WO2023181532A1 - 金属セラミックス複合材料 - Google Patents

金属セラミックス複合材料 Download PDF

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WO2023181532A1
WO2023181532A1 PCT/JP2022/046567 JP2022046567W WO2023181532A1 WO 2023181532 A1 WO2023181532 A1 WO 2023181532A1 JP 2022046567 W JP2022046567 W JP 2022046567W WO 2023181532 A1 WO2023181532 A1 WO 2023181532A1
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mass
metal
composite material
phase
ceramic composite
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PCT/JP2022/046567
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English (en)
French (fr)
Japanese (ja)
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寛紀 竹下
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三井金属鉱業株式会社
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Priority to CN202280091610.XA priority Critical patent/CN118715192A/zh
Priority to JP2024509757A priority patent/JP7591179B2/ja
Publication of WO2023181532A1 publication Critical patent/WO2023181532A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent

Definitions

  • the present invention relates to metal-ceramic composite materials. More specifically, the present invention relates to a metal-ceramic composite material in which a ceramic phase containing silicon carbide and a metal phase containing Cu and Si are dispersed and mixed with each other and have an antibacterial effect.
  • Ceramic materials formed from silicon carbide are lightweight and have excellent wear resistance, high-temperature mechanical strength, and corrosion resistance.
  • silicon carbide is a brittle material with low toughness, so by combining silicon carbide with copper (Cu) or a copper alloy, which is a highly thermally conductive material, a composite material with an excellent balance of toughness and thermal conductivity is created.
  • Cu copper
  • copper alloy which is a highly thermally conductive material
  • Patent Document 2 describes a metal-ceramic composite material that includes a Si--Cu alloy and a SiC ceramic, and in which the Si:Cu content of the Si--Cu alloy is 60 to 30% by mass: 40 to 70% by mass. is disclosed. According to this document, it is reported that by including such a Si:Cu content, a composite material with improved toughness and suppressed decrease in Young's modulus and increase in density is provided.
  • Patent Document 3 discloses a highly thermally conductive composite material in which a porous SiC preform having a skeletal structure is infiltrated with Cu to form a reaction prevention layer between the two. According to this document, it is reported that a composite material having high thermal conductivity and a low coefficient of thermal expansion, which is suitable as a heat dissipation material for electronic equipment and semiconductor devices, is provided.
  • Slatted flooring made of concrete or cast metal has traditionally been used as flooring material for livestock barns, and attempts have been made to improve its durability and antibacterial properties.
  • slatted flooring made of concrete or cast iron did not have sufficient antibacterial and antiviral properties.
  • a composite material containing silicon carbide and copper that has been demonstrated to exhibit sufficient antibacterial properties has not been reported to date.
  • the present inventors have investigated that it is not easy to impregnate the ceramic phase of silicon carbide with copper or a copper alloy, particularly a metal phase forming substance containing Cu and Si, and this is due to the low impregnating property. It has been found that it is difficult to achieve both mechanical properties such as strength and hardness and antibacterial properties in such composite materials, and internal cracks may occur in some cases. Therefore, it is desired to develop a composite material containing silicon carbide and copper that has good mechanical properties such as strength and hardness and also exhibits excellent antibacterial properties.
  • the first problem to be solved by the present invention is to create a novel metal ceramic, which has an antibacterial effect, in which a ceramic phase containing silicon carbide and a metal phase containing Cu and Si are mutually dispersed and mixed, which is not found in the prior art.
  • Our goal is to provide composite materials.
  • a further problem to be solved by the present invention is to provide a ceramic phase containing silicon carbide and a metal phase containing Cu and Si, which have good mechanical properties such as strength and hardness and exhibit excellent antibacterial properties.
  • the object of the present invention is to provide a novel metal-ceramic composite material in which the metals and ceramics are dispersed and mixed with each other.
  • the present inventors have found that when impregnating ceramics containing silicon carbide with an alloy and/or intermetallic compound consisting of Cu and Si, the alloy and/or intermetallic compound contains Cu or Si. This can be significantly improved by containing a predetermined amount of an additive element that is at least one metal other than the above, and by adjusting the resulting metal-ceramic composite material so that the ceramic phase and the metal phase have a predetermined area ratio.
