• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:SU1243612A3
    申请号:SU813279157
    申请日:1981-05-07
    公开日:1986-07-07
    发明作者:Бюттнер Гюнтер；Домацер Ханс-Гюнтер；Эггерт Хорст
    申请人:Т.Гольдшмидт Аг (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to powder metallurgy, in particular, to the recovery of doped metal powders by reduction with acid reducing metal.
    A known method for producing powders of titanium alloys by reducing the chloride melts of metals forming spl.d. with a reducing metal such as sodium l.
    The disadvantages of this method are its complexity and the limited use of the composition of the obtained alloys.
    The closest to the technical essence and the achieved effect to the invention is a method for producing titanium alloys, which involves the preparation of a mixture of oxides of titanium and alloying metals, the introduction of a reducing metal with an excess of 1.2-2.0 against the stoich. The quantity is reduced at a temperature of 1000-1300 ° C and the subsequent acid treatment of the reduced product 2j.
    In order to control the particle size distribution of alloy powders, the known method provides for the introduction of calcium oxide or sodium or calcium chloride to the mixture.
    The disadvantage of this method is the heterogeneity of the composition and structure of the obtained powders.
    The purpose of the invention is to increase the homogeneity and uniformity of the particle size distribution of the powder.
    To achieve this goal, according to the method for producing powders of titanium alloys, including the preparation of a mixture of titanium oxides and alloying metals, the introduction of a reducing metal with an excess of 1.2-2.0 against the stoichiometric amount, reduction at a temperature of 10
    the initial pressure, since in the case of heating the calcium-containing mixture to a temperature of lOOO-ISOO C, the vapor pressure of the metallic calcium is adjusted to this value. Metallic calcium 1-1 is in excess, so that it does not completely disappear during the reaction due to reduction. This means that during the reaction in the closed p € actor there is a significant
    20
    higher pressure than 10 mmHg. Art.
    The essence of the proposed method is as follows.
    A mixture of oxides of recoverable metals is prepared, to which also oxides or carbonates of alkaline-earth metals are added in an amount of 1: 1-6: 1, which, upon subsequent annealing of the mixture at a temperature of 1000–1300 ° C, form
    25
    complex oxide, which increases the homogeneity of the mixture. If calcium carbonate is added to the mixture, it decomposes, which. promotes the formation of active calcium oxide to the effusion of the mixture and the simplification of the subsequent grinding of the product after it is annealed.
    To the product obtained after annealing, a small amount of calcium, O, 5–8 mm in size (preferably 2–3 Miyi) and is added. potassium perchlorate, which in the process of the subsequent reduction of the mixture plays the role of a heating additive. The introduction of potassium perchlorate contributes to obtaining a homogeneity of the composition and form of particles of titanium alloy powder and accelerates the reduction process.
    After reduction, the reaction product is crushed to a particle size of less than 2 mm and washed off with dilute acids, for example hydrochloric or acetic acid. Alloy powder is washed and
    40
    Recovery of D 1000–1300 ° C and the subsequent acidic OZ are dried.
    Almost all operations are preferably carried out in inert gas. The method allows to obtain powders of titanium alloys: TiA16V4, TiA16V6Sn2, SO
    treatment of the reduced product, an oxide or alkaline earth metal carbonate is additionally introduced into the mixture of oxides in a molar ratio of 1: 1-6: 1 and annealed at a temperature
    , TiA114Mo4Sn2, TiAlZrSMoO, 5Si U, 25, TiAli2V11, 5Zr11Sn2, TiAl13V10Fe3 when the yield of a suitable product is more than 96%.
    1000-1300 ° C for 6-18 hours, after which granulated calcium and potassium perchlorate in the amount of 1: 0.01-1: 0.2 are added to the mixture, the mixture is pressed and reduced in a vacuum of 10 10 mm Hg. Art.
