EP3374107B1 - Composition de poudre pour la fabrication d'inserts de pièce coulée, insert de pièce coulée et procédé d'obtention de zones composites locales dans des pièces coulées - Google Patents

Composition de poudre pour la fabrication d'inserts de pièce coulée, insert de pièce coulée et procédé d'obtention de zones composites locales dans des pièces coulées Download PDF

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EP3374107B1
EP3374107B1 EP16820332.1A EP16820332A EP3374107B1 EP 3374107 B1 EP3374107 B1 EP 3374107B1 EP 16820332 A EP16820332 A EP 16820332A EP 3374107 B1 EP3374107 B1 EP 3374107B1
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casting
composite
powder
moderator
composition
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EP3374107A1 (fr
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Ewa Olejnik
Anna JESIOLOWSKA
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Innerco Sp Z OO
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Innerco Sp Z OO
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Priority to EP22204377.0A priority Critical patent/EP4166258A2/fr
Priority claimed from PCT/IB2016/056825 external-priority patent/WO2017081665A1/fr
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    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • 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
    • B22D19/02—Casting in, on, or around objects which form part of the product for making reinforced articles
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/23—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces involving a self-propagating high-temperature synthesis or reaction sintering step
    • 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
    • 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
    • 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
    • C22C29/08—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 based on tungsten carbide
    • 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
    • C22C29/10—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 based on titanium carbide
    • 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
    • C22C29/067—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 comprising a particular metallic binder

Definitions

  • the object of the present invention is powder composition for the manufacture of casting inserts used in the fabrication of wear-resistant local composite zones; another object of the present invention is casting insert, the use of which allows increasing the resistance to abrasive wear in cast parts of machines operating under conditions of heavy mechanical loads.
  • the present invention also provides a method for the fabrication of local composite zones in castings, wherein said local composite zones increase the resistance of castings to the degradation process and the resistance to abrasive wear of machinery operating under conditions of heavy mechanical loads.
  • the process of in situ synthesis of the silicon carbide SiC uses the method of Self-Propagating High Temperature Synthesis (SHS).
  • SHS Self-Propagating High Temperature Synthesis
  • TiC titanium carbide TiC
  • SHS reaction the problems concerning the control of the SHS reaction, wherein said reaction once initiated is a self-sustained process, which means that the amount of heat generated by the reaction can further spread out this reaction. Fading of the reaction can occur only then, when the heat volume dissipated by the system is larger than the heat volume generated during the reaction.
  • U.S. Patent US 20110303778A1 discloses a process which reduces the phenomenon of crack propagation.
  • the aim has been achieved through the use of material characterized by a hierarchical structure, wherein the reinforced phase comprises, spread in a ferrous alloy, millimetric granules containing micrometric coagulated particles of titanium carbide TiC, and wherein the areas between the particles of titanium carbide TiC are also filled with a ferrous alloy.
  • previously prepared granules of compressed powders of Ti and C are placed in selected areas of casting mould, and are prevented from being dispersed by separating means, and then the mould is poured with a ferrous alloy.
  • the granulated composite structure allows controlling the size of the areas with clusters of titanium carbide TiC and partial control of the distance between these clusters. Additionally, it also facilitates the removal of gases formed during the SHS synthesis, which reduces the number of pores in casting. On the other hand, the granular structure does not provide sufficient resistance of the material to abrasive wear. Large distances between the granules with particles of titanium carbide TiC are not preferred, since they facilitate the erosion process in the infiltrating material, and this, in turn, promotes chipping of the agglomerates of titanium carbide TiC. Hence the target is to develop a composite structure that will resist the effect of crack propagation and also the effect of erosion.
  • the target is to seek new simplified methods for the fabrication of local zones of increased strength and resistance to abrasive wear, thus improving further the durability of cast parts of said machines and equipment, allowing simultaneously for a convenient and easy application of these methods without the need to use any additional devices.
  • the essence of the present invention is a powder composition for the fabrication of casting inserts designed to produce local composite zones resistant to abrasive wear, wherein said composite zones are reinforced with carbides and borides formed in situ in castings, and wherein said powder composition is characterized in that it comprises powder reactants of the formation of carbides said carbides forming after crystallization particles reinforcing the composite zones in castings, and wherein said powder composition further comprises moderator powders in the form of a mixture of metal powders which after crystallization form matrix of the composite zone in casting.
  • the amount of powder reactants of the titanium carbide TiC formation in the composition according to the invention is from 3 to 40wt% and the amount of moderator powders is from 60 to 97wt%.
  • the amount of powder reactants of the tungsten carbide WC formation in the composition according to the invention is from 40 to 99wt% and the amount of moderator powders is from 1 to 60wt%.
  • the amount of the mixture of powder reactants of the coupled reaction of the formation of titanium carbide TiC and tungsten carbide WC in the composition according to the invention is from 10 to 70wt% and the amount of moderator powders is from 30 to 90wt%.
