EP4279201A1 - Procédé de coulée d'un composant destiné à être appliqué dans un environnement industriel à forte usure et un tel composant coulé - Google Patents

Procédé de coulée d'un composant destiné à être appliqué dans un environnement industriel à forte usure et un tel composant coulé Download PDF

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Publication number
EP4279201A1
EP4279201A1 EP22174579.7A EP22174579A EP4279201A1 EP 4279201 A1 EP4279201 A1 EP 4279201A1 EP 22174579 A EP22174579 A EP 22174579A EP 4279201 A1 EP4279201 A1 EP 4279201A1
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EP
European Patent Office
Prior art keywords
powder
bulk material
casting
mold cavity
component
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EP22174579.7A
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German (de)
English (en)
Inventor
Ewa Olejnik
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Innerco Sp Z OO
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Innerco Sp Z OO
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Priority to EP22174579.7A priority Critical patent/EP4279201A1/fr
Priority to PCT/EP2023/063636 priority patent/WO2023222921A1/fr
Publication of EP4279201A1 publication Critical patent/EP4279201A1/fr
Pending legal-status Critical Current

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    • 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
    • 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
    • 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
    • C22C1/1005—Pretreatment of the non-metallic additives
    • C22C1/1015—Pretreatment of the non-metallic additives by preparing or treating a non-metallic additive preform
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • 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
    • 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
    • C22C37/00—Cast-iron alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/06—Cast-iron alloys containing chromium
    • C22C37/08—Cast-iron alloys containing chromium with nickel
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • 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

Definitions

  • the present invention relates to a method for casting a component for application in a high wear industrial environment with a composite zone containing titanium carbides in a matrix material.
  • the composite zone is formed in-situ during casting of molten bulk material and obtained by using a powder composition comprising reactant powder, which forms the titanium carbides within the composite zone and comprises titanium and carbon, and moderator powder, which forms the matrix surrounding the titanium carbides within the composite zone and comprises metal powders.
  • finished components i.e. those that have been formed and are in or near their end-product dimensions
  • hard surface layers via such techniques as spraying, cladding, welding, plating etc. prior to fielding said component.
  • These layers usually contain a high content of ceramic phases, such as carbides, borides and/or nitrides, arranged in a matrix material, generally composed of a metallic material. Due to the application of the wear resistant coating subsequent to component forming, complications due to bonding with the underlying bulk material and complete covering, due to undercuts and other form specifications, arise. Furthermore, the fabrication of such a component requires a multi-step manufacturing process, which increases production time and therewith-associated costs.
  • a harder periphery zone of a component can be produced in-situ during the initial casting of molten bulk material, thereby reducing the required manufacturing steps for a component.
  • the WO 2017/081665 A1 discloses a casted component with a composite zone containing titanium carbides.
  • the reactant powders are composed of 50 at.% Ti and 50 at.% C, while the moderator powder is a high-manganese steel.
  • the inserts are subsequently placed and fixed to walls of a cavity of a casting mold.
  • molten cast steel Six kilograms of a molten cast steel are poured into the mold, initiating a reaction between titanium and carbon, by supplying thermal energy via the molten casting steel. Due to a self-propagating high temperature synthesis (SHS) reaction, a composite zone containing titanium carbides within a matrix composed of a high-manganese steel is fabricated, thereby producing a harder zone of the component where the powder composition, in the form of the casting inserts, was originally placed. The main dimensions of the casted component is composed of the cast steel.
  • SHS self-propagating high temperature synthesis
  • WO 2017/081665 A1 further discloses that for the casted components manufactured implementing minimal amounts of moderator powder (i.e. 0 wt.%, 10 wt.% and 30 wt.%), no stable composite zones are obtained. Rather, fragments of titanium carbides within a high-manganese steel matrix are randomly distributed throughout the main dimensions of the casted component and do not remain at their intended location. This prevents the local reinforcement of hardness values within the regions of the casted component that are exposed to harsh wear conditions. Furthermore, due to their random distribution, the titanium carbide phases do not establish an interconnected network, thereby reducing the component's resistance to crack propagation and promoting local chipping.
  • the present invention seeks to present a method for casting a component with improved hardness properties in the composite zone of such a casted component.
  • the present invention proposes a method for casting a component for application in a high wear industrial environment with a composite zone containing titanium carbides in a matrix material, the composite zone formed in-situ during casting of molten bulk material and obtained by using a powder composition comprising reactant powder, which forms the titanium carbides within the composite zone and comprises titanium and carbon, and moderator powder, which forms the matrix surrounding the titanium carbides within the composite zone and comprises metal powders, characterized in that a powder composition consisting of 55-80 wt.% reactant powder and 20-45 wt.% moderator powder is inserted into a mold cavity with a wall thickness of at least 40 mm and at least 30 kg, preferably at least 100 kg of molten bulk material is poured into the mold cavity.
  • the composite zone of the casted component is formed in-situ during casting of molten bulk material. This occurs due to a known self-propagating high temperature synthesis (SHS) reaction, which is initiated when molten bulk material reaches a powder composition contained within a mold cavity.
  • the powder composition encompasses elements and/or compounds that form phases of the resulting composite zone.
  • the powder composition comprises reactant powder and moderator powder, which form the strengthening phases and the surrounding matrix, respectively.
  • the powder composition consists of 55-80 wt.% reactant powder and 20-45 wt.% moderator powder.
  • the reactant powder consists of 45 at.% Ti to 55 at.% C or 55 at.% Ti to 45 at.% powder, with a certainty of 2 %.