    The indication of vacuum refers to the state at the beginning of the process, i.e. to
    the initial pressure, since in the case of heating the calcium-containing mixture to a temperature of lOOO-ISOO C, the vapor pressure of the metallic calcium is adjusted to this value. Metallic calcium 1-1 is in excess, so that it does not completely disappear during the reaction due to reduction. This means that during the reaction in the closed p € actor there is a significant
    higher pressure than 10 mmHg. Art.
    The essence of the proposed method is as follows.
    A mixture of oxides of recoverable metals is prepared, to which also oxides or carbonates of alkaline-earth metals are added in an amount of 1: 1-6: 1, which, upon subsequent annealing of the mixture at a temperature of 1000–1300 ° C, form
    false oxide, which increases the homogeneity of the mixture. When calcium carbonate is introduced into the mixture, its decomposition occurs, which. promotes the formation of active calcium oxide to the effusion of the mixture and the simplification of the subsequent grinding of the product after it is annealed.
    After the annealing, the product is added. Small sized calcium O, 5-8 mm in size (preferably 2-3 Miyi) and. potassium perchlorate, which in the process of the subsequent reduction of the mixture plays the role of a heating additive. The introduction of potassium perchlorate contributes to obtaining a homogeneity of the composition and form of particles of titanium alloy powder and accelerates the reduction process.
    After reduction, the reaction product is crushed to a particle size of less than 2 mm and washed off with dilute acids, for example hydrochloric or acetic acid. Alloy powder is washed and
    dried
    Almost all operations are preferably carried out in inert gas. The method allows to obtain powders of titanium alloys: TiA16V4, TiA16V6Sn2, O
    five
    , TiA114Mo4Sn2, TiAlZrSMoO, 5Si U, 25, TiAli2V11, 5Zr11Sn2, TiAl13V10Fe3 when the yield of a suitable product is more than 96%.
    Example 1. Getting alloy TiA16V4.
    1377.10 g of TiO, 85.63 g of Alj, 0 ,, 65.60 g and 1601.20 g of CaCOe are mixed, annealed for 12 hours, the sintered material is crushed to a particle size less than 1 mm (bulk density 1.40 g / cm after morning 2.30 g / cm). In 1000 g of this mixture, 1070.6 g of calcium and 91.40 g of KC104 (0.08 mol
    The annealed product was crushed to a particle size less than 1 mm (bulk density 1.58 g / cm, after the morning 2.48 g / cm) 1000 g of this product is mixed with
    CCS per 1 mole of doped powder - 5 1991.80 g of calcium and 11.43 g of CCU ka), pressed billet with a diameter (about 0.01 mol of KC104 per mole
    doped powder) and pressed billet And 50 mm and a height of 30 mm.
    50 mm and a height of 30 mm and restore at a temperature of 1150 C in a titanium crucible at a pressure of 10 mm Hg. within 8 hours. The reaction product is crushed, leached with dilute hydrochloric acid, the powder is dried in vacuum.
    The resulting powder has a bulk density of 1.96 g / cm, after the morning 2.56 g / cm 3.
    Granulometric soslav powder as follows, May.%:
    500 microns 1.5 63-90 microns 4.6 355-500 microns 1.2 45-63 microns 9.6 250-355 microns 1.3 32-45 microns 10.5 180-250 microns 2.7 25-32 µm 10.1 125-180 µm 3.5 25 µm 49.0
    90-125 microns 4.9
    The chemical composition of the powder, may.% A1 5.85, V 3.93, Fe 0.05, Si 40.05, H 0.008, N 0.0160, C 0.07, O 0.11, Ca 0.07, Mg 0.01, Ti else.
    The powder has particles of lamellar10
    t5
    The blanks are placed in the reactor, pumped out to 10 mm Hg, heated to 1000 ° C and restored within 8 hours.
    The resulting product is crushed to a particle size of less than 2 mm, and then leached with formic acid.
    PRI me R 4. Obtaining alloy TiAl, 2Vl15Zr11Sn2.
    1245.22 g Tug, 38.0 g, 207.5 g VjOy, 149.4 g ZrO. , 23.1 g 20 SuO and 1601.2 g CaCOj are mixed and annealed at 1250 ° C for 12 hours.
