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{{short description|Extremely hard ceramic compound}} |
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{{About|B<sub>4</sub>C|other boron carbides|Boron carbides}} |
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{{chembox |
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| verifiedrevid = 401933529 |
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| verifiedrevid = 430790006 |
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| Name = Boron carbide |
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| Name = Boron carbide |
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| ImageFile = Boron carbide.JPG |
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| ImageFile = File:Boron carbide.JPG |
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| ImageName = Boron carbide |
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| IUPACName = Boron carbide |
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| IUPACName = Boron carbide |
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| OtherNames = Tetrabor |
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| OtherNames = Tetrabor |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 109889 |
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| ChemSpiderID = 109889 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 12069-32-8 |
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| CASNo = 12069-32-8 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = T5V24LJ508 |
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| PubChem = 123279 |
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| PubChem = 123279 |
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}} |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = B<sub>4</sub>C |
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| Formula = B<sub>4</sub>C |
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| MolarMass = 55.255 g/mol |
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| MolarMass = 55.255 g/mol |
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| Appearance = dark gray or black powder, odorless |
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| Appearance = dark gray or black powder, odorless |
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| Density = 2.50 g/cm<sup>3</sup>, solid.<ref name=crc>{{cite book |ref=Haynes| editor= Haynes, William M. | date = 2016| title = ] | edition = 97th | publisher = ] | isbn = 9781498754293|page=4.52}}</ref> |
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| Density = 2.52 g/cm<sup>3</sup>, solid. |
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| Solubility = insoluble |
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| Solubility = insoluble |
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| MeltingPtC = 2763 |
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| MeltingPtC = 2350 |
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| MeltingPt_ref = <ref name=crc/> |
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| BoilingPtC = 3500 |
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| pKa = 6–7 (20 °C) |
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| BoilingPt = >3500 °C |
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| BoilingPt_ref = <ref name=crc/> |
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'''Boron carbide''' (chemical formula approximately B<sub>4</sub>C) is an extremely hard ]-] ] material used in ] ], ]s, and numerous industrial applications. With a ] of above 9, it is one of the hardest materials known, behind cubic ] and ]. |
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'''Boron carbide''' (chemical formula approximately B<sub>4</sub>C) is an extremely hard ]–] ], a ] material used in ], ]s, engine ] powders,<ref> |
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{{cite book |
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| last= Gray |
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| first= Theodore |
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| title= The Elements: A Visual Exploration of Every Known Atom in the Universe |
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| publisher= Black Dog & Leventhal Publishers |
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| date= 2012-04-03 |
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| isbn= 9781579128951 |
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| url= https://books.google.com/books?id=IOY-8hxTJVAC&q=boron+carbide+sabotage+powder&pg=PT24 |
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| access-date= 6 May 2014 |
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}} |
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</ref> |
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as well as numerous industrial applications. With a ] of >30 GPa, it is one of the hardest known materials, behind cubic ] and ].<ref> |
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{{cite news |
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| title= Rutgers working on body armor |
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| url= http://www.app.com/article/20120811/NJNEWS/308110051/Rutgers-working-on-body-armor |
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| quote= ... boron carbide is the third-hardest material on earth. |
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| newspaper= ] |