  • the present inventors have discovered that a metal-ceramic composite material can be formed that has an excellent impregnated state and at the same time exhibits an excellent antibacterial effect, and has completed the present invention.
  • a ceramic phase containing silicon carbide, and A metal-ceramic composite material comprising an alloy consisting of Cu and Si and/or a metal phase containing an intermetallic compound in a mutually dispersed state
  • the metal phase contains an additive element M that is at least one metal other than Cu or Si
  • the silicon carbide accounts for the majority of the total mass of the constituent materials of the ceramic phase, here,
  • SEM scanning electron microscope
  • a novel metal-ceramic composite material which has antibacterial and antiviral effects, in which a ceramic phase containing silicon carbide and a metal phase containing Cu and Si are mutually dispersed and mixed, which is not found in the prior art.
  • Ru a ceramic phase containing silicon carbide and a metal phase containing Cu and Si are mutually dispersed and mixed, which is not found in the prior art.
  • Ru a metal-ceramic composite material according to the present invention, the presence of a predetermined amount of the additive element M in the metal phase containing Cu and Si brings about a good impregnation state of the metal-ceramic composite material, and thus Due to the good impregnation state, excellent mechanical properties such as strength and hardness, as well as excellent antibacterial and antiviral properties due to copper can be exhibited.
  • the area ratio of the ceramic phase containing silicon carbide to the metal phase containing Cu and Si, the mass ratio of the additive element M to Si in the metal phase is adjusted by adjusting the mass ratio of Cu to Si in the metal phase within a predetermined range, the impregnation state of the metal-ceramic composite material becomes even better, resulting in improved mechanical properties, especially porosity (density of the sintered body). , bending strength and hardness (e.g. Vickers hardness: indentation hardness), and excellent antibacterial and antiviral effects can be achieved in a well-balanced manner.
  • FIG. 1 is an example of an image taken by a scanning electron microscope (SEM) at a magnification of 500 of a metal-ceramic composite material according to an embodiment of the present invention.
  • SEM scanning electron microscope
  • the metal-ceramic composite material according to the present invention comprises a ceramic phase containing silicon carbide (SiC) and a metal phase containing an alloy and/or an intermetallic compound of Cu and Si in a mutually dispersed state.
  • this metallic phase contains an additive element M that is at least one metal other than Cu or Si, and the silicon carbide accounts for a majority of the total mass of the constituent materials of the ceramic phase.
  • the respective amounts (mass%) of silicon carbide, free carbon, Cu, Si, and additive elements M constituting the metal phase in the metal-ceramic composite material and unavoidable impurities were measured using XRF (X-ray fluorescence spectroscopy). ), an ICP emission spectrometer, and a carbon analyzer (combustion-infrared absorption method).
  • XRF X-ray fluorescence spectroscopy
  • ICP emission spectrometer an ICP emission spectrometer
  • carbon analyzer combustion-infrared absorption method
  • the ceramic phase containing silicon carbide of the metal-ceramic composite material is not limited except that silicon carbide occupies a majority of the total mass of the constituent materials of the ceramic phase, that is, more than 50% by mass.
  • the ceramic phase of the metal-ceramic composite material may contain less than 50% by mass of ceramic materials other than silicon carbide. Examples of such ceramic materials other than silicon carbide include, but are not limited to, silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), boron nitride (BN), titanium nitride (TiN), and zirconium nitride (ZrN).
  • the proportion of silicon carbide in the ceramic phase of the metal-ceramic composite material is more preferably 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass.
  • the content may be 90% by mass or more, 95% by mass or more, 96% by mass or more, 97% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass.
  • the ceramic phase may be formed solely of silicon carbide (without other ceramic materials) with the exception of a small amount of free carbon. The higher the proportion of silicon carbide in the ceramic phase within the range of more than 50% by mass, the higher the wear resistance, corrosion resistance, and strength, which are the characteristics of silicon carbide, can be exhibited in the metal-ceramic composite material.