  • the titanium powder stems from a pure metal and merely contains impurities associated with the manufacturing and/or pulverizing process.
  • the titanium powder contains at least 95.5 at.% Ti, a maximum of 0.03 at.% H and a maximum of 0.4 at.% O.
  • the titanium powder has a particle size up to 70 ⁇ m, but preferably no larger than 50 ⁇ m, more preferably no larger than 40 ⁇ m and are most preferably 35 ⁇ m.
  • the titanium powder is preferably irregular sponge powder, usually manufactured by hydrogenation-dehydrogenation.
  • the carbon powder is preferably in the form of graphite, flake graphite, amorphous graphite, black carbon, a carbonaceous material or a mixture thereof.
  • the carbon powder contains at least 96.1 at.% C and a maximum of 0.05 at.% S.
  • the carbon powders have a particle size up to 20 ⁇ m, but preferably no larger than 10 ⁇ m, more preferably no larger than 5 ⁇ m and most preferably between 5-10 ⁇ m.
  • the moderator powder can comprise at least one pulverized metal from the group of Fe, Co, Ni, Mo, Cr, W, Al, Mn, Cu, Si, Ti, V, B, Li or Mg, preferably comprising at least two of these metals.
  • the moderator powder comprises a mixture containing Fe, Mn, Si and C powders, most preferably also containing Cr powder.
  • the maximum amount of H in the moderator powder is preferably 0.03 at.%.
  • the moderator powder has a chemical composition associated with a grey cast iron, white cast iron, chromium cast iron, chromium cast steel, unalloyed cast steel, low alloyed cast steel, martensitic cast steel, stainless cast steel, heat-resistant cast steel, manganese cast steel or a Ni-Cr cast iron. Due to its effect on compactability, the shape of the moderator powder is preferably irregular. Furthermore, in the case where Fe is the main component of the moderator powder, a powder size distribution of Fe is preferably between 45 ⁇ m and 150 ⁇ m. If Cr is the main component of the moderator powder, a powder size of 63 ⁇ m is preferred.
  • the powder composition is inserted into the mold cavity in the form of compacted inserts and/or coatings, for example.
  • the powder composition can be inserted and positioned so that it directly contacts the mold cavity wall(s), which encompass the mold's cavity.
  • the powder composition can also be inserted and positioned so that a distance between the powder composition and the wall(s) of the mold cavity is maintained. Preferably, a distance of 20 mm between the powder composition and the wall(s) of the mold cavity is not exceeded and preferably a distance of at least 5 mm is maintained.
  • the positioning of casting inserts within the mold cavity can be achieved via an assembly system, which can include such elements as metal wires, perforated metal sheets, screws, nuts, washers etc. Said components are then utilized to manufacture various ring and rail systems, for example, that thread the individual casting inserts together via metals wires or rods to ensure a defined position of said inserts. Subsequently, the casting inserts are fastened via metal bolts and/or screws, for example, to ensure the defined positions are maintained during insertion.
  • the synthesis reaction is initiated by point heating of the powders.
  • the heat energy of the liquid bulk material provides the activation energy to ignite the synthesis reaction between the titanium and the carbon. This initiates the formation of titanium carbides.
  • This synthesis reaction is a highly exothermic combustion reaction that generates heat and a combustion wave that passes through the powder composition, converting the reactant powder to the titanium carbide product. It is therefore self-sustained and consistently proceeds until the powder composition has completely reacted and/or until the thermal dissipation rate from the reaction front exceeds the thermal generation rate at the reaction front. Once the formation of titanium carbide phases is initiated, they continue to nucleate, grow and eventually coalesce.
  • the heat liberated by the reaction and the associated elevated temperature may be lost to local surroundings, leading to the evaporation of volatile components and the dissociation of the resulting products.
  • the emission and dissolution of such gaseous products result in imminent risk of the formation of cavities and pores within the intended composite zone. This further reduces the hardness and wear resistance values, while also reducing the flexural strength of the component.
  • the moderator powder component of the powder composition absorbs and dissipates the high heat energy produced during the SHS reaction of the titanium carbides, by melting. This reduces the infiltration of the molten bulk material between the carbides and hinders destructive fragmentation of the composite zone. Therefore, the moderator powder plays a central role in stabilizing the composite zone. Furthermore, since the moderator powder ultimately forms the matrix material within which the titanium carbide phases are embedded, the mechanical properties of the matrix, and therefore the chosen moderator powder, influence those of the resulting composite zone.
  • the ratio of reactant powder to moderator powder in the powder composition determines the stability and hardness values of the resulting composite zone. With an insufficient quantity of moderator powder, destructive fragmentation occurs and the locally targeted mechanical properties are not achieved. If, however, the moderator powder content exceeds stability requirements, the hardness values are not maximized, as the titanium carbide content is too low. It is therefore critical to maintain the moderator powder as low as possible in order to preserve the integrity of the composite zone while maximizing the titanium carbide content and the therewith-associated hardness values.
  • the optimal ratio between the reactant powder and the moderator powder is not an independent variable but is directly influenced by the casting parameters during fabrication of the casted component.
  • the destructive infiltration and fragmentation phenomena of the composite zone can be manipulated by altering the geometry of the mold cavity.
  • the amount of moderator powder required to stabilize the composite zone can be reduced. This ensures more titanium carbide phases can be produced, thereby increasing the overall hardness of the composite zone.
