WO1994017219A1 - Metal matrix alloys - Google Patents

Metal matrix alloys Download PDF

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Publication number
WO1994017219A1
WO1994017219A1 PCT/GB1994/000109 GB9400109W WO9417219A1 WO 1994017219 A1 WO1994017219 A1 WO 1994017219A1 GB 9400109 W GB9400109 W GB 9400109W WO 9417219 A1 WO9417219 A1 WO 9417219A1
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WO
WIPO (PCT)
Prior art keywords
titanium
reaction mixture
boron
particles
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Prior art date
Application number
PCT/GB1994/000109
Other languages
French (fr)
Inventor
Peter Davies
James Leslie Frederick Kellie
Richard Nigel Mckay
John Vivan Wood
Original Assignee
London & Scandinavian Metallurgical Co. Limited
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 London & Scandinavian Metallurgical Co. Limited filed Critical London & Scandinavian Metallurgical Co. Limited
Priority to EP94904292A priority Critical patent/EP0632845A1/en
Priority to JP6516797A priority patent/JPH07505680A/en
Publication of WO1994017219A1 publication Critical patent/WO1994017219A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides

Definitions

  • This invention relates to a method of making an alloy comprising hard particles comprising titanium boride dispersed in a predominantly metal matrix, and to the resulting alloy itself. Alloys of the aforementioned kind are hereinafter referred to as titanium boride metal matrix alloys.
  • a method of making an alloy comprising hard particles comprising titanium boride disper.sed in a predominantly metal matrix, the method comprising firing a particulate reaction mixture comprising titanium, matrix material and a source of boron, under conditions such that the titanium and boron react exothermically to form a dispersion of fine particles comprising titanium boride in a predominantly metal matrix.
  • the hard particles may be of generally globular shape. That would indicate that the reaction zone had reached a sufficiently high temperature to allow precipitation of the hard particles. However, in many preferred embodiments of the invention, at least some of the hard particles may be of angular shape, and indeed in many cases they -are all thus shaped. (iii) In order to promote uniformity of reaction conditions, and thus .also uniformity of the physical properties of the product, the bulk of the reaction mixture should not be too small (unlikely to occur in practice) or too large. Success in this regard can readily be asses.sed by observing the uniformity of the particle .size of the hard particles formed throughout the reaction mixture. Preferably, the average particle size of the hard particles is substantially uniform throughout the resulting dispersion.
  • the temperature can, of cour.se, be increased by reversing one or more of (a), (b), (c) and (d).
  • the titanium boride present in the product of the method of the invention will be in the form of titamum diboride.
  • the particulate reaction mixture which is fired may include reactable materials in addition to the source of boron and the titanium, which additional reactable materials may be present in the matrix material or otherwi.se; for example chromium, tungsten, vanadium, niobium, carbon and/or nitrogen.
  • the resulting fine particles comprising titanium boride will therefore not necessarily consist of titanium boride as such.
  • the available titanium content of the reaction mixture is equal to at least 30% by weight, and preferably greater than 50% and less than 70% by weight, of the total weight of the reaction mixture (the term "reaction mixture” as used herein means the total of all the materials present in the reaction body, including any which do not undergo any chemical reaction in the method of the invention and which may in effect be a diluent).
  • reaction mixture means the total of all the materials present in the reaction body, including any which do not undergo any chemical reaction in the method of the invention and which may in effect be a diluent.
  • This will generally enable sufficient heat to be generated in the exothermic reaction, and a u.seful concentration of hard particles to be formed in the product.
  • the source of boron in the reaction mixture may be boron itself, in the form of boron powder, for example.
  • the source of boron should comprise a suitable compound of boron, preferably boron carbide, B 4 C.
  • the matrix metal may be based on iron or aluminium, for example. It may be possible for the matrix metal to be based on other metals such as nickel, cobalt or copper, for example.
  • substantially all of the titanium should be present in the reaction mixture as an alloy of matrix metal and titanium. However, some or, in less preferred embodiments all, of the matrix metal may be present in the reaction mixture unalloyed with titanium.