  • the ceramic phase of the metal-ceramic composite material may contain a small amount of free carbon.
  • Free carbon refers to carbon atoms that exist alone without forming chemical bonds with silicon atoms or other metal atoms in the ceramic phase or near the interface of the ceramic phase with the metal phase.
  • the content of free carbon in the ceramic phase is not particularly limited, but may be, for example, usually 5% by mass or less, typically 3% by mass or less, based on the total weight of the ceramic phase.
  • the proportion of Cu to the total mass of the metal phase of the metal-ceramic composite material may be generally 60% by mass or more and 95% by mass or less, preferably 65% by mass or more and 90% by mass or less. Further, the proportion of Si to the total mass of the metal phase of the metal-ceramic composite material may be generally 3% by mass or more and 35% by mass or less, preferably 5% by mass or more and 30% by mass or less.
  • the proportion of the alloy and/or intermetallic compound consisting of Cu and Si with respect to the total mass of the metal phase of the metal-ceramic composite material is usually more than 70 mass%, preferably 71 mass% or more, 72 mass% or more, 73 mass%
  • the content may be 74% by mass or more, 75% by mass or more, 76% by mass or more, or 77% by mass or more.
  • this proportion is usually less than 99.7% by mass, preferably 99.5% by mass or less, 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, 95% by mass or less, It may be 94% by weight or less, 93% by weight or less, 92% by weight or less, 91% by weight or less, 90% by weight or less, 88% by weight or less, 86% by weight or less, or 84% by weight or less.
  • the proportion of the alloy and/or intermetallic compound consisting of Cu and Si in the metal phase within the above range, the strength and thermal conductivity, which are the characteristics of copper, as well as antibacterial and antiviral properties can be achieved in the metal-ceramic composite material. can be expressed higher.
  • the proportion of the alloy and/or intermetallic compound consisting of Cu and Si with respect to the total mass of the metal phase of the metal-ceramic composite material may be generally more than 70% by mass and less than 99.7% by mass, preferably 70% by mass or more. -99.5% by mass or less, 70% by mass or more - 99% by mass or less, 70% by mass or more - 98% by mass or less, 70% by mass or more - 97% by mass or less, 70% by mass or more - 96% by mass or less, 70% by mass % to 95 mass%, 70 mass% to 94 mass%, 70 mass% to 93 mass%, 70 mass% to 92 mass%, 70 mass% to 91 mass%, 70 mass% % to 90 mass%, 70 mass% to 88 mass%, 70 mass% to 86 mass%, 70 mass% to 84 mass%, 71 mass% to less than 99.7 mass%, 71% by mass or more - 99.5% by mass or less, 71% by mass or more - 99% by mass or less
  • the additive element M which is at least one metal other than Cu or Si in the metal phase of the metal-ceramic composite material, is not particularly limited except that it is an element other than Cu or Si, and may include Ni (nickel), Pd (palladium), Mg (magnesium), Ca (calcium), Zn (zinc), Ti (titanium), Zr (zirconium), S (sulfur), Mo (molybdenum), W (tungsten), Fe (iron), Mn (manganese), It may contain at least one member selected from the group containing V (vanadium), Nb (niobium), Ta (tantalum), and Y (yttrium).
  • the additive element M may include at least one selected from the group including Ni, Mg, Zn, and Ti.
  • the additive element M more preferably includes Ni.
  • the additive elements M include two of the above-mentioned Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y. It may include a combination or a combination of three or more elements.
  • the additive element M may include a combination of two of Ni, Mg, Zn, and Ti, or a combination of three or more elements.
  • the combination may be, for example, Ni/Mg, Ni/Zn, Ni/Ti, Mg/Zn, Mg/Ti, or Zn/Ti.
  • the additive element M includes a combination of three elements
  • the combination may be, for example, Ni/Mg/Zn, Ni/Mg/Ti, or Mg/Zn/Ti.
  • the additive element M is at least selected from the group including Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y. It is only one type and does not contain any other elements. In a preferred embodiment, the additive element M is at least one selected from the group containing Ni, Mg, Zn, and Ti, and does not contain any other elements. In another embodiment, the additive element M is two elements selected from Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y.
