WO2003066914A1 - Titane spongieux a purete elevee et son procede de production - Google Patents

Titane spongieux a purete elevee et son procede de production Download PDF

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Publication number
WO2003066914A1
WO2003066914A1 PCT/JP2002/001118 JP0201118W WO03066914A1 WO 2003066914 A1 WO2003066914 A1 WO 2003066914A1 JP 0201118 W JP0201118 W JP 0201118W WO 03066914 A1 WO03066914 A1 WO 03066914A1
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WO
WIPO (PCT)
Prior art keywords
vacuum separation
temperature
reaction vessel
center
oxygen
Prior art date
Application number
PCT/JP2002/001118
Other languages
English (en)
Japanese (ja)
Inventor
Hisayuki Wada
Original Assignee
Sumitomo Titanium Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2000238487A priority Critical patent/JP3756047B2/ja
Application filed by Sumitomo Titanium Corporation filed Critical Sumitomo Titanium Corporation
Priority to PCT/JP2002/001118 priority patent/WO2003066914A1/fr
Priority to CNB028274539A priority patent/CN100487144C/zh
Priority to EA200401055A priority patent/EA006077B1/ru
Priority to US10/502,732 priority patent/US20050145072A1/en
Priority to AU2002232157A priority patent/AU2002232157A1/en
Publication of WO2003066914A1 publication Critical patent/WO2003066914A1/fr

Links

Classifications

    • 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
    • C22B34/1295—Refining, melting, remelting, working up 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
    • 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
    • C22B34/1263—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, e.g. by reduction
    • C22B34/1268—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, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C22B34/1272—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, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/14—Refining in the solid state