  • the powder reactants of the formation of carbides and/or borides have particles of the size of up to 100 ⁇ m, but preferably not larger than 45 ⁇ m.
  • the moderator powders additionally comprise a non-metal in the form of C.
  • carbon as a reactant powder takes the form of graphite, amorphous graphite, a carbonaceous material or mixtures thereof, and in the case of Ti, W, Zr, Nb, Ta these are powders of pure metals or powders of alloys of these metals with other elements, or mixtures thereof.
  • the moderator powders have the chemical composition of an alloy selected from the group comprising grey cast iron, white cast iron, chromium cast iron, cast chromium steel, cast unalloyed steel, cast low-alloy steel, cast Hadfield manganese steel or Ni-Hard4 chromium cast iron containing Ni.
  • the moderator powders also include powders of ceramic phases increasing the resistance to wear, in particular powders selected from the group of ZrO 2 , stabilized ZrO 2 , Al 2 O 3 , or a mixture thereof, and/or a reducing component in the form of Al and/or Si, wherein the amount of the reducing component in the powder composition is maximum 5wt%.
  • the essence of the present invention is also a casting insert to produce wear-resistant local composite zones in castings, wherein said casting insert comprises the reactants of the carbide and/or boride formation, and wherein said casting insert is in the form of shapes, solids, preforms or granules, and is characterized in that it comprises a compacted powder composition according to the invention.
  • the invention also relates to a method for producing local composite zones in castings, involving the reaction of self-propagating high temperature synthesis (SHS), wherein a powder mixture comprising the reactants of the carbide and/or boride formation is prepared, said powder mixture being next subjected to compaction, conferring to the compacted powder mixture the form of particular shapes, solids, preforms or granules which serve as casting inserts, placing next at least one casting insert in the interior of the mould, and pouring next said mould with molten casting alloy in an amount sufficient to initiate the SHS reaction, and wherein said invention is characterized in that a powder mixture comprising the reactants of the carbide and ⁇ or boride formation is prepared, said powder mixture making powder composition according to the invention.
  • SHS self-propagating high temperature synthesis
  • the prepared powder mixture is dried, preferably at a temperature of 200°C until the content of moisture is maximum 2%.
  • the operation of compaction is performed under a pressure ranging from 450 MPa to 650 MPa.
  • the casting insert is placed in the mould cavity in a predetermined position and is fixed to the mould with bolts or is placed on a steel frame, said frame being placed inside the mould cavity, wherein preferably the steel frame consists of rods onto which the compacts having the holes are threaded.
  • the composite zones produced in situ in castings are characterized by stable and predictable size, and crystals of titanium carbide TiC have similar submicron dimensions.
  • the presence of a large number of the fine crystals of titanium carbide TiC of a relatively uniform distribution imparts to the composite zone an improved abrasive wear resistance and also an improved impact strength, as in the vicinity of fine crystals the mechanical stress is reduced, while smaller distances between these crystals increase the resistance of the composite zone to erosion.
  • the method according to the present invention provides a much more precise control of the SHS process during casting.
  • the typical SHS process is a self-sustained reaction, which once initiated proceeds rapidly until all the input material is reacted. Since the reaction is highly exothermic and results in a rapid increase of temperature combined with the emission of gases, there is an imminent risk of the formation of cavities and pores.
  • said moderator composition through careful selection of the composition of the moderator, wherein said moderator composition not only has the ability to effectively absorb the excess heat but has also the ability to increase hardness and wear resistance of the composite matrix, and additionally has the ability to absorb gases, the aforementioned drawbacks have been minimized.
  • Example 1 the mould cavity and casting inserts were prepared for the fabrication of composite zones reinforced with TiC carbide ( Fig. 1a ), including the operation of fixing said casting inserts by means of an assembly system in said mould cavity ( Fig. 1b ).
  • the casting inserts were made from a powder mixture comprising the reactants of TiC formation and a moderator having the composition of cast high-manganese steel containing 21% Mn.
  • the composition of the powder mixture used for the fabrication of casting inserts and the obtained results are included in Table 1. Symbols "+” and “-” in Tables 1-6 stand for the answers "yes” and "no", respectively, in a schematic description of the results of examinations of the polished cross-section of a casting with the composite zones fabricated by an in situ method.
  • casting inserts were fixed in the mould cavity to produce composite zones reinforced with titanium carbide TiC, as shown in Figures 1a and 1b .
  • the inserts contained various amounts of the moderator in the form of a powder mixture having the composition of cast Hadfield high-manganese steel with 21wt% Mn and reactants of the titanium carbide TiC formation.
  • the atomic ratio of the reactants was 50at% Ti : 50 at% C.
