EP1999070A1 - Matériau fritté, mélange pulvérulent frittable, procédés de production dudit matériau et son utilisation - Google Patents

Matériau fritté, mélange pulvérulent frittable, procédés de production dudit matériau et son utilisation

Info

Publication number
EP1999070A1
EP1999070A1 EP07723198A EP07723198A EP1999070A1 EP 1999070 A1 EP1999070 A1 EP 1999070A1 EP 07723198 A EP07723198 A EP 07723198A EP 07723198 A EP07723198 A EP 07723198A EP 1999070 A1 EP1999070 A1 EP 1999070A1
Authority
EP
European Patent Office
Prior art keywords
sintered material
phase
transition metal
material according
diboride
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP07723198A
Other languages
German (de)
English (en)
Inventor
Hubert Thaler
Clemens Dr. Schmalzried
Frank Wallmeier
Georg Victor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ESK Ceramics GmbH and Co KG
Original Assignee
ESK Ceramics GmbH and Co KG
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 ESK Ceramics GmbH and Co KG filed Critical ESK Ceramics GmbH and Co KG
Publication of EP1999070A1 publication Critical patent/EP1999070A1/fr
Withdrawn legal-status Critical Current

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    • 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
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    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
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    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium

Definitions

  • the invention relates to a sintered material based on transition metal diborides, pulverulent sinterable mixtures for producing such a sintered material, to processes for producing such sintered materials and to the use of the sintered material as a corrosion protection material for salt and metal melts, in particular kryolithhal- term Melting, for the production of thermocouple protection tubes for cryolite-containing melts, as electrode protection material, electrode material or material for the cell lining in the Al fused-salt electrolysis, as well as electrode material for sliding contacts, welding electrodes and erosion pins.
  • Titanium diboride has a number of advantageous properties, such as a high melting point of 3,225 ° C, a high hardness of 26-32 GPa (HV), excellent room temperature electrical conductivity and good chemical resistance.
  • titanium diboride A major disadvantage of titanium diboride is its poor sinterability.
  • the poor sinterability is due in part to impurities, especially oxygen impurities in the form of TiÜ 2 , which are contained in the commonly used titanium diboride powders, either by the carbothermal reduction of titanium oxide and boron oxide or by the known as Borcarbidvon reduction of me talloxide with Carbon and / or boron carbide are produced.
  • oxygen impurities enhance grain and pore growth in the sintering process by increasing surface diffusion.
  • Sintered titanium diboride materials can be made by the hot pressing process. For example, by axial hot pressing with sintered achieved temperatures above 1.800 0 C and a pressure of> 20 MPa densities of above 95% of the theoretical density, wherein the hot-pressed material typically has a grain size of more than 20 microns.
  • the disadvantage of the hot pressing method is that only simple body geometries can be produced thereby, while bodies or components with complex geometries can not be produced by this method.
  • components with more complex geometries can be produced via the pressure-loss sintering process.
  • suitable sintering aids are, for example, metals, such as iron and iron alloys.
  • metals such as iron and iron alloys.
  • By adding small amounts of iron dense materials with good mechanical properties and high fracture toughnesses of more than 8 MPa m 1/2 can be obtained.
  • Such materials are described for example in EP 433 856 B l.
  • these materials have the disadvantage that they have a poor corrosion resistance due to the metallic binder phase and in particular are not resistant to cryolite and cryolite-containing melts.
  • EP 0 073 743 B1 describes corrosion-resistant titanium diboride materials in comparison with aluminum melts, titanium hydride and boron being used as compaction additives for their production via a pressure-sintering process. Since these additives exert no obvious grain growth inhibiting effects, it comes at the applied sintering temperatures of up to 2,200 0 C to giant grain growth and, consequently, in reduced strength and increased micro-cracking due to grain sizes above the critical grain size.
  • US Pat. No. 4,500,643 discloses that a sintered material made of pure, fine-grained titanium diboride is resistant to the operating conditions of aluminum alloys.
  • the titaniboride material described in this US patent has a porosity of 10 to 45% by volume, the pores being interconnected, so that a continuous porosity is present. Due to the open porosity, this material, despite its resistance to cryolite, is not suitable for the separation of various media, in particular it is not suitable as a corrosion protection material for cryolite.
  • the material is also unsuitable for the production of thermocouple protection tubes for the Al melt flow electrolyte, and it can not be used as an anode protection material in the Al fused-salt electrolysis. Due to the high porosity, the material is also not mechanically strong enough.
