EP2334836B1 - Hierarchischer verbundwerkstoff - Google Patents

Hierarchischer verbundwerkstoff Download PDF

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Publication number
EP2334836B1
EP2334836B1 EP09782201A EP09782201A EP2334836B1 EP 2334836 B1 EP2334836 B1 EP 2334836B1 EP 09782201 A EP09782201 A EP 09782201A EP 09782201 A EP09782201 A EP 09782201A EP 2334836 B1 EP2334836 B1 EP 2334836B1
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titanium carbide
composite material
micrometric
granules
titanium
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French (fr)
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EP2334836A1 (de
EP2334836B9 (de
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Francesco Vescera
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Magotteaux International SA
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Magotteaux International SA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/14—Casting in, on, or around objects which form part of the product the objects being filamentary or particulate in form
    • 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
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1068—Making hard metals based on borides, carbides, nitrides, oxides or silicides
    • 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
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0242—Making ferrous alloys by powder metallurgy using the impregnating technique
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C22C1/1052—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576—Boride, carbide or nitride component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof

Definitions

  • the present invention relates to a hierarchical composite material having improved resistance to combined wear / impact stress.
  • the composite comprises a metal matrix of cast iron or steel, reinforced by a particular structure of titanium carbide.
  • Hierarchical composites are a family well known in the science of materials.
  • the reinforcement elements For composite wear parts made in the foundry, the reinforcement elements must be present in sufficient thickness to withstand severe and simultaneous stress in terms of wear and impact.
  • the composite wear parts reinforced with titanium carbide created in situ are one of the possibilities mentioned in this article under 2.4. Wear parts in this case are nonetheless made using exclusively powders as part of a self-propagating reaction at high temperature (SHS), where the titanium reacts exothermically with carbon to form titanium carbide in a matrix based on a ferrous alloy, also introduced in powder form.
  • SHS self-propagating reaction at high temperature
  • This type of synthesis makes it possible to obtain micrometric globular titanium carbide dispersed homogeneously within a matrix of a ferrous alloy ( Fig. 12A (c) ).
  • the article also describes very well the difficulty of controlling such a synthesis reaction.
  • the document EP 1 450 973 (Poncin ) describes a wear part reinforcement made by placing in the mold intended to receive the casting metal, an insert consisting of a mixture of powders which react with each other thanks to the heat provided by the metal during the casting at high temperature. temperature (> 1400 ° C). The reaction between the powders is initiated by the heat of the casting metal.
  • the powders of the reactive insert after reaction of the SHS type, will create a porous cluster (conglomerate) of hard particles of ceramics formed in situ; this porous mass, once formed and still at a very high temperature, will be immediately infiltrated by the casting metal.
  • the document WO 02/053316 discloses in particular a composite part obtained by SHS reaction between titanium and carbon in the presence of binders, which makes it possible to fill the pores of the skeleton constituted by titanium carbide.
  • the parts are made from powders put in compression in a mold.
  • the hot mass obtained after SHS reaction remains plastic and is compressed in its final form.
  • the ignition of the reaction does not However, it is not done by the heat of any external casting metal and, moreover, there is also no phenomenon of infiltration by an external casting metal.
  • the document EP 0 852 978 A1 and the document US5,256,368 disclose a similar technique related to the use of pressurized pressure or reaction to result in a reinforced workpiece.
  • the document GB 2,257,985 discloses a method for producing a titanium carbide reinforced alloy by powder metallurgy. This is in the form of globular microscopic particles less than 10 microns in size dispersed within the porous metal matrix.
  • the reaction conditions are chosen so as to propagate an SHS reaction front in the part to be produced.
  • the reaction is ignited by a burner and there is no infiltration by an external casting metal.
  • the document US 6,451,249 B1 discloses a reinforced composite part comprising a ceramic skeleton optionally with carbides which are bonded to each other by a metal matrix as a binder and which contains a thermite capable of reacting according to an SHS reaction to produce the heat of fusion necessary for agglomeration ceramic granules.