Definitions

  • the present invention relates to a high-purity sponge titanium material suitable for a material for an evening gate material for sputtering and a method for producing the same.
  • the Kroll method consists of a reduction step in which molten Mg reacts with titanium tetrachloride in a reaction vessel, and after reduction, heats the reaction vessel in a vacuum state to heat unreacted Mg contained in the material in the vessel. And a vacuum separation step of evaporating and removing residual by-products.
  • titanium metal is as a wiring material in semiconductor devices such as LSI.
  • This wiring is formed by performing sputtering using high-purity metallic titanium as a target material. It is required that the sputter material for sputtering has a small amount of impurities.
  • the sponge titanium material which is a material of the sputter material, has an oxygen content of 20 ppm or less, Fe, Ni, Cr, and A. The content of each metal element of 1 and Si is required to be 10 ppm or less.
  • the crawl method is a method that prioritizes productivity, it is not easy to secure an impurity level required for an evening gate material for sputtering. Therefore, the following method has been proposed.
  • One is the top and bottom of the titanium sponge material obtained in the reaction vessel after vacuum separation. Centering method to commercialize the part near the center excluding the outer part and outer periphery
  • Another method is a low-moisture crushing method in which a sponge titanium material taken out of the reaction vessel is cut and crushed in a low-humidity atmosphere (Japanese Patent No. 2863469). No. 2,179,900).
  • the former method of centering can secure the level required for the evening getter material for sputtering for each of the metal elements Fe, Ni, Cr, A1, and Si.
  • the latter method of low-moisture crushing as for oxygen, a force capable of securing a level required for a target material for sputtering ⁇ Fe, Ni, Cr, A1, and Si. It is difficult to secure the level of each metal element.
  • both the Fe, Ni, Cr, A1, and Si metal elements, and oxygen the former should be selected as the center. It is necessary to combine this method with the latter method of low-moisture crushing.
  • the former method of centering is easy to implement, while the latter method of low-moisture crushing has a stable oxygen level actually required for the target material for sputtering.
  • a very large isolated work space with a low humidity inside is required, and the construction and maintenance of the atmosphere require a great deal of expense. I can not say.
  • An object of the present invention is to provide a high-purity titanium sponge material which is low in both the amount of oxygen and the amount of a metal element and which is excellent in economical efficiency, and a method for producing the same. Disclosure of the invention
  • FIG. 1 is a longitudinal sectional view of a titanium sponge material in a reaction vessel in a vacuum separation step.
  • the reaction vessel 20 is housed in a heating furnace 30. Since the titanium sponge material 10 in the reaction vessel 20 causes precipitation of titanium on the rostrol 21 in the reaction vessel 20 and on the inner surface of the side wall of the reaction vessel 20 in the previous reduction step, the middle part is narrowed. Shape.
  • the content of each of the metal elements Fe, Ni, Cr, A1, and Si decreases as the distance from the upper surface, the lower surface, and the outer peripheral surface increases. This is because the content of each metal element is mainly due to contamination from the reaction vessel 20. For this reason, by removing the upper, lower, and outer peripheral portions of the sponge titanium material 10 and collecting the remaining portion 11 near the center, the level of the metal element required for the evening getter material for sputtering can be reduced. Can be relatively easily secured.
  • the oxygen content particularly the oxygen content after cutting and crushing, surprisingly decreases in the surface layer of the sponge titanium material 10.
  • the oxygen amount increases closer to 1/2 part C.
  • 1/4 part B is about 300 ppm, that is, 1/2 part. Then it becomes about 3501 m. Due to this tendency, even if the portion 11 near the center of the titanium sponge material 10 is sampled, it becomes difficult to secure the level of oxygen required for the sputtering target material after cutting and crushing.
  • the present inventors have investigated the cause of the decrease in the amount of oxygen in the surface layer of the titanium sponge material 10 from both the physical properties and the production method. As a result, the following facts became clear.
  • Figure 2 shows the temperature change of the titanium sponge material in the vacuum separation process.
  • the upper part A, 1Z4 part B and 1Z2 part C are shown.
  • the temperature in either part tends to drop temporarily after the start of vacuum separation, then rises and reaches a stable temperature close to the furnace temperature. This is because the residual Mg starts to evaporate together with the vacuum separation, and the temperature temporarily decreases due to the heat of vaporization.However, the temperature starts to increase as the residual Mg decreases, and the furnace temperature increases when the evaporation is completed. Due to temperature stabilization at a level close to
  • the surface portion far from the center of the titanium sponge material is continuously heated for a long time even after the evaporation of Mg is completed, and becomes a so-called dry-fired state.
  • the present inventor believes that the heating time after the evaporation of the Mg is related to the oxygen amount after the cutting and crushing, and conducted various investigations. As a result, the farther from the center of the titanium sponge material, the more the empty firing state The sintering proceeds during the heating of the steel to reduce the specific surface area, and the smaller the specific surface area, the more the increase in the amount of oxygen due to oxidation in the cutting and crushing process is suppressed.
  • the high-purity titanium sponge material is a titanium sponge material produced by the chlorine method, and has a specific surface area of 0.05 m measured by the BET method. 2 Zg or less, and the content of each metal element of Fe, Ni, Cr, A1, and Si is 10 ppm or less.
  • the oxygen content of titanium particles is 300 ppm or less. Is suppressed. It is preferably at most 0.04 m 2 Zg, more preferably at most 0.03 m 2 / g, whereby the oxygen content is further reduced.
  • the preferred oxygen content after cutting and crushing is 200 ppm or less, more preferably 100 ppm or less.
  • each of the metal elements Fe, Ni, Cr, A1, and Si is limited to 10 ppm or less in order to eliminate the upper, lower, and outer peripheral portions of the titanium sponge material.
  • These surface layers for example, the uppermost portion A shown in Fig. 1, have been heated in the dry state, and the specific surface area by the BET method has been reduced.
  • the content of each metal element exceeds 1 O ppm.
  • a particularly preferred content of each metal element is 7 ppm or less.
  • the vacuum separation time t By setting the vacuum separation time t to (to +15) hours or more, the specific surface area of the material in the reaction vessel near the center excluding the upper, lower, and outer peripheral parts is reduced, and low oxygen after cutting and crushing is reduced. Is realized.
