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WO1996014268A1 - Production de poudres de borure metallique - Google Patents

Production de poudres de borure metallique Download PDF

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Publication number
WO1996014268A1
WO1996014268A1 PCT/AU1995/000740 AU9500740W WO9614268A1 WO 1996014268 A1 WO1996014268 A1 WO 1996014268A1 AU 9500740 W AU9500740 W AU 9500740W WO 9614268 A1 WO9614268 A1 WO 9614268A1
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WO
WIPO (PCT)
Prior art keywords
boron
boride
oxide
metal
powder
Prior art date
Application number
PCT/AU1995/000740
Other languages
English (en)
Inventor
Patrice Millet
James Stanislaus Williams
Barry William Ninham
Original Assignee
The Australian National University
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
Application filed by The Australian National University filed Critical The Australian National University
Priority to AU37681/95A priority Critical patent/AU3768195A/en
Publication of WO1996014268A1 publication Critical patent/WO1996014268A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58071—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on titanium borides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides

Definitions

  • This invention concerns the production of metal borides, especially (but not exclusively) borides of metals which are in Group IVB of the Periodic Table.
  • the method of this invention involves the high energy milling of metallic oxides with boron in its amorphous or crystalline form, to produce, after annealing at a relatively low temperature, a reactive powder mixture from which boron oxide, B 2 0 2 , can be removed to leave the metal boride or a mixture of metal borides.
  • metal borides exhibit the properties of extreme hardness, high melting point, high electrical conductivity, good thermal shock resistance, chemical inertness and durability.
  • Borides of titanium and zirconium are refractory materials used as ballistic armour, as coatings for cutting tools, and, in the foundry and refractory industries, as crucibles and dies for handling molten metals. They are also used in the electrolytic production of aluminium, where their superior performance particularly their corrosion resistance - in comparison with the carbon cathodes normally used for this purpose is especially advantageous.
  • zirconium boride is used in hypersonic re-entry vehicles, for leading edges, nose caps, and rocket nozzle inserts.
  • TiB 2 and ZrB 2 are also used as components of high temperature composite materials such as TiB 2 /TiC, ZrB 2 /ZrC and Al 2 0 3 /TiB 2 .
  • titanium boride and zirconium boride usually involves the borothermic and carbothermic reduction of titania and zireonia, respectively.
  • the main disadvantages of such techniques are
  • the reaction requires the establishment of a high temperature, which is about 2,000°C when titanium boride is being produced, and is in the range of from 1,400°C to 1,700°C in the case of the production of zirconium boride; and (ii) the boride product is a polycrystalline material having an average grain size measured in microns ( ⁇ ) , whereas sub-micron particles are more useful when forming a dense refractory product.
  • This objective is achieved by high energy ball milling, preferably under vacuum conditions, of a dry powder mixture of a metal oxide (or a mixture of metal oxides) and boron. Heating the fine (nanostructural) powder so produced to a temperature in the range of from about 750°C to 1,100°C enables a thermochemical reaction (the borothermic reduction of the metal oxide or oxides) to take place, with the average particle size of the boride(s) produced by this reaction remaining in the sub-micron range.
  • the oxide of boron that is also produced by this reaction usually the dioxide, B 2 0 2 , in the amorphous state, can be removed from the product powder, preferably by the known technique of leaching with hot water - unless the (or a) required product boride is also soluble in hot water.
  • a method of producing a metal boride which comprises the sequential steps of (a) forming a powder mixture of the metal oxide and boron;
  • the metal oxide is preferably an oxide of a Group IVB metal, titania and zireonia being examples of Group IVB metal oxides.
  • step (a) more than one metal oxide may be mixed with boron in step (a) , in which case the product of this method will be a mixture of metal borides, which can be formed into a composite boride material.
  • a mixture of borides is also produced if the metal oxide of step (a) is a mixed oxide (such as ilmenite, FeTi0 3 ).
  • the boron used to form the mixture of step (a) may be amorphous boron or crystalline boron. If crystalline boron is used, a longer milling of the powder mixture will be required to produce the fine powder product of step (b), which is preferably a fine powder in which all the grains have a diameter of less than 1 micrometre (although, in practice, a number of crystallite grains may agglomerate to form a polycrystalline "particle" which has a diameter in excess of 1 micron).
  • the boride produced by the method of the present invention may be mixed with a fugitive binder and/or a sintering aid, then moulded under pressure and sintered (using either hot pressing or pressureless sintering) to produce a dense body.
  • the boride product may be mixed with another boride, a carbide, an oxide or other suitable material to produce a composite material having desirable properties.
  • the high energy milling step is performed under a primary vacuum of about 10 "2 torr, in a planar ball mill of the type described in the specification of Australian patent No 639,945. That ball mill is also described in the specification of International patent application No PCT/AU90/00471 (WIPO Publication No 91/04810).
  • suitable ball milling devices may be used to perform the present invention.
  • Figure 1 is a series of X-ray diffraction patterns, in graph form, with the intensity of the x-radiation of each pattern being shown in arbitrary units.
  • Figure 2 shows, also in graph form, differential thermal analysis data obtained from samples of titanium dioxide milled with amorphous boron.
  • Figure 3 comprises two further x-ray diffraction patterns, obtained from a sample of zireonia milled with amorphous boron.
  • Figure 4 presents differential thermal analysis data for the product of a sample of zireonia milled with amorphous boron.