    The annealed product was crushed to a particle size of less than 1 mm (bulk density 2.415 g / cm, after the morning, 3.185 g / 25 / cm), 1000 g of this product was mixed with 1640.2 g of calcium and 162.3 g of KC104 (0.01 mol KSYU per 1 mol of metal alloyed powder) is pressed into blanks And 50 mm and a height of 30 mm.
    structure and a homogeneous structure with a predominant content of d-phase p and an insignificant / 3-phase.
    Example 2. Getting alloy
    TiA16V4.
    1377.10 g TiOj, 85.63 g,
    65.60 g 1034.52 g CaO (1: 1) are mixed and annealed at 1000 ° C for 18 hours. The product is crushed to a particle size of less than 1 mm (bulk density 1.45 g / cm, after the morning, 2.28 g / cm is then added to 1000 g of oxide, 1051.62 g of calcium - 1: 1.2 mol) and 228 , 50 g KS104 (about 0.2 mol of JCO per 1 mol of powder) are mixed and pressed billet 0 50 mm and a height of 30 mm.
    The billets are placed in a reactor, from being pumped to 10 mm Hg, heated to 1300 ° C and reduced for 2 hours.
    Example 3. Getting alloy TiA16V4.
    1377.10 g of TiO, 85.63 g, 65.60 g, and 172.45 g of CaO (6: 1) are mixed and annealed at 1300 ° C for 6 hours.
    g,
    VNIIPI Order 3720/5
    Produced-software.PIGR. pr-tie, Uzhgorod, st. Project, 4
    The annealed product was crushed to a particle size of less than 1 mm (bulk density 1.58 g / cm, after the morning 2.48 g / cm), 1000 g of this product is mixed with

    The blanks are placed in the reactor, pumped out to 10 mm Hg, heated to 1000 ° C and restored within 8 hours.
    The resulting product is crushed to a particle size of less than 2 mm, and then leached with formic acid.
    PRI me R 4. Obtaining alloy TiAl, 2Vl15Zr11Sn2.
    1245.22 g Tug, 38.0 g, 207.5 g VjOy, 149.4 g ZrO. , 23.1 g of SuO and 1601.2 g of CaCOj are mixed and annealed at 1250 ° C for 12 hours.
    The annealed product was crushed to a particle size of less than 1 mm (bulk density 2.415 g / cm, after the morning 3,185 g / / cm), 1000 g of this product is mixed with 1640.2 g of calcium and 162.3 g of KC104 (0.01 mol of CAS per 1 mole of metal alloyed powder), pressed into billet And 50 mm and a height of 30 mm.
    The billet is placed in the reactor, it is pumped out to 10 mm Hg. and vozOg
    Set at 1150 ° C for .8 h. The reaction product is crushed, leached with dilute hydrochloric acid, and the powder is dried under vacuum.
    The resulting powder has a bulk density of 2.68 g / cm, after the morning 3.13 g / cm3.
    The granulometric composition of the powder next, May.%:
     - g .-- 500 microns 1,8
    355-500 microns 250-355 microns 180-250 microns 10.2 125-180 microns 13.2 90-125 microns
    The chemical composition of the powder, wt.%: A1 1.90, V 11.20, Zr 10, 7, Su 1.80, Si 0.05., Fe 0.05, H 0.010, N 0.014, C 0.07, O 0.10, Ca 0.10, Mg 0.01, Ti the rest.
    The powder has a homogeneous structure with a predominant content of the / 3-phase.