  • the content of each of the metal elements Fe, Ni, Cr, A1, and Si is also reduced. It is suppressed to a low level.
  • the particularly preferable vacuum separation time t has a lower limit of (t 0 +20) hours or more and an upper limit of (t 0 +30) hours or less.
  • the temperature at the center of the titanium sponge material is not measured. From the temperature change data obtained by test operation and temperature analysis for each operating facility, determine the time until the center temperature reaches a stable temperature, and set the heating time in the vacuum separation process based on this time.
  • Fig. 1 is a vertical cross-sectional view of the titanium sponge material in the reaction vessel in the vacuum separation process.
  • Fig. 2 shows the time-dependent temperature change of the titanium sponge material in the vacuum separation process.
  • B s 1/2
  • Fig. 3 is a graph showing the preferred vacuum separation time in the vacuum separation process with the diameter of the reaction vessel (retort diameter) as a parameter, and
  • Fig. 4 shows the different vacuum separation times. It is a micrograph of the sample taken from the central part of various kinds of sponge titanium materials.
  • the sponge titanium material is manufactured by melting Mg in a reaction vessel and dropping a titanium tetrachloride solution. When this reduction step is completed, the process proceeds to the vacuum separation step. In the vacuum separation process, the unreacted Mg and by-products are removed by evacuating the inside of the reaction vessel and heating it to a predetermined temperature with a heating furnace.
  • the temperature Ta at the top A of the titanium sponge material in the reaction vessel slightly decreases at the beginning of the vacuum separation, but immediately rises and reaches a stable temperature in about 20 to 30 hours after the start of the vacuum separation.
  • the temperature Tc at the center (1/2 part C) continues to drop for about 30 hours from the start of vacuum separation, and then rises to reach a stable temperature T0 70 hours after the start of vacuum separation.
  • the central portion temperature Tc reaches the stable temperature To
  • heating is continued for another 15 to 35 hours, preferably 20 to 30 hours.
  • the specific surface area by the BET method is reduced to 0.05 m 2 / g or less due to the progress of sintering.
  • cutting near the center after vacuum separation The increase in the amount of oxygen due to oxidation during the crushing process is suppressed, and the impurity level required for the evening getter material for sputtering can be achieved in both the amount of oxygen and the amount of metal elements.
  • the lump height of sponge titanium material 10 is H
  • the lump diameter is D
  • the thickness h1 from the upper surface is 0.1 H or more.
  • the thickness h2 from the lower surface is 0.25 H or more
  • the lower part is 0.18 D or more from the outer peripheral surface, and the outer peripheral part is 0.18 D or more.
  • the sample near the center 11 is usually cut and crushed in an air atmosphere to obtain titanium sponge particles having a predetermined particle size. Despite cutting and crushing in the air atmosphere, the amount of oxygen is suppressed to 300 ppm or less, and the amounts of metallic elements Fe, Ni, Cr, A1, and Si are also reduced. It is suppressed below 10 p pm.
  • the average particle size after crushing is preferably 10 to 300 mm.
  • FIG. 3 shows the result of investigation of a preferable vacuum separation time in the vacuum separation step.
  • a preferable vacuum separation time is a region indicated by hatching in FIG. The vacuum separation time is affected by the diameter (retort diameter) of the reaction vessel, and the longer the diameter, the longer the time.
  • the vacuum separation time in the present invention is +15 hours to +35 hours compared to the conventional vacuum separation time indicated by the solid line.
  • the specific surface area by the BET method in the vicinity of the center becomes less than 0.05 m 2 / g, and the oxygen content after cutting and breaking becomes less than 300 ppm.
  • the specific surface area by the BET method in the vicinity of the center becomes less than 0.03 m 2 Zg in more than +20 hours, and the oxygen content after cutting and crushing becomes less than 200 ppm.
  • the diameter (retort diameter) of the reaction vessel is preferably 135 to 200 mm. If it is less than 135 mm, metal impurities tend to increase even if the center is used. If it exceeds 2000 mm, equipment problems such as thermal deformation of the reaction vessel may occur.
  • the temperature change shown in Fig. 2 is when the diameter (retort diameter) of the reaction vessel is 100 mm, the conventional vacuum separation time is 70 hours, and in this case, the vacuum separation time in the present invention is 85 1105 hours, with 90-100 hours being especially preferred.
  • high-purity titanium sponge material of the present invention by limiting the specific surface area by BET method is less than 0. 05 m 2 Zg, cut crushed in the atmosphere means pursuant also the amount of oxygen in the low It is possible to economically secure the impurity level required for the evening getter material for sputtering, in combination with the reduction of metal impurities by centering.
  • the vacuum separation time t in the vacuum separation step is set such that the temperature Tc at the center of the material in the reaction vessel from the start of vacuum separation is set to a stable temperature To near the furnace temperature.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un titane spongieux à pureté élevée présentant une faible teneur en oxygène et en éléments métalliques, ce titane étant produit de manière économique. Le temps t de séparation sous vide dans une étape de séparation sous vide est t = t0 + 15 à + 35 heures, t0 étant le temps depuis le début de la séparation sous vide jusqu'au temps où la température de la partie centrale du matériau dans une cuve de réaction atteint une valeur stable. Au niveau et au voisinage de la partie centrale du matériau, dont la teneur en éléments métalliques est faible, la zone spécifique mesurée au moyen d'une méthode BET est inférieure à 0,05 m2/g. La teneur en oxygène après la coupe et le broyage est réduite à un faible niveau même si la coupe et le broyage sont réalisés dans l'atmosphère.
PCT/JP2002/001118 2000-08-07 2002-02-08 Titane spongieux a purete elevee et son procede de production WO2003066914A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2000238487A JP3756047B2 (ja) 2000-08-07 2000-08-07 高純度スポンジチタン材及びその製造方法
PCT/JP2002/001118 WO2003066914A1 (fr) 2000-08-07 2002-02-08 Titane spongieux a purete elevee et son procede de production
CNB028274539A CN100487144C (zh) 2000-08-07 2002-02-08 高纯度海绵钛材料及其制造方法
EA200401055A EA006077B1 (ru) 2000-08-07 2002-02-08 Губчатый титановый материал высокой чистоты и способ его изготовления
US10/502,732 US20050145072A1 (en) 2002-02-08 2002-02-08 High-purity sponge titanium material and its production method
AU2002232157A AU2002232157A1 (en) 2000-08-07 2002-02-08 High-purity spongy titanium material and its production method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000238487A JP3756047B2 (ja) 2000-08-07 2000-08-07 高純度スポンジチタン材及びその製造方法
PCT/JP2002/001118 WO2003066914A1 (fr) 2000-08-07 2002-02-08 Titane spongieux a purete elevee et son procede de production