  • the product alloy is to be iron-based, we prefer that the titanium should be present in the reaction mixture as ferrotitanium, -and most preferably as eutectic ferrotitanium, which contains about 70% by weight titanium. In the latter case, we have found that a suitable particle size for the eutectic ferrotitanium is generally in the range 0.5 mm down to 3.0 mm down.
  • the titanium should be present in the reaction mixture as titanium-aluminium, wherein the titanium content is preferably about 60% by weight, and the particle size is preferably about 300 microns down.
  • the reaction mixture may need to be pre-heated in order to get it to fire .and react without further heat input.
  • the temperature of the body of the reaction mixture should be at less than 600° C, and preferably at less than 500°C, immediately prior to firing.
  • the temperature of the body of the particulate reaction mixture is substantially at ambient temperature (i.e. at no more than 100°C) immediately prior to firing.
  • ambient temperature i.e. at no more than 100°C
  • the particulate reaction mixture which is fired is a loose mixture (i.e. a mixture which, although it may have been packed, has not been compressed to such an extent as to cause it to become fully cohesive, as occurs in briquetting).
  • briquetting of the reaction mixture very much reduces its ability to be fired so as to produce a self-sustaining reaction.
  • the reaction mixture, if packed at all is preferably not compressed sufficiently to produce any substantial degree of cohesion.
  • the amount of the .source of boron in the reaction mixture should be substantially the stoichiometric -amount required to react with all of the available titanium in the reaction mixture.
  • the -amount of B C is such that the total -amount of boron and carbon in it is stoichiometrically equivalent to the available titanium.
  • the average particle size of the hard particles in the product is less than 25 microns, and an average particle size of less than 10 microns can be achieved without difficulty; generally the average particle size will be greater than 1 micron.
  • the method of the invention comprises firing a reaction mixture comprising boron carbide and crushed eutectic ferrotitanium under conditions such that a molten zone moves through the body of the reaction mixture, to form a dispersion of a mixture of titamum diboride particles and titanium carbide particles of average particle size greater than 1 micron and less than 10 microns in a ferrous metal matrix.
  • a reaction mixture comprising boron carbide and crushed eutectic ferrotitanium under conditions such that a molten zone moves through the body of the reaction mixture, to form a dispersion of a mixture of titamum diboride particles and titanium carbide particles of average particle size greater than 1 micron and less than 10 microns in a ferrous metal matrix.
  • a reaction mixture comprising boron carbide and crushed eutectic ferrotitanium under conditions such that a molten zone moves through the body of the reaction mixture, to form a dispersion of a mixture of t
  • Fig. 1 shows a scanning electron micrograph, at a magnification of 1000, of the alloy produced in Example 1.
  • Fig. 2 shows a photomicrograph, at a magnification of 1000, of the alloy produced in Example 2.
  • Figure 1 is a scanning electron micrograph of the product, and shows that it consists of a uniform dispersion of a larger proportion of TiB2 particles (about 53% by weight of the product, as those shown at 1) and a lesser number of TiC particles (about 23% by weight of the product, as those which can be -seen relatively raised at 2) in an iron matrix (.about 24% by weight of the product, as can be seen at 3). This proportion is consistent with the stoichiometry of the B4C and FeTi reactants.
  • the mounting resin can be -seen at 4.
  • Example 1 1 kg of titanium-aluminium powder (60% titanium by weight) produced by London & Scandinavian Metallurgical Co Limited having a particle size less than 300 microns were mixed with 229 g of boron carbide of less than 500 microns particle size The mixture was loosely packed into a refractory lined vessel and fired as in Example 1.
  • Figure 2 is a photomicrograph of the product, and shows that it consists of a uniform di.spersion of TiB2 particles (as those shown at 21) and TiC particles (as those shown at 22) in an aluminium matrix (as shown at 23).
  • Example 2 300 g of crushed eutectic ferrotitanium as used in Example 1 were mixed with 94.5 g of fine boron powder having a particle size of 45 microns down. The mixture was loosely packed into a refractory lined vessel and fired as in Example 1.
  • the product was comminuted. It consisted of a uniform dispersion of TiB2 particles in an iron matrix.

