WO2022224046A1 - Fe-al-si-x-based alloy and its use - Google Patents

Fe-al-si-x-based alloy and its use Download PDF

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Publication number
WO2022224046A1
WO2022224046A1 PCT/IB2022/051167 IB2022051167W WO2022224046A1 WO 2022224046 A1 WO2022224046 A1 WO 2022224046A1 IB 2022051167 W IB2022051167 W IB 2022051167W WO 2022224046 A1 WO2022224046 A1 WO 2022224046A1
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Prior art keywords
alloy
group
resistance
alloy according
alloys
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PCT/IB2022/051167
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French (fr)
Inventor
Jaromir MORAVEC
Pavel Hanus
Pavel Novak
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Technicka Univerzita V Libereci, Fakulta Strojni, Katedra Strojirenske Technologie
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Publication of WO2022224046A1 publication Critical patent/WO2022224046A1/en

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    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
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    • C—CHEMISTRY; METALLURGY
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    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/106—Coating with metal alloys or metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D65/00—Parts or details
    • F16D65/02—Braking members; Mounting thereof
    • F16D65/12—Discs; Drums for disc brakes
    • F16D65/125—Discs; Drums for disc brakes characterised by the material used for the disc body
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
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    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/14766—Fe-Si based alloys
    • H01F1/14791—Fe-Si-Al based alloys, e.g. Sendust
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    • 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
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
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    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying