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WO2003066914A1 true WO2003066914A1 (fr) 2003-08-14

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JP (1) JP3756047B2 (fr)
CN (1) CN100487144C (fr)
AU (1) AU2002232157A1 (fr)
EA (1) EA006077B1 (fr)
WO (1) WO2003066914A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100383266C (zh) * 2006-08-11 2008-04-23 遵义钛业股份有限公司 一种镁法生产海绵钛的四氯化钛雾化方法
CN102534261A (zh) * 2012-01-18 2012-07-04 深圳市新星轻合金材料股份有限公司 一种制备海绵钛的工艺方法
JP2019085599A (ja) * 2017-11-02 2019-06-06 東邦チタニウム株式会社 スポンジチタンの製造方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3756047B2 (ja) * 2000-08-07 2006-03-15 住友チタニウム株式会社 高純度スポンジチタン材及びその製造方法
JP4766931B2 (ja) * 2005-06-16 2011-09-07 Ｎｔｎ株式会社 誘電体セラミックスおよびその製造方法
LV13528B (en) * 2006-09-25 2007-03-20 Ervins Blumbergs Method and apparatus for continuous producing of metallic tifanium and titanium-bases alloys
CN101948961B (zh) * 2010-10-08 2011-11-30 洛阳双瑞万基钛业有限公司 一种用于制取海绵钛的反应器排氯化镁管制作方法
CN113718104A (zh) * 2021-08-31 2021-11-30 新星轻合金材料(洛阳)有限公司 一种低氧高钛铁合金制备工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6160839A (ja) * 1984-08-29 1986-03-28 Hiroshi Ishizuka 耐火金属の精製法
JPH07258765A (ja) * 1994-03-24 1995-10-09 Sumitomo Sitix Corp 高純度チタン材の製造方法
JP2001262246A (ja) * 2000-03-17 2001-09-26 Toho Titanium Co Ltd スポンジチタンの製造方法
JP2001279345A (ja) * 2000-03-30 2001-10-10 Toho Titanium Co Ltd チタンの製造方法
JP2002053922A (ja) * 2000-08-07 2002-02-19 Sumitomo Sitix Of Amagasaki Inc 高純度スポンジチタン材及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6160839A (ja) * 1984-08-29 1986-03-28 Hiroshi Ishizuka 耐火金属の精製法
JPH07258765A (ja) * 1994-03-24 1995-10-09 Sumitomo Sitix Corp 高純度チタン材の製造方法
JP2001262246A (ja) * 2000-03-17 2001-09-26 Toho Titanium Co Ltd スポンジチタンの製造方法
JP2001279345A (ja) * 2000-03-30 2001-10-10 Toho Titanium Co Ltd チタンの製造方法
JP2002053922A (ja) * 2000-08-07 2002-02-19 Sumitomo Sitix Of Amagasaki Inc 高純度スポンジチタン材及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100383266C (zh) * 2006-08-11 2008-04-23 遵义钛业股份有限公司 一种镁法生产海绵钛的四氯化钛雾化方法
CN102534261A (zh) * 2012-01-18 2012-07-04 深圳市新星轻合金材料股份有限公司 一种制备海绵钛的工艺方法
JP2019085599A (ja) * 2017-11-02 2019-06-06 東邦チタニウム株式会社 スポンジチタンの製造方法

Also Published As

Publication number Publication date
EA006077B1 (ru) 2005-08-25
CN1633511A (zh) 2005-06-29
CN100487144C (zh) 2009-05-13
AU2002232157A1 (en) 2003-09-02
EA200401055A1 (ru) 2004-12-30
JP2002053922A (ja) 2002-02-19
JP3756047B2 (ja) 2006-03-15

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