Abstract

The invention provides a method of making a titanium boride metal matrix alloy, by firing a particulate reaction mixture comprising titanium, matrix material and a source of boron (e.g. boron carbide), under conditions such that the titanium and boron react exothermically to form a dispersion of fine particles (preferably greater than 1 micron and less than 10 microns in size) comprising titanium boride (plus titanium carbide where the source of boron is boron carbide) in a predominantly metal matrix. The titanium and matrix are preferably added as a titanium alloy such as ferrotitanium (e.g. eutectic ferrotitanium) or titanium-aluminium. The reaction conditions are preferably selected so that during the reaction a molten zone moves through the body of the reaction mixture, and the average size of the resulting hard particles is uniform throughout the resulting dispersion.

Description

Metal Matrix Alloys
This invention relates to a method of making an alloy comprising hard particles comprising titanium boride dispersed in a predominantly metal matrix, and to the resulting alloy itself. Alloys of the aforementioned kind are hereinafter referred to as titanium boride metal matrix alloys.
Our U. K. patent application no. 9116174.5, which was filed on 26th July 1991, and which was published on 27th January 1993 as GB 2257985 A, describes and claims a method of making an alloy comprising hard particles comprising titanium carbide dispersed in a predominantly metal matrix, the method comprising firing a particulate reaction mixture comprising carbon, titanium and matrix material, under conditions such that the titanium and carbon react exothermically to form a dispersion of fine particles comprising titanium carbide in a predominantly metal matrix.
According to the present invention, there is provided a method of making an alloy comprising hard particles comprising titanium boride disper.sed in a predominantly metal matrix, the method comprising firing a particulate reaction mixture comprising titanium, matrix material and a source of boron, under conditions such that the titanium and boron react exothermically to form a dispersion of fine particles comprising titanium boride in a predominantly metal matrix.
It is surprising that the exothermic reaction of the method of the invention is capable of producing a dispersion of fine, hard particles in the matrix. However, we have found that it is possible, using simple trial and error experiments, to find suitable conditions to achieve that end, when the following principles are borne in mind:
(i) It is highly desirable to adjust the reaction conditions such that the exothermic reaction is carried out under conditions such that during the reaction a molten zone moves through the body of the reaction mixture, so that at a given point during reaction the reaction mixture ahead of the reaction zone is solid, and so is that behind the reaction zone.
(ii) The hard particles may be of generally globular shape. That would indicate that the reaction zone had reached a sufficiently high temperature to allow precipitation of the hard particles. However, in many preferred embodiments of the invention, at least some of the hard particles may be of angular shape, and indeed in many cases they -are all thus shaped. (iii) In order to promote uniformity of reaction conditions, and thus .also uniformity of the physical properties of the product, the bulk of the reaction mixture should not be too small (unlikely to occur in practice) or too large. Success in this regard can readily be asses.sed by observing the uniformity of the particle .size of the hard particles formed throughout the reaction mixture. Preferably, the average particle size of the hard particles is substantially uniform throughout the resulting dispersion.
(iv) The longer the hard particles are present in a melt before solidification, the larger their final size will be. If the hard particles are found to be undesirably large through being present in a melt for too long a time, the process conditions can be adjusted so that the temperature reached in the reaction is decreased and/or the cooling rate is increased.
(v) The temperature reached in the exothermic reaction can be decreased by one or more of the following measures:
(a) decreasing the concentration of the reactants, e.g. by increasing the concentration of matrix material;
(b) increasing the particle size of the reactants; and
(c) decreasing the weight of the reaction mixture.
(d) replacing a part of the titanium reactant by an additional carbide-forming reactant which reacts with the carbon less exothermically than does the titanium reactant.
The temperature can, of cour.se, be increased by reversing one or more of (a), (b), (c) and (d).