  • the inserts were made by compaction under a pressure of 600 MPa and had dimensions of 20 ⁇ 100 ⁇ X mm, where X for individual inserts was from 8 to 15 mm, respectively.
  • a 6 kg weighing casting measuring 70 ⁇ 150 ⁇ 150 mm was made from the L35GSM steel and had the composite zones visible in Figure 1c formed in situ from the casting inserts containing 50wt%, 70wt% and 90wt% of the moderator addition in zones A4 to A6, respectively, whereas the composite zones formed in situ from the casting inserts containing 0wt%, 10wt% and 30wt% of the moderator addition were scattered and invisible (the area marked with symbols A1 to A3 in Figure 1c ). Fragments of the scattered composite zones are visible in the milled upper casting surface shown in Figure Id.
  • the composite zones produced without the addition of moderator and with the addition of moderator in an amount of 10wt% and 30wt% have undergone the process of fragmentation ( Fig. 1c ) with a significant share of macroporosity and fragments of composite layer present in the upper part of casting ( Fig. 1d ).
  • This macrostructure was the result of intense infiltration induced by a significant increase in temperature during the reaction of the SHS synthesis of titanium carbide TiC caused by the absence of moderator. Since the reaction of synthesis is highly exothermic, the significant increase in temperature promotes the process of infiltration as well as the production and dissolution of gases.
  • top surface of the casting shows fragments of composite zones obtained with the moderator addition of 0wt%, 10wt%, 30wt%, wherein said composite zones during the in situ reaction of TiC synthesis in molten alloy have undergone the process of fragmentation and floated to the top.
  • This effect was observed in a series of 15 tests.
  • the results of experimental studies have also indicated that when the casting inserts for the in situ fabrication of composite zones in castings contain only powder reactants of the TiC synthesis, local composite zones are not formed due to the disadvantageous phenomenon of the fragmentation of these zones.
  • the mould cavity and casting inserts were prepared for the fabrication of composite zones reinforced with TiC carbide ( Fig. 2a ), including the operation of fixing said casting inserts by means of an assembly system in said mould cavity.
  • the casting inserts were made from a powder mixture comprising the reactants of TiC formation and a moderator having the composition of pure Fe powder added in the amounts as indicated in Table 2.
  • the composition of the powder mixture used for the fabrication of casting inserts and the obtained results are included in Table 2.
  • the atomic ratio of the reactants was 55at% Ti : 45at% C.
  • casting inserts to produce the composite zones reinforced with TiC carbide were fixed in the mould cavity, as shown in Figure 3a .
  • the inserts contained various amounts of the moderator powder having the composition of cast high-manganese steel with 21wt% Mn.
  • the composition of the powder mixture used for the fabrication of casting inserts and the obtained results are included in Table 3.
  • the atomic ratio of the reactants was 55at% Ti : 45at% C.
  • the inserts were made by compaction under a pressure of 500 MPa and had dimensions of 20 ⁇ 50 ⁇ X mm, where X for individual inserts was from 15 to 25 mm, respectively.
  • the powder compositions were tested for the fabrication of local composite zones reinforced with TiC carbide, which contained the addition of moderator in the form of a powder mixture having the composition of Ni-Hard4 chromium cast iron containing Ni.
  • the composition of the powder mixture used for the fabrication of casting inserts and the obtained results are included in Table 4.
  • the atomic ratio of the reactants was 55wt%Ti : 45at%C.
  • the inserts were made by compaction under a pressure of 500 MPa and had dimensions of 20 ⁇ 50 ⁇ X mm, where X for individual inserts was from 15 to 25 mm, respectively.
  • the casting inserts were fixed in the mould cavity as shown in Figure 4a .
  • the casting wall thickness was set in the range of 50 to 150 mm, which is a typical value for a number of cast structural components used in the conical, jaw, hammer and impact crushers, and also for the rolls or balls of ball or roller mills.
  • the composite zones produced with the moderator content exceeding 60wt% were stable and did not undergo fragmentation.
  • powder compositions with higher content of the moderator can be used to reduce infiltration and produce stable composite zones in such castings.
  • Example 2 casting inserts were fixed in the mould cavity to produce composite zones reinforced with WC carbide as shown in Figure 5a .
  • the casting inserts contained the reactants of WC carbide formation and varying amounts of the powder moderator having the composition of NiHard 4 white cast iron containing Ni.
  • the composition of the powder mixture used for the fabrication of casting inserts and the obtained results are included in Table 5.
  • the atomic ratio of the reactants to form WC carbide was 94.93% W: 5.07% C.
  • the moderator used for the manufacture of casting inserts E2-E9 contained the addition of a deoxidizer in the form of Al powder introduced in an amount of 2wt%.
  • the inserts were made by compaction under a pressure of 500 MPa and had dimensions of 20 ⁇ 50 ⁇ X mm, where the value of dimension X depended on the compactability of individual powder compositions.