  • the two main aspects that characterize the geometry of the mold cavity are the total volume and the specific dimensions, i.e. shape, of the mold cavity.
  • the total volume of the mold cavity is commonly represented by the weight of the molten bulk material to be poured into the mold cavity.
  • the relationship between these parameters is established via the density of the bulk material.
  • an effective mold cavity volume which reflects the amount of molten bulk material to be poured, can be calculated by subtracting the volume of powder composition inserted into the mold cavity from the total mold cavity volume.
  • volume merely quantifies a three-dimensional space enclosed by a surface. It can therefore not singularly provide sufficient information regarding the solidification processes of the molten bulk material, as the distribution of this volume within the mold cavity is also of consequence.
  • the volume distribution of molten bulk material within the mold cavity occurs due to the specific shape or dimensions of said mold cavity. This can result in local volumes that differ throughout the mold cavity, due to the form of the casted component.
  • the smallest of the three dimensions that define the local volume is known as the wall thickness. Local volumes with smaller wall thickness values exhibit increased cooling rates and shorted solidification rates. In comparison, local volumes with larger wall thickness values exhibit decreased cooling rates and prolonged solidification rates. This is a result of the associated heat transfer processes and paths, in addition to the thermal conductivity and heat capacity properties of the molten bulk material and/or the mold material, for example.
  • the local volume of interest is a region of the mold cavity that includes the powder composition. Therefore, the wall thickness according to the invention is associated with the smallest value of the three dimensions that define the local volume within a mold cavity containing the powder composition. It is understood that the mold cavity can have various wall thickness values but preferably exhibits only a singular value.
  • the mold cavity volume expressed as the weight of the molten bulk material to be poured, and the mold cavity dimensions, more specifically the wall thickness, influence the occurrence of destructive infiltration and fragmentation.
  • the synergetic relationship between wall thickness and total casting weight provides the means to anticipate which mold cavity geometries will inherently lead to a reduction of necessary moderator powder to stabilize the resulting composite zone.
  • casting at least 30 kg, preferably at least 100 kg, of molten bulk material into a mold cavity with a wall thickness of at least 40 mm requires a powder composition consisting of 55-80 wt.% reactant powder and 20-45 wt.% moderator powder to produce a casted component with composite zone.
  • a powder composition consisting of 60-80 wt.% reactant powder and 20-40 wt.% moderator powder should be inserted into the mold cavity.
  • the molten bulk material can be a manganese steel or a martensitic steel.
  • a powder composition consisting 70-80 wt.% reactant powder and 20-30 wt.% moderator powder should be inserted into the mold cavity.
  • the molten bulk material can be a manganese steel or a martensitic steel.
  • a powder composition consisting 60-80 wt.% reactant powder and 20-40 wt.% moderator powder should be inserted into the mold cavity.
  • the molten bulk material can be a cast iron, grey cast iron or a white chromium cast iron.
  • a powder composition consisting 55-70 wt.% reactant powder and 30-45 wt.% moderator powder should be inserted into the mold cavity.
  • the molten bulk material can be a manganese steel or a martensitic steel.
  • the present invention also proposes a casted component for application in a high wear industrial environment with a composite zone containing titanium carbides in a matrix material, the composite zone formed in-situ during casting of molten bulk material and obtained by using a powder composition comprising reactant powder, which forms the titanium carbides within the composite zone and comprises titanium and carbon, and moderator powder, which forms the matrix surrounding the titanium carbides within the composite zone and comprises metal powders, characterized in that the bulk material of the casted component weighs at least 30 kg, preferably at least 100 kg and the casted component has a wall thickness of at least 40 mm.
  • the casted component comprises a bulk material, which forms the main dimensions of the component, and a composite zone, which is located at the periphery of the component.
  • the periphery refers to an outer surface of the component, which is in direct contact with the surrounding environment, and/or a near surface region, which lies beneath the outer surface of the component without necessarily contacting said outer surface.
  • a near surface region remains distant from the main dimensions of the component and is surrounded by casted bulk material.
  • the bulk material is a metallic material, based on iron, nickel or cobalt.
  • the bulk material is an iron alloy containing carbon, chromium, manganese and/or silicon.
  • the bulk material is unalloyed cast steel, low alloyed cast steel, a manganese cast steel, a martensitic cast steel, a cast iron, a grey cast iron, or a white chromium cast iron. It is understood that impurities related to the manufacturing of the bulk material, regardless if a pure metal or an industrial alloy, are to be disregarded, as their inclusion within the material is not intentional nor is their removal economically feasible.
  • Such impurities are commonly referred to as incidental impurities and can include sulfides, oxides and nitrides, such as MnS, Al 2 O 3 , TiN, respectfully, and/or elements such as S, P, Ti, Al and/or Ca.
  • the composite zone is a region of the component that contains at least one type of phase that chemically and/or physically differs from that of the bulk material and does not originate from the bulk material. Furthermore, this phase also chemically and/or physically differs from the matrix material with which it is surrounded.
  • the composite zone according to the invention contains at least titanium carbide, preferably only titanium carbide, as the ceramic phase.
  • the matrix material and the bulk material are preferably not the same material.
  • the matrix material is preferably a metallic material and contains at least one metal from the group of Fe, Co, Ni, Mo, Cr, W, Al, Mn, or Cu, preferably comprising at least two of these metals.
  • the matrix material contains Fe, Mn, Si and C, most preferably also containing Cr powder.
  • the matrix material has a chemical composition associated with a grey cast iron, white cast iron, chromium cast iron, chromium cast steel, unalloyed cast steel, low alloyed cast steel, manganese cast steel or a Ni-Cr cast iron.