Generally, the titanium boride present in the product of the method of the invention will be in the form of titamum diboride.
It will be appreciated that in the method of the invention, the particulate reaction mixture which is fired may include reactable materials in addition to the source of boron and the titanium, which additional reactable materials may be present in the matrix material or otherwi.se; for example chromium, tungsten, vanadium, niobium, carbon and/or nitrogen. The resulting fine particles comprising titanium boride will therefore not necessarily consist of titanium boride as such.
Desirably, the available titanium content of the reaction mixture is equal to at least 30% by weight, and preferably greater than 50% and less than 70% by weight, of the total weight of the reaction mixture (the term "reaction mixture" as used herein means the total of all the materials present in the reaction body, including any which do not undergo any chemical reaction in the method of the invention and which may in effect be a diluent). This will generally enable sufficient heat to be generated in the exothermic reaction, and a u.seful concentration of hard particles to be formed in the product.
The source of boron in the reaction mixture may be boron itself, in the form of boron powder, for example. However, we prefer that the source of boron should comprise a suitable compound of boron, preferably boron carbide, B4C.
The matrix metal may be based on iron or aluminium, for example. It may be possible for the matrix metal to be based on other metals such as nickel, cobalt or copper, for example. We prefer that substantially all of the titanium should be present in the reaction mixture as an alloy of matrix metal and titanium. However, some or, in less preferred embodiments all, of the matrix metal may be present in the reaction mixture unalloyed with titanium. Where the product alloy is to be iron-based, we prefer that the titanium should be present in the reaction mixture as ferrotitanium, -and most preferably as eutectic ferrotitanium, which contains about 70% by weight titanium. In the latter case, we have found that a suitable particle size for the eutectic ferrotitanium is generally in the range 0.5 mm down to 3.0 mm down.
Where the product alloy is to be aluminium-based, we prefer that the titanium should be present in the reaction mixture as titanium-aluminium, wherein the titanium content is preferably about 60% by weight, and the particle size is preferably about 300 microns down.
In some instances, for example where the concentration of titanium in the reaction mixture is particularly low, the reaction mixture may need to be pre-heated in order to get it to fire .and react without further heat input. However, we prefer that the temperature of the body of the reaction mixture should be at less than 600° C, and preferably at less than 500°C, immediately prior to firing.
We most prefer that the temperature of the body of the particulate reaction mixture is substantially at ambient temperature (i.e. at no more than 100°C) immediately prior to firing. Where a particular reaction mixture will not fire at ambient temperature, it may be modified, using the principles described above, so that it can be fired at ambient temperature and react without requiring further heat input. Preferably the particulate reaction mixture which is fired is a loose mixture (i.e. a mixture which, although it may have been packed, has not been compressed to such an extent as to cause it to become fully cohesive, as occurs in briquetting). We have found that briquetting of the reaction mixture very much reduces its ability to be fired so as to produce a self-sustaining reaction. For the same reason, the reaction mixture, if packed at all, is preferably not compressed sufficiently to produce any substantial degree of cohesion.
The firing of the particulate reaction mixture in the method according to the invention may be performed in any suitable manner. For example, an ignitable firing material (e.g. titanium particles) may be positioned at the surface of the particulate reaction mixture and sufficient heat applied to the ignitable material to cau.se ignition. Alternatively, the particulate reaction mixture may be fired by heating in such a way that an outer skin of the particulate reaction mixture is heated to a high temperature, sufficient to initiate the exothermic reaction, the body of the particulate reaction mixture having undergone relatively little heating at that stage; this can be achieved by, for example, heating the particulate reaction mixture in a heat-inducing (e.g. clay graphite or silicon carbide ) crucible, in a coreless induction furnace.
