Patent Grant
8602131
The present application is a 371 filing from PCT/FR2009/051910, filed Oct. 7, 2009, which claims priority from French Application for Patent No. 0856771, filed Oct. 7, 2008, the disclosures of which are hereby incorporated by reference.
The present invention relates to a process for manufacturing a component comprising a block of dense material made up of hard particles dispersed in a binder phase by thermo-chemical treatment, the component having a property gradient.
Numerous components, in particular the cutting edges of drilling tools or machine tools, are formed by blocks of material of the cemented carbide type which are made up of carbide particles dispersed in a metal binder phase. These materials, which are extremely hard, and therefore resistant to wear, may also be brittle. Therefore, in order to reinforce their toughness, they are subjected to treatments which are intended to introduce into them a ductile-phase composition gradient with or without the formation of new phases, the hardness of which differs from the initial hardness of the block, which result either in blocks of which the external surface, or at least a portion of that surface, is extremely hard and the internal portion is tougher, or in blocks of which the external surface, or at least a portion thereof, is tougher and the internal portion is harder.
To do this, it is possible to manufacture blocks of non-dense cemented carbide having a porosity gradient, which blocks are produced by powder metallurgy and which are caused to be infiltrated by a binder phase in order to improve their core ductility. This method is poorly suited, in particular, to the system of the WC-Co type because it leads to the partial destruction of the carbide skeleton existing before infiltration, and therefore does not enable the desired properties for a cutting edge to be obtained.
It has also been proposed to produce cemented carbides having a composition gradient by the solid-phase natural sintering of a multi-layered component, each of the layers having a different composition. However, this method does not enable the material to be completely densified and has to be followed by an expensive hot isostatic compaction treatment. Furthermore, the preparation of the cemented carbide having a composition gradient is complex since it requires the production of a succession of basic layers which fit into one another. Finally, this process has the disadvantage of not generating a continuous composition gradient.
It has also been proposed to produce such materials by liquid-phase natural sintering, which enables a material having a completely dense composition gradient to be obtained very rapidly and in a single step. However, this process has the disadvantage of attenuating the composition gradient to a fairly great extent owing to the migration of liquid between the layers of small thickness under the combined effect of infiltration and impregnation phenomena. In addition, and against all expectation, the composition gradient remains discontinuous when the duration of maintenance in the liquid state is less than a critical duration beyond which complete homogenization of the cemented carbide is observed, but is sufficient to densify the material.
Furthermore, it has been proposed to improve the operating performance of cutting tools by depositing hard coatings of nitride, carbonitride, oxide or boride on the surface of the cemented carbide. Such methods have been described, for example, in U.S. Pat. Nos. 4,548,786 and 4,610,231 (the disclosures of which are hereby incorporated by reference). However, these methods have the disadvantage of improving only the resistance of the cemented carbide to wear by abrasion, and of doing this only over small thicknesses (a few microns).
It has also been proposed to improve both the resistance to wear of the surface and the shock resistance of cemented carbides of the WC-Co type by bringing a carbon-rich gaseous phase into contact with a dense cemented carbide sub-stoichiometric in carbon. Under the effect of temperature, the carbon of the gaseous phase diffuses in the sub-stoichiometric cemented carbide and reacts with the phase η-Co3W3C, which leads to a release of cobalt which migrates towards the external surface of the cemented carbide, that is to say, behind the carbon diffusion front. This method described in the U.S. Pat. No. 4,743,515 (the disclosure of which is hereby incorporated by reference) has the disadvantage of leading to a cobalt-rich binder phase gradient over 1 or 2 mm while preserving a brittleness of the core of the component treated.
In order to overcome the various shortcomings of the methods which have just been set forth, it has been proposed to manufacture blocks of cemented carbide having a binder phase composition gradient over distances of the order of millimeters by enriching the cemented carbides by impregnation from the outside from a liquid phase capable of penetrating (or migrating) into the cemented carbide. This impregnation phenomenon corresponds to the migration of external liquid having a composition similar to that of the solid/liquid system regarded as completely dense under the sole moving force of the migration pressure generated by a local imbalance of the volume fraction of binder phase and/or the size and morphology of the solid grains. This phenomenon concerns any system made up of (solid and liquid) condensed phases which exhibits an aptitude to adapt the shape of its solid grains by absorbing liquid, thus rendering it energetically more stable, that is to say, which exhibits an Ostwald ripening with modification of the shape of the hard particles without necessarily generating an enlargement of those particles by the phenomenon of dissolution and re-precipitation.
