CN101018894A - Production of titanium - Google Patents
Production of titanium Download PDFInfo
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- CN101018894A CN101018894A CNA2005800253377A CN200580025337A CN101018894A CN 101018894 A CN101018894 A CN 101018894A CN A2005800253377 A CNA2005800253377 A CN A2005800253377A CN 200580025337 A CN200580025337 A CN 200580025337A CN 101018894 A CN101018894 A CN 101018894A
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- pelletizing
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
- C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Powder Metallurgy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A method of producing titanium semi-finished or ready-to-use products from titanium oxide powders and/or pellets is disclosed. The method produces products that are not affected adversely by levels of chlorine that have an impact on performance, particularly weldability, of products made by other methods.
Description
The present invention relates to the manufacturing of a kind of titanium metal and titanium metal alloy.
The present invention especially but be to relate to a kind of manufacture method of making half-finished or standby titanium metal (comprising titanium alloy) product uniquely anything but, these products are products as thin slice, rod, pipe and other form of the titanium metal that obtains from titanium dioxide powder and/or pelletizing.
Now, Kroll and Hunter method are only commercial runs that is used to make titanium metal.
These methods comprise TiCl
4Carry out chemical reduction with molten magnesium or sodium metal in a sealed reactor, this reactor has been evacuated and has used the rare gas element backfill.In a method, the material after reduction is finished in thermal reactor is by metal and the muriate of vacuum distilling with the vaporization magnesium and sodium.Make this reactor cooling and from reactor, reclaim solid material, i.e. titanium sponge then.
This titanium sponge can use two kinds of methods to process.
A kind of method is again a melting method, is included in the inert atmosphere fusion titanium sponge and forms ingot casting from molten mass.Afterwards, this ingot casting quilt is by being processed into work in-process or alternate products as forging, hot-work technology rolling and extruding, such as the product of thin slice, rod, pipe and other form.
Another kind method is direct drawing method, comprises this titanium sponge is crushed to granular normally powder and uses the standard powder metallurgical processing method as roll compaction that particle directly is pressed into work in-process or alternate products.
Kroll and shortcoming of Hunter product of forming by direct drawing method are that the weldability of this product when using the welding technology welding is relatively poor.Thereby relatively poor weldability is owing to the instability of the chlorine that is generally 1000-1500ppm and tungsten electrode reaction the causing electric arc of the high density in product when these products of arc-welding.
Relatively poor weldability is not because fused product has lower basically cl concn again by the problem of the Kroll of scorification formation again and Hunter product.Yet scorification is a kind of method more expensive than straight pressing again.
EI Du Pont Nemours ﹠amp in the fifties in 20th century and the sixties; Company has developed following technology and product:
A) a kind of technology that is used to make titanium metal powder, this technology are applicable to that by powder metallurgic method directly compacting is to form the titanium metal product of work in-process or backup form, such as the product of thin slice, rod, pipe and other form; With
B) a kind of titanium metal powder processing technology that is used to make these end products.
Du Pont technical description comprises United States Patent (USP) 29846560,3072347,3478136 and 3084042 in a lot of United States Patent (USP)s.
The Kroll method is the source technology that is used for titanium sponge that is used by Du Pont in Du Pont technology.
Du Pont finds that it can make a kind of frangible titanium sponge metal, and this titanium sponge grinds when having salt to exist can make a kind of highly purified needle powder.Du Pont finds that also this powder is to be applicable to well in the roll gap of milling train directly to suppress to make thin slice.In addition, Du Pont finds that this powder can be applicable to well and is pressed into blank, then, this blank can in squeezer, be processed to half-finished or alternate products as rod, pipe and other shape.
Yet Du Pont finds that the weldability of Du Pont product is relatively poor.
As the situation of the Kroll product of the direct compacting made from routine, the weldability difference of Du Pont product is owing to the chlorine in the product.
Du Pont has reported following discovery: the chlorine in the Kroll product volatilizees fast in welding and causes the accumulation of salt on the tungsten grid for welding, and this has caused unsettled electric arc and has finally caused the weldability of difference.The amount of chlorine is greater than 50ppm.
Problem and final Du Pont that Du Pont can not reduce the weldability difference that the concentration of chlorine in the titanium metal or otherwise address cause because of chlorine do not make this technology commercialization.
The applicant has carried out big quantity research to the electrochemical method that is used to reduce as the metal oxide of titanium oxide.
Applicant's electrochemical process is described among International Application PCT/AU03/00306 of applicant with embodiment.Disclosure in the international application at this by cross reference.