  • the invention is therefore based on the object of providing a sintered material which not only has good mechanical properties, but is also corrosion-resistant to salt and metal melts, in particular cryolite-containing melts. Furthermore, the material should have a closed porosity to be effective as corrosion protection. Furthermore, such a sintered material should be producible by a simple and inexpensive process, which also allows the production of moldings with complex geometries.
  • the invention thus provides a sintered material based on transition metal diborides containing a) as the main phase 90-99 wt .-% of a fine-grained transition metal diboride or transition metal diboride mixed crystal of at least two transition metal diborides or mixtures of such diboride mixed crystals or mixtures of such diboride mixed crystals with one or more transition metal diborides, wherein the transition metals from IV.
  • the invention further provides a pulverulent sinterable mixture for producing a sintered material based on transition metal diborides, comprising 1) 0.05-2% by weight of Al and / or Si as metallic Al and / or Si and / or a content thereof corresponding amount of an Al and / or Si compound, 2) optionally at least one component selected from carbides and borides of transition metals of IV. to VI. Subgroup of the Periodic Table, 3) 0.5-12% by weight of boron,
  • Component 2 is different.
  • the invention further provides a process for producing such a sintered material by hot pressing or hot isostatic pressing or gas pressure sintering or spark plasma sintering of a pulverulent mixture as described above, optionally with the addition of organic binding and pressing aids.
  • the invention likewise provides a process for producing a sintered material as described above by pressure-sintering, comprising the steps: a) mixing a powdery mixture as described above, optionally with the addition of organic binding and pressing aids in water and / or organic solvents to produce a homogeneous powder suspension, b) preparing a powder granules from the powder suspension, c) pressing the powder granules into green bodies of high density , and d) pressureless sintering of the obtained green bodies in vacuo or under protective gas at a temperature of 1,800-2,200 0 C.
  • the sintered material according to the invention is suitable as a corrosion protection material for salt and metal melts, in particular cryolite-containing melts.
  • the invention therefore also relates in particular to the use of the sintered material for the production of thermocouple protection tubes for cryolite-containing melts.
  • the sintered material according to the invention is likewise suitable as an electrode protection material, electrode material or material for the cell lining in the Al fused-salt electrolysis and as electrode material for sliding contacts, welding electrodes and erosion pins.
  • the above-mentioned object is achieved by providing a sintered, dense material based on transition metal diborides whose matrix (main phase) consists of a fine-grained transition metal diboride or transition metal diboride mixed crystal or combinations thereof.
  • the material contains particulate boron carbide and / or silicon carbide, which acts as a grain growth inhibitor.
  • the material may contain as a third phase an oxygen-containing, non-continuous grain boundary phase.
  • the mixed crystal formation of the main phase has an additional grain growth inhibiting effect, so that a sintered material having good mechanical properties is obtained.
  • Residual contents of impurities such as, for example, oxygen-containing impurities, may be present in particulate form between the grain boundaries or at the triple points of the grain boundaries.
  • the sintered material according to the invention has a surprisingly excellent corrosion resistance. resistance to salt and metal melts, including cryolite-containing melts.
  • the microstructure of the material according to the invention consists of a transition metal diboride or transition metal diboride mixed crystal of at least two transition metal diborides or mixtures of such diboride mixed crystals or mixtures of such diboride mixed crystals with one or more transition metal diborides.
  • a second phase is present in a small proportion particulate Borcabid and / or silicon carbide, which is located mainly at the grain boundaries.
  • the boron carbide and / or silicon carbide additionally acts as a particle-reinforcing agent.
  • an oxygen-containing third phase can be present in a small proportion at the triple points of the material. It is important that the oxygen-containing phase does not form a continuous grain boundary film.
  • particulate carbon and / or particulate boron present may also be present in the material.
  • low contents of these elements may be present in the main phase. If the oxygen-containing third phase is present, its proportion is preferably up to 2.5 wt .-%.
  • the main phase preferably has an average particle size of less than 20 ⁇ m, more preferably less than 10 ⁇ m.
  • the boron carbide and / or silicon carbide of the second phase preferably has an average particle size of less than 20 microns, more preferably less than 5 microns.
  • the determination of the average grain size of the main phase and the average particle size of the boron carbide and / or silicon carbide is carried out by the linear intercept length method on the etched ground.
  • transition metals of IV. To VI. Subgroups are preferably selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W.