  • the amount of titanium carbide within the composite zone is at least 40 vol.%, preferably at least 50 vol.%, more preferably at least 60 vol.% and most preferably at least 70 vol. %.
  • the remaining volume within the composite zone contains the matrix material.
  • bulk material may also be contained within the composite zone.
  • the amount of bulk material is below 60 vol.%, more preferably below 40 vol.%, even more preferably below 20 vol.% and most preferably below 10 vol.%.
  • the boundary between the composite zone and the main dimensions of the casted component are defined by an amount of titanium carbide below 40 vol. %.
  • the composite zone manifests globular titanium carbide phases that are preferably coalesced together, forming what can be considered a scaffold, or spider web, of titanium carbide phases.
  • said scaffold can also be composed of individual titanium carbide phases clustered together, so that they are directly adjacent to one another yet remain separate phases.
  • This scaffold interconnects the individual titanium carbides phases, most preferably all of the titanium carbide phases within the composite zone, while the matrix material is located in the interspatial regions formed by the titanium carbide scaffold.
  • Such a scaffold hinders crack propagation, due to its blocking and redirecting effect.
  • the risk of cracking and chipping of the composite zone can be reduced.
  • the matrix material preferably manifests a limited amount, most preferably zero, individual titanium carbide phases.
  • a composite zone as described above can be considered to display a lake-landscape or "foam on water"-like appearance, when imaged using an optical light microscope or a scanning electron microscope, for example.
  • a casted component as described above is a hammer, a blow bar, a roller, a cone, a mantle, a plate, a screen liner, teeth, a chute or a duct.
  • a casted component with a wall thickness of at least 80 mm and a manganese steel or martensitic steel bulk material weighting at least 100 kg.
  • a casted component with a wall thickness of at least 80 mm and a manganese steel or martensitic steel bulk material weighting at least 250 kg.
  • a casted component with a wall thickness of at least 40 mm and a manganese steel or martensitic steel bulk material weighting at least 800 kg.
  • this example aims to produce a jaw component 100, as shown in Figure 1A , for a jaw crusher and reinforced with titanium carbide composite zones.
  • a powder composition is produced by mixing a 70 wt.% reactant powder with 30 wt.% moderator powder.
  • the reactant powder contains titanium sponge powder, which is manufactured by hydrogenation-dehydrogenation and is composed of at least 99 at.% Ti and maximally 0.4 at.% O and 0.03 at.% H, and flake graphite, which is composed of at least 96 at.% C and maximally 0.05 at.% S. Both the titanium and carbon powders manifest irregular shapes and exhibit an average diameter of 35 ⁇ m and 5-10 ⁇ m, respectively.
  • the ratio of titanium powder to carbon powder is 45 at.% to 55 at. %C.
  • the moderator powder has the composition of a manganese steel with 21 wt.% Mn and Fe, Si, and C. Furthermore, the minor inclusion of other elements due to the use of ferroalloys to fabricate the moderator powder cannot be excluded.
  • the powders are subsequently mixed, dried and compressed by uniaxial cold pressing under a compaction pressure of 500 MPa or isostatically under a pressure of 200 MPa, to obtain 136 casting inserts 101 with dimensions of 20 x 20 x 100 mm.
  • the produced casting inserts 101 are subsequently provided with two through-holes 102 via a conventional drilling means, as shown in Figure 1B , in order to construct seventeen assembly systems 103 for placement within a mold cavity.
  • a section of an assembly system 103 is illustrated in Figure 1C , each assembly system 103 consisting of eight casting inserts 101 positioned at a separation distance of 8 mm from another and fixed to the same perforated metal sheet 104 via screws 105.
  • the assembly systems 103 are placed and positioned in a mold cavity 106 of a sand mold, a cross-section of which is illustrated in Figure 1D , at locations associated with the highest wear expectation of the jaw component 100, i.e. at the vertexes 107 of the jaw teeth.
  • the wall thickness 108 of the vertex 102 associated with the tooth width is 40 mm while the wall thickness 109 of the vertex 102 associated with the tooth root is 40 mm.
  • a molten bulk material consisting of a manganese steel containing 12 wt. % Mn and a weight of 800 kg is poured into the mold cavity.
  • the thermal energy of the molten steel initiates a self-propagating high temperature synthesis (SHS) reaction between the titanium and carbon components of the powder composition.
  • SHS high temperature synthesis
  • the moderator powder melts, thereby dissipating the produced heat energy and preventing infiltration of the molten bulk material and subsequent destructive fragmentation.
  • the produced composite zones 110 exhibit globular titanium carbide phases homogenously distributed within matrix material comprising a manganese steel with 21 wt.% Mn and Fe, Si, and C.
  • Further testing parameters include a friction radius of approximately 3.5 mm, a disc speed of 192 RPM, a testing load of 10 N and a friction path of 704 m. After the ball-on-disc tests were undergone, three-dimensional scans of the samples as well as depth measurements of the cross-sections of the produced tracks enabled the determination of the wear index.
  • Table 1 Hardness and wear properties of the composite zone and bulk material of the jaw component. Casted Component Testing Location Vickers Hardness [HV30] Wear Index *10 -9 [ ⁇ m 3 /N*m] Jaw 100 composite zone 110 670.00 6.80 bulk material 111 242.70 85.90
  • the composite zones 110 of the jaw component 100 manifest over twice the hardness and almost fifteen times the wear resistance of the surrounding bulk material 111.