  • Compacts E1-E8 were made from samples of powder compositions weighing 100 g each, whereas compact E9 was made from a sample weighing 150 g. Then, polished cross-section was made ( Fig. 5b ) in a 7 kg weighing L450 steel casting measuring 43 ⁇ 70 ⁇ 250 mm and with a wall thickness of 48 mm.
  • the polished cross-sectional area shows the presence of composite zones formed in situ from the casting inserts E1-E5, wherein said inserts have produced the dimensionally stable zones reinforced with WC carbide, whereas zones E6-E9 have defects resulting from the incomplete reaction taking place in compacts with a higher content of the moderator. This points out to a different nature of the reaction of the SHS synthesis of the formation of titanium carbide TiC and tungsten carbide WC.
  • Example 3 casting inserts were fixed in the mould cavity to initiate the coupled reaction of the SHS synthesis and produce the (Ti, W)C carbide as shown in Figure 6a .
  • the casting inserts contained the TiC and WC reactants of the coupled SHS synthesis of the (Ti, W)C carbide and varying amounts of the moderator in the form of a powder mixture having the composition of NiHard4 white cast iron containing Ni.
  • the composition of the powder mixture used for the fabrication of casting inserts and the obtained results are included in Table 6.
  • the weight fraction of the reactants was 50% TiC (where 55at% Ti : 45at% C) and 50wt% WC (where 94.93 at% W : 5.07 at% C).
  • the moderator used for the manufacture of casting inserts F1-F4 contained the addition of a deoxidizer in the form of A1 powder introduced in an amount of 5%, whereas in the case of inserts F5-F8, the amount of the deoxidizer was reduced to 0.1%.
  • the inserts were made by compaction under a pressure of 500 MPa and had dimensions of 20 ⁇ 60 ⁇ X mm, where the value of dimension X depended on the compactability of individual powder compositions.
  • polished cross-section was made ( Fig. 5b ) in a 7 kg weighing LGS30 steel casting measuring 43 ⁇ 70 ⁇ 250 mm and with a wall thickness of 48 mm, said polished cross-section being made on the top surface ( Fig.
  • microstructure was examined in a cross-section of the transition region located between the composite zone and the remaining part of the steel casting and also in a cross-section of the composite zone. Tests were performed on experimental models included in Table 7. Table 7 Sample No. D1 D2 D9 Matrix cast L35GSM steel cast L35GSM steel cast L450 steel Moderator type Cast high-manganese steel with 21wt% Mn Ni-Hard4 chromium cast iron Moderator content 70wt% 90wt% 97wt % Results Fig. 5 Fig. 6 Fig.
  • composition of moderators used in the examples of embodiments Composition of moderator Chemical composition [wt% ] C Mn Si Ni Cr Mo Fe Cast Hadfield high-manganese steel with 21% Mn 1.2 21 0.5 - - - rest NiHard 4 chromium cast iron containing Ni 3.6 0.8 2.2 5.5 10 0.5 rest High-chromium cast iron 3.31 0.69 0.87 - 26.6 1.25 rest
  • Figures 7 and 8 show the images of microstructures of the composite zones produced in cast L35GSM steel.
  • the composite zones were made from the casting inserts containing 70wt% of moderator addition having the composition of cast Hadfield high-manganese steel with 21wt% Mn, said moderator being a mixture of powders of Fe, FeMn, C, FeSi, Al.
  • the transition region between the composite zone and the rest of casting visible in Figure 7a is characterized by a strong bond obtained in the controlled process of infiltration and diffusion occurring in the liquid state between the area of the in situ reaction zone and liquid alloy poured into the mould cavity.
  • the phase boundary between the composite zone and the rest of casting forms a straight line and is characterized by continuity and dimensional stability.
  • the fabricated composite zone contains mainly the submicron-sized TiC carbides uniformly distributed within the area of the zone.
  • the visible effect of fragmentation enhances surface development of the TiC carbide and its even distribution within the area of the zone, as observed in Figure 7 c-d .
  • Figure 8 shows that with a high content of the moderator added in an amount of 90wt%, the distribution of the crystals of titanium carbide TiC in the composite zone is less uniform, while clusters of the TiC crystals assume a specific shape of self-organizing structures in the form of rings and chains visible in Figure 8f .
  • the rings of these chains are of a submicron and nanometric thickness.
  • moderator in powdered form favourably affects the nucleation kinetics and crystal growth in alloy melt during the reaction of the synthesis of carbides, such as, for example, TiC, WC, (W, Ti) C, and other carbides undergoing the SHS reaction that occurs between powder reactants of carbide formation contained in the powder mixture, said powder mixture forming after compaction a casting insert.
  • carbides such as, for example, TiC, WC, (W, Ti) C
  • SHS reaction that occurs between powder reactants of carbide formation contained in the powder mixture, said powder mixture forming after compaction a casting insert.