Applicant's electrochemical process is the substitute technology of a kind of Kroll and Hunter method.
Described in applicant's electrochemical process such as the international application relate to a kind of in electrolyzer the solid-state metal oxide of reduction, this electrolyzer comprises an anode, negative electrode and a kind of molten electrolyte that comprises a kind of metallic cation that can the chemical reduction metal oxide.
International application is paid close attention to especially as the titanium oxide with titanium dioxide and is reduced into titanium metal.
Electrochemical process as the applicant described in the international application is characterised in that following operation steps: metal can be deposited on the negative electrode with metallic forms under the current potential of the current potential that is higher than metallic cation that can the chemical reduction metal oxide, and this metallochemistry reduces this metal oxide thus.
Although the applicant has been surprised to find powder and/or pelletizing that applicant's electrochemical process has made the titanium metal (also comprising titanium alloy) with high concentration cl, this chlorine not to the weldability that makes product from powder and/or pelletizing produce with the Kroll that forms by straight pressing and Hunter product the identical harmful effect of situation of chlorine.
Applicant's test work shows that the electrochemical process by the applicant has significantly much better weldability from the product that titanium metal makes than those Kroll products, can compare with the Hunter product with the Kroll that straight pressing forms although the cl concn of this product has, be generally 1000-1500ppm.
The applicant believes that Kroll that straight pressing forms is the key factor of cl concn to the relative little influence of weldability generation of applicant's product with chlorine form (mainly being magnesium chloride and sodium-chlor) and the chlorine form (mainly being calcium chloride) in applicant's product in the Hunter product.
Exactly, the chlorine in the Kroll of straight pressing and the Hunter product can think and be a kind of evaporable form that is easier to, the chlorosity of this form easily and the tungsten of grid for welding react and make the electric arc instability.
On the other hand, the chlorine in applicant's product seem be not easy to the volatilization.
This is a great discovery, because it means that not needing titanium metal powder that the electrochemical process to the applicant makes and/or pelletizing to carry out a large amount of back electrolyzers handles to reduce cl concn to usually less than the concentration of 50ppm.Consider the Kroll that straight pressing makes and the experience of Hunter product, it is essential with the work in-process that obtain to make from titanium metal powder and/or pelletizing or the acceptable weldability of alternate products that these cl concns are considered to.Therefore, under weldability was important situation, applicant's product can be the surrogate of the lower cost of the Kroll that makes by melt-processed method again and Hunter product.
The invention provides a kind of method of making titanium metal (comprising titanium alloy) work in-process or alternate products from titanium dioxide powder and/or pelletizing, this method comprises the following steps:
(a) electrochemical reduction titanium dioxide powder and/or pelletizing and make titanium metal powder and/or pelletizing in an electrolyzer, this electrolyzer comprises an anode, a negative electrode and a kind of molten electrolyte, this electrolytic solution contains a kind of positively charged ion of metal, and this positively charged ion can chemical reduction titanium oxide and muriatic negatively charged ion; With
(b) titanium metal powder that in step (a), makes of processing and/or pelletizing and form and have the work in-process or the alternate products of 100ppm cl concn at least.
The work in-process that step (b) makes or the cl concn of alternate products can be at least 200ppm, normally 500ppm and more commonly 1000ppm and the weldability of product do not had harmful effect at least at least.Usually, the cl concn in work in-process or the alternate products is less than 2000ppm.
Preferred titanium dioxide powder and/or pelletizing have 3.5mm or the littler powder and/or the small size of pelletizing.Under powder and/or pelletizing situation spherical in shape usually, " little " size will powder and/or the diameter of pelletizing to mention " little " size be unessential.Yet, be to be configured as the selectable shape of dish and when having different size, " little " size of mentioning is important at powder and/or pelletizing.For example, be that the size of measurement is considered to minimum size, and this is a kind of important consideration when having the dish of cylinder side wall, flat-top and diapire and 20mm diameter and 2mm thickness at pelletizing.
More preferably, the size of titanium dioxide powder and/or pelletizing is less than 2.5mm.
More preferably, powder and/or pelletizing are of a size of 1-2mm.
Preferred step (a) comprises titanium oxide is electrochemically reduced to have the titanium metal that oxygen concn is no more than 0.5% weight.
More preferably, oxygen concn is no more than 0.3% weight.
More preferably, oxygen concn is no more than 0.1% weight.
Preferred electrolytic solution is the CaCl that comprises as the CaO of one of component
2Base electrolytic solution.