For most end uses of the product, we prefer that the amount of the .source of boron in the reaction mixture should be substantially the stoichiometric -amount required to react with all of the available titanium in the reaction mixture. In particular, in the preferred embodiment where the source of boron is boron carbide, we prefer that the -amount of B C is such that the total -amount of boron and carbon in it is stoichiometrically equivalent to the available titanium.
We have found that by practising the invention taking into account the points discussed above, it is easily possible to arrange that the average particle size of the hard particles in the product is less than 25 microns, and an average particle size of less than 10 microns can be achieved without difficulty; generally the average particle size will be greater than 1 micron.
In accordance with a preferred embodiment, the method of the invention comprises firing a reaction mixture comprising boron carbide and crushed eutectic ferrotitanium under conditions such that a molten zone moves through the body of the reaction mixture, to form a dispersion of a mixture of titamum diboride particles and titanium carbide particles of average particle size greater than 1 micron and less than 10 microns in a ferrous metal matrix. For many end uses it is desirable to reduce the dispersion produced by the method of the invention to a powder; one having an average particle size of less than 250 microns is preferred.
In order that the invention may be more fully understood, some preferred embodiments in accordance therewith will now be described in the following Examples, with reference to the accompanying drawings wherein:
Fig. 1 shows a scanning electron micrograph, at a magnification of 1000, of the alloy produced in Example 1.
Fig. 2 shows a photomicrograph, at a magnification of 1000, of the alloy produced in Example 2.
Example 1.
1 kg of eutectic ferrotitanium (70 % titamum, by weight) produced by London & Scandinavian Metallurgical Co Limited were crushed to less than 2 mm. This was then mixed with 267 g of boron carbide (B4C) ground to less than 500 microns. The mixture was loosely packed into a refractory lined vessel. The mixture was ignited by forming a depression in its top surface, which was filled with titanium sponge powder, to which a flame was applied.
Once ignited, an exothermic re-action propagated throughout the whole of the powder bed, such that, at a given point during the reaction the reaction mixture -ahead of the reaction zone was solid, the reaction zone itself was liquid and the reacted material behind the reaction zone was solid.
After cooling, the product was crushed to a 2 mm down powder. Figure 1 is a scanning electron micrograph of the product, and shows that it consists of a uniform dispersion of a larger proportion of TiB2 particles (about 53% by weight of the product, as those shown at 1) and a lesser number of TiC particles (about 23% by weight of the product, as those which can be -seen relatively raised at 2) in an iron matrix (.about 24% by weight of the product, as can be seen at 3). This proportion is consistent with the stoichiometry of the B4C and FeTi reactants. The mounting resin can be -seen at 4. Example 2
1 kg of titanium-aluminium powder (60% titanium by weight) produced by London & Scandinavian Metallurgical Co Limited having a particle size less than 300 microns were mixed with 229 g of boron carbide of less than 500 microns particle size The mixture was loosely packed into a refractory lined vessel and fired as in Example 1.
Once ignited an exothermic reaction propagated throughout the whole of the powder bed, such that, at a given point during the reaction, the reaction mixture ahead of the reaction zone was solid, the reaction zone itself was liquid and the reacted material behind the reaction zone was solid.
After cooling, the product was comminuted. Figure 2 is a photomicrograph of the product, and shows that it consists of a uniform di.spersion of TiB2 particles (as those shown at 21) and TiC particles (as those shown at 22) in an aluminium matrix (as shown at 23).
Example 3
300 g of crushed eutectic ferrotitanium as used in Example 1 were mixed with 94.5 g of fine boron powder having a particle size of 45 microns down. The mixture was loosely packed into a refractory lined vessel and fired as in Example 1.
Once ignited, a very vigorous exothermic reaction propagated throughout the whole of the powder bed, such that, at a given point during the reaction the reaction mixture ahead of the reaction zone was solid, the reaction .zone itself was liquid and the reacted material behind the reaction zone was solid.
After cooling, the product was comminuted. It consisted of a uniform dispersion of TiB2 particles in an iron matrix.