  • Example 2 relates to a casted mantle component 200, as shown in Figure 2A , which is produced so as to exhibit areas reinforced with titanium carbides for suitable application in a cone crusher.
  • the cross-sectional view of the mantle wall 201 in in Figure 2B illustrates, as sectioned from the corresponding circle in Figure 2A , the mantle 200 is reinforced with three titanium carbide composite zones, an upper composite zone 202, a lower inner composite zone 203, both located at the inner circumference of the mantle wall 201, and a lower outer composite zone 204.
  • a powder composition for the upper composite zone 202 is produced by mixing 60 wt. % reactant powder with 40 wt.% moderator powder.
  • the reactant powder contains titanium sponge powder, which is manufactured by hydrogenation-dehydrogenation and is composed of at least 99 at.% Ti and maximally 0.4 at.% O and 0.03 at.% H.
  • the reactant powder also contains flake graphite, which is composed of at least 99 at.% C and maximally 0.05 at.% S. Both the titanium and carbon powders manifest irregular shapes and exhibit an average diameter of 35 ⁇ m and between 5-10 ⁇ m, respectively.
  • the ratio of titanium powder to carbon powder is 45 at.% Ti to 55 at.% C.
  • the moderator powder has the composition of a manganese steel with 21 wt.% Mn and Fe, Si, and C. Furthermore, the minor inclusion of other elements due to the use of ferroalloys to fabricate the moderator powder cannot be excluded.
  • a powder composition for the lower inner composition zone 203 is produced by mixing 63 wt. % reactant powder with 37 wt.% moderator powder.
  • the specifics to the composition, size, form and production of both the reactant powder and the moderator powder are identical to that of the powder composition for the upper composite zone 202, detailed above.
  • the ratio of titanium powder to carbon powder is also 45 at.% Ti to 55 at.% C.
  • the moderator powder also has the composition of a manganese steel with 21 wt.% Mn and Fe, Si, and C, with possible minor inclusion of other elements, due to the selected powder manufacturing method.
  • a powder composition for the lower outer composition zone 204 is produced by mixing 60 wt. % reactant powder with 40 wt.% moderator powder.
  • the specifics to the composition, size, form and production of both the reactant powder and the moderator powder are identical to that of the powder composition for the upper composite zone 202, detailed above.
  • the ratio of titanium powder to carbon powder is also 45 at.% Ti to 55 at.% C.
  • the moderator powder also has the composition of a manganese steel with 21 wt.% Mn and Fe, Si, and C, with possible minor inclusion of other elements, due to the selected powder manufacturing method.
  • Each of the three powders are subsequently mixed, dried and compressed by uniaxial cold pressing under a compaction pressure of 500 MPa or isostatically under a pressure of 200 MPa, to obtain a total of 371 casting inserts 205 with dimensions of 20 x 20 x 100 mm.
  • 115 are composed of the powder for the upper composite zone 202
  • 128 are composed of the powder for the lower inner composite zone 203
  • 128 are composed of the powder for the lower outer composite zone 204.
  • the casting inserts 205 are inserted into the mold cavity of a sand mold via an assembly system 206, as shown in Figure 2C .
  • An enlarged section of the assembly system 206 is shown in Figure 2D .
  • the assembly system 206 comprises three separate rings, and upper ring 207, a lower inner ring 208 and a lower outer ring 209, each corresponding to the upper composite zone 202, the lower inner composite zone 203 and the lower outer composite zone 204, respectively.
  • the upper ring 207, a lower inner ring 208 and a lower outer ring 209 each consist of 115, 128 and 128 casting inserts 205, respectively.
  • the casting inserts 205 which each exhibit two through-holes , are threaded by two rods 210 to build each of the three rings of the assembly system 206. During threading and positioning of the casting inserts 205 on the rods 210, a separation distance of 8 mm is maintained between each casting insert 205. Furthermore, after every ninth casting insert 205, the separation distance is increased to 10 mm.
  • the constructed assembly system 206 is then inserted into the mold cavity 211 of the sand mold at a location associated with the highest wear expectation of the cone crusher.
  • both the lower inner ring 208 and the upper ring 207 are placed at a position 10 mm from the inner mold cavity wall.
  • the lower outer ring 209 is positioned at a distance of 10 mm from the lower inner ring 208, which distance is maintained by spacers that exhibit identical material properties as the rods 220 implemented in the assembly system 206.
  • the wall thickness 212 of the mold cavity 211 associated with the upper ring 207 and the lower rings 208;209 is 90 mm and 80 mm, respectively, as shown in Figure 2E .
  • a molten bulk material consisting of a manganese steel containing 13 wt. % Mn and exhibiting a weight of 1005 kg is poured into the mold cavity 211.
  • the thermal energy of the molten steel initiates a self-propagating high temperature synthesis (SHS) reaction between the titanium and carbon components of the powder composition.
  • SHS high temperature synthesis
  • the moderator powder melts, thereby dissipating the produced heat energy and preventing infiltration of the molten bulk material and subsequent destructive fragmentation.
  • the bulk material 213 of the mantle component 200 which surrounds the composite zones 202, 203 and 204, manifests a softer austenitic microstructure composed of a manganese cast steel, as given in Table 2 below.
  • Mechanical properties of the composite zones 202; 203; 204 and the bulk material 213 of the mantle component 200 were measured analogous to the testing methods as described for the jaw component 100 in example 1.
  • Table 2 Hardness and wear properties of the composite zones and bulk material of the mantle component.