  • the main phase is preferably fine-grained TiB 2 and / or ZrB 2 and / or a mixed crystal of (Ti 1 W) B 2 and / or (Zr 1 W) B 2 and / or (Ti 1 Zr) B 2 , more preferably a mixed crystal of (Ti 1 W) B 2 and / or (Zr 1 W) B 2 , including the ternary diborides (Ti 1 Zr 1 W) B 2 .
  • it is preferably the mixed crystal (Ti 1 W) B 2 or the mixed crystal (Zr 1 W) B 2 .
  • the proportion of WB 2 in the main phase is preferably not more than 7% by weight.
  • the pulverulent, sinterable mixture according to the invention for producing a sintered material according to the invention contains the following components:
  • Al and / or Si as metallic Al and / or Si and / or an amount of an Al corresponding to this content. and / or Si compound.
  • Al or oxygen-containing Al compounds, in particular Al 2 O 3 or boehmite, are preferably used.
  • transition metal carbides and borides of transition metals of IV optionally, preferably> 0.25% by weight of at least one component selected from carbides and borides of transition metals of IV.
  • component 2 transition metals of IV.
  • component 2 transition metals of IV.
  • component 2 transition metals of IV.
  • component 2 transition metals of transition metal carbides, their proportion may be up to 15% by weight.
  • the added carbon serves to reduce the oxides contained in the starting materials as impurities or oxides formed during sintering.
  • suitable carbon compounds are dispersed carbon black, phenolic resins and sugars.
  • the radical at least one transition metal diboride of IV.
  • the transition metals are selected from Ti, Zr, Hf, V, Nb 1 Ta 1 Cr, Mo and W.
  • the transition metals transition metal diboride of component 6) is preferably ⁇ B 2 and / or ZrB 2 , more preferably ⁇ B 2 .
  • the above components of the pulverulent mixture are preferably used in the highest possible purity and with a small particle size.
  • the transition metal diboride of component 6) preferably has an average particle size of not more than 4 ⁇ m, more preferably not more than 2 ⁇ m.
  • the sintered material according to the invention can be produced in a manner known per se by hot pressing, hot isostatic pressing, gas pressure sintering or spark plasma sintering of a pulverulent mixture as described above, optionally with the addition of organic binding and pressing aids.
  • customary organic binders such as polyvinyl alcohol (PVA), water-soluble resins and polyacrylic acids and customary pressing aids such as fatty acids and waxes can be used.
  • At least one transition metal diboride of IV At least one transition metal diboride of IV.
  • To VI. Subgroup processed with the other powder-shaped components and optionally organic binding and pressing aids in water and / or organic solvents to form a homogeneous powder suspension.
  • the homogeneous powder suspension is then converted into a powder granules, preferably by spray drying. This powder granulate can then be further processed by hot pressing or hot isostatic pressing or gas pressure sintering to form a sintered material.
  • the production of the sintered material according to the invention by Drucklossintern by Drucklossintern.
  • a powder granules obtained as described above are pressed into green bodies of high density.
  • customary shaping methods such as axial pressing or calcostatic pressing, but also extrusion, injection molding, slip casting and pressure slip casting.
  • the green bodies obtained are then transferred in a vacuum or under protective gas at a temperature of 1,800-2,200 0 C, preferably 1,900-2,100 0 C, more preferably about 2,000 0 C, by pressureless sintering in a sintered material.
  • Vorzugswelse the green bodies are annealed prior to Drucklossintern in an inert atmosphere at temperatures below the sintering temperature to remove the organic binding or pressing aids.
  • the materials obtained by pressure-sintering have a density of at least about 94% of the theoretical density, preferably a density of at least 97% of the theoretical density. Such density values ensure that porosity, if present, is present as closed porosity.
  • the sintered material may be densified by hot isostatic pressing to increase the density and to reduce the closed porosity.
  • the transition metal boride formed and / or the added transition metal boride of the above-mentioned component 2) may form a mixed crystal with the transition metal diboride of component 6), such as titanium diboride.
  • This boride mixed crystal formation has a grain growth inhibiting effect.
  • the boron carbide, both the added and the example of tungsten carbide and boron formed, also acts grain growth inhibiting.
  • the oxygen impurities contained in the powder mixture react as completely as possible in order to prevent the formation of continuous, oxygen-containing grain boundary films. This is done by reduction with boron and the added carbon and / or carbon compounds, but also by evaporation in vacuo. Preferably, volatile oxides in the temperature range between 1600 and 1700 0 C can be removed at higher temperatures.
  • the Al and / or Si or their compounds act as sintering aids, the microstructure formed indicating a liquid-phase sintering process.
  • the cryolite-resistant and dense, fine-grained material according to the invention is suitable for wear applications.
  • the sintered material according to the invention is furthermore outstandingly suitable as a corrosion protection material for salt and metal melts, such as Al and Cu melts, in particular cryolite-containing melts.