  • the additive element M is three elements among Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y. or a combination of three elements, Ni/Mg/Zn, Ni/Mg/Ti, or Mg/Zn/Ti, containing no other elements. Does not include.
  • the mass ratio of Ni to the total mass of the additive element M may be 5% by mass or more and 100% by mass or less (that is, Ni only), preferably 10% by mass or more and 100% by mass. % or less, 20% by mass or more - 100% by mass or less, 30% by mass or more - 100% by mass or less, 40% by mass or more - 100% by mass or less, 50% by mass or more - 100% by mass or less, 60% by mass or more - 100% by mass % or less, 70% by mass or more and 100% by mass or less, 80% by mass or more and 100% by mass or less, or 90% by mass or more and 100% by mass or less.
  • the metal phase of the metal-ceramic composite material contains impurities that are unavoidably mixed without active addition operations, so-called unavoidable impurities. Contains impurities. Unavoidable impurities may include any impurities known to be included in known metal-ceramic composite materials. Unavoidable impurities are not particularly limited, but include, for example, Mn, Sr, Sn, P, and Cr. The content of unavoidable impurities in the metal phase is not particularly limited, but may be 5% by mass or less based on the total mass of the metal phase.
  • the total area of the ceramic phase was When the percentage (%) is A and the percentage (%) of the total area of the metal phase is B, the area ratio A/B of the ceramic phase/metal phase is 2 or more and 60 or less.
  • the mass percentage (%) of Si is a and the mass percentage (%) of the additive element M is m with respect to its total mass, the following The relational expression holds true. 0.01 ⁇ m/a ⁇ 1.4, and 0.3 ⁇ m ⁇ 20
  • the ceramic phase/metal phase area ratio A/B within the above specific range and the above two relational expressions are all satisfied, so that the ceramic phase containing silicon carbide and the Cu It becomes easy to form a good impregnated state in which the metal phases containing Si and Si are sufficiently dispersed and mixed with each other.
  • the wear resistance, corrosion resistance, and strength which are the inherent characteristics of silicon carbide contained in the ceramic phase, as well as the characteristics inherent to the copper of the copper alloy contained in the metal phase, are improved. The strength, thermal conductivity, and antibacterial/antiviral properties can be more effectively exhibited.
  • the state of impregnation of the metal phase into the ceramic phase is improved.
  • metal ceramics with improved mechanical properties especially porosity (density of the sintered body), bending strength and hardness (e.g. Vickers hardness: indentation hardness), and a better balance of antibacterial and antiviral effects.
  • Composite materials can be obtained.
  • the metal-ceramic composite material of the present invention contains a ceramic phase containing silicon carbide and a metal phase containing an alloy and/or an intermetallic compound of Cu and Si in a mutually dispersed state, that is, a ceramic phase and a metal phase.
  • a state is formed in which these are dispersed and intermingled with each other. Therefore, when using a scanning electron microscope (SEM) on a metal-ceramic composite material to obtain an image with an area of 256 ⁇ m x 192 ⁇ m at a magnification of 500, it is difficult to detect images due to the dispersion and mixing of the ceramic phase and the metal phase.
  • SEM scanning electron microscope
  • the image to be acquired is usually only one arbitrary field of view is sufficient. From the viewpoint of further increasing the accuracy of the calculation reproducibility of A/B, images are acquired from two or more arbitrary fields of view, the average value of the area ratio A/B in those images is calculated, and this is It may be considered as the area ratio A/B for the material.
  • FIG. 1 shows an example of an image taken by a scanning electron microscope (SEM) at a magnification of 500 of a metal-ceramic composite material according to an embodiment of the present invention.
  • the embodiment shown in this image is an example in which Ni, which is an additive element M, is added in an amount of 5% by mass based on the total mass of the metal phase of the composite material.
  • the white part is the metal phase containing the copper alloy and the additive element Ni
  • the gray part is the ceramic phase whose main component is SiC, and it can be seen that both phases are dispersed and mixed with each other. .