  • the aim is to produce a cone 300, as shown in Figure 3A , reinforced with titanium carbide containing composite zones.
  • Figure 3B which depicts a cross-sectional view of the cone wall 301, as sectioned via the circle in Figure 3A , shows that the cone 300 is reinforced with three titanium carbide composite zones, an upper composite zone 302, a lower inner composite zone 303 and a lower outer composite zone 304, at the outer circumference of the cone wall 301.
  • a powder composition for the upper composite zone 302 is produced by mixing 60 wt. % reactant powder with 40 wt.% moderator powder.
  • the reactant powder contains titanium sponge powder, which is manufactured by hydrogenation-dehydrogenation and is composed of at least 99 at.% Ti and maximally 0.4 at.% O and 0.03 at.% H, and flake graphite, which is composed of at least 99 at.% C and maximally 0.05 at.% S. Both the titanium and carbon powders manifest irregular shapes and exhibit an average diameter of 35 ⁇ m and 5-10 ⁇ m, respectively.
  • the ratio of titanium powder to carbon powder is 45 at.% Ti to 55 at.% C.
  • the moderator powder has the composition of a manganese steel with 21 wt.% Mn and Fe, Si, and C. Furthermore, the minor inclusion of other elements due to the use of ferroalloys to fabricate the moderator powder cannot be excluded.
  • a powder composition for the lower inner composition zone 303 is produced by mixing 63 wt. % reactant powder with 37 wt.% moderator powder.
  • the specifics to the composition, size, form and production of both the reactant powder and the moderator powder are identical to that of the powder composition for the upper composite zone 201, detailed above.
  • the ratio of titanium powder to carbon powder is also 45 at.% Ti to 55 at.% C.
  • the moderator powder also has the composition of a manganese steel with 21 wt.% Mn and Fe, Si, and C, with possible minor inclusion of other elements, due to the selected powder manufacturing method.
  • a powder composition for the lower outer composition zone 304 is produced by mixing 60 wt. % reactant powder with 40 wt.% moderator powder.
  • the specifics to the composition, size, form and production of both the reactant powder and the moderator powder are identical to that of the powder composition for the upper composite zone 301, detailed above.
  • the ratio of titanium powder to carbon powder is also 45 at.% Ti to 55 at.% C.
  • the moderator powder also has the composition of a manganese steel with 21 wt.% Mn and Fe, Si, and C, with possible minor inclusion of other elements, due to the selected powder manufacturing method.
  • Each of the three powders are subsequently mixed, dried and compressed by uniaxial cold pressing under a compaction pressure of 500 MPa or isostatically under a pressure of 200 MPa, to obtain a total of 289 casting inserts 306 with dimensions of 20 x 20 x 100 mm.
  • 371 casting inserts 306, 87 are composed of the powder for the upper composite zone 302
  • 101 are composed of the powder for the lower inner composite zone 303
  • 101 are composed of the powder for the lower outer composite zone 304.
  • the casting inserts 306 are provided with through-holes to construct an assembly system 307, for the ensuring insertion and positioning of said casting inserts 306 in a sand mold.
  • the assembly system 307 comprises three separate rings, an upper ring 308, a lower inner ring 309 and a lower outer ring 310, ultimately corresponding to the upper composite zone 302, the lower inner composite zones 303 and the lower outer composite zone 304, respectively.
  • the casting inserts 306 of each individual ring are each threaded by two rods 311 to build the corresponding ring of the assembly system 307.
  • a separation distance of 8 mm is maintained between each casting insert 306. Furthermore, after every ninth casting insert 306, the separation distance is increased to 10 mm.
  • the separation distance pattern between the casting inserts 306 is illustrated in Figures 3C and 3D . Furthermore, the two lower rings 309;310 of the assembly system 307 are separated by spacers, which exhibit identical dimensions and material properties as the rods 311 with which the casting inserts 306 are threaded.
  • the constructed assembly system 307 is then inserted into a mold cavity 312 of the sand mold at a location associated with the highest wear expectation of the cone. As shown in Figure 3E , during installation of the assembly system 307 into the mold cavity 312, all three rings are placed at a position 10 mm from the mold cavity wall.
  • the wall thickness 313 of the mold cavity associated with the upper 308 and lower 309; 310 rings is 70 mm and 95 mm, respectively.
  • a molten bulk material consisting of a manganese steel containing 13 wt. % Mn and a weight of 840 kg is poured into the mold cavity 312.
  • the thermal energy of the molten steel initiates a self-propagating high temperature synthesis (SHS) reaction between the titanium and carbon components of the powder composition.
  • SHS high temperature synthesis
  • the moderator powder melts, thereby dissipating the produced heat energy and preventing infiltration of the molten bulk material and subsequent destructive fragmentation.
  • the bulk material 314 of the cone component 300 which surrounds the composite zones 302, 303 and 304, manifests a softer austenitic microstructure composed of a manganese cast steel, as given in Table 3 below.
  • Mechanical properties of the composite zones 302; 303; 304 and the bulk material 314 of the mantle component 300 were measured analogous to the testing methods as described for the jaw component 100 in example 1.
  • Table 3 Hardness and wear properties of the composite zones and bulk material of the cone component.
  • a cross-section of the roller wall 401 as taken from the section circle in Figure 4A and depicted in Figure 4B , illustrates the roller 400 exhibits two composite zones containing titanium carbide, namely an upper composite zone 402 and a lower composite zone 403.
