,E+15 [

y t

i 1,E+12 v i t

s 1,E+09 i s e 1,E+06 R

. Graphite Amorphous Carbon r t 1,E+03 c e l

e 1,E+00 0 500 1000 1500 2000 2500 thermal Conductivity {W/mK] Dr. H. Ti

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Physical Properties of Graphite f(structure)

] 1,E+04 m

O ab

µ Graphite [ 1,E+03 y t i

v Polycryst. graphite i t

s 1,E+02 i s e R

. 1,E+01 r t

c Pyro-graphite c e Graphite l

e 1,E+00 1 10 100 1000 thermal Conductivity {W/mK]

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Characteristics of Bulk Carbon - Crytallite Size

3,65 ]

A Diamond [

3,60 e c

n 3,55 a t

s By Harry Marsh i 3,50 d

e 3,45 y

a Graphite L

3,40 2 / c 3,35 0 200 400 600 800 1000 Lc Stack height [A] Dr. H. Ti

© Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 16 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH -

Characteristics of Bulk Carbon - Crystallite Size

3,65 ]

A Diamond [

3,60 e c

n 3,55 a t

s By Harry Marsh i 3,50 d

e 3,45 y

a Graphite L

3,40 2 / c 3,35 0 200 400 600 800 1000 La Layer size [A] Dr. H. Ti

© Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 17 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH -

Proposal of schematic structuring bulk carbon materials (Dr. H. Ti)

Manufactured Inital C-Group (structure) Name CAS# EINECS# Annex Particle Size Diamond (sp3) Diamond 7782-40-3 231-953-2 IV

Initial Carbon 7440-44-0 231-153-3 IV bulk Intermediate C (sp3 - sp2) Coke (coal) 65996-77-2 266-010-4 IV carbon material Coke (petroleum),64743-05-1 calcined 265-210-9 IV

Graphite (sp2) Graphite 7782-42-5 231-955-3 IV

Proposal of schematic structuring bulk carbon materials (Dr. H. Ti)

If a separate grouping of natural and synthetic bulk carbon material is needed due to excessive content of inorganic mineral constituents.

Manufactured Inital C-Group (structure) Name CAS# EINECS# Annex Particle Size Diamond (sp3) Diamond 7782-40-3 231-953-2 Synthetic Intermediate C (sp3 - sp2) Coke (petroleum), calcined64743-05-1 265-210-9 3 2 IV carbon material Intermediate C (sp - sp ) Carbon 7440-44-0 231-153-3 Graphite (sp2) Graphite 7782-42-5 231-955-3 Initial bulk carbon material Diamond (sp3) Diamond 7782-40-3 231-953-2 IV Natural Intermediate C (sp3 - sp2) Coke (coal) *) 65996-77-2 266-010-4 IV carbon material Intermediate C (sp3 - sp2) Carbon Graphite (sp2) Graphite *) 7782-42-5 231-955-3 IV

*) It might by suitable to identify the bulk, natural carbon material as mono-constiuent or as multi- constituent. in accordance with RIP 3.10 Figure 4.1 and section 4.2.3; containing inorganic constituents, i.e. like silca (quartz) or other minerals exceeds 20 %

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Structural aspects of nano scaled carbon materials

Comparision of particle size initially formed while manufacturing carbon black and nano materials like fullerene and nano-tubes

Carbon black is build from very small, mostly spherical individual primal particles of approximately 10 – 300 nm. These indivdual particulates agglomarate to clusters up to several hunderd time in diameter.

The properties of carbon black may differ significantly depending on the manufacturing process and especially on the formation- or final heat treatment- temperature. According to the grade individual properties assessments are needed.

Carbon black Image Ref.: http://de.wikipedia.org/wiki/Ru%C3%9F

Fullerene and nanotubes have only one basal layer forming in the first case a spherical and in the second case a tube having complete different properties than bulk graphite and being formed by more or less defined molecules. The diameter of the individual particles range from < 1 nm up to ~ 10 nm. For some applications multilayer nanomaterial can be formed, having a onoin like structure sometimes destribed as graphitic. The diameter of the individual particles range from ~ 10 nm up to ~ 200 nm.

Nanotubes Fullerene Image Ref.: http://de.wikipedia.org/wiki/Kohlenstoff A grouping with graphite is incorrect because some of determining properties of the graphite and the particle range are significantly different.. © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 20 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH -

Comparable formation procedure of carbon black and nano material like fullerene or C-nanotubes

An HPLC trace showing fullerenes found in carbon soot. Many fullerenes have now been discovered in carbon soot, uncovered by electron microscopy, including tubes of carbon many thousands of times long as they are wide, with the same icosahedral structure as the fullerenes. These have diameters as small as 2nm. Carbon "onions" have also been discovered, and consist of carbon cages one inside the other rather like Russian dolls. These carbon particles have millions of atoms, and many have been observed with dozens of concentric shells. Hypothetical structures have been postulated for carbon cages consisting of not pentagonal and hexagonal rings (like C60), but heptagonal (7 membered) rings. Take the bell-jar off and scrape the glass surfaces clean, collect all the material. 10 % of the soot should be made up of C60 Ref.: http://www.ch.ic.ac.uk/local/projects/unwin/Fullerenes.html

The structure and formation/growth mechanism of soot particles (carbon blacks) have recently been elucidated by TEM experiments, and this study led to a surprising conclusion that the primary particles of carbon blacks are highly defective multi-shell fullerenes. Ref.:‘Carbon Nanotechnology’, Dai, L. (Ed.), Chapt. 6, p. 127-151, Elsevier: Dordrecht, 2006.

Proposal of schematic structuring nano scaled carbon materials (Dr. H. Ti)

Manufactured Inital C-Group (structure) Name CAS# EINECS# Annex Particle Size

Initial Carbon black (sp3 - sp2) Carbon black 1333-86-4 215-609-9 ? nano scaled carbon material i.e. Fullerene, Nanotubes Fullerene 99685-96-8 n.a. ? © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 21 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns D1.a Contribution to a final consultation on substances of Annex IV and Annex V of the REACh Regulation, respectively on the Draft Guidance on Annex V Submitted to DG ENTR / DG ENV /ECHA) by Dr. Harald Tillmanns PRO-Coaching GmbH -

Initial particle size while formed

Bulk Carbon

Carbon black

Nano Carbon

0,1 1 10 100 1000 10000 100000 1000000 Initial particle size [nm] Dr. H. Ti

The structure of nano scaled carbons i.e. like fullerene and C-nanotubes including multilayer C-nano materials are still distinct molecules better comparable to individual primal particles of carbon black powders and their principle of formation are similar.

Therefore all C-nano materials can not be grouped with carbon and/or graphite and have to be evaluated individually and as a separate substance. Due to their similarity with carbon black is might the evaluated as an independent subgroup there-of. Ref.: http://de.wikipedia.org/wiki/Kohlenstoff and numerous links to all forms of carbon materials are available in wikipedia and citied literature Ref.: Numerous articles, MSDS and producer informations have been evaluated by Dr. H. Ti © Copyright 2009, Dr. Harald Tillmanns PRO – Coaching GmbH, Idstein 22 Dr. Harald Tillmanns PRO-Coaching GmbH, Bahnofstr. 30; D-65510 Idstein -- Wiesbaden HRB 20712 / GF: Dr. Harald Tillmanns