  • Figure 5 comprises further x-ray diffraction patterns, obtained from a sample of ilmenite that has been milled with amorphous boron.
  • Figure 6 shows the differential thermal analysis data obtained from a sample of ilmenite which has been milled with amorphous boron. Best modes of performing the invention Example 1
  • the evolution of the structure of the powder as the milling time increased was monitored by observing the x-ray diffraction patterns of the milled powder, obtained using cobalt K ⁇ radiation.
  • the thermal properties of the milled powder were studied using a Shimadzu differential thermal analyser model No DTA-50.
  • the size of the particles in the milled powder was also monitored, using a scanning electron microscope.
  • Trace (a) of Figure 1 is the x-ray diffraction pattern of the sample milled in vacuo for 25 hours. This trace shows that the Ti0 2 component of the milled powder had retained the anatase structure. The broadening of the x-ray diffraction peaks and the low intensity observed are due to the very small grain size of the milled powder; they are characteristic features of milled powders.
  • trace (b) of Figure 1) After milling for 140 hours (trace (b) of Figure 1), there has been a phase transformation of the titanium dioxide, from the anatase structure (which is stable below 700 ⁇ C) to the rutile structure. This mechanically induced phase transition is consistent with other reported observations of milled titanium dioxide.
  • FIG. 2 shows the conventional differential thermal analysis (DTA) traces which were obtained for the samples of the powder mixture which had been milled for 25 hours (trace (a)) and 140 hours (trace (b)).
  • DTA trace for the powder mixture milled for 25 hours includes three exothermic peaks, at 762.62°C, at 857.21 ⁇ C and at 897.56 ⁇ C.
  • the higher temperature peaks overlap and form a broad second exothermic peak in the temperature range 785°C to 1,000°C.
  • the DTA trace for the powder mixture milled for 140 hours contains a similar first exothermic peak, but with a small shift to a lower temperature (760.07 ⁇ C), and a second broad peak having a more complicated structure. Several overlapping peaks are clearly visible in a temperature range which begins at a lower temperature than that of the beginning of the broad peak of the powder sample milled for 25 hours.
  • thermochemical reaction corresponding to the first DTA trace peak the powder sample milled for 25 hours was heated (in the Differential Thermal Analyser) in an atmosphere of argon to 785°C, maintained at that temperature for about two minutes, then cooled rapidly.
  • the x-ray diffraction pattern of the resultant material is shown as trace (c) of Figure 1.
  • This XRD trace clearly shows that there has been a reaction of the titanium dioxide with the amorphous boron, leading to the production of a mixture of Ti 2 0 3 and TiB0 3 .
  • Removal of the B 2 0 2 product could have been achieved by heating to a temperature of about 1,500°C, to vaporise the B 2 0 2 .
  • the B 2 0 2 went into solution and the fine particle size of TiB 2 product was not destroyed.
  • a powder mixture of zirconium dioxide (the material marketed by Hopkin and Williams Ltd, having a baddeleyite structure) and amorphous boron was prepared such that the atomic ratio of zirconium to boron was 1:4.
  • This powder mixture was dry milled in the ball mill used for Example 1, for 20 hours, under the same vacuum conditions.
  • the x-ray diffraction pattern obtained from the milled powder is shown as trace (a) of Figure 3. It will be noted that the peaks in this XRD pattern correspond to the zireonia structure, with broadening due to a decrease in the crystallite size of the milled powder.
  • the differential thermal analysis trace obtained for this milled powder is presented in Figure 4.
  • the DTA trace of Figure 4 is clearly different from the DTA traces obtained from the milled Ti0 2 /boron powder mixtures.
  • the trace of Figure 4 has a weak exothermic peak at approximately 750°C and a more pronounced exothermic peak at 1,012°C.
  • the closest standard diffraction pattern to the XRD pattern obtained of the higher symmetry structure material was the pattern of Zr0 2 JCPDS file No 27-997.
  • the zireonia/boron mixture milled for 20 hours, was heated to 1,100° (which is a temperature above the second exothermic peak of the DTA trace) , held at that temperature for several minutes, then cooled.
  • the x-ray diffraction pattern of the resultant powder is shown as trace (b) of Figure 3. Most of the peaks of this trace correspond to zirconium boride, ZrB 2 . Some small peaks corresponding to zireonia are also present, together with two small peaks which the present inventors have not yet matched with a chemical compound. It is clear from the XRD pattern, however, that ZrB 2 is the major product of the thermochemical reaction that has occurred during the short annealing at 1,100°C.
  • Boron dioxide which was also present in the material annealed at 1,100°C, was removed by washing with hot water.
  • Ilmenite supplied as a mineral sand by Westralian Sands Limited, was mixed with amorphous boron and samples of this powder mixture were dry milled in the ball mill used for Examples 1 and 2, under the same vacuum conditions.
  • the ilmenite had the following composition:
  • the powder product obtained by annealing the milled ilmenite/boron mixture at 1,100°C contained the amorphous B 2 0 2 phase.
  • Hot water leaching of the product powder removed the B 2 0 2 and also a significant amount of the FeB.
  • an alternative technique for removing the B 2 0 2 would be required if the desired end-product of the borothermic reduction is a mixture of iron boride and titanium boride.
  • the present invention provides a convenient and economic method for producing borides, which has the following advantageous features:
  • a high purity boride product is obtained; (c) only a relatively short period of high energy dry milling is required; (d) the annealing of the milled powder product requires a relatively low energy input as the annealing time is short and the annealing temperature is relatively low; and (e) the powder product comprises fine (sub-micron) grains, which are particularly useful for the production of refractory and other dense bodies, and composites with other materials.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