  • the present invention proposes to overcome the disadvantages of the state of the art and discloses a hierarchical composite material with improved wear resistance while maintaining good impact resistance. This property is obtained by a particular reinforcement structure which takes the form of a macro-microstructure comprising discrete millimetric zones concentrated in micrometric globular particles of titanium carbide.
  • the present invention also provides a hierarchical composite material having a particular titanium carbide structure obtained by a particular method.
  • the present invention further provides a method for obtaining a hierarchical composite material having a particular titanium carbide structure.
  • the present invention discloses a hierarchical composite material comprising a ferrous alloy reinforced with titanium carbides according to a defined geometry in which said reinforced portion comprises an alternating macro-microstructure of millimetric zones concentrated in micrometric globular particles of titanium carbide separated by zones. millimeters substantially free of micrometric globular particles of titanium carbide, said micrometrically concentrated micron-sized globular particles of titanium carbide forming a microstructure in which the micrometric interstices between said globular particles are also occupied by said ferrous alloy.
  • the present invention also discloses a hierarchical composite material obtained according to the process of any one of claims 11 to 13.
  • the present invention also discloses a tool or machine comprising a hierarchical composite material according to any one of claims 1 to 10 or claim 14.
  • the figure 1 shows a diagram of the macro-microstructure of reinforcement within a matrix of steel or cast iron constituting the composite.
  • the clear phase represents the metal matrix and the dark phase, concentrated zones of globular titanium carbide.
  • the photo is taken at low magnification under an optical microscope on an unpicked polished surface.
  • the figure 2 represents the limit of a concentrated zone of globular titanium carbide towards a zone generally free of globular titanium carbide at higher magnification.
  • the space between micrometric particles of titanium carbide (micrometric interstices or pores) is also infiltrated by the casting metal (steel or cast iron).
  • the photo is taken at low magnification under an optical microscope on an unpicked polished surface.
  • the figure 4 represents a binocular view of a polished, untouched surface of the macro-microstructure according to the invention with millimetric zones (in light gray) concentrated micrometric globular titanium carbide (TiC globules).
  • the shades are inverted: the dark part represents the metal matrix (steel or cast iron) filling both the space between these concentrated zones micrometric globular titanium carbide but also the spaces between the globules themselves (see Fig. 5 & 6 ).
  • the figures 5 and 6 represent SEM electron microscopic views of micrometric globular titanium carbides on polished and untouched surfaces at different magnifications. We see that in this particular case most of the globules of titanium carbide have a size less than 10 microns.
  • the figures 7 and 8 represent views of micrometric globular titanium carbides at different magnifications, but this time on fracture surfaces taken under SEM electron microscopy. It can be seen that the globules of titanium carbide are perfectly incorporated in the metal matrix. This proves that the casting metal completely infiltrates (impregnates) the pores during casting once the chemical reaction between titanium and carbon is initiated.
  • the figures 9 and 10 are spectra of analysis of Ti as well as Fe in a reinforced part according to the invention. This is a mapping of the distribution of Ti and Fe by EDX analysis, taken under the electron microscope from the fracture surface shown in FIG. figure 7 .
  • the light spots in the figure 9 show the Ti and the light spots in the figure 10 show the Fe (thus the pores filled by the casting metal).
  • the figure 11 shows, at high magnification, a surface of rupture taken by SEM electron microscope with an angular titanium carbide which formed by precipitation, in an area generally free of titanium carbide globules.
  • the figure 12 shows, at high magnification, a fracture surface taken by SEM electron microscopy with a gas bubble. We always try to limit as much as possible this kind of defect.
  • the figure 13 shows an arrangement of anvils in a vertical axis crusher which has been used to perform comparative tests between wearing parts having reinforced areas with bulky inserts and parts having reinforced areas with the macro-microstructure of the present invention. invention.
  • the figure 14 shows a schematic diagram illustrating the macro-microstructure according to the present invention already partially illustrated at the figure 3 .
  • the SHS or " s elf-propagating h igh temperature s ynthesis" reaction is a self-propagating, high-temperature synthesis reaction in which reaction temperatures are generally greater than 1500 ° C or even 2000. ° C.