The use of this process to manufacture cutting edges for drilling tools or cutting tools requires the production of preliminary assemblies of a dense sintered block which is to be enriched and a compacted powder pellet of impregnation material which is to introduce the binder phase by the impregnation phenomenon, and the placing of the assembly in an oven in order to effect the appropriate heat treatment. This process has the disadvantage of requiring an impregnation material which should be dimensioned relative to the desired composition gradient, which complicates the process and generally necessitates an adjustment of the impregnation surface.
Very unexpectedly, the inventors have found that it is possible to generate binder phase concentration gradients over distances of the order of millimeters inside blocks of dense cemented carbide with the sole proviso that a suitable coating is deposited on all or part of the surface of the dense block of cemented carbide and that it is subjected to a suitable heat treatment, the temperature of which must be at least equal to the temperature that enables the binder phase to pass into the liquid state (solidus of the cemented carbide concerned).
The material constituting the coating becomes unstable (or decomposes) and one or more of the chemical elements of which it is composed diffuse(s) and react(s), or not, with the material of the block, thus generating a binder phase gradient in the block and/or the formation of phases the hardness of which differs from the initial hardness of the block over more or less great distances, depending on the duration of the heat treatment applied. The shape of the gradient so generated in the block: hardening of the surface beneath which the coating has been deposited and softening of the core or, conversely, softening of the surface beneath which the coating has been applied and hardening of the core, depends in particular on the nature and thickness of the coating used, the proportion of the surface coated and the heat treatment. The parameters of the heat treatment can be determined by the person skilled in the art, in particular in accordance with the shape of the desired gradient.
Therefore, the invention relates to a process for manufacturing a component comprising a block of dense material made up of hard particles, of the same or different nature, dispersed in a binder phase, the material having a solidus temperature Ts above which the binder phase is liquid, characterized in that there is deposited on at least a portion of the surface of the block of dense material an active coating composed of a material capable of reacting chemically with the dense material when the assembly is heated to beyond a minimum reaction temperature Tr, and in that the block coated with the active coating is subjected to a heat treatment comprising heating, then maintenance for a time tm at a maintenance temperature Tm greater than or equal to the minimum reaction temperature Tr, followed by cooling to ambient temperature.
Preferably, the maintenance temperature Tm is greater than or equal to the solidus temperature Ts of the dense material.
Preferably, the maintenance temperature Tm is less than or equal to Ts+200° C.
Preferably, the maintenance time tm is from 1 minute to 10 minutes.
The active coating may be deposited on only a portion of the surface of the block.
The active coating may be deposited on the entire surface of the block.
The dense material is, for example, a cemented carbide composed of metal carbide particles dispersed in a metal matrix.
The cemented carbide may also contain particles of natural or synthetic diamond measuring up to 1 mm in diameter.
The cemented carbide is, for example, of the WC-M type, M being one or more metals selected from Co, Ni and Fe, the sum of the contents by weight of these metals in the binder phase being greater than 50%.
The coating material capable of reacting with the dense material of the block is composed, for example, of at least one compound selected from compounds of the nitride, boride, carbide, oxide, hydride, carbonitride, borocarbide and graphite type. This material may be composed of any mixture of these various compounds.
The coating can be deposited by a process of the PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition) type, or by a spraying process or using a brush or by dipping or by serigraphy.
The block of dense material is, for example, a cutting edge or a support block of a cutting edge of a tool for drilling or hewing or machining rocks or metals.
In addition, it is possible to deposit on a face of the support block a diamond wafer of the PDC (Polycrystalline Diamond Compact) or TSP (Thermally Stable Polycrystalline diamond) type.
The diamond wafer can be attached to the block by brazing, after the block has been treated.
This thermal process therefore has the advantage of producing in a very simple manner blocks of cemented carbide having a property gradient suitable for use as the cutting edge of a drilling tool or a cutting tool, or as a support block of the cutting edge of a drilling tool or a cutting tool.