Preferred step (a) comprises that the current potential of keeping electrolyzer is higher than the decomposition potential of CaO.
Preferred step (a) comprises that the current potential of keeping electrolyzer is lower than CaCl
2Decomposition potential.
Step (a) can batch-wise, successive or semi-continuous form are carried out.
For example, step (a) can be carrying out based on successive or semi-continuous form described in International Application PCT/AU03/001657 of applicant.Disclosure in the international application at this by cross reference.
Preferred step (b) comprises processes the titanium metal powder and/or the pelletizing that make in the step (a) in the following way: with titanium metal powder and/or pelletizing from high temperature to low temperature quenching, titanium metal has low relatively rate of oxidation in air under this low temperature.
Preferably low temperature is envrionment temperature.
Preferred step (b) comprises that water quenches titanium metal powder and/or pelletizing.
Step (b) can comprise by titanium metal powder and/or pelletizing being pressed into work in-process or alternate products and processing treatment by the titanium metal powder and/or the pelletizing that make in the step (a).
When work in-process or alternate products were thin slice, step (b) can comprise: with titanium metal powder and/or pelletizing rolling compacting slivering, this bar of sintering is with the mechanical property of promoting this with the cold rolling sheet step of this agglomerating bar.
Selectively, step (b) is except rolling is suppressed these powder and/or pelletizing, can comprise by powder metallurgy processing treatment titanium metal powder and/or pelletizing, titanium metal powder and/or the pelletizing that makes in the step (a) is processed into work in-process or alternate products.
Preferred steps (b) comprises that compacting titanium metal powder and/or pelletizing are to form work in-process or the alternate products such as thin slice, rod, pipe and other form.
The present invention also provides a kind of and has had titanium metal work in-process or an alternate products that cl concn is at least 100ppm by what aforesaid method made.
As mentioned above, the cl concn of work in-process or alternate products can be 200ppm at least, usually 500ppm and more common 1000ppm at least and the weldability of product is not produced harmful effect at least.Usually, the cl concn of work in-process or alternate products is less than 2000ppm.
As mentioned above, the present invention is based on applicant's test work.Test work is summarized as follows:
1.0 foreword
The weldability of following product is assessed in test work:
(a) 15-20mm * 10mm * 2mm titanium metal bar, this metal strip are by obtain (sample NTC (1) NIC (3)) at the titanium metal pelletizing that the method described in International Application PCT/AU03/00306 makes by the applicant
(b) to be the applicant obtain from commerce 2 grades of titanium bars on sale that it has less than the cl concn of 20ppm and is (sample WM (1) and the WM (2)) that the Kroll that forms by scorification again and Hunter product make for 45mm * 15mm * 2mm titanium metal bar, this metal strip.
(c) 45mm * 15mm * 2mm titanium metal bar, metal strip (sample WK (1)-WK (4)) that to be the applicant obtain from the titanium sponge metal of the cl concn with 1000-1500ppm of Kroll that forms by straight pressing and Hunter products production.
The NTC sample makes through the following steps.The titanium metal pelletizing that makes according to the method described in International Application PCT/AU03/00306 is the 15mm rank.Clean these pelletizings to remove residual electrolytic solution and to process the carbide that is bonded at the pelletizing surface to remove then.The pelletizing of crushing then becomes the 1-1.5mm particle size and cleans once more to remove also residual electrolytic solution.Then the mold pressing particle become density be 80-85% and afterwards sintering to increase density to 85-90%.Cold rolling then this particle to be to form the bar of complete densification, and promptly density is at least 98% bar and cuts into little of above-mentioned size.
The WM sample is by making from Kroll and the Hunter product that forms by scorification again, and cl concn cuts into little of above-mentioned size less than the titanium bar of 20ppm and makes.
The WK sample is to obtain from commerce Kroll and Hunter powder on sale, and this product is then this to be cut into little of above-mentioned size by the bar that above-mentioned and mould compacting, sintering and cold rolling step NTC sample identical sequence directly are pressed into complete densification.
2.0 equipment
In order to assess these weldability, use the technology GTAW of welding source (Migatronic Navigator400AC/DC) and make up a kind of specific rare gas element protection cell and backing plate.Use a kind of stepper motor driver to implement welding torch lower linear workpiece movement.Use is based on data gathering system (AMC Weld check
TM) computer monitor electrical parameter (voltage and current).The profile of electric arc is to monitor by the video recorder of analog ccd camera (Panasonic F15) and high quality VHS (S).Welding setting is summarised in the following table.
