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Glassy carbon - Wikipedia, the free encyclopedia

Glassy carbon
From Wikipedia, the free encyclopedia

Glass-like carbon, often called glassy carbon or vitreous

carbon, is a non-graphitizing carbon which combines glassy and
ceramic properties with those of graphite. The most important
properties are high temperature resistance, hardness (7 Mohs), low
density, low electrical resistance, low friction, low thermal
resistance, extreme resistance to chemical attack and impermeability
to gases and liquids. Glassy carbon is widely used as an electrode
material in electrochemistry, as well as for high temperature
crucibles and as a component of some prosthetic devices, and can
be fabricated as different shapes, sizes and sections.
The names glassy carbon and vitreous carbon have been
introduced as trademarks; therefore, IUPAC does not recommend
their use as technical terms.[1]

A small rod of glassy carbon.

Contents
1 History
2 Structure
3 Electrochemical properties
4 Advantages

vitreous-glassy carbon
crucibles

5 See also
6 References
7 External links

History
It was first observed in the laboratories of The Carborundum Company, Manchester, UK, in the mid-1950s by
Bernard Redfern, the inventor, a materials scientist and diamond technologist. He noticed that Sellotape he used to
hold ceramic (rocket nozzle) samples in a furnace maintained a sort of structural identity after firing in an inert
atmosphere. He searched for a polymer matrix to mirror a diamond structure and discovered a resole resin that
would, with special preparation, set without a catalyst. Using this phenolic resin, crucibles were produced.
Crucibles were distributed to organisations such as UKAEA Harwell.
Redfern left The Carborundum Co., which officially wrote off all interests in the glassy carbon invention. Whilst
working at the Plessey Company laboratory (in a disused church) in Towcester, UK, Redfern received a glassy
carbon crucible for duplication from UKAEA. He identified it as one he had made from markings he had engraved
into the uncured precursor prior to carbonisation. (It is almost impossible to engrave the finished product.) The
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Plessey Company set up a laboratory first in a factory previously used to make briar pipes, in Litchborough, UK,
and then a permanent facility at Caswell, near Blakesly, UK. Caswell became the Plessey Research Centre and
then the Allen Clark Research Centre. Glassy carbon arrived at the Plessey Company Limited as a fait accompli.
Redfern was assigned J.C. Lewis, as a laboratory assistant, for the production of glassy carbon. F.C. Cowlard was
assigned to Redfern's department later, as a laboratory administrator. Cowlard was an administrator who
previously had some association with Silane (Silane US Patent assignee 3,155,621 3 Nov 1964). Neither he nor
Lewis had any previous connection with glassy carbon.
Refern's contribution to the invention and production of glassy / Vitreous carbon is acknowledged by his coauthorship of early articles,.[2] But references to Redfern were not obvious in subsequent publications by Cowlard
and Lewis.[3] Original boat crucibles and precursor samples exist.
UK patent application were filed in 11 Jan.1960 and US patent filed 9 Jan. 1961 (finalised as US patent
3,109,712). This prior art is not referenced in US patent 4,668,496, 26 May 1987 for Vitreous Carbon. Patents
were filed "Bodies and shapes of carbonaceous materials and processes for their production" and the name
"Vitreous Carbon" presented to the product by the son of Redfern.
Glassy/Vitreous Carbon was under investigation used for components for thermonuclear detonation systems and at
least some of the patents surrounding the material were rescinded (in the interests of national security) in the 1960s.
Large sections of the precursor material were produced as castings, moldings or machined into a predetermined
shape. Large crucibles and other forms were manufactured. Carbonisation took place in two stages. Shrinkage
during this process is considerable (48.8%) but is absolutely uniform and predictable. A nut and bolt can be made
to fit as the polymer, processed separately and subsequently give a perfect fit.
Some of the first ultrapure samples of Gallium Arsenide were zone refined in these crucibles. (Glassy carbon is
extremely pure and unreactive to GaAs).
Doped/impure glassy carbon exhibited semiconductor phenomena.
Uranium carbide inclusions were fabricated (using U238 carbide at experimental scale).
On October 11, 2011, research conducted at the Carnegie Geophysical Laboratory led by Stanfords Wendy L.
Mao and her graduate student Yu Lin described a new form of glassy carbon formed under high pressure with
hardness equal to diamond. Unlike diamond, however its structure is that of amorphous carbon so its hardness may
be isotropic. Research is ongoing.[4]