    Circulation 757 Subscription
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING POWDERS OF TITANIUM ALLOYS, including the preparation of a mixture of titanium oxides and alloying metals, the introduction of a metal reducing agent in excess
    1.2-2.0 against a stoichiometric amount, reduction at a temperature of 1000-1300 ° C and subsequent acid treatment of the reduced product, characterized in that, in order to increase the homogeneity and uniformity of the particle size distribution, an oxide or carbonate is additionally introduced into the mixture of oxides alkaline earth metal in a molar ratio of 1: 1-6: 1 and anneal it at a temperature of 1000-1300 ° C for 6-18 hours, after which granular calcium and potassium perchlorate are added to the mixture in an amount of 1: 0.01-1 : 0.2, the mixture is pressed and reduced in vacuo IU 10 ' 4 -10 mmHg
    SU, 1243612 AZ to the initial pressure, since in the case of heating a calcium-containing mixture to a temperature of 1000–1300 ° С, the vapor pressure of metallic calcium is adjusted to this value. There is an excess of metallic calcium, so that during the reaction it does not completely disappear due to reduction. ' This means that during the reaction in a closed reactor there is a significantly higher pressure than 10 * 4 10 6 mm RT. Art.
    The essence of the proposed method is as follows.
    A mixture of oxides of reduced metals is prepared, to which alkali-earth metal oxides or carbonates are also added in an amount of 1: 1-6: 1, which, upon subsequent annealing of mixture 20 at a temperature of 1000 ~ 1300 ° C, form a complex oxide, which increases the uniformity of the mixture composition. In the case of introducing a mixture of calcium carbonate is its decomposition something contributing to the formation 25 is subsequently grinding the active product mixture loosening calcium oxide and simplify after annealing.
    To the product obtained after annealing about 30 , small-sized calcium of 0.5-8 mm (preferably 2-3 mm) and is added. potassium perchlorate, which during the subsequent recovery of the mixture plays the role of a heating additive. The introduction of potassium perchlorate promotes the production of particles of a titanium alloy powder that are uniform in composition and shape and accelerates the recovery process.
    40 After reduction, the reaction product is crushed to a particle size of less than 2 mm and washed with dilute acids, for example, hydrochloric or acetic acid. The alloy powder is washed and dried.
    Almost all operations are preferably carried out in an inert gas environment. The method allows to obtain powders of titanium alloys: T1A16V4, TiA16V6Sn2, 50 TiA114Mo4Sn2, TiAlZr5MoO, 5Si U, 25, TiAll‘2Vl1, 5Zr11Sn2, TiAl13V10Fe3 with a yield of more than 96X.
    Example 1. Obtaining alloy T1A16V4.
    55 1377.10 g Ti0 2 , 85.63 g A1 0 ,
    65.60 g V 2 0 and 1601.20 g of CaCO e are mixed, annealed at 1100 ° C for 12 hours, the cake is ground to large
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1243612A3|1986-07-07|Method of producing titanium alloy powders
    US4980141A|1990-12-25|Hexagonal-bipyramid crystalline scandium oxide powder and a process for preparing the same
    US4954169A|1990-09-04|Fine-grained, high-purity earth acid metal powders, a process for their production and their use
    RU2406593C2|2010-12-20|Removal of magnesium from powders recovered by magnesium
    JPH0791636B2|1995-10-04|Sputtering target and method for producing the same
    HU203854B|1991-10-28|Process for producing clean aluminium-oxide
    US2992095A|1961-07-11|Process of separating niobium and tantalum values in oxidic ores and of producing pure niobium
    RU2408450C2|2011-01-10|Producing barrier metal powders with improved physical and electrical properties
    EP1215175B1|2007-03-21|Preparation of epsilon-phase silver vanadium oxide | from gamma-phase SVO starting material
    US2750271A|1956-06-12|Process of making pulverulent metallic titanium