  • reaction temperatures are generally greater than 1500 ° C or even 2000. ° C.
  • the reaction between titanium powder and carbon powder to obtain titanium carbide TiC is highly exothermic. Only a little energy is needed to initiate the reaction locally. Then, the reaction will spontaneously propagate to the entire mixture of reagents thanks to the high temperatures reached. After initiation of the reaction, there is a reaction front which propagates spontaneously (self-propagated) and which makes it possible to obtain titanium carbide from titanium and carbon.
  • the titanium carbide thus obtained is said to be "obtained in situ" because it does not come from the cast ferrous alloy.
  • the reactant powder mixtures comprise carbon powder and titanium powder and are compressed into plates and then crushed to obtain granules ranging in size from 1 to 12 mm, preferably from 1 to 6 mm, and particularly preferably from 1.4 to 4 mm. These granules are not 100% compacted. They are generally compressed between 55 and 95% of the theoretical density. These granules are easy to use / handle (see Fig. 3a-h ).
  • the millimeter granules of mixed carbon and titanium powders obtained according to the diagrams of the figure 3a-h are the precursors of the titanium carbide to be created and make it easy to fill mold parts of various shapes or irregular. These granules can be held in place in the mold 15 by means of a dam 16, for example. The shaping or assembly of these granules can also be done using an adhesive.
  • the hierarchical composite according to the present invention and in particular the reinforcing macro-microstructure which may alternatively be called an alternating structure of zones concentrated in globular micrometric particles of titanium carbide separated by zones which are practically free from them, is obtained by the reaction in the mold of the granules comprising a mixture of carbon powders and titanium. This reaction is initiated by the heat of casting of the cast iron or steel used to pour the whole piece, and thus both the unreinforced part and the reinforced part (see Fig. 3rd ).
  • the casting therefore triggers an exothermic reaction of self-propagating synthesis at high temperature of the mixture of powders of carbon and titanium compacted in the form of granules (self-propagating high-temperature synthesis - SHS) and previously placed in the mold 15.
  • the reaction then has the distinction of continuing to spread as soon as it is initiated.
  • This high temperature synthesis allows easy infiltration of all interstices millimeters and micrometres by casting or casting steel ( Fig. 3g & 3h ). By increasing the wettability, the infiltration can be done on any thickness of reinforcement. It advantageously makes it possible, after SHS reaction and infiltration by an external casting metal, to create zones with a high concentration of micrometric titanium carbide globular particles (which could also be called nodule clusters), which zones having a size of the order of a millimeter or a few millimeters, and which alternate with areas substantially free of globular titanium carbide. Areas with low carbide concentration are actually millimeter spaces or interstices 2 between the granules infiltrated by the casting metal. We call this superstructure a macro-microstructure reinforcement.
  • the zones where these granules were found show a concentrated dispersion of micrometric globular particles 4 of TiC (globules) whose micrometric interstices 3 have also been infiltrated by the casting metal.
  • the casting metal which here is cast iron or steel. It is important to note that the millimetric and micrometric interstices are infiltrated by the same metal matrix as that which constitutes the non-reinforced part of the hierarchical composite, which allows a total freedom of choice of the casting metal.
  • the areas with a high concentration of titanium carbide are composed of micrometric globular TiC particles in a large percentage (between about 35 and 75% by volume) and ferrous alloy infiltration.
  • micrometric globular particles are meant globally spheroidal particles which have a size ranging from ⁇ m to a few tens of ⁇ m, at most. We also call them TiC globules. The vast majority of these particles having a size less than 50 microns and even 20 microns, or even 10 microns. This globular form is characteristic of a method for obtaining titanium carbide by self-propagating synthesis SHS (see Fig. 6 ).
  • the reinforced structure according to the present invention can be characterized under an optical or electronic microscope.
  • the macro-microstructure of reinforcement is visible visually or at low magnification.
  • globular 4 titanium carbide with a volume percentage in these areas of between about 35 and about 75%, depending on the level of compaction of the granules, can be distinguished. the origin of these areas (see tables).