Welding setting | ||
Power supply | Migatronic?Navigator | 400AC/DC |
Polarity | DCEN | |
Protection gas | Argon gas | 12L/ minute |
Chamber gas | Argon gas | 18L/ minute |
The chamber clarification time | 1 minute | |
Electrode diameter | 3.2mm | |
The electrode drift angle | 120 degree | |
The arc length degree | 2mm | |
Translational speed | 40mm/ minute |
3.0 assessment technology
Have approximately and welding for the first time on the austenite stainless steel bar of titanium metal bar same size to determine welding setting and protection effect.
Then titanium metal bar (sample NTC (1)-NTC (3), WM (1), WM (2) and WK (1)-WK (4)) is carried out butt welding with 25 amperes rated current.
Electric current and voltage are every automatic record and by using macroscopical telephoto lens and suitable welding strainer to carry out the videograph of electric arc in 1 second.Video after the electrode tip situation is directly finished by welding and visual examination and grinding spark outward appearance are monitored.
4.0 result
Test-results is summarised in the following table.
Sample number | Remarks |
NTC(1) | Stable arc is compared less electric arc swing sign and voltage change and better welding bead outward appearance with the WK sample |
NTC(2) | Same NTC (1) |
NTC(3) | Same NTC (1) |
WM(1) | Very stable electric arc, small voltage change, good welding bead outward appearance and because of the slight through welding of thickness of sample |
WM(2) | Very stable electric arc, small voltage change, good welding bead outward appearance and homogeneity through welding |
WK(1) | Obviously the swing of visible electric arc is changed the outward appearance that can confirm, significant ripple is arranged in the possible electrode fouling, welding bead by arc voltage |
WK(2) | Serious electric arc swing, electrode fouling and fusion, the weld appearance of extreme difference are polluted obviously during electrode regrinding, the grinding before each test |
WK(3) | Same WK (2) |
WK(4) | Same WK (2) |
5.0 discuss
Use the standard operating procedure of titanium in rare gas element surrounds, to use the method for GTAW that the titanium metal bar is welded.
Although be intended that assessment originally based on porosity and brittle weldability but find that the sample that provides can clearly be implemented with electric arc and electrode fouling be distinguished.Even these effects will make material become " can not weld " before considering porosity under the poorest situation.
The welding of sample NTC (the 1)-NTC (3) that makes according to the present invention has good arc stability and good welding bead outward appearance is arranged.
The sample WM (1) and the WM (2) that are made by the commercial low chlorine level 2 titanium bars of buying have good arc stability and welding bead outward appearance.
Be easy to identify by the Kroll/Hunter powder that contains 1000-1500ppm chlorine and sample WK (1)-WK (4) that pelletizing makes by arc instability, unacceptable welding bead and serious electrode corrosion.In addition, sample WK (1) and WK (2) show tangible welding bead ripple and some electrode corrosions and sample WK (3) and WK (4) have shown more serious electrode corrosion and unstable.
Can carry out many modifications to above-mentioned preferred implementation without departing from the spirit and scope of the present invention.
Claims (23)
1. method of making titanium metal (comprising titanium alloy) work in-process or alternate products from titanium dioxide powder and/or pelletizing, this method comprises the following steps:
(a) electrochemical reduction titanium dioxide powder and/or pelletizing and make titanium metal powder and/or pelletizing in an electrolyzer, this electrolyzer comprises an anode, a negative electrode and a kind of molten electrolyte, this electrolytic solution contains a kind of positively charged ion of metal, and this positively charged ion can chemical reduction titanium oxide and muriatic negatively charged ion; With
(b) titanium metal powder that makes in the processing treatment step (a) and/or pelletizing and formation have the work in-process or the alternate products of 100ppm cl concn at least.
2. the process of claim 1 wherein that titanium dioxide powder and/or pelletizing have 3.5mm or the littler powder and/or the small size of pelletizing.
3. the method for claim 2, wherein the size of titanium dioxide powder and/or pelletizing is the small size less than powder and/or the pelletizing of 2.5mm.
4. the method for claim 2, wherein powder and pelletizing are of a size of the small size of powder and/or the pelletizing of 1-2mm.
5. aforesaid right requires arbitrary method, and wherein step (a) comprises titanium oxide is electrochemically reduced to the titanium metal that oxygen concn is no more than 0.5% weight.
6. the method for claim 5, wherein oxygen concn is no more than 0.3% weight.