Des borures de titane et de zirconium ont traditionnellement été produits par réduction borothermique et carbothermique. Ce procédé requiert des températures extrêmement élevées, de l'ordre d'environ 2000 °C pour le carbure de titane et de 1400 °C à 1700 °C pour le borure de zirconium, ce qui résulte en un matériau polycristallin d'une granulométrie de l'ordre du micron, moins utile que les particules de dimensions sous-microniques dans la formation de produits réfractaires denses. On a résolu ce problème en effectuant le broyage à sec et à énergie élevée du matériau de départ (ilménite, zircone) et du bore agissant comme agent réducteur, sous vide ou en atmosphère inerte, pour former des particules de dimensions sous-microniques, et en réalisant ensuite une réduction borothermique à une température comprise entre 750 °C et 1100 °C en atmosphère inerte pour produire le borure (TiB2ZrB2) et un sous-produit de B2O2 amorphe. Le bore est un réducteur modéré qui réagit aisément avec les parties oxyde de fer du minerai, mais pas avec TiO2/ZrO2, qu'il convertit en métaborate, puis en TiB2/ZrB2. Le bore contenu dans le matériau de départ peut être à l'état cristallin ou amorphe. Le borure obtenu est de l'ordre du sous-micron (∫1ν), moins coûteux que ses prédécesseurs et aisément compacté et fritté sous forme d'un corps dense. Le produit final s'applique notamment aux blindages anti-projectiles, aux revêtements pour outils de coupe, aux creusets et aux matrices pour métaux fondus, aux cathodes pour la production électrolytique de l'aluminium, aux bords d'attaque et aux coiffes destinés à des véhicules effectuant une rentrée dans l'atmosphère à des vitesses hypersoniques, à des cols rapportés de tuyères de fusées, et à des composites haute température. Le sous-produit B2O2 peut être séparé du borure par lessivage à l'eau chaude.
PCT/AU1995/000740 1994-11-08 1995-11-08 Production de poudres de borure metallique WO1996014268A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37681/95A AU3768195A (en) 1994-11-08 1995-11-08 Production of metal boride powders

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AUPM9330A AUPM933094A0 (en) 1994-11-08 1994-11-08 Production of borides
AUPM9330 1994-11-08

