GB2387176A - Manufacture of Sub-oxides via Electrolysis - Google Patents
Manufacture of Sub-oxides via Electrolysis Download PDFInfo
- Publication number
- GB2387176A GB2387176A GB0207625A GB0207625A GB2387176A GB 2387176 A GB2387176 A GB 2387176A GB 0207625 A GB0207625 A GB 0207625A GB 0207625 A GB0207625 A GB 0207625A GB 2387176 A GB2387176 A GB 2387176A
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- electrode
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
An electrolytic method for producing a material having the composition M<1>jXk comprising a substance X and a metal, semi-metal, or alloy M<1>, comprises the steps of:- <UL ST=" ¦ "> <LI> arranging an electrode comprising a material having the composition M<1>jX(k+1) in an electrolyte M<2>Y comprising a fused salt or a mixture of salts, including one or more cations M<2> <LI>applying to the electrode a negative potential lower than a deposition potential for the cation M<2> at a surface of the electrode and such that the substance X dissolves in the electrolyte <LI>removing the electrode from the electrolyte when the material has been reduced to the composition M<1>jXk. </UL> The process can be worked in reverse, and coupled forward and reverse reactions can be used.
Description
23371 76
Manufacture of sub-oxides and other materials This invention relates to the manufacture of sub-oxides, other like phases, and non-
s stoichiometric materials.
Many materials are known in which two or more given elements may form phases of different stoichiometry. The most widely known such case may be the oxides of iron. Iron has three common oxides, FeO, Fe3O4, and Fe2O3.
À FeO is the oxide of iron (II) and is generally slightly nonstoichiometric typically having a composition of Fe0 95O due to the presence of some iron (III) atoms in the material. Fe3O4 could perhaps be described as Fei"[Fei',Fe"']Oó, having an inverse spinet 15 structure in which the bracketed Fe" and Fell' ions occupy similar sites.
À Fe2O3 is the oxide of iron (III).
In the iron-oxygen system these three oxides are phases of defined composition and are not merely arbitrary combinations of the components.
20 Another known system in which phases of different stoichiometry form is the titanium oxygen system. The stable compound of titanium and oxygen at room temperature is TiVO2, but the compounds Ti'2O3 and Ti"O are known, as are a range of titanium suboxides known generally as Magneli phases. Magneli phases have a composition TinO(2n I) in which n>4 (i.e. halfway between TiVO2 and Tip) and have individually recognizable x-ray diffraction 25 spectra based on, but distinguishable from, the futile structure of triclinic titanium dioxide.
The crystals of the Magneli phases are built up of TiO2 octahedra which share edges and corners to form a slab and which are repeated indefinitely in two dimensions. The Magneli phase oxides are substiochiometric, that is, the oxides are oxygen deficient with respect to 30 fulfilling the valence requirements of the classical titanium dioxide stoichiometry in the rutile structure.
In these Magneli phases, at certain "n" layers of octahedra, the oxygen atoms are forced to a: along a shear defect face to accommodate the lack of oxygen in the nonstoichiometric oxide Tino(2n-).
s This shear plane occurs at n spacings in the layers of octahedra. The n is the same value as the n in the particular Magneli phase, for example Ti407 (3TiO2 +TiO=Ti4O7) has three layers of TiO2 octahedra and at the 4th layer only TiO is left and this creates the shear plane.
In the case of the higher Magneli phases the value of n is higher, shear planes occur at greater intervals.
Such materials have been shown to be useful as electrode materials (see for example US Patent No. 5173215, the contents of which are incorporated by way of reference as showing conventional means of making such suboxides).
5 Titanium sub-oxides and other sub-oxides tend to be made by reduction at elevated temperatures. US Patent No. 5173215 for example discloses the use oftemperatures of l 000 C in a hydrogen atmosphere to produce Magneli phases. Such treatment can be hazardous on an industrial scale.
20 There is a need for a method of producing sub-oxides without the use of potentially explosive atmospheres such as hydrogen atmospheres.
International Patent Application no. W099/64638 discloses a method of removing oxygen from oxides, metals, and alloys to produce materials having extremely low oxygen contents.
2s This method may also be applied to removing other contaminants (e.g. phosphorus) from semiconductors. The method comprises making a substrate material the cathode in an electrolytic cell having a molten salt electrolyte, under conditions such that, rather than an anion from the electrolyte being plated out onto the surface, a cation is removed from the substrate.
International Patent Application no. WO99/64638 discloses in great detail how the oxygen level in a TiO2 substrate can be reduced to below the detection level of the analytical equipment used (<200ppm), i.e. to produce effectively pure metal. Where the substrate is a mixed oxide an alloy is the result of applying the process.