7. the method for claim 5, wherein oxygen concn is no more than 0.1% weight.
8. aforesaid right requires arbitrary method, and wherein electrolytic solution is the CaCl that comprises as the CaO of one of component
2Base electrolytic solution.
9. aforesaid right requires arbitrary method, and wherein electrolytic solution is the CaCl that comprises as the CaO of one of component
2Base electrolytic solution and step (a) comprise that the current potential of keeping electrolyzer is higher than the decomposition potential of CaO.
10. aforesaid right requires arbitrary method, and wherein electrolytic solution is the CaCl that comprises as the CaO of one of component
2Base electrolytic solution and step (a) comprise that the current potential of keeping electrolyzer is lower than CaCl
2Decomposition potential.
11. aforesaid right requires arbitrary method, wherein step (a) can batch-wise, successive or semi-continuous form carry out.
12. aforesaid right requires arbitrary method, wherein step (b) comprises the titanium metal powder that will make in the step (a) and/or pelletizing processing treatment in the following way: with titanium metal powder and/or pelletizing from high temperature to low temperature quenching, titanium metal has low relatively rate of oxidation in air under this low temperature.
13. the method for claim 12, wherein low temperature is envrionment temperature.
14. the method for claim 12 or 13, wherein step (b) comprises that water quenches titanium metal powder and/or pelletizing.
15. aforesaid right requires arbitrary method, wherein step (b) comprises titanium metal powder and/or the pelletizing that makes in the processing treatment step (a) by titanium metal powder and/or pelletizing are pressed into work in-process or alternate products.
16. the method for claim 15, wherein when work in-process or alternate products are thin slice, step (b) comprises titanium metal powder and/or pelletizing rolling compacting slivering, and this bar of sintering is with the mechanical property that increases this and with the cold rolling sheet step of this agglomerating bar.
17. the method that claim 1-15 is arbitrary, wherein step (b) is except that rolling is suppressed this powder and/or pelletizing, also comprises processing this titanium metal powder and/or pelletizing by powder metallurgy and titanium metal powder and/or the pelletizing processing treatment that makes in the step (a) being become work in-process or alternate products.
18. aforesaid right requires arbitrary method, wherein work in-process or alternate products comprise the product of thin slice, rod, form of tubes.
19. one kind by aforesaid right require that either party's method makes a kind of to have be the titanium metal work in-process or the alternate products of 100ppm cl concn at least.
20. the titanium metal work in-process or the alternate products of claim 19, wherein cl concn is 200ppm at least.
21. the titanium metal work in-process or the alternate products of claim 19, wherein cl concn is 500ppm at least.
22. the titanium metal work in-process or the alternate products of claim 19, wherein cl concn is 1000ppm at least.
23. the titanium metal work in-process or the alternate products of claim 19, wherein cl concn is 2000ppm at least.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2004903532 | 2004-06-28 | ||
AU2004903532A AU2004903532A0 (en) | 2004-06-28 | Production of titanium |
Publications (1)
Publication Number | Publication Date |
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CN101018894A true CN101018894A (en) | 2007-08-15 |
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ID=35781502
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CNA2005800253377A Pending CN101018894A (en) | 2004-06-28 | 2005-06-23 | Production of titanium |
Country Status (10)
Country | Link |
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US (1) | US20070181436A1 (en) |
EP (1) | EP1776491A4 (en) |
JP (1) | JP2008504438A (en) |
CN (1) | CN101018894A (en) |
AU (1) | AU2005256146B2 (en) |
BR (1) | BRPI0512782A (en) |
CA (1) | CA2572300A1 (en) |
RU (1) | RU2370575C2 (en) |
WO (1) | WO2006000025A1 (en) |
ZA (1) | ZA200700107B (en) |
Cited By (1)