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| location = Asbury Park, N.J. |
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| date= August 11, 2012 |
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| access-date= 2012-08-12 |
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}} |
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</ref> |
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== History== |
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Boron carbide was discovered in the 19th century as a ] of reactions involving metal borides, however, its ] was unknown. It was not until the 1930s that the chemical composition was estimated as B<sub>4</sub>C.<ref>Ridgway, Ramond R , European Patent CA339873 (A), publication date: 1934-03-06</ref> There remained, however, controversy as to whether or not the material had this exact 4:1 stoichiometry, as in practice the material is always slightly carbon-deficient with regard to this formula, and ] shows that its structure is highly complex, with a mixture of C-B-C chains and B<sub>12</sub> ]. These features argued against a very simple exact B<sub>4</sub>C empirical formula.<ref name=stoi>{{cite journal|title=Structure and bonding in boron carbide: The invincibility of imperfections|author=Musiri M. Balakrishnarajan, Pattath D. Pancharatna and Roald Hoffmann|journal=New J. Chem.|year=2007|volume=31|page=473|doi=10.1039/b618493f|url=http://www.rsc.org/Publishing/Journals/nj/Hotarticles/B618493F_Hoffmann.asp}}</ref> Because of the B<sub>12</sub> structural unit, the chemical formula of "ideal" boron carbide is often written not as B<sub>4</sub>C, but as B<sub>12</sub>C<sub>3</sub>, and the carbon deficiency of boron carbide described in terms of a combination of the B<sub>12</sub>C<sub>3</sub> and B<sub>12</sub>C<sub>2</sub> units. |
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Boron carbide was discovered in the 19th century as a ] of reactions involving metal borides, but its ] was unknown. It was not until the 1930s that the chemical composition was estimated as B<sub>4</sub>C.<ref>Ridgway, Ramond R , European Patent CA339873 (A), publication date: 1934-03-06</ref> |
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Controversy remained as to whether or not the material had this exact 4:1 ], as, in practice the material is always slightly carbon-deficient with regard to this formula, and ] shows that its structure is highly complex, with a mixture of C-B-C chains and B<sub>12</sub> ]. |
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These features argued against a very simple exact B<sub>4</sub>C empirical formula.<ref name=stoi> |
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{{cite journal |
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| title= Structure and bonding in boron carbide: The invincibility of imperfections |
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| first1= Musiri M. |
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| last1= Balakrishnarajan |
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| first2= Pattath D. |
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| last2= Pancharatna |
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| first3= Roald |
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| last3= Hoffmann |
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| journal= New J. Chem. |
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| year= 2007 |
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| issue= 4 |
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| volume= 31 |
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| page= 473 |
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| doi= 10.1039/b618493f |
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| url= http://www.rsc.org/Publishing/Journals/nj/Hotarticles/B618493F_Hoffmann.asp |
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}} |
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</ref> |
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Because of the B<sub>12</sub> structural unit, the chemical formula of "ideal" boron carbide is often written not as B<sub>4</sub>C, but as B<sub>12</sub>C<sub>3</sub>, and the carbon deficiency of boron carbide described in terms of a combination of the B<sub>12</sub>C<sub>3</sub> and B<sub>12</sub>CBC units. |
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== Crystal structure == |
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The ability of boron carbide to absorb neutrons without forming long lived ]s makes it attractive as an absorbent for ] arising in ]s. Nuclear applications of boron carbide include shielding, ] and shut down pellets. Within control rods, boron carbide is often powdered, to increase its surface area.<ref name=w330>Weimer, p. 330</ref> |
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] consist of boron atoms, and black spheres are carbon atoms.<ref name=zhangyb28.5c4>{{cite journal|vauthors=Zhang FX, Xu FF, Mori T, Liu QL, Sato A, Tanaka T |year=2001|title=Crystal structure of new rare-earth boron-rich solids: REB28.5C4|journal=J. Alloys Compd.|volume=329|issue=1–2|pages=168–172|doi=10.1016/S0925-8388(01)01581-X}}</ref>]] |
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] |