Definitions

  • the invention relates to a Fe-Al-Si-X-based alloy with oxidation resistance at temperatures up to 1,100 °C and excellent mechanical and tribological resistance up to at least 750 °C, particularly for thermally and mechanically stressed components of combustion engines. It is a material capable of working with increased durability and abrasion resistance in specific conditions. It is a material capable of withstanding high temperatures and cyclic and thermal fatigue while maintaining very good tribological resistance. These iron-containing alloys feature a significant proportion of aluminium with silicon and other elements that modify the properties and processability of the material.
  • the primary intended application is valve pairs and valve seats in combustion engine heads. Still, alloys will also be able to be used in other areas, such as turbine components, brake system components, furnace components, etc.
  • austenitic steel- based materials with a composition such as 13 % Ni, 13 % Cr, 2.5 % W and 1.5, or cobalt-based stellites, 17 to 32 % Cr, 2 to 16 % W, 0.1 to 2.5 % C, 3 to 22 % Ni, 1 to 8 % Mo and a few per cent of Fe and Si are commonly used to manufacture valves and valve seats operating at temperatures around 800 °C.
  • the seats and valves are usually made of one piece of material, but the functional surfaces are often improved by weld overlays or joining/welding in several parts. It is similar to other types of components.
  • Minimal silicon content can have a negative effect on high-temperature mechanical properties and thermal and oxidation resistance. Higher C content can cause weather damage. Mechanical properties, especially toughness, are relatively low, while their corrosion resistance at elevated temperatures is lower.
  • a Fe-Al-Si-X-based alloy largely eliminates the above drawbacks with excellent oxidation resistance at temperatures up to 1,100 °C and excellent mechanical and tri bological resistance up to at least 750 °C according to the invention. Its essence is that it comprises a Fe-Al-Si alloy matrix containing A1 16+4, Si 6+4 wt%, at least one alloying element X in an amount of 4+3 wt% selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V and Mo, and the rest is Fe. [0006] In a preferred embodiment, the alloy further contains at least one other alloying element Y in the range of 0.01 to 1.5 wt%, selected from the group consisting of Zr,
  • Another aspect of the invention is the use of the alloy in the form of a cast blank, a formed blank, a wire for welding, a wire for thermal spraying, a powder using an atomizer or mechanical alloying.
  • the alloy is used in the form of powders for 3D printing of metallic materials, sintering and the formation of functional layers realized by weld overlays and cold and thermal spraying, or for metal powder injection technologies.
  • the invention relates to a new material with a precisely defined mutual ratio of the mean content of individual elements and a defined maximum and minimum content of individual alloying elements.
  • the mutual ratio and defined range of elements guarantee the refractoriness and heat resistance of the material up to temperatures around 1,100 °C. At the same time, it also guarantees mechanical and tribological resistance at tem peratures up to 750 °C, even in environments containing S.
  • the material can be used in cast and formed state, but the given ratios of elements can also be applied in powder form and used for weld overlays, thermal spraying, diffusion plating and for the production of parts using sintering and additive technologies.
  • the invention makes it possible to completely replace or substantially reduce the content of existing expensive and rare alloying elements, such as Co, Cr, W, Ni, Mo, which occur in considerable volumes in the materials currently used.
  • the alloys of the present invention will allow the use of higher working tem peratures, while maintaining or extending the life of the above components.
  • the benefit is also a significant reduction in the content of critical alloying elements, es pecially those imported from outside the EU, which will lower the price of input raw materials, and thus the price of the resulting product.
  • component weight saving of up to 25 per cent due to lower specific gravity is also possible.
  • the alloys are also characterized by higher corrosion re sistance in aqueous environments. The reason is the formation of a passive layer of alumina at a pH higher than about 3. At lower pH values, the passive layer is made of silica and also has a protective effect.
  • the said critical elements i.e. Cr, Ni and Co
  • Cr, Ni and Co are not represented in the proposed Fe-Al-Si-X and Fe-Al-Si-X-Y alloys either at all or in a few per cent.
  • the useful properties of the proposed alloys are better or remain similar to those of commercially used alloys.
  • the proposed alloys Compared to Pyroferal, the proposed alloys have a lower aluminium content, which leads to higher toughness, while increased silicon content compared to Pyroferal alloy (Patent 115312) has a positive effect on high-temperature mechanical properties and thermal and oxidative resistance. The proposed alloy has a lower C content, so weather damage is avoided and this leads to product stability.
  • the proposed alloys show significantly smaller grain size and thus better mechanical properties, especially higher toughness, but also higher corrosion re sistance at elevated temperatures, especially oxidation.
  • FIG.l shows the mechanical properties in a compression test of the Fe-Al-Si5 alloy prepared by casting.
  • Fig.2 shows the oxidation resistance of the Fe-Al-Si5 alloy prepared by powder metallurgy in comparison with a binary Fe-Al alloy.
  • Fig.3 shows a blank for the production of a valve seat from the Fe-Al-Si alloy.
  • Fe-Al-Si-X-based alloy with oxidation resistance at temperatures up to 1,100 °C and mechanical and tribological resistance up to at least 750 °C, which comprises a Fe-Al-Si alloy matrix containing A1 16+4 wt%, Si 6+4 wt%, at least one alloying element X in an amount of 4+3 wt%, which is selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V and Mo, and the rest is Fe.
  • the alloy matrix further comprises at least one other alloying element in the range of 0.01 to 1.5 wt%, selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V, B and Sc, which is different from the element in the previous alloy.
  • a Fe-Al-Si5 alloy was prepared by mechanical alloying and plasma sintering. The oxidation resistance at 800 °C was tested and compared with a binary Fe-Al alloy. The alloy with added silicone achieves a significantly lower oxidation rate than the reference binary Fe-Al alloy.
  • Example 3 A Fe-Al-Si5 alloy was prepared by mechanical alloying and plasma sintering and the manufacture of a valve seat by means of electric spark machining process was tested on the heat-treated material, see the blank in [Fig.3].
  • the powder is used for thermal spraying using plasma or the HVOF method to create a functional layer with significantly increased tribological resistance up to temperatures of 700 °C.
  • An example of use is for brake discs in creating a compact layer and composite spray layout.
  • the powder is used for 3D printing using the SLS method, for the production of shaped inserts into moulds for injection using the MIM and CIM methods.
  • the insert created in this way has increased temperature and abrasion re sistance against ceramic and metal particles injected by the MIM and CIM methods.
  • the powder is used for 3D printing using the SLM method, for the production of components usable in energy sector.
  • it is specifically a steam distribution house located in front of the first stage of the steam turbine. The part created in this way has sufficient corrosion and abrasion resistance at temperatures up to 580 °C and long-term temperature stability.
  • the powder is used for laser weld overlaying of functional bearing surfaces on parts of welding jigs intended for large-scale production of components for automotive.
  • the layers formed in this way have about 1.2 times greater abrasion resistance than parts with nitrided or cemented surfaces.
  • Thermal arc spray wire made by casting and subsequent forming from a base alloy Fe, A1 16+4, Si 3+2 wt.%, added with element X, which is Cr in an amount of 2+0.5 wt.% and element Y, which is Ti in an amount of 1+0.4 wt.%.
  • the wire is used to renovate worn gate valves and valves in the primary circuit and at steam su perheaters.
  • the alloy according to the present invention is intended for products intended mainly for two industrial segments, namely for high-temperature applications up to 1,100 °C, which include, for example, furnace components such as load-bearing parts, refractory partitions, grates, muffles, resistance heaters, etc. and high-temperature heat pipes, burner nozzles, gate valves and valves, and also products intended for applications with excellent mechanical and tribological resistance, at least up to a temperature of 750 °C.
  • furnace components such as load-bearing parts, refractory partitions, grates, muffles, resistance heaters, etc. and high-temperature heat pipes, burner nozzles, gate valves and valves
  • products intended for applications with excellent mechanical and tribological resistance at least up to a temperature of 750 °C.
  • Examples include components of combustion engines and turbochargers, components of combustion, steam, gas and steam-gas turbines, or components of braking systems such as discs, brake segments, etc.