The invention relates also to a cutting edge for a tool for cutting rocks, which comprises a block made up of hard particles dispersed in a binder phase, which block can be obtained by the process according to the invention and which has, over a distance greater than 0.5 mm, preferably greater than 1 mm, and more preferably greater than 3 mm, a continuous gradient of binder phase content, the difference in binder phase content between the richest zone and the poorest zone being greater than 1% by volume, preferably greater than 2%, and more preferably greater than 5%.
The cutting edge may comprise an attached diamond wafer of the PDC or TSP type of a thickness which may be from 0.4 mm to 5 mm.
The invention relates also to a tool for cutting rocks which comprises at least one cutting edge or blade of impregnated material composed of a mixture of cemented carbide and particles of natural or synthetic diamond (which may measure up to 1 mm in diameter).
The invention will now be described in a more detailed but non-limiting manner with reference to the appended Figures, in which:
In the following, blocks intended in particular for the manufacture of cutting edges for drilling tools or more generally for cutting tools, of a generally parallelepipedal shape or of a cylindrical shape, having dimensions of the order of a few millimeters or a few tens of millimeters, will be considered. These blocks, obtained by powder metallurgy, are composed of a dense material, the structure of which comprises, on the one hand, hard particles, such as metal carbides, and in particular tungsten carbides, and, on the other hand, a binder phase composed principally of a metal or a metal alloy. When in contact with the carbides, this binder phase can form, at a suitable temperature, a eutectic, the melting point of which is lower than both the melting point of the carbides and the melting point of the metal or metal alloy. This metal or metal alloy constituting the binder phase is, for example, cobalt, but may also be iron or nickel or a mixture of these metals, these elements representing at least 50% by weight of the binder phase.
The binder phase may also contain addition elements, the sum of the contents of which may be at most 15% by weight but in general does not exceed 5%. These addition elements may be copper in order to improve the electrical conductivity, or silicon which has a surfactant effect with respect to the system made up of the carbides and the binder phase. The addition elements may also be carbide-producing elements permitting the formation of mixed carbides or carbides of the MxCy type other than tungsten carbide. These elements are, in particular, manganese, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium.
In addition, the binder phase may comprise addition elements which modify the shape and/or inhibit the enlargement of the hard particles and with which the person skilled in the art is familiar.
Finally, the chemical composition of these materials comprises inevitable impurities which result from the production processes.
For some applications, in order to reinforce the resistance to wear of the cutting edges, it is possible to add particles of natural or synthetic diamond, the diameter of which may be as much as 1 mm. These diamond particles are added to the powder mixture which is used to manufacture the block by sintering and which is known as impregnated material.
According to the invention, in order to produce a block of cemented carbide having a property gradient, the block 1 of dense material is coated with a layer 2 of a thickness of generally approximately from 50 μm to 2 mm, of a material capable of reacting chemically with the binder phase and/or the carbide phase of the dense material. This coating is produced by spraying, PVD deposition (Physical Vapor Deposition) or CVD deposition (Chemical Vapor Deposition) if the coating material is supplied in gaseous form, or using a brush, or by dipping or by serigraphy if the coating material is supplied in liquid form. The assembly is then placed at the bottom 3 of an oven 4 and the assembly is heated to a maintenance temperature Tm and the assembly is maintained at that temperature for a time tm in order to ensure the interaction of the external coating or one of its constituent elements with the dense material and to bring about the formation of a property gradient inside the block. In order to do this, the maintenance temperature Tm must be greater than or equal to the minimum reaction temperature Tr which is the temperature above which the external coating or one of its elements starts to react or diffuse without reacting in a significant manner inside the block. This reaction temperature Tr must be greater than or equal to the solidus temperature Ts of the cemented carbide constituting the block. This solidus temperature is the minimum temperature at which the binder phase of the cemented carbide is in the liquid state. This condition is desirable so that the coating or one of its constituent elements can rapidly diffuse and then react or not, depending on the coating concerned, with the constituents (solid grains or liquid phase) of the block being treated. If the coating is composed of a compound with a metalloid, such as boron or any other metalloid, or a non-metal, such as carbon, nitrogen, oxygen, or any other non-metal, the reaction temperature Tr is greater than or equal to the destabilization or decomposition temperature Td of the compound which is not necessarily greater than the solidus temperature Ts of the cemented carbide. The reaction temperature Tr, the destabilization temperature Td and the solidus temperature Ts depend on the nature of the material of which the coating is made and the material of which the block is made. The person skilled in the art knows how to determine these temperatures.