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Boron carbide has a complex crystal structure typical of ]. There, B<sub>12</sub> ] form a ] lattice unit (space group: ''R{{overline|3}}m'' (No. 166), lattice constants: ''a'' = 0.56 nm and ''c'' = 1.212 nm) surrounding a C-B-C chain that resides at the center of the ], and both carbon atoms bridge the neighboring three icosahedra. This structure is layered: the B<sub>12</sub> icosahedra and bridging ] form a network plane that spreads parallel to the ''c''-plane and stacks along the ''c''-axis. The lattice has two basic structure units – the B<sub>12</sub> icosahedron and the B<sub>6</sub> ]. Because of the small size of the B<sub>6</sub> octahedra, they cannot interconnect. Instead, they bond to the B<sub>12</sub> icosahedra in the neighboring layer, and this decreases bonding strength in the ''c''-plane.<ref name=zhangyb28.5c4/> |
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==Crystal structure== |
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] consist of boron atoms, and black spheres are carbon atoms.<ref name=zhangyb28.5c4>{{cite journal|author=Zhang F X, Xu F F, Mori T, Liu Q L, Sato A and Tanaka T|year=2001|title=Crystal structure of new rare-earth boron-rich solids: REB28.5C4|journal=J. Alloys Compd.|volume=329|page=168|doi=10.1016/S0925-8388(01)01581-X}}</ref>]] |
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] |
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Because of the B<sub>12</sub> structural unit, the chemical formula of "ideal" boron carbide is often written not as B<sub>4</sub>C, but as B<sub>12</sub>C<sub>3</sub>, and the carbon deficiency of boron carbide described in terms of a combination of the B<sub>12</sub>C<sub>3</sub> and B<sub>12</sub>C<sub>2</sub> units.<ref name=stoi/><ref name=gr/> Some studies indicate the possibility of incorporation of one or more carbon atoms into the boron icosahedra, giving rise to formulas such as (B<sub>11</sub>C)CBC = B<sub>4</sub>C at the carbon-heavy end of the stoichiometry, but formulas such as B<sub>12</sub>(CBB) = B<sub>14</sub>C at the boron-rich end. "Boron carbide" is thus not a single compound, but a family of compounds of different compositions. A common intermediate, which approximates a commonly found ratio of elements, is B<sub>12</sub>(CBC) = B<sub>6.5</sub>C.<ref name="Domnich2011">{{cite journal | last1 = Domnich | first1 = Vladislav | last2 = Reynaud | first2 = Sara | last3 = Haber | first3 = Richard A. | last4 = Chhowalla | first4 = Manish | year = 2011 | title = Boron Carbide: Structure, Properties, and Stability under Stress | url = http://nanotubes.rutgers.edu/PDFs/Domnich.2011.JACerS.pdf | journal = J. Am. Ceram. Soc. | volume = 94 | issue = 11 | pages = 3605–3628 | doi = 10.1111/j.1551-2916.2011.04865.x | access-date = 23 July 2015 | archive-url = https://web.archive.org/web/20141227081802/http://nanotubes.rutgers.edu/PDFs/Domnich.2011.JACerS.pdf | archive-date = 27 December 2014 | url-status = dead }}</ref> Quantum mechanical calculations have demonstrated that configurational disorder between boron and carbon atoms on the different positions in the crystal determines several of the materials properties – in particular, the crystal symmetry of the B<sub>4</sub>C composition<ref>{{cite journal | last1 = Ektarawong | first1 = A. | last2 = Simak | first2 = S. I. | last3 = Hultman | first3 = L. | last4 = Birch | first4 = J. | last5 = Alling | first5 = B. | year = 2014 | title = First-principles study of configurational disorder in B<sub>4</sub>C using a superatom-special quasirandom structure method | journal = Phys. Rev. B | volume = 90 | issue = 2| page = 024204 | doi = 10.1103/PhysRevB.90.024204 |arxiv = 1508.07786 |bibcode = 2014PhRvB..90b4204E | s2cid = 39400050 }}</ref> and the non-metallic electrical character of the B<sub>13</sub>C<sub>2</sub> composition.<ref>{{cite journal | last1 = Ektarawong | first1 = A. | last2 = Simak | first2 = S. I. | last3 = Hultman | first3 = L. | last4 = Birch | first4 = J. | last5 = Alling | first5 = B. | year = 2015 | title = Configurational order-disorder induced metal-nonmetal transition in B<sub>13</sub>C<sub>2</sub> studied with first-principles superatom-special quasirandom structure method | journal = Phys. Rev. B | volume = 92 | issue = 1| page = 014202 | doi = 10.1103/PhysRevB.92.014202 |arxiv = 1508.07848 |bibcode = 2015PhRvB..92a4202E | s2cid = 11805838 }}</ref> |
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Boron carbide has a complex crystal structure typical of ]. There, B<sub>12</sub> ] form a ] lattice unit (space group: ''R{{overline|3}}m'' (No. 166), lattice constants: ''a'' = 0.56 nm and ''c'' = 1.212 nm) surrounding a C-B-C chain that resides at the center of the ], and both carbon atoms bridge the neighboring three icosahedra. This structure is layered: the B<sub>12</sub> icosahedra and bridging ] form a network plane that spreads parallel to the ''c''-plane and stacks along the ''c''-axis. The lattice has two basic structure units – the B<sub>12</sub> icosahedron and the B<sub>6</sub> ]. Because of the small size of the B<sub>6</sub> octahedra, they cannot interconnect. Instead, they bond to the B<sub>12</sub> icosahedra in the neighboring layer, and this decreases bonding strength in the ''c''-plane.<ref name=zhangyb28.5c4/> |
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Because of the B<sub>12</sub> structural unit, the chemical formula of "ideal" boron carbide is often written not as B<sub>4</sub>C, but as B<sub>12</sub>C<sub>3</sub>, and the carbon deficiency of boron carbide described in terms of a combination of the B<sub>12</sub>C<sub>3</sub> and B<sub>12</sub>C<sub>2</sub> units.<ref name=stoi/><ref name=gr/> |