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Abstract

A Fe-Al-Si-X-based alloy with oxidation resistance at temperatures up to 1,100 °C and mechanical and tribological resistance at least up to 750 °C comprising a base Fe-Al-Si alloy matrix containing Al 16±4, Si 6±4 wt%, at least one alloying element X in an amount of 4±3 wt%,which is selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V and Mo, and the rest is Fe. The base alloy matrix may further contain at least one other alloying element Y in the range of 0.01 to 1.5 wt.%, selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V, B and Sc,different from the element X. The alloy can be used in the form of a cast blank, in the form of products selected from the group consisting of a formed blank, a wire for welding and a wire for thermal spraying and in the form of a powder using an atomizer or mechanical alloying.

Description

Fe-Al-Si-X-based alloy and its use
Field of the Invention
[0001] The invention relates to a Fe-Al-Si-X-based alloy with oxidation resistance at temperatures up to 1,100 °C and excellent mechanical and tribological resistance up to at least 750 °C, particularly for thermally and mechanically stressed components of combustion engines. It is a material capable of working with increased durability and abrasion resistance in specific conditions. It is a material capable of withstanding high temperatures and cyclic and thermal fatigue while maintaining very good tribological resistance. These iron-containing alloys feature a significant proportion of aluminium with silicon and other elements that modify the properties and processability of the material. The primary intended application is valve pairs and valve seats in combustion engine heads. Still, alloys will also be able to be used in other areas, such as turbine components, brake system components, furnace components, etc.
State of the Art
[0002] At present, when we seek to reduce emissions to the environment, austenitic steel- based materials with a composition such as 13 % Ni, 13 % Cr, 2.5 % W and 1.5, or cobalt-based stellites, 17 to 32 % Cr, 2 to 16 % W, 0.1 to 2.5 % C, 3 to 22 % Ni, 1 to 8 % Mo and a few per cent of Fe and Si are commonly used to manufacture valves and valve seats operating at temperatures around 800 °C. The seats and valves are usually made of one piece of material, but the functional surfaces are often improved by weld overlays or joining/welding in several parts. It is similar to other types of components.
[0003] These alloys contain critical elements such as Cr, Ni and Co, which are expensive and can cause problems in the final material.
[0004] Existing alloys have a higher aluminium content, which reduces their toughness.
Minimal silicon content can have a negative effect on high-temperature mechanical properties and thermal and oxidation resistance. Higher C content can cause weather damage. Mechanical properties, especially toughness, are relatively low, while their corrosion resistance at elevated temperatures is lower.
Summary of the Invention
[0005] A Fe-Al-Si-X-based alloy largely eliminates the above drawbacks with excellent oxidation resistance at temperatures up to 1,100 °C and excellent mechanical and tri bological resistance up to at least 750 °C according to the invention. Its essence is that it comprises a Fe-Al-Si alloy matrix containing A1 16+4, Si 6+4 wt%, at least one alloying element X in an amount of 4+3 wt% selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V and Mo, and the rest is Fe. [0006] In a preferred embodiment, the alloy further contains at least one other alloying element Y in the range of 0.01 to 1.5 wt%, selected from the group consisting of Zr,
Cr, Nb, Ni, Ti, W, V, B and Sc, different from X.
[0007] Another aspect of the invention is the use of the alloy in the form of a cast blank, a formed blank, a wire for welding, a wire for thermal spraying, a powder using an atomizer or mechanical alloying.
[0008] In a preferred embodiment, the alloy is used in the form of powders for 3D printing of metallic materials, sintering and the formation of functional layers realized by weld overlays and cold and thermal spraying, or for metal powder injection technologies.
[0009] The invention relates to a new material with a precisely defined mutual ratio of the mean content of individual elements and a defined maximum and minimum content of individual alloying elements. The mutual ratio and defined range of elements guarantee the refractoriness and heat resistance of the material up to temperatures around 1,100 °C. At the same time, it also guarantees mechanical and tribological resistance at tem peratures up to 750 °C, even in environments containing S. The material can be used in cast and formed state, but the given ratios of elements can also be applied in powder form and used for weld overlays, thermal spraying, diffusion plating and for the production of parts using sintering and additive technologies. At the same time, the invention makes it possible to completely replace or substantially reduce the content of existing expensive and rare alloying elements, such as Co, Cr, W, Ni, Mo, which occur in considerable volumes in the materials currently used.
[0010] The alloys of the present invention will allow the use of higher working tem peratures, while maintaining or extending the life of the above components. The benefit is also a significant reduction in the content of critical alloying elements, es pecially those imported from outside the EU, which will lower the price of input raw materials, and thus the price of the resulting product. Compared to currently used high- temperature alloys, component weight saving of up to 25 per cent due to lower specific gravity is also possible. The alloys are also characterized by higher corrosion re sistance in aqueous environments. The reason is the formation of a passive layer of alumina at a pH higher than about 3. At lower pH values, the passive layer is made of silica and also has a protective effect.
[0011] It is also possible to use recycled material as input raw materials for the preparation of alloys, e.g. engine blocks made of Al-Si alloys, even with a proportion of steel parts.