  • the ceramic phase/metal phase was The area ratio A/B is 2 or more and 60 or less, preferably 2.5 or more and 50 or less, 3 or more and 45 or less, 3 or more and 40 or less, 3 or more and 35 or less, 3 or more and 30 or less, 3 or more and 25 or less, 3 or more and 20 or less, 3 or more and 15 or less, 3 or more and 10 or less, 3 or more and 8 or less, 3.3 or more and 8 or less, 3.5 or more and 8 or less, 3.7 or more and 8 or less, 3 or more and 5 or less, 3.3 or more 5 or less, 3.5 or more and 5 or less, 3.7 or more and 5 or less, 3 or more and 4.5 or less, 3.3 or more and 4.5 or less, 3.3 or more and 4.5 or less, 3.5 or more and 4.5 or less, or 3.7 and 4.5 or less, 3.3 or more and 4.5 or less, 3.5 or more and 4.5 or less, or 3.7 and 4.5 or less, 3.3 or more and 4.5 or less,
  • the impregnation of the metal phase into the ceramic phase progresses favorably. It has a good balance of properties, effectively suppressing the decline in porosity (density of the sintered body), bending strength and hardness (e.g. Vickers hardness: indentation hardness), as well as antibacterial and antiviral effects.
  • a metal-ceramic composite material can be obtained.
  • the range of m is not particularly limited, but for example, 0.5 ⁇ m ⁇ 20, 1 ⁇ m ⁇ 20, 2 ⁇ m ⁇ 20, 3 ⁇ m ⁇ 20, 4 ⁇ m ⁇ 20, 5 ⁇ m ⁇ 20, 0.3 ⁇ m ⁇ 18, 0.5 ⁇ m ⁇ 18, 1 ⁇ m ⁇ 18, 2 ⁇ m ⁇ 18, 3 ⁇ m ⁇ 18, 4 ⁇ m ⁇ 18, 5 ⁇ m ⁇ 18 , 0.3 ⁇ m ⁇ 16, 0.5 ⁇ m ⁇ 16, 1 ⁇ m ⁇ 16, 2 ⁇ m ⁇ 16, 3 ⁇ m ⁇ 16, 4 ⁇ m ⁇ 16, or 5 ⁇ m ⁇ 16.
  • the impregnation of the metal phase into the ceramic phase can proceed favorably.
  • the porosity density of the sintered body
  • a good balance of properties between bending strength and hardness for example, Vickers hardness: indentation hardness
  • the area ratio A/B of the ceramic phase/metal phase to the area of the entire scanning electron microscope (SEM) image is more than 5 (and less than 60). In some cases, it is preferable that the ratio between the mass percentage m (%) of the additive element M and the mass percentage a (%) of Si is m/a ⁇ 1.
  • the area ratio A/B of the ceramic phase/metal phase is more than 5 (and less than 60), that is, even when the proportion of the metal phase impregnated into the ceramic phase is relatively small, m
  • the porosity density of the sintered body
  • bending strength and hardness e.g. Vickers hardness: Indentation hardness
  • the mass percentage (%) of Cu is b and the mass percentage (%) of Si is a, based on the total mass, b/a
  • the relational expression ⁇ 2.5 holds true.
  • a metal ceramic whose porosity (density of the sintered body), bending strength and hardness, and the balance between antibacterial and antiviral effects are further improved by having the mass ratio of Cu and Si in the metal phase satisfy this relational expression.
  • Composite materials can be obtained. From the viewpoint of improving the balance of these various properties, it is recommended that the relational expression b/a ⁇ 3 holds between the mass percentage (%) b of Cu and the mass percentage (%) a of Si in the metal phase.
  • b/a ⁇ 3.5 is even more preferable, and b/a ⁇ 4 is even more preferable.
  • the difference between the mass percentage (%) b of Cu and the mass percentage (%) a of Si in the metal phase is b/a. It is more preferable that the relational expression ⁇ 4.5 holds true, and even more preferable that b/a ⁇ 5.