    JPH0624747A|1994-02-01|Production of lead metal niobate
    US2486530A|1949-11-01|Manganate type contact mass and production thereof
    US3236634A|1966-02-22|Process for production of high surface area tungsten and tungsten trioxide powders
    JP3398318B2|2003-04-21|Manufacturing method of titanium ingot
    JP2590091B2|1997-03-12|Refractory metal silicide target and its manufacturing method
    RU2052528C1|1996-01-20|Scandium obtaining method
    JPH04191340A|1992-07-09|Production of high purity tin
    JP2610575B2|1997-05-14|W-Ti alloy target
    CA1069868A|1980-01-15|Hydration-disintegration of alloy containing material produced by a reduction-diffusion process
    RU2043873C1|1995-09-20|Titanium powder production method
    JPH06124815A|1994-05-06|Manufacture of material powder of r-tm-b group permanent magnet
    JP2934469B2|1999-08-16|Method for producing small soluble palladium lumps
    JP3843165B2|2006-11-08|Method for removing antimony from hydrofluoric acid solution containing Ta / Nb
    SU1201224A1|1985-12-30|Method of producing stannous chloride
    RU2060290C1|1996-05-20|Method for production of magnetic alloys
    同族专利:
    公开号 | 公开日
    EP0039791A1|1981-11-18|
    JPS5925003B2|1984-06-13|
    US4373947A|1983-02-15|
    AT3214T|1983-05-15|
    DE3160220D1|1983-06-09|
    CA1174083A|1984-09-11|
    DD158799A5|1983-02-02|
    DE3017782A1|1981-11-19|
    EP0039791B1|1983-05-04|
    DE3017782C2|1982-09-30|
    JPS572806A|1982-01-08|
    CS342581A2|1991-10-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US8216508B2|2002-06-14|2012-07-10|General Electric Company|Method for preparing a metallic article having an other additive constituent, without any melting|DE179403C|1904-05-20|
    DE935456C|1938-08-26|1955-11-17|Hartmetallwerkzeugfabrik Meuts|Process for the production of alloy powders|
    US2287771A|1940-01-09|1942-06-30|Peter P Alexander|Production of powdered alloys|
    US2922712A|1952-12-30|1960-01-26|Chicago Dev Corp|Method for producing titanium and zirconium|
    US2834667A|1954-11-10|1958-05-13|Dominion Magnesium Ltd|Method of thermally reducing titanium oxide|
    US2800404A|1955-08-15|1957-07-23|Dominion Magnesium Ltd|Method of producing titanium alloys in powder form|
    DE1129710B|1956-02-08|1962-05-17|Dominion Magnesium Ltd|Process for the production of titanium alloys in powder form|
    US2984560A|1960-02-08|1961-05-16|Du Pont|Production of high-purity, ductile titanium powder|
    FR1343205A|1962-12-18|1963-11-15|Hoeganaes Sponge Iron Corp|Processes for obtaining alloys and powders of metallic alloys and obtained by these processes|
    US4164417A|1978-04-28|1979-08-14|Kawecki Berylco Industries, Inc.|Process for recovery of niobium values for use in preparing niobium alloy products|DE3343989C1|1983-12-06|1984-12-13|Th. Goldschmidt Ag, 4300 Essen|Process for the production of fine-particle, low-oxygen chrome metal powder|
    US4525206A|1983-12-20|1985-06-25|Exxon Research & Engineering Co.|Reduction process for forming powdered alloys from mixed metal iron oxides|
    GB8519379D0|1985-08-01|1985-09-04|Shell Int Research|Processing by melt-spinning/blowing|
    US4923531A|1988-09-23|1990-05-08|Rmi Company|Deoxidation of titanium and similar metals using a deoxidant in a molten metal carrier|
    US5354354A|1991-10-22|1994-10-11|Th. Goldschmidt Ag|Method for producing single-phase, incongruently melting intermetallic phases|
    US5211775A|1991-12-03|1993-05-18|Rmi Titanium Company|Removal of oxide layers from titanium castings using an alkaline earth deoxidizing agent|
    US6010661A|1999-03-11|2000-01-04|Japan As Represented By Director General Of Agency Of Industrial Science And Technology|Method for producing hydrogen-containing sponge titanium, a hydrogen containing titanium-aluminum-based alloy powder and its method of production, and a titanium-aluminum-based alloy sinter and its method of production|