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999059754A1 (fr) * 1998-05-15 1999-11-25 Advanced Nano Technologies Pty Ltd Procede de produciton de poudres ultrafines
US6203768B1 (en) 1995-08-28 2001-03-20 Advanced Nano Technologies Pty Ltd Process for the production of ultrafine particles
SG106032A1 (en) * 1998-10-02 2004-09-30 Univ Singapore Method for the production of ultrafine particles and nanocomposites
US7170138B2 (en) 1993-10-01 2007-01-30 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device
KR100839827B1 (ko) 2007-03-23 2008-06-19 한국과학기술연구원 전이금속 붕화물 분말의 제조 방법
CN102417188A (zh) * 2011-08-30 2012-04-18 中国科学院上海硅酸盐研究所 一种低氧含量亚微米级过渡金属硼化物粉体的制备方法
WO2014153637A1 (fr) * 2013-03-28 2014-10-02 Hydro-Quebec Procédé de production d'un matériau de gradient de champ aux propriétés sur-mesure
CN106517225A (zh) * 2016-11-15 2017-03-22 广东工业大学 一种超细M1‑xTixB2粉体的制备方法
WO2017223481A1 (fr) * 2016-06-23 2017-12-28 Alcoa Usa Corp. Systèmes et procédés de fabrication de poudres céramiques et de produits céramiques
CN110078489A (zh) * 2019-05-13 2019-08-02 海宁联丰磁业股份有限公司 一种低损耗软磁铁氧体材料及其制备方法
CN110818432A (zh) * 2019-11-19 2020-02-21 华南理工大学 一种超细高熵硼化物纳米粉体及其制备方法
WO2020077771A1 (fr) * 2018-10-15 2020-04-23 广东工业大学 Poudre de métal fondue solide ultrafine à entropie élevée, son procédé de préparation et son application
CN112919913A (zh) * 2021-03-16 2021-06-08 矿冶科技集团有限公司 高纯超细硼化铪粉体的制备方法、硼化铪粉体
CN113104857A (zh) * 2021-04-14 2021-07-13 吉林大学 一种过渡金属硼化物的低温制备方法

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CN110642261B (zh) * 2019-10-18 2022-08-05 福州大学 一种自组装无模板制备磷酸硼负载氧化硼复合物的三明治型空心球的方法
CN113816392A (zh) * 2021-10-14 2021-12-21 北京华威锐科化工有限公司 一种硼化铪粉体的制备方法

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* Cited by examiner, † Cited by third party
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US7170138B2 (en) 1993-10-01 2007-01-30 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device
US6203768B1 (en) 1995-08-28 2001-03-20 Advanced Nano Technologies Pty Ltd Process for the production of ultrafine particles
WO1999059754A1 (fr) * 1998-05-15 1999-11-25 Advanced Nano Technologies Pty Ltd Procede de produciton de poudres ultrafines
SG106032A1 (en) * 1998-10-02 2004-09-30 Univ Singapore Method for the production of ultrafine particles and nanocomposites
KR100839827B1 (ko) 2007-03-23 2008-06-19 한국과학기술연구원 전이금속 붕화물 분말의 제조 방법
CN102417188A (zh) * 2011-08-30 2012-04-18 中国科学院上海硅酸盐研究所 一种低氧含量亚微米级过渡金属硼化物粉体的制备方法
CN102417188B (zh) * 2011-08-30 2013-10-16 中国科学院上海硅酸盐研究所 一种低氧含量亚微米级过渡金属硼化物粉体的制备方法
EP2978712A4 (fr) * 2013-03-28 2016-11-16 Hydro Québec Procédé de production d'un matériau de gradient de champ aux propriétés sur-mesure
WO2014153637A1 (fr) * 2013-03-28 2014-10-02 Hydro-Quebec Procédé de production d'un matériau de gradient de champ aux propriétés sur-mesure
WO2017223481A1 (fr) * 2016-06-23 2017-12-28 Alcoa Usa Corp. Systèmes et procédés de fabrication de poudres céramiques et de produits céramiques
CN106517225A (zh) * 2016-11-15 2017-03-22 广东工业大学 一种超细M1‑xTixB2粉体的制备方法
CN106517225B (zh) * 2016-11-15 2021-02-12 广东工业大学 一种超细M1-xTixB2粉体的制备方法
WO2020077771A1 (fr) * 2018-10-15 2020-04-23 广东工业大学 Poudre de métal fondue solide ultrafine à entropie élevée, son procédé de préparation et son application
CN110078489A (zh) * 2019-05-13 2019-08-02 海宁联丰磁业股份有限公司 一种低损耗软磁铁氧体材料及其制备方法
CN110818432A (zh) * 2019-11-19 2020-02-21 华南理工大学 一种超细高熵硼化物纳米粉体及其制备方法
CN110818432B (zh) * 2019-11-19 2024-05-17 华南理工大学 一种超细高熵硼化物纳米粉体及其制备方法
CN112919913A (zh) * 2021-03-16 2021-06-08 矿冶科技集团有限公司 高纯超细硼化铪粉体的制备方法、硼化铪粉体
CN113104857A (zh) * 2021-04-14 2021-07-13 吉林大学 一种过渡金属硼化物的低温制备方法

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