  • These globular TiCs are of micrometric size (see Fig. 6 ).
  • Titanium carbide will be obtained by the reaction between the carbon powder and the titanium powder. These two powders are mixed homogeneously. Titanium carbide can be obtained by mixing 0.50 to 0.98 moles of carbon to 1 mole of titanium, the stoichiometric composition Ti + 0.98 C ⁇ TiC 0.98 being preferred.
  • the process for obtaining the granules is illustrated in Fig. 3a-3h .
  • the granules of carbon / titanium reagents are obtained by compaction between rollers 10 in order to obtain strips that are then crushed in a crusher 11.
  • the mixture of the powders is made in a mixer 8 consisting of a tank equipped with blades , to promote homogeneity.
  • the mixture then passes into a granulation apparatus through a hopper 9.
  • This machine comprises two rollers 10 through which the material is passed. Pressure is applied to these rollers 10, which compresses the material. A strip of compressed material is obtained at the outlet, which is then crushed in order to obtain the granules.
  • These granules are then sieved to the desired particle size in a sieve 13.
  • the degree of compaction of the bands depends on the applied pressure (in Pa) on the rollers (diameter 200 mm, width 30 mm). For a low level of compaction, of the order of 10 6 Pa, we obtain a density on the bands of the order of 55% of the theoretical density. After passing through the rollers 10 to compress this material, the apparent density of the granules is 3.75 x 0.55, ie 2.06 g / cm 3 .
  • the granules obtained from the raw material Ti + C are porous. This porosity varies from 5% for highly compressed granules, to 45% for slightly compressed granules.
  • the granules obtained generally have a size between 1 and 12 mm, preferably between 1 and 6 mm, and particularly preferably between 1.4 and 4 mm.
  • the granules are made as described above. To obtain a three-dimensional structure or superstructure / macro-microstructure with these granules justifying the hierarchical composite name, they are available in the areas of the mold where it is desired to reinforce the part. This is achieved by agglomerating the granules either by means of an adhesive, or by confining them in a container, or by any other means (dam 16).
  • the bulk density of the stack of Ti + C granules is measured according to ISO 697 and depends on the level of compaction of the bands, the granulometric distribution of the granules and the crushing mode of the bands, which influences the shape of the granules .
  • the bulk density of these Ti + C granules is generally of the order of 0.9 g / cm 3 to 2.5 g / cm 3 depending on the level of compaction of these granules and the density of the stack.
  • a compaction band is realized at 85% of the theoretical density of a mixture of C and Ti.
  • the granules are sieved to obtain a pellet size of between 1.4 and 4 mm.
  • a bulk density of the order of 2.1 g / cm 3 (35% of space between the granules + 15% of porosity in the granules) is obtained.
  • the granules are placed in the mold at the location of the part to be reinforced, which thus comprises 65% by volume of porous granules.
  • a chromium cast iron (3% C, 25% Cr) was then cast at about 1500 ° C in a non-preheated sand mold.
  • the reaction between Ti and C is initiated by the heat of melting. This casting is done without a protective atmosphere.
  • a compaction band is realized at 70% of the theoretical density of a mixture of C and Ti.
  • the granules are sieved to obtain a pellet size of between 1.4 and 4 mm.
  • the granules are placed in the part to be reinforced, which thus comprises 55% by volume of porous granules.
  • 55% by volume of zones with a high concentration of approximately 53% of globular titanium carbide are obtained, ie approximately 30% by global volume of TiC in the reinforced part of the piece of wear.
  • a part whose reinforced zones comprise an overall volume percentage of TiC of about 20% is intended to produce a part whose reinforced zones comprise an overall volume percentage of TiC of about 20%.
  • a band is made by compaction at 60% of the theoretical density of a mixture of C and Ti. After crushing, the granules are sieved so as to obtain a granule size of 1 and 6 mm. A bulk density of the order of 1.0 g / cm 3 (55% of space between the granules + 40% of porosity in the granules) is obtained.