The inventor has realised that the process of International Patent Application no. W099/64638 can be used to produce the sub-oxides of titanium, and in particular can be used to produce Magneli phases.
lo Further, the inventor has realised that the process can be used to produce other sub-oxides such as, for example, those of zirconium, aluminium, cerium, molybdenum, tungsten and vanadium. Further still, the inventor has realised that other non-stoichiometric materials such as, for 15 example, phosphides, and nitrides may be made in analogous manner.
Accordingly, the present invention comprises a method for producing a material having the composition MjXk comprising a substance X and a metal, semi-metal, or alloy Me comprising the steps of: 20. arranging an electrode comprising a material having the composition MjX(k+,) in an electrolyte M2Y comprising a fused salt or a mixture of salts, including one or more cations M2 applying to the electrode a negative potential lower than a deposition potential for the cation M2 at a surface of the electrode and such that the substance X dissolves in the 25 electrolyte À removing the electrode from the electrolyte when the material has been reduced to the composition M jXk.
To prevent reaction going too far (which would produce the pure metal or semi-metal) the 30 reduction process may use potentiostatic control as described in WO99/64638.
The same process can be worked in reverse, namely to provide a method for producing a material having the composition MijXk comprising a substance X and a metal, semi-metal, or alloy M' comprising the steps of: À arranging an electrode comprising a material having the composition MijX(k m) in an s electrolyte M2Y comprising a fused salt or a mixture of salts, including one or more cations M2 and a source of anions X À applying to the electrode a positive potential such that the substance X is drawn from the electrolyte to react with the electrode removing the electrode from the electrolyte when the material has been oxidised to lo the composition M jXk.
These processes can be coupled so that the oxidation of one electrode is accompanied by the reduction of the other electrode such that the method provides a method for producing a material having the composition MjXk comprising a substance X and a metal, semi-metal, or is alloy Mi comprising the steps of: arranging a first electrode comprising a material having the composition MjX(k+) and a second electrode comprising a material having the composition MjX(k m) in an electrolyte M2Y comprising a fused salt or a mixture of salts, including one or more cations M2 20. applying to the first electrode a negative potential lower than a deposition potential for the cation M2 at a surface of the electrode and such that the substance X dissolves in the electrolyte applying to the second electrode a positive potential such that the substance X is drawn from the electrolyte to react with the electrode 2s. removing the first and/or second electrode from the electrolyte when the material has been reduced or oxidised respectively to the composition MjXk.
The invention is illustrated schematically in Fig. 1 in which a pair of electrodes 1,2 are immersed in a molten salt electrolyte 3, and a voltage applied across them. If electrode 1 is 30 of titanium oxide, oxygen from the electrode is drawn out of the electrode in preference to deposition of calcium from the electrolyte. This produces a titanium sub-oxide material.
If electrode 2 is of titanium, oxygen from the melt may oxidise the titanium in preference to either dissolution of the titanium or formation of titanium chloride. The net result is the production of titanium suboxides at both the anode and the cathode.
5 Either the anode or the cathode may be an inert counter electrode if desired but coupling the reactions in this way is preferred.
Claims (4)
1. A method for producing a material having the composition M'jXk comprising a 5 substance X and a metal, semi-metal, or alloy M' comprising the steps of: À arranging an electrode comprising a material having the composition M jX(k+ in an electrolyte M2Y comprising a fused salt or a mixture of salts, including one or more cations M2 À applying to the electrode a negative potential lower than a deposition l o potential for the cation M2 at a surface of the electrode and such that the substance X dissolves in the electrolyte À removing the electrode from the electrolyte when the material has been reduced to the composition M jXk.
2. A method for producing a material having the composition M'jXk comprising a substance X and a metal, semi-metal, or alloy Me comprising the steps of: À arranging an electrode comprising a material having the composition M'jX(k m) in an electrolyte M2Y comprising a fused salt or a mixture of salts, ho including one or more cations M2 and a source of anions X applying to the electrode a positive potential such that the substance X is drawn from the electrolyte to react with the electrode À removing the electrode from the electrolyte when the material has been oxidised to the composition Mi;Xk.
3. A method for producing a material having the composition M'jXk comprising a substance X and a metal, semi-metal, or alloy Me, comprising the steps of: À arranging a first electrode comprising a material having the composition 5 MjX(k+) and a second electrode comprising a material having the composition MjX(k l,l) in an electrolyte M2Y comprising a fused salt or a mixture of salts, including one or more cations M2 À applying to the first electrode a negative potential lower than a deposition potential for the cation M2 at a surface of the electrode and such that the lo substance X dissolves in the electrolyte À applying to the second electrode a positive potential such that the substance X is drawn from the electrolyte to react with the electrode À. removing the first and/or second electrode from the electrolyte when the material has been reduced or oxidised respectively to the composition MijXk.