  • the upper limit of the ratio b/a between the mass percentage (%) b of Cu and the mass percentage (%) a of Si in the metal phase is not particularly limited, but may be From the viewpoint of obtaining a sufficient amount, it is preferable that the relational expression b/a ⁇ 20 holds true, and it is more preferable that b/a ⁇ 18, b/a ⁇ 16, or b/a ⁇ 14.
  • the ratio b/a between the mass percentage (%) b of Cu and the mass percentage (%) a of Si in the metal phase is preferably 2.5 ⁇ b/a ⁇ 20, 2.5 ⁇ b/a ⁇ 18, 2.5 ⁇ b/a ⁇ 16, 2.5 ⁇ b/a ⁇ 14, 3 ⁇ b/a ⁇ 20, 3 ⁇ b/a ⁇ 18, 3 ⁇ b/a ⁇ 16, 3 ⁇ b/a ⁇ 14, 3.5 ⁇ b/a ⁇ 20, 3.5 ⁇ b/a ⁇ 18, 3.5 ⁇ b/a ⁇ 16, 3.5 ⁇ b/a ⁇ 14, 4 ⁇ b/a ⁇ 20, 4 ⁇ b/a ⁇ 18, 4 ⁇ b/a ⁇ 16, 4 ⁇ b/a ⁇ 14, 4.5 ⁇ b/a ⁇ 20, 4.5 ⁇ b/a ⁇ 18, 4.5 ⁇ b/a ⁇ 16, or 4.5 ⁇ b/a ⁇ 14.
  • the metal phase of the metal-ceramic composite material includes unavoidable impurities such as Mn, Sr, Sn, P, and Cr.
  • the sum of the mass percentage a (%), the mass percentage b (%) of Cu, and the mass percentage m (%) of the additional element M does not equal 100 mass %.
  • a+b+m ⁇ 95 (mass%), and a+b+m ⁇ It is more preferable that it is 96 (mass%), and even more preferable that a+b+m ⁇ 97 (mass%), a+b+m ⁇ 98 (mass%) or a+b+m ⁇ 99 (mass%).
  • the area ratio A/B of the ceramic phase/metal phase to the area of the entire scanning electron microscope (SEM) image is 5 or less (and 2 or more), and in the metal phase, the ratio of the mass percentage m (%) of the additive element M to the mass percentage a (%) of Si is m/a ⁇ 1 (and 0.01 or more), and It is more preferable that the ratio between the mass percentage b (%) of Cu and the mass percentage a (%) of Si is b/a ⁇ 3.
  • the area ratio A/B of the ceramic phase/metal phase is 4.5 or less, and the ratio of the mass percentage m (%) of the additive element M to the mass percentage a (%) of Si is m It is even more preferable that /a ⁇ 0.9 and the ratio of the mass percentage b (%) of Cu to the mass percentage a (%) of Si is b/a ⁇ 3.5.
  • the area ratio A/B of the ceramic phase/metal phase is 4.5 or less, and the ratio of the mass percentage m (%) of the additive element M to the mass percentage a (%) of Si is m It is even more preferable that /a ⁇ 0.8 and the ratio of the mass percentage b (%) of Cu to the mass percentage a (%) of Si is b/a ⁇ 4.
  • the metal-ceramic composite material according to the present invention can be used as an anti-pathogen material that exhibits anti-bacterial and anti-viral effects, that is, as an anti-bacterial and anti-viral material.
  • Target bacteria include, for example, Staphylococcus aureus, Klebsiella pneumoniae, Pseudomonas aeruginosa, Escherichia coli, Moraxella bacteria, and methicillin-resistant Staphylococcus aureus.
  • target viruses include bacteriophage Q ⁇ , bacteriophage ⁇ 6, influenza virus, coronavirus, and human immunodeficiency virus.
  • the antibacterial effect and antiviral effect can be evaluated by the test described below.
  • the metal-ceramic composite material according to the present invention has an antibacterial effect R of 2.2 as measured using Staphylococcus aureus as a test bacterium in accordance with JIS Z2801:2012 and JIS R1752:2020 that cites this. It may be 0 or more.