  • Particularly preferred is the excellent dispersion of the crystals of, for example, TiC in a matrix of the composite zone. It allows obtaining favourable operating parameters of the composite zone at a relatively low percent content of carbides such as, for example, titanium carbide TiC.
  • moderator introduced as a mixture of metal and non-metal powders, significantly improves both hardness and wear resistance of the composite zones obtained in situ in castings
  • Hardness testing was performed in local composite zones fabricated by the method according to the present invention from materials of different compositions with different content of the moderator according to the present invention. The results are shown in Figures 10-13 . Hardness of composite zones was tested in 7 kg weighing castings measuring 43 ⁇ 70 ⁇ 250 mm with a wall thickness of 48mm, wherein said composite zones were fabricated by the in situ method.
  • the matrix of the composite zone according to the present invention can be made from materials of the chemical composition characterized by properties substantially different from the properties of the base casting alloy poured into the mould cavity. This allows careful selection of the alloy providing the predictable mechanical and functional properties, a repeatable process of synthesis and reproducible distribution of the crystals of carbides such as, for example, titanium carbide TiC in local composite zones.
  • Figure 11 shows the relationship between hardness of composite zones obtained in situ in a casting made from the L450 steel and the amount of moderator in the form of pure iron powder having properties close to the properties of the base casting alloy
  • Figure 12 shows the relationship between hardness of composite zones obtained in situ in a casting made from the L35GSM steel and the amount of moderator, wherein the applied reactants of the formation of titanium carbide TiC are mixed with moderator powders, which by the reaction of the SHS synthesis form chromium cast iron having properties substantially different from the properties of the base casting alloy.
  • the results of experimental studies indicate two important parameters influencing the course of hardness changes.
  • the first is the effect of moderator, which by stabilizing the reactive infiltration process controls the dimensional stability of composite zones.
  • the dimensional stability ensures the maximum volume fraction of carbides in the zone at a given content of the reactants of the formation of these carbides, and hardness of the composite zone corresponding to this fraction.
  • the volume fraction of the obtained carbides of some importance is also their morphology and interconnections between the bridges formed.
  • the highest hardness is obtained in the zones reinforced with TiC carbide, when the moderator content is 60 ⁇ 70wt% of the powder composition used for the fabrication of casting insert.
  • This range of the moderator percent content in the composite zone is optimal for moderators in the form of a powder mixture having the composition of chromium cast iron, a powder mixture having the composition of cast Hadfield high-manganese steel with 21% Mn and a powder mixture having the composition of Ni-Hard4 chromium cast iron containing Ni.
  • the moderator having the composition of Ni-Hard4 chromium cast iron (70wt%) was chosen as an optimal one to increase the hardness of composite zones fabricated in a relatively soft cast L450 steel.
  • the resulting high value of hardness (1400HV1, Fig. 13 ) was due to a synergy between moderator powders used in an amount of 70wt% to produce phases typical of Ni-Hard4 chromium cast iron and reactants of the formation of titanium carbide TiC.
  • the moderator having the composition of cast manganese steel ( Fig. 14 ) added in an amount of 70wt% produces high hardness values in the composite zone (1200HV1) at a relatively low hardness of the base cast L450 steel (550HV1).
  • the moderator composition may be supplemented with ceramic phases such as aluminium oxide Al 2 O 3 or zirconium oxide ZrO 2 , including its stabilized varieties.
  • ceramic phases such as aluminium oxide Al 2 O 3 or zirconium oxide ZrO 2 , including its stabilized varieties.
  • the introduction of ceramic phases to the composite zones can increase, through limited infiltration, the percent content of the reactants of the formation of titanium carbide and thus significantly improve the resistance to abrasion.
  • the ceramic phases in the form of oxides introduced by themselves can also increase the wear resistance of the composite zones and are less expensive than, for example, titanium Ti used for the formation of TiC carbide.
  • the high percent content of the reactants of the formation of titanium carbide TiC does not result in the composite zone fragmentation, since ceramic phases, especially aluminium oxide, by having a high specific heat, absorb the heat formed during the SHS synthesis, thus exerting control over the SHS process.
  • ceramic phases, especially aluminium oxide by having a high specific heat, absorb the heat formed during the SHS synthesis, thus exerting control over the SHS process.
  • aluminium oxide Al 2 O 3 or zirconium oxide ZrO 2 in the moderator composition produces composite zones characterized by very high resistance to abrasive wear, but practical use of such inserts is limited to those applications where high impact resistance is not required.
  • the highest hardness shown in Figure 15 is obtained with a low content of the moderator. In this particular case, however, hardness does not decrease with the increasing addition of the moderator. As a consequence, preferably, using the addition of moderator, it is possible to produce a reinforcement in the casting with a reduced amount of the expensive tungsten W.