    US6935917B1|1999-07-16|2005-08-30|Mitsubishi Denki Kabushiki Kaisha|Discharge surface treating electrode and production method thereof|
    US6428823B1|2001-03-28|2002-08-06|Council Of Scientific & Industrial Research|Biologically active aqueous fraction of an extract obtained from a mangrove plant Salvadora persica L|
    US6638336B1|2002-05-13|2003-10-28|Victor A. Drozdenko|Manufacture of cost-effective titanium powder from magnesium reduced sponge|
    US7410610B2|2002-06-14|2008-08-12|General Electric Company|Method for producing a titanium metallic composition having titanium boride particles dispersed therein|
    US6737017B2|2002-06-14|2004-05-18|General Electric Company|Method for preparing metallic alloy articles without melting|
    US7329381B2|2002-06-14|2008-02-12|General Electric Company|Method for fabricating a metallic article without any melting|
    US7531021B2|2004-11-12|2009-05-12|General Electric Company|Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix|
    US7001443B2|2002-12-23|2006-02-21|General Electric Company|Method for producing a metallic alloy by the oxidation and chemical reduction of gaseous non-oxide precursor compounds|
    US6926755B2|2003-06-12|2005-08-09|General Electric Company|Method for preparing aluminum-base metallic alloy articles without melting|
    US7410562B2|2003-08-20|2008-08-12|Materials & Electrochemical Research Corp.|Thermal and electrochemical process for metal production|
    US7794580B2|2004-04-21|2010-09-14|Materials & Electrochemical Research Corp.|Thermal and electrochemical process for metal production|
    US20050220656A1|2004-03-31|2005-10-06|General Electric Company|Meltless preparation of martensitic steel articles having thermophysically melt incompatible alloying elements|
    US7604680B2|2004-03-31|2009-10-20|General Electric Company|Producing nickel-base, cobalt-base, iron-base, iron-nickel-base, or iron-nickel-cobalt-base alloy articles by reduction of nonmetallic precursor compounds and melting|
    US7833472B2|2005-06-01|2010-11-16|General Electric Company|Article prepared by depositing an alloying element on powder particles, and making the article from the particles|
    US20070017319A1|2005-07-21|2007-01-25|International Titanium Powder, Llc.|Titanium alloy|
    US20070141374A1|2005-12-19|2007-06-21|General Electric Company|Environmentally resistant disk|
    NZ548675A|2006-07-20|2008-12-24|Titanox Dev Ltd|A process for producing titanium metal alloy powder from titanium dioxide and aluminium|
    US9150943B2|2007-01-22|2015-10-06|Materials & Electrochemical Research Corp.|Metallothermic reduction of in-situ generated titanium chloride|
    JP4514807B2|2008-04-10|2010-07-28|山本貴金属地金株式会社|Method for producing noble metal fine particles|
    US8007562B2|2008-12-29|2011-08-30|Adma Products, Inc.|Semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder|
    DE102015102763A1|2015-02-26|2016-09-01|Vacuumschmelze Gmbh & Co. Kg|A method of manufacturing a thermoelectric article for a thermoelectric conversion device|
    CN106282661B|2016-08-26|2018-01-02|四川三阳激光增材制造技术有限公司|A kind of method for preparing block titanium matrix composite|
    CN107236869B|2017-05-23|2019-02-26|东北大学|A kind of method of multistage drastic reduction preparation reduction titanium valve|
    CN107151752B|2017-06-13|2018-10-23|东北大学|The method for preparing titanium alloy with wash heat refining based on the reduction of aluminothermy self- propagating gradient|
    CN107775011B|2017-10-26|2020-08-11|攀钢集团攀枝花钢铁研究院有限公司|Method for preparing titanium powder|
    CN113510246A|2020-03-25|2021-10-19|中国科学院过程工程研究所|Preparation method of Ti-6Al-4V alloy powder and Ti-6Al-4V alloy powder prepared by same|
    US20220062993A1|2020-08-28|2022-03-03|Velta Holdings US Inc.|Method for producing alloy powders based on titanium metal|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE3017782A|DE3017782C2|1980-05-09|1980-05-09|Process for the production of sinterable alloy powders based on titanium|
    [返回顶部]