  • JIS Z2801:2012 stipulates an action temperature of 35 ⁇ 1°C and an action time of 24 ⁇ 1 hour as the culture conditions for a test piece inoculated with a test bacterial solution in measuring the antibacterial effect. ⁇ Measurements are carried out in the dark at an action temperature of 25°C and an action time of 6 hours.
  • JIS R1752:2020 stipulates that the duration of light irradiation on a test piece inoculated with a test bacterial solution is 8 hours, but the culture and measurement here are performed without light irradiation and with a duration of 6 hours. Do it in the dark.
  • Specific conditions for measuring the antibacterial effect can typically be set as follows.
  • This antibacterial effect R is more preferably 2.5 or more, even more preferably 3.0 or more, even more preferably 3.5 or more, even more preferably 3.9 or more, even more preferably 4.2 or more. , most preferably 4.5 or more.
  • the upper limit of this antibacterial effect R is not particularly limited, but may actually be about 5.5 to 6. Since the antibacterial effect R of the metal-ceramic composite material according to the present invention is 2.0 or more, or preferably within the above range, the composite material can be suitably used as a material having antibacterial properties in a wide range of applications. .
  • the metal-ceramic composite material according to the present invention has an antiviral effect R of 2 as measured using bacteriophage Q ⁇ or bacteriophage ⁇ 6 as a test phage in accordance with ISO18071:2016 and JIS R1756:2020. It may be .5 or more.
  • ISO18071:2016 and JIS R1756:2020 stipulate that the action time of visible light irradiation is 4 hours as the culture condition for the test piece inoculated with the test solution in measuring the antiviral effect. ⁇ Measurements are carried out in the dark without light irradiation and with an action time of 6 hours. Specific conditions for measuring the antiviral effect can typically be set as follows.
  • This antiviral effect R is more preferably 3.0 or more, even more preferably 3.5 or more, even more preferably 4.0 or more, even more preferably 4.5 or more, and even more preferably 4.6. More preferably, it may be 4.7 or more.
  • the upper limit of this antiviral effect R is not particularly limited, but may actually be about 6.5 to 7. Since the antiviral effect R of the metal-ceramic composite material according to the present invention is 2.5 or more, or preferably within the above range, the composite material can be suitably used as a material having antiviral properties in a wide range of applications. I can do it.
  • the above-mentioned working temperature and working time in the culture conditions for measuring the antibacterial effect and antiviral effect can be changed depending on the bacteria or virus employed.
  • the operating temperature can be appropriately selected within the range of 10°C to 40°C.
  • the culture when conducting a test by culturing Escherichia coli, the culture can be carried out by setting the operating temperature to 37° C., where Escherichia coli grows actively.
  • the culture may be carried out for an appropriate action time in the range of 2 hours to 72 hours, or for a longer action time. For example, in the case of a virus with a slow growth rate, culture can be performed with the action time set to 96 hours.
  • the metal-ceramic composite material of the preferred embodiment of the present invention can be used as an anti-pathogen material that exhibits sufficient anti-bacterial and anti-viral effects even in the dark. That is, according to the metal-ceramic composite material of the preferred embodiment, it is possible to provide an anti-pathogen material that exhibits anti-bacterial and anti-viral effects regardless of illuminance.
  • the metal-ceramic composite material according to the present invention may have a porosity of 10% or less as measured by the Archimedes method according to JIS R1634:1998. This porosity is more preferably 9% or less, even more preferably 8% or less, even more preferably 7% or less, even more preferably 6% or less, even more preferably 5% or less, and most preferably 4%. It may be the following.
  • the lower limit of this porosity is not particularly limited (as long as it is 0% or more), but in reality, the lower limit may be about 2 to 3%. Since the porosity of the metal-ceramic composite material according to the present invention is 10% or less, or preferably within the above range, the density of the sintered body is further improved, and it is easy to obtain a composite material with higher hardness. become.
  • the metal-ceramic composite material according to the present invention has a bulk density D1 of the metal-ceramic composite material and a true density D2 of the metal phase of the metal-ceramic composite material when measured by the Archimedes method according to JIS R1634:1998.