  • Composite zones reinforced with the (Ti, W)C carbide, formed as a result of the coupled reaction of synthesis, have preferable hardness values shown in Figure 16 at a 55% level of the moderator addition.
  • Table 9 compares the results of abrasion resistance testing carried out in selected composite zones.
  • the measurements of the wear index of the composite zones and of the cast L35GSM steel were taken by a Ball-on-Disc method according to ISO 20808: 2004.
  • the test results disclosed in the table below confirm that the composite zones with high hardness are characterized by a low wear index.
  • the composite zone based on a matrix made from the Ni-Hard4 chromium cast iron has the hardness of 1400HV1 and, at the same time, the lowest wear index of 7.07 ⁇ 10 -6 [mm 3 /Nm].
  • Composite casting for use in an environment of high abrasive wear and low dynamic loads.
  • a mixture of titanium powders with the average diameter of less than 44.5 ⁇ m and carbon powders with the average diameter of less than 3 ⁇ m was prepared, maintaining the mutual atomic ratio of 1: 1.
  • a moderator To 40wt% of the powder mixture of reactants of the formation of titanium carbide TiC, the addition of 59wt% of a moderator was introduced, said moderator being a powder mixture having the composition of Ni-Hard4 chromium cast iron comprising Fe, Cr, Ni, Mn, Si, Mo and C, some of which were introduced in the form of ferroalloys.
  • the addition of 1wt% of a reducing component in the form of A1 powder was introduced.
  • Composite casting for use in an environment of high abrasive wear and high dynamic loads A mixture of titanium powders with the average diameter of less than 44.5 ⁇ m and carbon powders with the average diameter of less than 3 ⁇ m was prepared, maintaining the mutual atomic ratio of 1: 1.
  • a moderator To 30wt% of the powder mixture of reactants of the formation of titanium carbide TiC, the addition of 69wt% of a moderator was introduced, said moderator being a powder mixture having the composition of cast high-manganese steel with 21wt% Mn comprising Fe, Mn, Si, C, some of which were introduced in the form of ferroalloys, introducing also minor additions of other elements.
  • the addition of 1wt% of a reducing component in the form of A1 powder was introduced.
  • the reducing component was introduced in order to bind the gases present in the compact.
  • all the powders were mixed, dried and compressed under a pressure of 500MPa.
  • the obtained casting inserts of 15 ⁇ 20 ⁇ 100mm dimensions produced in an amount of 100 pieces were placed in the area of the estimated highest wear occurring in a 200 kg weighing casting.
  • mould with the fixed set of casting inserts was dried with a gas burner. Said mould was next poured with molten casting alloy having the composition of manganese steel containing 18wt% Mn.
  • a casting was obtained, reinforced with the composite zones containing mainly submicron particles of the TiC carbide disposed in an austenitic matrix.
  • Ultra-high abrasive wear resistant casting for use in an environment free from high dynamic loads.
  • a mixture of titanium powders with the average diameter of less than 44.5 ⁇ m and carbon powders with the average diameter of less than 3 ⁇ m was prepared, maintaining the mutual atomic ratio of 1: 1.
  • the addition of the following moderators was introduced: 10wt% of ZrO 2 -Y 2 O 3 , 10wt% of Al 2 O 3 and 29wt% of a powder mixture having the composition of cast high-manganese steel containing 21wt% Mn.
  • a 40 kg weighing casting was obtained, reinforced with the zones comprising a hybrid composite of the TiC/Al 2 O 3 /ZrO 2 -Y 2 O 3 /matrix type, consisting mainly of submicron and micron particles of the TiC carbide, and of micron and millimeter particles of the Al 2 O 3 and ZrO 2 -Y 2 O 3 oxides.
  • Ultra-high abrasive wear resistant casting for use in an environment free from high dynamic loads.
  • a mixture of titanium powders with the average diameter of less than 44.5 ⁇ m and carbon powders with the average diameter of less than 3 ⁇ m was prepared, maintaining the mutual atomic ratio of 1: 1.
  • a moderator being a powder mixture having the composition of cast high-manganese steel containing 21% Mn, said mixture comprising Fe, Mn, Si, C, some of which were introduced in the form of ferroalloys, introducing also minor additions of other elements with the average diameter of less than 44.5 ⁇ m, and 30wt% of a ceramic moderator in the form of Y 2 O 3 -stabilized ZrO 2 powder with the average diameter of less than 1 mm.
  • 1wt% of a reducing component in the form of Al powder was introduced. The reducing component was introduced in order to bind the gases present in the compact. Then all the powders were mixed, dried and compressed under a pressure of 500 MPa.
  • Casting inserts of 15 ⁇ 20 ⁇ 100 mm dimensions based on the powder mixture according to Example 7 were produced and in an amount of 5 pieces were next fixed in a 7 kg weighing casting in the area of the expected highest wear.
  • mould with the set of casting inserts fixed inside was dried with a gas burner.