The maintenance temperature Tm must not be too high. Preferably, it must remain below Ts+200° C. and preferably below Ts+100° C. and more preferably below Ts+50° C. The maintenance time tm must for its part be suitable for the shape and the amplitude of the desired gradient and is deduced from experiment. It is generally of the order of a few minutes.
The coating material capable of becoming unstable or of decomposing and/or reacting with the material constituting the dense block to be treated is, for example, a metalloid or metal nitride, such as boron nitride, aluminum nitride, titanium nitride, or a boride, such as titanium boride, a metalloid or metal carbide, such as boron carbide, titanium carbide, or a hydride, such as titanium hydride, or graphite or a refractory oxide, such as alumina, or a carbonitride or a borocarbide of metal, or a mixture of such materials.
As indicated above, the materials used to produce the coating of the block to be treated must be active or even in some cases reactive above the solidus temperature Ts, but it is preferable for them to remain stable, that is to say, not to decompose, below that temperature.
It will be appreciated that, depending on the nature of the coating material and that of the material constituting the block, the property gradient obtained may result from a relative hardening of the surface of the block compared with the core, or conversely a softening.
The heat treatment comprises, as shown in
The maintenance time tm and the maintenance temperature Tm are adapted in accordance with the dimensions of the block to be treated and the property gradient which it is desired to obtain.
The heat treatment can be carried out in a resistance oven, or an induction oven or a microwave oven, under a protective atmosphere or under vacuum. The protective atmosphere is, for example, argon or a mixture of argon and hydrogen but as a general rule any neutral atmosphere such as argon, nitrogen, hydrogenated argon, hydrogenated nitrogen, hydrogen, or optionally a rough or high vacuum.
As shown in
The extent of the zone affected by the variation in the binder phase content of course depends on the maximum maintenance temperature Tm, the maintenance time tm and the thickness of the coating material. With an equal thickness of the coating layer, the higher the temperature Tm and the longer the time tm, the more extensive is the zone affected; that is to say, the more the block is affected in depth.
The person skilled in the art knows how to adapt the treatment conditions to the results he wishes to obtain. It will also be appreciated that the block as just described is covered on all of its faces with an active material. However, the active material may be deposited on only a portion of the external surface of the block and therefore may lead to the hardening or softening of only the zones of the block located beneath the coating and may therefore have a softened or hardened zone at the core which may extend as far as the external surface of the block that is not coated.
It will be appreciated that this variation in the distribution of the binder phase inside the block over distances of the order of millimeters occurs without the supply of external binder phase. However, this does not mean that the total binder phase content of the block which has been treated remains identical, because binder phase has been able to combine with one or more elements of the coating to form a solid phase, thus depleting the binder phase content of the block.
The variation in hardness, which may be as much as several hundred Vickers, may occur over distances greater than 0.5 mm and may extend throughout the entire block.
By way of example, three treatments were carried out on blocks made of the same material, WC-Co containing approximately 13% by weight of cobalt (HV2kg/10s=1220), in accordance with the same heat cycle (Tm=1350° C., tm=5 min) with two different coatings (boron nitride, alumina) under vacuum and under hydrogenated argon.
The first block, marked 10 in
As shown schematically in
The second block, marked 20 in
As shown in
The third block, marked 30 in
Thus, in the case of the material WC-Co considered, the boron nitride enables the zone of the block close to the coating layer to be hardened, while the alumina enables it to be softened.
On the other hand, the atmosphere of the oven (vacuum or hydrogenated argon) used to carry out the treatments has no effect on the result.
As indicated above, the blocks so treated may constitute cutting edges of a drilling tool or of a cutting tool and may have dimensions of a few millimeters or even more since it is possible to consider producing cutting blades which have dimensions of several centimeters and which may be hardened by this process.
As shown in
In particular, the support block 20 treated in accordance with the invention can be assembled after the HPHT process by brazing, for example in accordance with the process referred to as “LS Bond” and described in U.S. Pat. Nos. 4,225,322 and 5,111,895 (the disclosures of which are incorporated by reference) without this operation bringing about a drastic modification of the binder phase concentration gradient in the block.
Other cutting edges which the person skilled in the art can envisage may be produced by this process. These cutting edges can be incorporated in various tools known to the person skilled in the art, such as tools for breaking up rocks, for drilling heads, or machine tools.
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