[0012] In contrast to the materials mentioned above, the said critical elements, i.e. Cr, Ni and Co, are not represented in the proposed Fe-Al-Si-X and Fe-Al-Si-X-Y alloys either at all or in a few per cent. At the same time, the useful properties of the proposed alloys are better or remain similar to those of commercially used alloys.
[0013] Compared to Pyroferal, the proposed alloys have a lower aluminium content, which leads to higher toughness, while increased silicon content compared to Pyroferal alloy (Patent 115312) has a positive effect on high-temperature mechanical properties and thermal and oxidative resistance. The proposed alloy has a lower C content, so weather damage is avoided and this leads to product stability.
[0014] When comparing the proposed alloys and purely binary Fe3Al alloy or alloys of ternary alloys, the proposed alloys show significantly smaller grain size and thus better mechanical properties, especially higher toughness, but also higher corrosion re sistance at elevated temperatures, especially oxidation.
Explanation of Drawings
[0015] The Fe-Al-Si-X-based alloy of the present invention will be described in more detail in specific examples with the aid of the accompanying drawings, in which: [Fig.l] shows the mechanical properties in a compression test of the Fe-Al-Si5 alloy prepared by casting. [Fig.2] shows the oxidation resistance of the Fe-Al-Si5 alloy prepared by powder metallurgy in comparison with a binary Fe-Al alloy. [Fig.3] shows a blank for the production of a valve seat from the Fe-Al-Si alloy.
Examples of Embodiments of the Invention
[0016] The invention will be described in more detail below with the aid of specific examples, which are merely illustrative and do not limit the scope of the invention in any way.
[0017] It is a Fe-Al-Si-X-based alloy with oxidation resistance at temperatures up to 1,100 °C and mechanical and tribological resistance up to at least 750 °C, which comprises a Fe-Al-Si alloy matrix containing A1 16+4 wt%, Si 6+4 wt%, at least one alloying element X in an amount of 4+3 wt%, which is selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V and Mo, and the rest is Fe.
[0018] In another case, the alloy matrix further comprises at least one other alloying element in the range of 0.01 to 1.5 wt%, selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V, B and Sc, which is different from the element in the previous alloy.
Example 1
[0019] Preparation of a Fe-Al-Si5 alloy by casting: The alloy containing 16+4 wt.% A1 and 3+2 wt.% Si was prepared by melting in a vacuum furnace. A copper mould was used for casting.
Example 2
[0020] A Fe-Al-Si5 alloy was prepared by mechanical alloying and plasma sintering. The oxidation resistance at 800 °C was tested and compared with a binary Fe-Al alloy. The alloy with added silicone achieves a significantly lower oxidation rate than the reference binary Fe-Al alloy.
Example 3 [0021] A Fe-Al-Si5 alloy was prepared by mechanical alloying and plasma sintering and the manufacture of a valve seat by means of electric spark machining process was tested on the heat-treated material, see the blank in [Fig.3].
Example 4
[0022] Powder made by atomization of base alloy Fe, A1 16+4, Si 6+2 wt.%, added with element X, which is Ti in an amount of 2+1 wt.% and element Y, which in this case is B in an amount of 0.6+0.2 wt.%. The powder is used for thermal spraying using plasma or the HVOF method to create a functional layer with significantly increased tribological resistance up to temperatures of 700 °C. An example of use is for brake discs in creating a compact layer and composite spray layout.
Example 5
[0023] Powder made by grinding from base alloy Fe, A1 16+4, Si 6+2 wt.%, added with element X which is W in an amount of 1+0.5 wt.% and element Y, which is Nb in an amount of 0.4+0.15 wt.%. The powder is used for 3D printing using the SLS method, for the production of shaped inserts into moulds for injection using the MIM and CIM methods. The insert created in this way has increased temperature and abrasion re sistance against ceramic and metal particles injected by the MIM and CIM methods.
Example 6
[0024] Powder made by grinding from base alloy Fe, A1 16+4, Si 3+2 wt.%, added with element X which is Mo in an amount of 1.5+0.5 wt.% and element Y, which is V in an amount of 0.3+0.1 wt.%. The powder is used for 3D printing using the SLM method, for the production of components usable in energy sector. In this case, it is specifically a steam distribution house located in front of the first stage of the steam turbine. The part created in this way has sufficient corrosion and abrasion resistance at temperatures up to 580 °C and long-term temperature stability.
Example 7
[0025] Powder made by grinding from base alloy Fe, A1 16+4, Si 3+2 wt.%, added with element X, which is Zr in an amount of 1.2+0.5 wt.%. The powder is used for laser weld overlaying of functional bearing surfaces on parts of welding jigs intended for large-scale production of components for automotive. The layers formed in this way have about 1.2 times greater abrasion resistance than parts with nitrided or cemented surfaces.
Example 8
[0026] Thermal arc spray wire made by casting and subsequent forming from a base alloy Fe, A1 16+4, Si 3+2 wt.%, added with element X, which is Cr in an amount of 2+0.5 wt.% and element Y, which is Ti in an amount of 1+0.4 wt.%. The wire is used to renovate worn gate valves and valves in the primary circuit and at steam su perheaters. Industrial Applicability
[0027] The alloy according to the present invention is intended for products intended mainly for two industrial segments, namely for high-temperature applications up to 1,100 °C, which include, for example, furnace components such as load-bearing parts, refractory partitions, grates, muffles, resistance heaters, etc. and high-temperature heat pipes, burner nozzles, gate valves and valves, and also products intended for applications with excellent mechanical and tribological resistance, at least up to a temperature of 750 °C. Examples include components of combustion engines and turbochargers, components of combustion, steam, gas and steam-gas turbines, or components of braking systems such as discs, brake segments, etc.