  • a powder composition for the upper composite zone 402 is produced by mixing 75 wt. % reactant powder with 25 wt.% moderator powder.
  • the reactant powder contains titanium sponge powder, which is manufactured by hydrogenation-dehydrogenation and is composed of at least 99 at.% Ti and maximally 0.4 at.% O and 0.03 at.% H, and flake graphite, which is composed of at least 99 at.% C and maximally 0.05 at.% S. Both the titanium and carbon powders manifest irregular shapes and exhibit an average diameter of 35 ⁇ m and 5-10 ⁇ m, respectively.
  • the ratio of titanium powder to carbon powder is 45 wt.% to 55 wt. %C.
  • the moderator powder has the composition of a high chromium cast iron with 16.0 wt.% Cr, 3.0 wt.% C, 0.6 wt.% Si, 0.7 wt.% Mn, 0.2 wt.% Ni, 2.0 wt.% Mo, rest wt.% is Fe. Furthermore, the minor inclusion of other elements due to the use of ferroalloys to fabricate the moderator powder cannot be excluded.
  • a powder composition for the lower composite zone 403 is produced by mixing 75 wt. % reactant powder with 25 wt.% moderator powder.
  • the specifics to the composition, size, form and production of both the reactant powder and the moderator powder are identical to that of the powder composition for the upper composite zone 201, detailed above.
  • the ratio of titanium powder to carbon powder is also 45 at.% Ti to 55 at.% C.
  • the moderator powder also has the composition of a manganese steel with 21 wt.% Mn and Fe, Si, and C, with possible minor inclusion of other elements, due to the selected powder manufacturing method.
  • Each of the two powders are subsequently mixed, dried and compressed by uniaxial cold pressing under a compaction pressure of 500 MPa or isostatically under a pressure of 200 MPa, to obtain a total of 289 casting inserts 404 with dimensions of 15 x 20 x 100 mm.
  • 120 are composed of the powder for the upper composite zone 402 and 118 are composed of the powder for the lower composite zone 403.
  • an assembly system 4 comprising two separate rings 405, and example of which is shown in Figure 4C is fashioned.
  • Said assembly system is similarly constructed as those assembly systems 206; 307 implemented for the mantle 200 and cone 300 components, as described above. Consequently, the two rings 405 relate to the upper 402 and lower 403 composite zones formed during casting of the roller 400.
  • a separation distance of 8 mm is maintained between each casting insert while the separation distance after every ninth casting insert is increased to 10 mm.
  • the separation distance pattern between the casting inserts 404 is illustrated in Figures 4C .
  • the assembly system is then subsequently inserted into a mold cavity 406 of a sand mold at a location associated with the highest wear expectation of the roller 400; see Figure 4D .
  • both rings 405 are fixed to the mold cavity walls so that the casting inserts 404 of the respective rings 405 are in direct contact with the mold cavity wall.
  • the wall thickness 407 of the mold cavity 406 associated with the upper and lower rings 405 is 60 mm and 70 mm, respectively.
  • molten bulk material consisting of a chromium cast iron containing 15 wt.% Cr and exhibiting a weight of 850 kg is poured into the mold cavity 406.
  • the thermal energy of the molten steel initiates a self-propagating high temperature synthesis (SHS) reaction between the titanium and carbon components of the powder composition.
  • SHS high temperature synthesis
  • FIG. 5 Microstructural micrographs, as obtained from a scanning electron microscope (SEM), of the upper composite zone 402 of the roller 400, are illustrated in Figure 5 .
  • the titanium carbide phases which are designated with the label "TiC” are globular in shape and exhibit a strong network-skeleton, due to their local coalescence to each other in the matrix phase.
  • the matrix material i.e. the high chromium cast iron, forms individual "lake-like" formations that do not contain individual titanium carbide phases, but are surrounded by a TiC carbides network.
  • Figure 5E displays the transition area between the composite zone and the chromium cast iron bulk material.
  • Figure 6A exhibits, the aim of this example is to produce a blow bar 500 reinforced with titanium carbide composite zones 501, as shown in Figure 6B.
  • Figure 6B which is a he cross-sectional view of the blow bar 500 taken along the section line X_X in Figure 6A , illustrates two double rows of composite zones 501 parallel to the length of the blow bar 500.
  • a powder composition is produced by mixing a 70 wt.% reactant powder with 30 wt.% moderator powder.
  • the reactant powder contains titanium sponge powder, which is manufactured by hydrogenation-dehydrogenation and is composed of at least 99 at.% Ti and maximally 0.4 at.% O and 0.03 at.% H, and flake graphite, which is composed of at least 96 at.% C and maximally 0.05 at.% S.
  • Both the titanium and carbon powders manifest irregular shapes and exhibit an average diameter of 35 ⁇ m and 5-10 ⁇ m, respectively.
  • the ratio of titanium powder to carbon powder is 45 at.% to 55 at. %C.
  • the moderator powder has the composition of a martensitic cast steel with 4,5 wt.% Cr and Fe, Mn, Si, and C. Furthermore, the minor inclusion of other elements due to the use of ferroalloys to fabricate the moderator powder cannot be excluded.
  • the powders are subsequently mixed, dried and compressed via cold uniaxial pressing under a compaction pressure of 500 MPa or isostatically under a pressure of 200 MPa, to obtain 80 casting inserts 502 with dimensions of 18 x 20 x 100 mm.
  • casting inserts 502 are then inserted into a mold cavity of a sand mold via an assembly system 503, illustrated in Figure 6C .