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==Properties== |
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==Properties== |
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Boron carbide is known as a robust material having high hardness, high cross section for absorption of ] (i.e. good shielding properties against neutrons), stability to ] and most chemicals.<ref name=w330/> Its ] (38 GPa) and ] (3.5 MPa·m<sup>1/2</sup>) approach the corresponding values for diamond (115 GPa and 5.3 MPa·m<sup>1/2</sup>).<ref>{{cite journal| title = Ultimate Metastable Solubility of Boron in Diamond: Synthesis of Superhard Diamondlike BC5| first = V. L.|last = Solozhenko|journal = Phys. Rev. Lett.| volume = 102| page = 015506|year = 2009| doi = 10.1103/PhysRevLett.102.015506| last2 = Kurakevych| first2 = Oleksandr O.| last3 = Le Godec| first3 = Yann| last4 = Mezouar| first4 = Mohamed| last5 = Mezouar| first5 = Mohamed| pmid=19257210| bibcode=2009PhRvL.102a5506S}}</ref> |
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Boron carbide is known as a robust material having extremely high hardness (about 9.5 up to 9.75 on ]), high cross section for absorption of ] (i.e. good shielding properties against neutrons), stability to ] and most chemicals.<ref name=w330>Weimer, p. 330</ref> Its ] (38 GPa), ] (460 GPa)<ref>{{cite journal | last1 = Sairam | first1 = K. | last2 = Sonber | first2 = J.K. | last3 = Murthy | first3 = T.S.R.Ch. | last4 = Subramanian | first4 = C. | last5 = Hubli | first5 = R.C. | last6 = Suri | first6 = A.K. | year = 2012 | title = Development of B4C-HfB2 composites by reaction hot pressing | journal = Int.J. Ref. Met. Hard Mater | volume = 35 | pages = 32–40 | doi=10.1016/j.ijrmhm.2012.03.004}}</ref> and ] (3.5 MPa·m<sup>1/2</sup>) approach the corresponding values for diamond (1150 GPa and 5.3 MPa·m<sup>1/2</sup>).<ref>{{cite journal| title = Ultimate Metastable Solubility of Boron in Diamond: Synthesis of Superhard Diamondlike BC5| first1 = V. L.|last1 = Solozhenko|journal = Phys. Rev. Lett.| volume = 102| page = 015506|year = 2009| doi = 10.1103/PhysRevLett.102.015506| last2 = Kurakevych| first2 = Oleksandr O.| last3 = Le Godec| first3 = Yann| last4 = Mezouar| first4 = Mohamed| last5 = Mezouar| first5 = Mohamed| pmid=19257210| bibcode=2009PhRvL.102a5506S| issue = 1| url = http://bib-pubdb1.desy.de/record/87949/files/GetPDFServlet.pdf}}</ref> |
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{{As of|2015}}, boron carbide is the third hardest substance known, after ] and ], earning it the nickname "black diamond".<ref>{{cite web |url= http://www.precision-ceramics.co.uk/boron-carbide.htm |title= Boron Carbide |publisher= Precision Ceramics |access-date= 2015-06-20 |url-status= dead |archive-url= https://web.archive.org/web/20150620124737/http://www.precision-ceramics.co.uk/boron-carbide.htm |archive-date= 2015-06-20 }}</ref><ref>{{cite journal |doi= 10.1142/S2010194512001894 |author1=A. Sokhansanj |author2=A.M. Hadian |title= Purification of Attrition Milled Nano-size Boron Carbide Powder |journal= International Journal of Modern Physics: Conference Series |volume= 5 |year= 2012 |pages= 94–101 |bibcode = 2012IJMPS...5...94S }}</ref> |
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===Semiconductor properties=== |
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Boron carbide is a ], with electronic properties dominated by hopping-type transport.<ref name="Domnich2011" /> The energy ] depends on composition as well as the degree of order. The band gap is estimated at 2.09 eV, with multiple mid-bandgap states which complicate the ] spectrum.<ref name="Domnich2011" /> The material is typically p-type. |
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==Preparation== |
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==Preparation== |
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Boron carbide was first synthesized by ] in 1899,<ref name=gr>{{Greenwood&Earnshaw2nd|p=149}}</ref> by reduction of ] either with ] or ] in presence of carbon in an electric ]. In the case of carbon, the reaction occurs at temperatures above the melting point of B<sub>4</sub>C and is accompanied by liberation of large amount of carbon monoxide:<ref name=w131>Weimer, p. 131</ref> |
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Boron carbide was first synthesized by ] in 1899,<ref name=gr>{{Greenwood&Earnshaw2nd|p=149}}</ref> by reduction of ] either with ] or ] in presence of carbon in an electric ]. In the case of carbon, the reaction occurs at temperatures above the melting point of B<sub>4</sub>C and is accompanied by liberation of large amount of ]:<ref name=w131>Weimer, p. 131</ref> |
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:2 B<sub>2</sub>O<sub>3</sub> + 7 C → B<sub>4</sub>C + 6 CO |
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:2 B<sub>2</sub>O<sub>3</sub> + 7 C → B<sub>4</sub>C + 6 CO |
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If magnesium is used, the reaction can be carried out in a ], and the magnesium byproducts are removed by treatment with acid.<ref>Pradyot Patnaik. ''Handbook of Inorganic Chemicals''. McGraw-Hill, 2002, ISBN 0070494398</ref> |
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If magnesium is used, the reaction can be carried out in a graphite ], and the magnesium byproducts are removed by treatment with acid.<ref>Patnaik, Pradyot (2002). ''Handbook of Inorganic Chemicals''. McGraw-Hill. {{ISBN|0-07-049439-8}}</ref> |