Structure
The structure of glassy carbon has long been a subject of debate. Early structural models assumed that both sp2and sp3-bonded atoms were present, but it is now known that glassy carbon is 100% sp2. However, more recent
research has suggested that glassy carbon has a fullerene-related structure.[5]
Note that glassy carbon should not be confused with amorphous carbon. This from IUPAC: "Glass-like carbon
cannot be described as amorphous carbon because it consists of two-dimensional structural elements and does not
exhibit dangling bonds."[1]
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It exhibits a conchoidal fracture.

Electrochemical properties
Glassy carbon electrode (GCE) in aqueous solutions is considered to be an inert electrode for hydronium ion
reduction:[6]
H3O+(aq) + e-

H (aq) Eo = 2.10 V versus NHE at 25 C

Comparable reaction on platinum:

H3O+(aq) + Pt(s) + e-

Pt:H(s) Eo = 0.000 V versus NHE at 25 C

The difference of 2.1 V is attributed to the properties of platinum which stabilizes a covalent Pt-H bond.[6]

Advantages
Due to their specific surface orientation glassy carbon is employed as an electrode material for the fabrication of
sensors. Glassy carbon paste, glassy carbon, carbon paste etc. electrodes when modified are termed as chemically
modified electrodes. Chemically modified electrodes have been employed for the analysis of organic molecules
(viz., Paracetamol, aspirin, caffeine, phenol, catechol, resorcinol, hydroquinone, dopamine, L-dopa, epinephrine,
nor epinephrine, methyl parathion, ethyl parathion, venlafaxine, desvenlafaxine, imipramine, trimipramine,
desipramine etc.) as well as metal ions (bismuth, antimony etc.).[7][8][9][10][11][12][13][14][15]

See also
Graphite
Electrochemistry
Fullerenes

References
1. ^ a b The entry for "Glass-like carbon" in IUPAC Goldbook. (http://goldbook.iupac.org/G02639.html)
2. ^ Lewis, J.C.; Redfern, B.; Cowlard, F.C. (1963). "Vitreous carbon as a crucible material for semiconductors".
Solid-State Electronics 6 (3): 251254. Bibcode:1963SSEle...6..251L
(http://adsabs.harvard.edu/abs/1963SSEle...6..251L). doi:10.1016/0038-1101(63)90081-9
(http://dx.doi.org/10.1016%2F0038-1101%2863%2990081-9).
3. ^ Cowlard, F.C.; Lewis, J.C. (1967). "Vitreous carbon A new form of carbon". Journal of Materials Science 2
(6): 507512. Bibcode:1967JMatS...2..507C (http://adsabs.harvard.edu/abs/1967JMatS...2..507C).
doi:10.1007/BF00752216 (http://dx.doi.org/10.1007%2FBF00752216).
4. ^ New form of superhard carbon observed (http://www.physorg.com/news/2011-10-superhard-carbon.html)
5. ^ Fullerene-related structure of commercial glassy carbons
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(http://www.personal.rdg.ac.uk/~scsharip/PM_glassy.pdf), P.J.F. Harris, 2003.