  • the granules are placed in the part to be reinforced, which thus comprises 45% by volume of porous granules. After reaction, 45% by volume of zones concentrated to about 45% of globular titanium carbide, or 20% by volume of TiC in the reinforced part of the wear part, are obtained in the reinforced part.
  • Example 2 it was sought to attenuate the intensity of the reaction between carbon and titanium by adding a ferrous alloy powder.
  • a wear part whose reinforced areas comprise an overall volume percentage of TiC of about 30%.
  • a band is produced by compaction at 85% of the theoretical density of a mixture by weight of 15% of C, 63% of Ti and 22% of Fe. crushing, the granules are sieved so as to obtain a granule size of between 1.4 and 4 mm.
  • a bulk density of the order of 2 g / cm 3 (45% of space between the granules + 15% of porosity in the granules) is obtained.
  • the granules are placed in the part to be reinforced, which thus comprises 55% by volume of porous granules. After reaction, in the reinforced part, 55% by volume of zones are obtained with a high concentration of approximately 55% of globular titanium carbide, ie 30% by volume of total titanium carbides in the reinforced macro-microstructure of the piece of titanium. 'wear.
  • the inventor has targeted a mixture to obtain 15% by volume of iron after reaction.
  • the proportion of mixture that has been used is: 100g Ti + 24.5g C + 35.2g Fe
  • Theoretical density of the mixture 4.25 g / cm 3
  • Volumetric shrinkage during the reaction 21% ⁇ b> ⁇ u> Table 4 ⁇ / u> ⁇ /b>
  • Overall percentage of TiC obtained in the reinforced microstructure after Ti + 0.98 C + Fe reaction in the reinforced part of the wear part Compaction of the granules (% of theoretical density which is 4.25 g / cm 3 ) 55 60 65 70 75 80 85 90 95
  • Comparative tests between wearing parts having reinforced areas with fairly large inserts (150x100x30 mm) and parts having zones reinforced with the macro-microstructure of the present invention were made.
  • the grinding machine in which these tests were carried out is shown in FIG. Fig. 13 .
  • the inventor alternately disposed an anvil comprising an insert according to the state of the art surrounded on either side of a unreinforced anvil, and an anvil with a zone reinforced by a macro-microstructure according to the present invention, also framed by two unreinforced reference anvils.
  • the performance index is the ratio of the wear of the non-reinforced reference anvils to the wear of the reinforced anvil.
  • An index of 2 therefore means that the reinforced part has worn out twice as fast as the reference parts. We measure the wear in the working part (mm worn), where is the reinforcement.
  • the performance of the insert according to the state of the art is similar to that of the macro-microstructure of the invention, except for the compaction rate of 85% of the granules which shows a slightly higher performance.
  • the same performance is obtained as with 1100 g of Ti + C powder in the form of insert. Since this mixture costs around 75 Euro / kg in 2008, the advantage provided by the invention is measured.
  • the porous millimetric granules are crimped in the metal infiltration alloy. These millimetric granules are themselves composed of microscopic particles with globular tendency, TiC, also crimped in the metal alloy infiltration. This system makes it possible to obtain a composite part with a macrostructure within which there is an identical microstructure on a scale approximately a thousand times smaller.
  • this material comprises small globular particles of titanium carbide, hard and finely dispersed in a metal matrix which surrounds them, makes it possible to prevent the formation and propagation of cracks (see FIG. Fig. 4 and Fig. 6 ). There is thus a double dissipative system of cracks.
  • Cracks usually originate at the most fragile places, which are in this case the TiC particle, or the interface between this particle and the infiltration metal alloy. If a crack originates at the interface, or in the micrometric particle of TiC, the propagation of this crack is then impeded by the infiltration alloy which surrounds this particle.
  • the toughness of the infiltration alloy is greater than that of the TiC ceramic particle. The crack needs more energy to pass from one particle to another to cross the micrometric spaces that exist between the particles.
  • the expansion coefficient of the TiC reinforcement is lower than that of the ferrous alloy matrix (TiC expansion coefficient: 7.5 ⁇ 10 -6 / K and the ferrous alloy: about 12.0 ⁇ 10 -6 / K).