Amendments to the claims have been filed as follows CLAIMS
1. A method for producing sub-oxides having the composition M'jXk in which X is s oxygen and Mi is a metal, semi-metal, or alloy comprising the steps of: arranging an electrode comprising a material having the composition Mijrk+' in an electrolyte M2Y comprising a fused salt or a mixture of salts, including one or more cations tvI2 À applying to the electrode a negative potential lower than a deposition lo potential for the cation M2 at a surface of the electrode and such that the substance X dissolves in the electrolyte removing the electrode from the electrolyte when the material has been reduced to the composition MliXk.
2. A method for producing sub-oxides having the composition MijXk in which X is oxygen and Me is a metal, seini-metal, or alloy comprising the steps of: arranging an electrode comprising a material having the composition M'jX(k m) in an electrolyte M2Y comprising a fused salt or a mixture of salts, 20 including one or more cations M2 and a source of anions X applying to the electrode a positive potential such that the substance X is drawn from the electrolyte to react with the electrode removing the electrode from the electrolyte when the material has been oxidised to the composition MjXk.
A<,ent's ref: BP-09-0194 i 3. A method for producing sub-oxides having the composition Monk in which X is oxygen and Mi is a metal, semi-metal, or alloy comprising the steps of: arranging a first electrode comprising a material having the composition s Mij(k+) and a second electrode comprising a material having the composition MijX(k m) in an electrolyte M2Y comprising a fused salt or a mixture of salts, including one or more cations M2 applying to the first electrode a negative potential lower than a deposition potential for the cation M2 at a surface of the electrode and such that the 0 substance X dissolves in the electrolyte À applying to the second electrode a positive potential such that the substance X is drawn from the electrolyte to react with the electrode À removing the first and/or second electrode from the electrolyte when the material has been reduced or oxidised respectively to the composition MjXk.
4. A method as claimed in any one of Claims 1 to 3, in which the suboxide is a
titanium sub-oxide.
S. A method as claimed in Claim 4, in which the titanium sub-oxide is Ti4O7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0207625A GB2387176B (en) | 2002-04-02 | 2002-04-02 | Manufacture of sub-oxides and other materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0207625A GB2387176B (en) | 2002-04-02 | 2002-04-02 | Manufacture of sub-oxides and other materials |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0207625D0 GB0207625D0 (en) | 2002-05-15 |
| GB2387176A true GB2387176A (en) | 2003-10-08 |
| GB2387176B GB2387176B (en) | 2004-03-24 |
Family
ID=9934126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0207625A Expired - Fee Related GB2387176B (en) | 2002-04-02 | 2002-04-02 | Manufacture of sub-oxides and other materials |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2387176B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960907A (en) * | 2020-08-26 | 2020-11-20 | 攀枝花学院 | Emulsion explosive and preparation method thereof |
| CN112744858A (en) * | 2021-01-08 | 2021-05-04 | 孙淑珍 | Solvothermal preparation method of titanium suboxide powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999064638A1 (en) * | 1998-06-05 | 1999-12-16 | Cambridge University Technical Services Limited | Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt |
| GB2359564A (en) * | 2000-02-22 | 2001-08-29 | Secr Defence | Electrolytic reduction of metal oxides |
| WO2001062994A1 (en) * | 2000-02-22 | 2001-08-30 | Qinetiq Limited | Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction |
-
2002
- 2002-04-02 GB GB0207625A patent/GB2387176B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999064638A1 (en) * | 1998-06-05 | 1999-12-16 | Cambridge University Technical Services Limited | Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt |
| GB2359564A (en) * | 2000-02-22 | 2001-08-29 | Secr Defence | Electrolytic reduction of metal oxides |
| WO2001062994A1 (en) * | 2000-02-22 | 2001-08-30 | Qinetiq Limited | Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction |
Non-Patent Citations (1)
| Title |
|---|
| New Scientist Magazine, Vol 170, 30/06/2001 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960907A (en) * | 2020-08-26 | 2020-11-20 | 攀枝花学院 | Emulsion explosive and preparation method thereof |
| CN112744858A (en) * | 2021-01-08 | 2021-05-04 | 孙淑珍 | Solvothermal preparation method of titanium suboxide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2387176B (en) | 2004-03-24 |
| GB0207625D0 (en) | 2002-05-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20060402 |