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CN109082686A (en) * | 2018-09-20 | 2018-12-25 | 成都先进金属材料产业技术研究院有限公司 | Rod-like shape titanium valve and preparation method thereof |
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CN101006204A (en) * | 2004-06-22 | 2007-07-25 | Bhp比利顿创新公司 | Electrochemical reduction of metal oxides |
WO2006010229A1 (en) * | 2004-07-30 | 2006-02-02 | Bhp Billiton Innovation Pty Ltd | Electrochemical reduction of metal oxides |
CA2575580A1 (en) * | 2004-07-30 | 2006-02-02 | Bhp Billiton Innovation Pty Ltd | Electrochemical reduction of metal oxides |
AT509526B1 (en) * | 2010-02-26 | 2012-01-15 | Univ Wien Tech | METHOD AND DEVICE FOR PREPARING METALS FROM THEIR OXIDES |
GB201208698D0 (en) * | 2012-05-16 | 2012-06-27 | Metalysis Ltd | Electrolytic method,apparatus and product |
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US6143241A (en) * | 1999-02-09 | 2000-11-07 | Chrysalis Technologies, Incorporated | Method of manufacturing metallic products such as sheet by cold working and flash annealing |
WO2001062995A1 (en) * | 2000-02-22 | 2001-08-30 | Qinetiq Limited | Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms |
AUPR712101A0 (en) * | 2001-08-16 | 2001-09-06 | Bhp Innovation Pty Ltd | Process for manufacture of titanium products |
AU2002356516A1 (en) * | 2001-09-12 | 2003-03-24 | F.W. Gartner Thermal Spraying Company | Nanostructured titania coated titanium |
JP2003129268A (en) * | 2001-10-17 | 2003-05-08 | Katsutoshi Ono | Method for smelting metallic titanium and smelter therefor |
AUPS117002A0 (en) * | 2002-03-13 | 2002-04-18 | Bhp Billiton Innovation Pty Ltd | Minimising carbon transfer in an electrolytic cell |
EA007046B1 (en) * | 2002-03-13 | 2006-06-30 | Би Эйч Пи БИЛЛИТОН ИННОВЕЙШН ПТИ ЛТД. | Reduction of metal oxides in an electrolytic cell |
JP2004156130A (en) * | 2002-09-11 | 2004-06-03 | Sumitomo Titanium Corp | Titanium oxide porous sintered compact for production of metal titanium by direct electrolysis process, and its manufacturing method |
RU2334024C2 (en) * | 2002-12-12 | 2008-09-20 | Би Эйч Пи БИЛЛИТОН ИННОВЕЙШН ПТИ ЛТД | Electrochemical reduction of metal oxides |
JP2004360025A (en) * | 2003-06-05 | 2004-12-24 | Sumitomo Titanium Corp | Method for manufacturing metallic titanium with direct electrolysis method |
JP2004360053A (en) * | 2003-06-09 | 2004-12-24 | Sumitomo Titanium Corp | Method for manufacturing low-carbon metallic titanium with direct electrolysis method |
JP4347089B2 (en) * | 2004-03-01 | 2009-10-21 | 株式会社大阪チタニウムテクノロジーズ | Method for producing Ti or Ti alloy by Ca reduction |
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2005
- 2005-06-23 AU AU2005256146A patent/AU2005256146B2/en not_active Ceased
- 2005-06-23 BR BRPI0512782-3A patent/BRPI0512782A/en not_active IP Right Cessation
- 2005-06-23 RU RU2007103181/02A patent/RU2370575C2/en not_active IP Right Cessation
- 2005-06-23 JP JP2007518407A patent/JP2008504438A/en active Pending
- 2005-06-23 WO PCT/AU2005/000907 patent/WO2006000025A1/en active Application Filing
- 2005-06-23 CN CNA2005800253377A patent/CN101018894A/en active Pending
- 2005-06-23 EP EP05752414A patent/EP1776491A4/en not_active Withdrawn
- 2005-06-23 CA CA002572300A patent/CA2572300A1/en not_active Abandoned
-
2006
- 2006-12-27 US US11/616,419 patent/US20070181436A1/en not_active Abandoned
-
2007
- 2007-01-02 ZA ZA200700107A patent/ZA200700107B/en unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109082686A (en) * | 2018-09-20 | 2018-12-25 | 成都先进金属材料产业技术研究院有限公司 | Rod-like shape titanium valve and preparation method thereof |
CN109082686B (en) * | 2018-09-20 | 2020-04-07 | 成都先进金属材料产业技术研究院有限公司 | Rod-shaped titanium powder and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CA2572300A1 (en) | 2006-01-05 |
WO2006000025A1 (en) | 2006-01-05 |
RU2370575C2 (en) | 2009-10-20 |
JP2008504438A (en) | 2008-02-14 |
RU2007103181A (en) | 2008-08-10 |
BRPI0512782A (en) | 2008-04-08 |
ZA200700107B (en) | 2008-05-28 |
US20070181436A1 (en) | 2007-08-09 |
AU2005256146A1 (en) | 2006-01-05 |
EP1776491A4 (en) | 2007-10-10 |
EP1776491A1 (en) | 2007-04-25 |
AU2005256146B2 (en) | 2010-11-25 |
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