  • Said mould was next poured with molten casting alloy having the composition of L35GSM steel.
  • a casting was obtained, reinforced with the zones comprising a hybrid composite of the TiC/ZrO 2 -Y 2 O 3 /matrix type consisting mainly of submicron and micron particles of the TiC carbide, and of micron and millimeter particles of the ZrO 2 -Y 2 O 3 oxide.
  • a mixture of titanium powders with the average diameter of less than 44.5 ⁇ m and carbon powders with the average diameter of less than 3 ⁇ m was prepared, maintaining the mutual atomic ratio of 1: 1.
  • a moderator is a powder mixture having the composition of chromium cast iron comprising Fe, Cr, Mn, Mo, Si, C, some of which were introduced in the form of ferroalloys, introducing also minor additions of other elements with the average diameter of less than 44.5 ⁇ m, and the addition of 45wt% of a ceramic moderator composed in 5wt% of the Y 2 O 3 -stabilized ZrO 2 powder with the average diameter of less than 100 ⁇ m and in 40wt% of the Al 2 O 3 powder with the average diameter of less than 130 ⁇ m. Additionally, to the powder mixture, 1wt% of a moderator composed in 5wt% of the Y 2 O 3 -stabilized ZrO 2 powder with the average diameter of less than 100 ⁇ m and in 40wt% of the Al 2
  • Casting insert in a second variant of the second embodiment A mixture of titanium powders with the average diameter of less than 44.5 ⁇ m and carbon powders with the average diameter of less than 3 ⁇ m was prepared, maintaining the mutual atomic ratio of 1: 1.
  • a moderator being a powder mixture having the composition of chromium cast iron comprising Fe, Cr, Mn, Si, C, some of which were introduced in the form of ferroalloys, and the addition of 60wt% of a ceramic moderator composed of the Y 2 O 3 -stabilized ZrO 2 powder with the average diameter of less than 0.5 mm.
  • 1wt% of a reducing component in the form of Al powder was introduced. Then all the powders were mixed, dried and compressed under a pressure of 500MPa to produce casting inserts of 15 ⁇ 20 ⁇ 100 mm dimensions.
  • Local composite zones are produced by placing casting inserts in the mould cavity, said inserts being obtained by compacting a powder mixture comprising the reactants of the formation of carbides undergoing the SHS synthesis, for example TiC carbides, and a mixture of selected powders of metals and non-metals, which after casting solidification form a composite matrix, said matrix being a casting iron-based alloy.
  • the moderator introduced in an amount of from 60 to 97wt% stabilizes the geometric dimensions of the composite zones and prevents fragmentation of said zones in the course of reactive infiltration that takes place during the synthesis of titanium carbide TiC in castings with the wall thickness of from 10 to 150 mm.
  • the minimum amount of the reactants of the formation of titanium carbide TiC providing the in situ formation of a composite matrix is 3wt%. Reducing the amount of the reactants of the formation of titanium carbide TiC is not effective and does not lead to the formation of designed structure of the composite matrix in the composite zone.
  • the use of ceramic structures based on aluminium oxide and zirconium oxide can increase the percent content of TiC crystals (> 30%) in the composite zone, thereby producing a significant increase in both hardness and abrasion resistance.
  • the moderator may be used in amounts of up to 60wt%, as above this level the reaction is inefficient and suppressed.
  • the reactants of WC carbide formation with the addition of moderator in an amount of up to 60wt% it is possible to obtain dimensionally stable composite zones, as illustrated in Figure 5 .
  • the powder compositions and casting inserts for the in situ fabrication of composite zones in castings according to the present invention allow an extensive use of different types of carbides and borides undergoing the reaction of the SHS synthesis.
  • Examples of the fabrication of composite zones in castings comprise two extreme cases of the use of carbides and mixtures thereof; these are the TiC and WC carbides, and a (W, Ti) C carbide, respectively.

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Claims (7)

  1. Composition de poudres pour la fabrication d'inserts de pièce coulée conçus pour produire des zones composites locales résistantes à une usure par abrasion, dans laquelle lesdites zones composites renforcées avec des carbures, sont constituées in situ dans des pièces coulées, et dans laquelle ladite composition de poudres est caractérisée en ce que la composition consiste en :
    des réactifs en poudre de la formation de carbures sélectionnés à partir du groupe de Tic, WC, ou d'un mélange de ceux-ci, dans laquelle lesdits carbures après cristallisation forment des particules renforçant les zones composites dans des pièces coulées,
    dans laquelle la quantité de réactifs en poudre de la formation de Tic va de 3 à 40 wt% (pour cent de poids), de carbure WC va de 40 à 99 wt% et de mélange de Tic et de carbures WC va de 10 à 70 wt% avec les quantités restantes consistant en
    des poudres modératrices constituant un mélange de poudres métalliques présentant une composition chimique d'un alliage sélectionné à partir du groupe de fonte grise, fonte blanche, fonte chromée, acier chromé moulé, acier non allié moulé, acier faiblement allié moulé, acier Hadfield au manganèse, ou fonte chromée Ni-Hard4 contenant du Ni, dans laquelle lesdites poudres métalliques après cristallisation forment une matrice de la zone composite dans une pièce coulée, et comprenant facultativement un élément non métallique supplémentaire sous forme de carbone et/ou incluant facultativement des phases de poudres de céramique accroissant la résistance à l'usure, en particulier les phases de poudres de céramique sélectionnées à partir du groupe de ZrO2, ZrO2 stabilisé, Al2O3 ou un mélange de ceux-ci, et/ou incluant facultativement un composant de réduction sous la forme d'Al et/ou de Si, dans laquelle la quantité du composant de réduction est au maximum de 5 wt% de la composition de poudres.