  • Specific applications of the sintered material according to the invention are thermocouple protection tubes for cryolite-containing melts, electrode protection materials, electrode materials or materials for the cell lining in the Al fused-salt electrolysis, as well as electrode materials for sliding contacts, welding electrodes and erosion pins.
  • FIG. 1 shows a light micrograph of the microstructure of the material obtained in Example 1;
  • Figure 2 shows a light micrograph of the microstructure of Figure 1 after the cryolite test
  • Figure 3 is a photomicrograph of the microstructure of the sintered material obtained in Example 2.
  • Figure 4 shows a light micrograph of the microstructure of Figure 3 after the cryolite test
  • FIG. 5 shows a light micrograph of the microstructure of the sintered material obtained in Reference Example 1; 1 Figure 6 shows a light micrograph of the microstructure of Figure 5 after the cryolite test;
  • FIG. 7 shows a light micrograph of the microstructure of the sintered material obtained in Reference Example 2;
  • Figure 8 shows a light micrograph of the microstructure of Figure 7 after the cryolite test
  • Figure 9 shows a light micrograph of the microstructure of the sintered material obtained in Reference Example 3.
  • Figure 10 shows a light micrograph of the microstructure of Figure 9 after the cryolite test
  • Figure 11 shows a TEM brightfield image of a representative area of the microstructure of Figure 1;
  • Figure 12 shows a TEM bright field image (left) perpendicular to the grain boundary of the microstructure from Figure 1 1 and the associated one-dimensional spectrum image (right) along the white line shown in the left image.
  • the sample together with an amount of pure cryolite completely covering the material, is heated in a closed carbon crucible and kept at 1000 ° C. for 24 hours. Subsequently, the interface is assessed microscopically.
  • the spray granules are cold isostatically pressed into green bodies at 1200 bar.
  • the green bodies are heated at a heating rate of 10 K / min under vacuum to 2020 0 C and held at sintering temperature for 45 minutes. Cooling takes place with switched off heating power under Ar.
  • the density of the obtained sintered bodies is 98% of the theoretical density.
  • the resulting microstructure consists of a (Ti, W) B 2 mixed crystal matrix, particulate B 4 C and particulate boron (see TEM images in Figure 1 1).
  • the TEM studies performed on this sample show that the grain boundaries are free of oxygen and other impurities.
  • the (Ti, W) B 2 mixed crystal also contains low levels of aluminum.
  • Example 2 a sample of the dimension 10 ⁇ 10 ⁇ 10 mm 3 is subjected to a cryolite test and exposed to a Cryolithschmelze for 24 hours at 1000 0 C. Subsequent microstructural examination of the sample shows that the grain boundaries are stable compared to the cryolite attack (see Figure 2).
  • Example 2
  • the spray granules are cold isostatically pressed into green bodies at 1200 bar.
  • the green bodies are heated at a heating rate of 10 K / min in vacuo to 1650 0 C, the holding time at 1650 ° C is 45 min, then is heated at 10 K / min to 2020 0 C and 45 min held at sintering temperature. Cooling takes place with switched off heating power under Ar.
  • the density of the resulting sintered bodies is 97.8% of the theoretical density.
  • the resulting microstructure consists of a (Ti, W) B 2 mixed crystal matrix, particulate B 4 C and particulate boron.
  • Oxide impurities in the grain boundary can be removed by evaporation and the reduction of oxides during the additional annealing at 1650 0 C.
  • the spray granules are cold isostatically pressed into green bodies at 1200 bar.
  • the green bodies are heated at a heating rate of 10 K / min under vacuum to 2020 0 C and 45 minutes held at sintering temperature. Cooling takes place with switched off heating power under Ar.
  • the density of the obtained sintered bodies is 97.9% of the theoretical density.
  • the resulting microstructure consists of a (Ti, W) B 2 mixed crystal matrix, particulate B 4 C, a particulate Ti-Al-BO phase and a continuous amorphous oxygen-containing grain boundary film. Due to the formation of a continuous approximately 2 nm thick oxygen-containing grain boundary film, the material has a grain boundary penetration of cryolite at 1000 0 C. Due to grain boundary corrosion, massive material disintegration occurs ( Figure 6)
  • the spray granules are cold isostatically pressed into green bodies at 1200 bar.
  • the green bodies are heated at 10 K / min under vacuum to 2020 0 C and 45 minutes held at sintering temperature. Cooling takes place with switched off heating power under Ar.
  • the density of the obtained sintered bodies is 96.9% of the theoretical density.
  • thermocouple protective tube Production of a thermocouple protective tube
  • Sinter density is 98% of the theoretical density.
  • the sintered tube is post-densified at 2000 ° C. at 1,950 bar.
  • the density after re-densification is 99.3% of the theoretical density.
  • the green bodies are heated at 10 K / min in vacuo to 2,170 0 C and 45 minutes held at sintering temperature. Cooling takes place with switched off heating power under Ar.
  • the sintered body is subsequently recompressed at 1,950 bar Ar pressure for one hour at 2,000 0 C. The density is 97.9% of the theoretical density.
  • the resulting microstructure consists of a (Ti, W) B 2 mixed crystal matrix and particulate boron carbide, partly in the grain boundary and partly in the
  • the average grain diameter is about 100 microns.
  • a higher sintering temperature was needed here. The result is a coarse-grained structure.