  • This difference in the expansion coefficients has the consequence of generating tensions in the material during the solidification phase and also during the heat treatment. If these voltages are too great, cracks may appear in the room and lead to scrapping it.
  • a small proportion of TiC reinforcement (less than 50% by volume) is used, resulting in less stress in the part.
  • the presence of a matrix more ductile between the micrometric globular particles of TiC alternating zones of low and high concentration makes it possible to better assume any local tensions.
  • the boundary between the reinforced portion and the non-reinforced portion of the hierarchical composite is not abrupt because there is a continuity of the metal matrix between the reinforced portion and the unreinforced portion, thereby allowing the protect against a complete tearing of the reinforcement.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Glass Compositions (AREA)
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  • Mounting, Exchange, And Manufacturing Of Dies (AREA)

Claims (15)

  1. Hierarchisches Verbundmaterial, das eine Eisenlegierung aufweist, die mit Titancarbiden gemäß einer festgelegten Geometrie verstärkt ist, wobei der verstärkte Abschnitt eine Makro-Mikrostruktur aufweist, in der sich Millimeterzonen (1) abwechseln, in denen sich körnige Titancarbid-Mikrometerpartikel (4) konzentrieren, die durch Millimeterzonen (2) getrennt sind, die im wesentlichen keine körnigen Titancarbid-Mikrometerpartikel (4) enthalten, wobei die Zonen, in denen körnige Titancarbid-Mikrometerpartikel (4) konzentriert sind, eine Mikrostruktur bilden, in der die Mikrometer-Zwischenräume (3) zwischen den körnigen Partikeln (4) ebenfalls von der Eisenlegierung belegt sind.
  2. Verbundmaterial nach Anspruch 1, wobei die konzentrierten Millimeterzonen eine Titancarbidkonzentration (4) von über 36,9 Volumenprozent haben.
  3. Verbundmaterial nach Anspruch 1, wobei der verstärkte Abschnitt einen allgemeinen Gehalt an Titancarbid zwischen 16,6 und 50,5 Volumenprozent aufweist.
  4. Verbundmaterial nach einem der Ansprüche 1 oder 2, wobei die körnigen Titancarbid-Mikrometerpartikel (4) eine Größe von weniger als 50 µm aufweisen.
  5. Verbundmaterial nach einem der vorangehenden Ansprüche, wobei der größte Teil der körnigen Titancarbid-Mikrometerpartikel (4) eine Größe von weniger als 20 µm aufweist.
  6. Verbundmaterial nach einem der vorangehenden Ansprüche, wobei die Zonen, in denen körnige Partikel Titancarbid (1) konzentriert sind, 36,9 bis 72,2 Volumenprozent Titancarbid aufweisen.
  7. Verbundmaterial nach einem der vorangehenden Ansprüche, wobei die Millimeterzonen, in denen Titancarbid (1) konzentriert ist, eine Größe aufweisen, die von 1 bis 12 mm variiert.
  8. Verbundmaterial nach einem der vorangehenden Ansprüche, wobei die Millimeterzonen, in denen Titancarbid (1) konzentriert ist, eine Größe aufweisen, die von 1 bis 6 mm variiert.
  9. Verbundmaterial nach einem der vorangehenden Ansprüche, wobei die Zonen, in denen Titancarbid (1) konzentriert ist, eine Größe aufweisen, die von 1,4 bis 4 mm variiert.