  2. La composition de poudres selon la revendication 1, caractérisée en ce que les poudres des réactifs de la formation de carbures présentent des particules de la taille allant jusqu'à 100 µm, mais de préférence inférieure à 45 µm.
  3. La composition de poudres selon la revendication 1, caractérisée en ce que le carbone en tant que réactif en poudre se présente sous la forme de graphite, graphite amorphe, matériau carboné ou un mélange de ceux-ci, et dans le cas de Ti et/ou W ceux-ci sont les poudres de métaux purs ou d'alliages desdits métaux avec d'autres éléments, ou des mélanges de ceux-ci.
  4. Insert de pièce coulée pour la fabrication de zones composites locales résistantes à l'usure, comprenant des réactifs de la formation de carbure, dans lequel ledit insert sous la forme de formes, solides, préformes ou granules est caractérisé en ce qu'il comprend une composition compactée de poudres selon les revendications 1 à 3.
  5. Procédé pour la fabrication de zones composites locales dans des pièces coulées, qui utilise la synthèse par réaction auto-entretenue à haute-température, SHS (Self-propagating High-temperature Synthesis), ledit procédé comprenant la préparation d'un mélange de poudres, dans lequel ledit mélange comprend les réactifs de formation de carbure, et dans lequel ledit mélange est ensuite compacté conférant à la composition de poudres compactée une forme particulière, particulièrement de formes, de solides, de préformes ou de granules constituant un insert de pièce coulée, et dans lequel au moins un insert de pièce coulée est ensuite placé à l'intérieur du moule, et ledit moule est rempli d'alliage de coulée fondu dans une quantité suffisante pour initier la réaction SHS, et dans lequel ledit procédé est en outre caractérisé en ce qu'un mélange de poudres comprenant les réactifs de formation de carbure est préparé, ledit mélange étant la composition de poudres selon les revendications 1 à 3 et en ce que le fonctionnement du compactage est exécuté sous une pression allant de 450 MPa à 650 MPa.
  6. Le procédé selon la revendication 5, caractérisé en ce qu' après préparation du mélange de poudres, ledit mélange est séché, de préférence à 200 °C, jusqu'à ce que la teneur en humidité soit au maximum de 2 %.
  7. Le procédé selon la revendication 5, caractérisé en ce que l'insert de pièce coulée est placé dans la cavité de moule dans une position prédéterminée et est fixé au moule au moyen de boulons ou est placé sur un cadre en acier, ledit cadre étant placé à l'intérieur de la cavité de moule, dans lequel de préférence le cadre en acier consiste en des tiges sur lesquelles des éléments compacts présentant les trous sont filetés.
EP16820332.1A 2015-11-12 2016-11-11 Composition de poudre pour la fabrication d'inserts de pièce coulée, insert de pièce coulée et procédé d'obtention de zones composites locales dans des pièces coulées Active EP3374107B1 (fr)

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PL414755A PL414755A1 (pl) 2015-11-12 2015-11-12 Sposób wytwarzania lokalnych stref kompozytowych w odlewach i wkładka odlewnicza
PCT/IB2016/056825 WO2017081665A1 (fr) 2015-11-12 2016-11-11 Composition de poudre pour la fabrication d'inserts de pièce coulée, insert de pièce coulée et procédé d'obtention de zones composites locales dans des pièces coulées

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EP16820332.1A Active EP3374107B1 (fr) 2015-11-12 2016-11-11 Composition de poudre pour la fabrication d'inserts de pièce coulée, insert de pièce coulée et procédé d'obtention de zones composites locales dans des pièces coulées

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CN108348995A (zh) 2018-07-31
PL3374107T3 (pl) 2023-03-06
FI3374107T3 (fi) 2023-01-31
DK3374107T3 (da) 2022-11-21
ES2932022T3 (es) 2023-01-09
EP3374107A1 (fr) 2018-09-19
PL414755A1 (pl) 2017-05-22
EP4166258A2 (fr) 2023-04-19

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