6. ^ a b Sawyer, D. T.; Sobkowiak, A.; Roberts, J. L., Jr. (1995). Electrochemistry for Chemists (Second ed.). New
York: John Wiley & Sons. ISBN 0-471-59468-7.
7. ^ Sanghavi, Bankim; Srivastava, Ashwini (2010). "Simultaneous voltammetric determination of acetaminophen,
aspirin and caffeine using an in situ surfactant-modified multiwalled carbon nanotube paste electrode"
(http://www.sciencedirect.com/science/article/pii/S0013468610010510). Electrochimica Acta 55: 86388648.
doi:10.1016/j.electacta.2010.07.093 (http://dx.doi.org/10.1016%2Fj.electacta.2010.07.093).
8. ^ Sanghavi, Bankim; Mobin, Shaikh; Mathur, Pradeep; Lahiri, Goutam; Srivastava, Ashwini (2013). "Biomimetic
sensor for certain catecholamines employing copper(II) complex and silver nanoparticle modified glassy carbon
paste electrode" (http://www.sciencedirect.com/science/article/pii/S0956566312004289). Biosensors and
Bioelectronics 39: 124132. doi:10.1016/j.bios.2012.07.008 (http://dx.doi.org/10.1016%2Fj.bios.2012.07.008).
9. ^ Sanghavi, Bankim; Srivastava, Ashwini (2011). Simultaneous voltammetric determination of acetaminophen and
tramadol using Dowex50wx2 and gold nanoparticles modified glassy carbon paste electrode
(http://www.sciencedirect.com/science/article/pii/S0003267011011706) 706. pp. 246254.
doi:10.1016/j.aca.2011.08.040 (http://dx.doi.org/10.1016%2Fj.aca.2011.08.040).
10. ^ Sanghavi, Bankim; Srivastava, Ashwini (2011). "Adsorptive stripping differential pulse voltammetric
determination of venlafaxine and desvenlafaxine employing Nafioncarbon nanotube composite glassy carbon
electrode" (http://www.sciencedirect.com/science/article/pii/S001346861100171X). Electrochimica Acta 56:
41884196. doi:10.1016/j.electacta.2011.01.097 (http://dx.doi.org/10.1016%2Fj.electacta.2011.01.097).
11. ^ Sanghavi, Bankim; Hirsch, Gary; Karna, Shashi; Srivastava, Ashwini (2012). "Potentiometric stripping analysis
of methyl and ethyl parathion employing carbon nanoparticles and halloysite nanoclay modified carbon paste
electrode" (http://www.sciencedirect.com/science/article/pii/S0003267012007672). Analytica Chimica Acta 735:
3745. doi:10.1016/j.aca.2012.05.029 (http://dx.doi.org/10.1016%2Fj.aca.2012.05.029).
12. ^ Mobin, Shaikh; Sanghavi, Bankim; Srivastava, Ashwini; Mathur, Pradeep; Lahiri, Goutam (2010). "Biomimetic
Sensor for Certain Phenols Employing a Copper(II) Complex" (http://pubs.acs.org/doi/abs/10.1021/ac1004037).
Analytical Chemistry 82: 59835992. doi:10.1021/ac1004037 (http://dx.doi.org/10.1021%2Fac1004037).
13. ^ Gadhari, Nayan; Sanghavi, Bankim; Srivastava, Ashwini (2011). "Potentiometric stripping analysis of antimony
based on carbon paste electrode modified with hexathia crown ether and rice husk"
(http://www.sciencedirect.com/science/article/pii/S0003267011009585). Analytica Chimica Acta 703: 3140.
doi:10.1016/j.aca.2011.07.017 (http://dx.doi.org/10.1016%2Fj.aca.2011.07.017).
14. ^ Gadhari, Nayan; Sanghavi, Bankim; Karna, Shashi; Srivastava, Ashwini (2010). "Potentiometric stripping analysis
of bismuth based on carbon paste electrode modified with cryptand 2.2.1 and multiwalled carbon nanotubes"
(http://www.sciencedirect.com/science/article/pii/S0013468610013599). Electrochimica Acta 56: 627635.
doi:10.1016/j.electacta.2010.09.100 (http://dx.doi.org/10.1016%2Fj.electacta.2010.09.100).
15. ^ Sanghavi, Bankim; Srivastava, Ashwini (2013). "Adsorptive stripping voltammetric determination of imipramine,
trimipramine and desipramine employing titanium dioxide nanoparticles and an Amberlite XAD-2 modified glassy
carbon paste electrode" (http://pubs.rsc.org/en/Content/ArticleLanding/2013/AN/C2AN36330E). Analyst.
Bibcode:2013Ana...138.1395S (http://adsabs.harvard.edu/abs/2013Ana...138.1395S). doi:10.1039/C2AN36330E
(http://dx.doi.org/10.1039%2FC2AN36330E).

External links
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HTW, supplier's website (http://www.htw-gmbh.de), for Glassy Carbon SIGRADUR

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