  • the assembly system 503 encompasses two double rows of casting inserts 502 placed on the top and bottom surfaces of a rail 504 and fixed thereupon with screws 505, which are inserted through two through-holes of each casting insert 502. During positioning of the casting inserts 502, a separation distance of 8 mm is maintained between them.
  • Each singular row of casting inserts contains 20 individual casting inserts 502.
  • the assembly system 503 is then inserted into the mold cavity at a distance of 10 mm from the mold cavity wall. The wall thickness if said location is 80 mm.
  • a molten bulk material consisting of a martensitic cast steel 3 wt.% Cr and a weight of 280 kg is poured into the mold cavity.
  • the thermal energy of the molten steel initiates a self-propagating high temperature synthesis (SHS) reaction between the titanium and carbon components of the powder composition.
  • SHS high temperature synthesis
  • the moderator powder melts, thereby dissipating the produced heat energy and preventing infiltration of the molten bulk material and subsequent destructive fragmentation.
  • a composite zone 501 containing titanium carbide phases (TiC) within a martensitic cast steel matrix material is fabricated.
  • the titanium carbide phases are globular und manifest a network-skeleton within which the martensitic cast steel matric material forms individual "lake-like" formations.
  • these formations rarely contain individual titanium carbide phases therein, bur are rather surrounded by the titanium carbide network skeleton.
  • the aim is to produce a hammer 600 reinforced with titanium carbide based composite zones 601.
  • the cross-sectional view in Figure 8B shows, which is taken along the X-X section line in Figure 8A , the hammer 600 manifests four composite zones 601 within its lower corners, each corner exhibiting two composite zones 601 oriented orthogonal to each other.
  • a powder composition is produced by mixing a 65 wt.% reactant powder with 35 wt.% moderator powder.
  • the reactant powder contains titanium sponge powder, which is manufactured by hydrogenation-dehydrogenation and is composed of at least 99 wt.% Ti and maximally 0.4 wt.% O and 0.03 wt.% H, and flake graphite, which is composed of at least 96 wt.% C and maximally 0.05 wt.% S. Both the titanium and carbon powders manifest irregular shapes and exhibit an average diameter of 35 ⁇ m and 5-10 ⁇ m, respectively.
  • the ratio of titanium powder to carbon powder is 45 at.% to 55 at.%C.
  • the moderator powder has the composition of a martensitic cast steel with 10 wt.% Cr and Fe, Mn, Si, and C. Furthermore, the minor inclusion of other elements due to the use of ferroalloys to fabricate the moderator powder cannot be excluded.
  • the powders are subsequently mixed, dried and compressed via cold uniaxial pressing under a compaction pressure of 500 MPa or isostatically under a pressure of 200 MPa, to obtain 36 casting inserts 602 with dimensions of 30 x 20 x 100 mm.
  • the casting inserts 602 Prior to insertion into the mold cavity of a sand mold, the casting inserts 602, which each exhibit two through-holes, are threaded together via screws 605 and fixed to perforated metal sheets 604, see Figure 8C , which displays a section of said assembly system.
  • a separation distance of 8 mm is maintained between the casting inserts 602, with this distance increasing to 10 mm after every fourth casting insert 602.
  • the constructed assembly system 603 is then placed in the sand mold at a location associated with the highest wear expectation at a distance of 5 mm from the mold cavity wall.
  • the wall thickness of said location is 80 mm.
  • molten bulk material consisting of a martensitic cast steel 10 wt.% Cr and a weight of 100 kg is poured into the mold cavity.
  • the thermal energy of the molten steel initiates a self-propagating high temperature synthesis (SHS) reaction between the titanium and carbon components of the powder composition.
  • SHS high temperature synthesis
  • the moderator powder melts, thereby dissipating the produced heat energy and preventing infiltration of the molten bulk material and subsequent destructive fragmentation.
  • a composite zone 601 containing titanium carbide within matrix material comprising a martensitic cast steel with 10 wt.% Cr and Fe, Mn, Si, and C is fabricated.

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EP22174579.7A 2022-05-20 2022-05-20 Procédé de coulée d'un composant destiné à être appliqué dans un environnement industriel à forte usure et un tel composant coulé Pending EP4279201A1 (fr)

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PCT/EP2023/063636 WO2023222921A1 (fr) 2022-05-20 2023-05-22 Procédé de coulée d'un élément destiné à être appliqué dans un environnement industriel à usure rapide et élément coulé de ce type

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US20110226882A1 (en) * 2008-09-19 2011-09-22 Magotteaux International S.A. Composite impactor for percussion crushers
WO2017081665A1 (fr) 2015-11-12 2017-05-18 Innerco Sp. Z O.O. 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
CN111482579A (zh) * 2020-03-17 2020-08-04 内蒙古科技大学 一种耐磨钢结硬质合金复合锤头及其制造方法
WO2022008038A1 (fr) * 2020-07-07 2022-01-13 Sandvik Srp Ab Pièce de broyage ou d'usure ayant une zone d'usure composite localisée

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WO2017081665A1 (fr) 2015-11-12 2017-05-18 Innerco Sp. Z O.O. 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
US20180369905A1 (en) * 2015-11-12 2018-12-27 Innerco Sp. Z O.O. Powder Composition For The Manufacture Of Casting Inserts, Casting Insert And Method Of Obtaining Local Composite Zones In Castings
CN111482579A (zh) * 2020-03-17 2020-08-04 内蒙古科技大学 一种耐磨钢结硬质合金复合锤头及其制造方法
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