Claims

Claims
[Claim 1] A Fe-Al-Si-X-based alloy with oxidation resistance at temperatures up to 1,100 °C and mechanical and tribological resistance at least up to 750 °C, characterized in that the alio comprises a Fe-Al-Si alloy matrix containing A1 16+4, Si 6+4 wt%, at least one alloying element X in an amount of 4+3 wt%, which is selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V and Mo, and the rest is Fe.
[Claim 2] The alloy according to claim 1, characterized in that it further contains at least one further alloying element Y in the range of 0.01 to 1.5 wt.%, selected from the group consisting of Zr, Cr, Nb, Ni, Ti, W, V, B and Sc, different from the element X.
[Claim 3] Use of the alloy according to claim 1 or 2 for cast blanks.
[Claim 4] Use of the alloy according to claim 1 or 2 for products selected from the group consisting of a formed blank, a wire intended for welding and a wire intended for thermal spraying.
[Claim 5] Use of the alloy according to claim 1 or 2 for the production of a powder. [Claim 6] Use of the alloy according to claim 5 in the form of powders for 3D printing of metallic materials, sintering and formation of functional layers realized by means of cold and thermal spraying, or for metal powder injection technologies.
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Citations (2)

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CN108611580A (en) * 2018-05-16 2018-10-02 蔡明东 A kind of high-effect Fe-based amorphous alloy electric heating material and preparation method thereof

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ŠVEC MARTIN, VODIČKOVÁ VĚRA, HANUS PAVEL, PAZOURKOVÁ PROKOPČÁKOVÁ PETRA, ČAMEK LIBOR, MORAVEC JAROMÍR: "Effect of Higher Silicon Content and Heat Treatment on Structure Evolution and High-Temperature Behaviour of Fe-28Al-15Si-2Mo Alloy", MATERIALS, vol. 14, no. 11, 2 June 2021 (2021-06-02), pages 3031, XP093001102, DOI: 10.3390/ma14113031 *
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