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], UK]] |
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==Uses== |
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==Applications== |
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]s]] |
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Boron's exceptional hardness can be used for the following applications: |
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*]s |
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*Personal and vehicle anti-ballistic ]. |
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*Personal and vehicle ballistic ] |
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*] nozzles. |
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*] nozzles |
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*] jet cutter nozzles. |
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*] jet cutter nozzles |
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*Scratch and wear resistant coatings. |
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*Scratch and wear resistant coatings |
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*Cutting tools and dies. |
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*Cutting tools and dies |
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*]. |
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*] in ]. |
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*In brake linings of vehicles |
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*]s. |
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*High energy fuel for solid fuel ]. |
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Boron carbide's other properties also make it suitable for: |
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*] in ] (see below) |
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*] for solid fuel ] |
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===Nuclear applications === |
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The ability of boron carbide to ] without forming long-lived ]s makes it attractive as an ]<ref>'''', Wisnyi, L. G. and Taylor, K.M., in "ASTM Special Technical Publication No. 276: Materials in Nuclear Applications", Committee E-10 Staff, ], 1959</ref> and from anti-personnel ]s. Nuclear applications of boron carbide include shielding.<ref name=w330>Weimer, p. 330</ref> |
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===Boron carbide filaments=== |
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Boron carbide filaments exhibit auspicious prospects as reinforcement elements in resin and metal composites, attributed to their exceptional strength, elastic modulus, and low density characteristics.<ref>{{cite journal |last1=Higgins |first1=J.B |last2=Gatti |first2=A. |title=Preparation and Properties of Boron Carbide Continuous Filaments |url=https://iopscience.iop.org/article/10.1149/1.2411733 |journal=Journal of the Electrochemical Society |date=1969 |volume=116 |issue=1 |article-number=1 |page=137 |doi=10.1149/1.2411733 |bibcode=1969JElS..116..137H |access-date=May 28, 2024}} </ref> In addition, boron carbide filaments are not affected by radiation due to its ability to absorb neutrons.<ref>{{cite web |url=https://www.preciseceramic.com/blog/boron-carbide-filament-properties-applications.html |title=Boron Carbide Filament: Properties & Applications |last=Rose |first=Lisa |website=Precise Ceramic |access-date=May 28, 2024}}</ref> It is less harmful than filaments made of other materials, such as cadmium.<ref>{{cite web |url=https://www.nanotrun.com/blog/what-is-boron-carbide_b0434.html |title=What is boron carbide? |date=July 29, 2022 |website=Trunnano |access-date=May 28, 2024}}</ref> |
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==See also== |
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* ] |
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==References== |
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==References== |
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{{reflist|2}} |
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{{reflist|30em}} |
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==Bibliography== |
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==Bibliography== |
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*{{cite book|url=http://books.google.com/books?id=PC4f40ETjeUC&pg=PA330|author = Alan W. Weimer| title = Carbide, Nitride and Boride Materials Synthesis and Processing| isbn = 0-412-54060-6| year = 1997| publisher = Chapman & Hall (London, New York)}} |
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*{{cite book|url=https://books.google.com/books?id=PC4f40ETjeUC&pg=PA330|author = Weimer, Alan W. | title = Carbide, Nitride and Boride Materials Synthesis and Processing| isbn = 0-412-54060-6| year = 1997| publisher = Chapman & Hall (London, New York)}} |
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==External links== |
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==External links== |
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{{Boron compounds}} |
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{{Boron compounds}} |
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{{Carbides}} |
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