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Abstract

L'invention concerne un matériau fritté à base de diborures de métaux de transition, contenant a) une phase principale comprenant 90 à 99 % en poids d'un diborure de métaux de transition à grains fins ou d'un cristal mixte de diborures de métaux de transition à grains fins comprenant au moins deux diborures de métaux de transition ou encore de mélanges à base de cristaux mixtes de diborures de ce type ou de mélanges de cristaux mixtes de diborures de ce type avec un ou plusieurs diborures de métaux de transition, lesdits métaux de transition étant choisis dans les sous-groupes IV à VI de la classification périodique, b) une deuxième phase comprenant 1 à 5 % en poids de carbure de bore et/ou de carbure de silicium particulaire et c) éventuellement une troisième phase comprenant jusqu'à 5 % en poids d'une phase intergranulaire oxygénée non perméable. L'invention concerne en outre un mélange pulvérulent frittable pour produire un tel matériau fritté, des procédés de production de ce matériau fritté, de préférence par frittage sans pression, ainsi que l'utilisation dudit matériau fritté comme matériau anticorrosion pour des sels et des métaux fondus, en particulier à base de cryolithe.
EP07723198A 2006-03-24 2007-03-12 Matériau fritté, mélange pulvérulent frittable, procédés de production dudit matériau et son utilisation Withdrawn EP1999070A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006013729A DE102006013729A1 (de) 2006-03-24 2006-03-24 Gesinterter Werkstoff, sinterfähige Pulvermischung, Verfahren zur Herstellung des Werkstoffs und dessen Verwendung
PCT/EP2007/002159 WO2007110148A1 (fr) 2006-03-24 2007-03-12 Matériau fritté, mélange pulvérulent frittable, procédés de production dudit matériau et son utilisation

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EP1999070A1 true EP1999070A1 (fr) 2008-12-10

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US (1) US20090121197A1 (fr)
EP (1) EP1999070A1 (fr)
CN (1) CN101410329A (fr)
CA (1) CA2643211A1 (fr)
DE (1) DE102006013729A1 (fr)
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WO (1) WO2007110148A1 (fr)

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RU2008142122A (ru) 2010-04-27
DE102006013729A1 (de) 2007-10-04
US20090121197A1 (en) 2009-05-14
WO2007110148A1 (fr) 2007-10-04
CA2643211A1 (fr) 2007-10-04

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