  10. Verbundmaterial nach einem der vorangehenden Ansprüche, wobei das Verbundmaterial ein Verschleißteil ist.
  11. Verfahren zur Herstellung durch Gießen des hierarchischen Verbundmaterials nach einem der Ansprüche 1 bis 10, das die folgenden Schritte umfasst:
    - Bereitstellung einer Form, die den Abdruck des hierarchischen Verbundmaterials mit einer vorher festgelegten Verstärkungsgeometrie aufweist,
    - Einleitung eines verdichteten Pulvergemischs, das Kohlenstoff und Titan in Form von Millimetergranulat als Vorläufer des Titancarbids enthält, in den Abschnitt des Abdrucks, der dazu bestimmt ist, den verstärkten Abschnitt zu bilden,
    - Gießen einer Eisenlegierung in die Form, wobei die Wärme des Schmelzguts innerhalb der Vorläuferpartikel eine selbstgängige exotherme Hochtemperatur-Titancarbid-Synthesereaktion (SHS) auslöst,
    - Ausbildung, innerhalb des verstärkten Abschnitts des hierarchischen Verbundmaterials, einer Makro-Mikrostruktur, in der sich Millimeterzonen (1), in denen sich körnige Titancarbid-Mikrometerpartikel (4) an der Stelle des Vorläufergranulats konzentrieren, abwechseln, wobei diese Zonen voneinander durch Millimeterzonen (2) getrennt sind, die im wesentlichen keine körnigen Titancarbid-Mikrometerpartikel (4) enthalten, wobei die körnigen Partikel (4) auch innerhalb der Millimeterzonen (1), in denen Titancarbid konzentriert ist, durch Mikrometer-Zwischenräume (3) getrennt sind,
    - Tränkung der Millimeter- (2) und Mikrometer-Zwischenräume (3) mit der Hochtemperatur-Eisengusslegierung im Anschluss an die Ausbildung körniger mikroskopischer Titancarbidpartikel (4).
  12. Herstellungsverfahren nach Anspruch 11, wobei das verdichtete Titan-Kohlenstoff-Pulvergemisch ein Pulver einer Eisenlegierung aufweist.
  13. Herstellungsverfahren nach Anspruch 11, wobei der Kohlenstoff Graphit ist.
  14. Hierarchisches Verbundmaterial, das nach einem der Ansprüche 11 bis 13 hergestellt wird.
  15. Werkzeug oder Maschine, das/die ein hierarchisches Verbundmaterial nach einem der Ansprüche 1 bis 10 oder nach Anspruch 14 aufweist.
EP09782201.9A 2008-09-19 2009-08-26 Hierarchischer verbundwerkstoff Active EP2334836B9 (de)

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BE2008/0521A BE1018130A3 (fr) 2008-09-19 2008-09-19 Materiau composite hierarchique.
PCT/EP2009/060980 WO2010031662A1 (fr) 2008-09-19 2009-08-26 Materiau composite hierarchique

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PL414755A1 (pl) * 2015-11-12 2017-05-22 Innerco Spółka Z Ograniczoną Odpowiedzialnością Sposób wytwarzania lokalnych stref kompozytowych w odlewach i wkładka odlewnicza
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US8999518B2 (en) 2015-04-07
BRPI0913538A2 (pt) 2015-12-15
BRPI0913538B1 (pt) 2019-12-17
EP2334836A1 (de) 2011-06-22
ZA201101791B (en) 2012-08-29
CN102187002A (zh) 2011-09-14
MX2011003029A (es) 2011-04-14
ATE549427T1 (de) 2012-03-15
US20110229715A1 (en) 2011-09-22
ES2383782T3 (es) 2012-06-26
PL2334836T3 (pl) 2012-08-31
BE1018130A3 (fr) 2010-05-04
AU2009294781B2 (en) 2013-06-13
EG26641A (en) 2014-04-16
CA2735912A1 (en) 2010-03-25
KR20110059720A (ko) 2011-06-03
CN102187002B (zh) 2013-06-05
JP2012502802A (ja) 2012-02-02
AU2009294781A1 (en) 2010-03-25
WO2010031662A1 (fr) 2010-03-25
CL2011000577A1 (es) 2011-08-26
CA2735912C (en) 2016-03-29
EP2334836B9 (de) 2013-08-07
JP5484468B2 (ja) 2014-05-07
MY156696A (en) 2016-03-15
DK2334836T3 (da) 2012-07-02
KR101614180B1 (ko) 2016-04-20
PT2334836E (pt) 2012-07-23
ES2383782T9 (es) 2013-11-05

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