Claims

Claims
1. A method of making an alloy comprising hard particles comprising titanium boride dispersed in a predominantly metal matrix, the method comprising firing a particulate reaction mixture comprising titanium, matrix material and a source of boron, under conditions such that the titanium and boron react exothermically to form a dispersion of fine particles comprising titanium boride in a predominantly metal matrix.
2. A method according to claim 1 , wherein the exothermic reaction is carried out under conditions such that during the reaction a molten zone moves through the body of the reaction mixture.
3. A method according to claim 1 or claim 2, wherein the average particle size of the particles comprising titanium boride is substantially uniform throughout the resulting dispersion.
4. A method according to any one of claims 1 to 3, wherein the available titanium content of the reaction mixture is equal to at least 30% by weight, and preferably greater than 50% and less than 70% by weight, of the total weight of the reaction mixture.
5. A method according to any one of claims 1 to 4, wherein the source of boron in the reaction mixture comprises a compound of boron.
6. A method according to any one of claims 1 to 5, wherein the source of boron in the reaction mixture comprises boron carbide.
7. A method according to any one of claims 1 to 6, wherein titanium is present in the reaction mixture as an alloy of matrix metal and titanium.
8. A method according to claim 7, wherein titamum is present in the reaction mixture as ferrotitanium.
9. A method according to claim 8, wherein titamum is present in the reaction mixture as eutectic ferrotitanium.
10. A method according to claim 9, wherein the particle size of the eutectic ferrotitanium is in the range 0.5 mm down to 3.0 mm down.
11. A method according to claim 7, wherein titanium is present in the reaction mixture as an alloy comprising aluminium and titanium.
12. A method according to c im 11, wherein the alloy comprising aluminium and titanium comprises about 70% by weight of titanium.
13. A method according to any one of claims 1 to 12, wherein the body of the particulate reaction mixture is at less than 600°C, and preferably at less than 500°C, immediately prior to firing.
14. A method according to claim 13, wherein the body of the particulate reaction mixture is substantially at ambient temperature immediately prior to firing.
15. A method according to any one of claims 1 to 14, wherein the particulate reaction mixture which is fired is a loose mixture.
16. A method according to any one of claims 1 to 15, wherein the average particle size of the particles comprising titanium boride is less than 25 microns.
17. A method according to claim 16, wherein the average particle size of the particles comprising titanium boride is greater than 1 micron and less than 10 microns.
18. A method according to claim 1, comprising firing a reaction mixture comprising boron carbide and crushed eutectic ferrotitanium under conditions such that a molten zone moves through the body of the reaction mixture, to form a dispersion of a mixture of titanium diboride particles and titanium carbide particles of average particle size greater than
1 micron and less than 10 microns in a ferrous metal matrix.
19. A method according to any one of claims 1 to 18, wherein the dispersion is reduced to a powder.
20. A method according to claim 19, wherein the dispersion is reduced to a powder of average particle size less than 250 microns.
21. A method according to claim 1, substantially as described in any one of the foregoing Examples 1 to 3.
22. A dispersion of fine particles comprising titanium boride in a predominantly metal matrix, whenever produced by a method in accordance with any one of claims 1 to 21.
PCT/GB1994/000109 1993-01-26 1994-01-20 Metal matrix alloys WO1994017219A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP94904292A EP0632845A1 (en) 1993-01-26 1994-01-20 Metal matrix alloys
JP6516797A JPH07505680A (en) 1993-01-26 1994-01-20 metal matrix alloy

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Application Number Priority Date Filing Date Title
GB9301458A GB2274467A (en) 1993-01-26 1993-01-26 Metal matrix alloys
GB9301458.7 1993-01-26

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