  • the relative density [D1/D2]*100 may be 90% or more. This relative density may be more preferably 91% or more, even more preferably 92% or more, even more preferably 93% or more, even more preferably 94% or more, and most preferably 95% or more.
  • the relative density of the metal-ceramic composite material according to the present invention is 90% or more, or preferably within the above range, the denseness of the sintered body can be further improved as in the case where the porosity is below the predetermined upper limit. , it becomes easier to obtain composite materials with higher hardness.
  • the metal-ceramic composite material according to the present invention may have a bending strength of 230 MPa or more as measured by a three-point bending strength test according to JIS R1601:2008.
  • This bending strength may be more preferably 250 MPa or more, even more preferably 270 MPa or more, even more preferably 280 MPa or more, even more preferably 290 MPa or more, and most preferably 300 MPa or more. Since the bending strength of the metal-ceramic composite material according to the present invention is 230 MPa or more, or preferably within the above range, the mechanical strength against bending operations is further improved, making it suitable for a wide range of applications requiring high bending resistance. It can be suitably used.
  • the metal-ceramic composite material according to the present invention may have a Vickers hardness of 25 GPa or more measured as a five-point average in a one-point load test according to JIS R1610:2003.
  • the Vickers hardness may be more preferably 26 GPa or higher, even more preferably 26.5 GPa or higher, even more preferably 27 GPa or higher, even more preferably 27.5 GPa or higher, and most preferably 28 GPa or higher. Since the Vickers hardness of the metal-ceramic composite material according to the present invention is 25 GPa or more, or preferably within the above range, its robustness against indentation operations is further improved, and it can be suitably used for a wide range of applications that require high rigidity. can do.
  • the metal-ceramic composite material according to the present invention can be processed into various shapes and used. Although its shape is not particularly limited, it may be a film, a sheet, a thin plate, a thick plate, a substantially prismatic column, a substantially circular column, or the like. Further, the metal-ceramic composite material according to the present invention can be used in a wide range of applications requiring antibacterial and antiviral properties.
  • the composite materials are used, for example, as components for various articles, structural materials constituting buildings, bridges, ships, railways, roads, ports, etc., and architectural materials such as flooring materials, wall materials, and ceilings of buildings, including flooring materials for livestock sheds. It can be suitably used as a material or the like.
  • Method for manufacturing metal-ceramic composite material is not particularly limited as long as a metal-ceramic composite material having the above-mentioned configuration and characteristics can be obtained as a result.
  • the metal-ceramic composite material according to the present invention can be manufactured, for example, as described below.
  • a preform of a porous ceramic sintered body is formed from a ceramic phase-forming material containing a majority of silicon carbide (SiC), and in the second step, this preform is heated at a high temperature.
  • the metal-ceramic composite material according to the present invention can be manufactured by impregnating a metal phase-forming material containing a molten alloy and/or intermetallic compound of Cu and Si and an additive element M under pressure.
  • Other substances other than silicon carbide that can be included in the ceramic phase-forming material, the additive element M included in the metal phase-forming material, and the types of inevitable impurities are as described above for the metal-ceramic composite material.
  • Mass ratio of ceramic phase forming material used in the first step and metal phase forming material used in the second step, mass ratio of Cu and Si in the alloy and/or intermetallic compound, Cu in the metal phase forming material By appropriately adjusting the mass ratio of the alloy and/or intermetallic compound consisting of Si and Si and the additive element M, the area ratio A/B of the ceramic phase/metallic phase within a predetermined range, and the mass of the additive element M within a predetermined range.
  • a preform of a porous ceramic sintered body is produced by, for example, molding a ceramic phase-forming material containing a majority of silicon carbide by a molding method such as molding, and then molding the material at a temperature of usually 2000°C or higher, preferably 2200°C or higher. It can be produced by a so-called recrystallization method in which high temperature is maintained.
  • a preform of a porous ceramic sintered body containing silicon carbide can be obtained by heating a mixture containing high-purity silicon (Si) particles and carbon (C) particles at 1400°C or higher and performing reaction sintering. It is possible.
  • a binder substrate that carbonizes by sintering
  • Carbon fibers can also be used as a carbon source.
  • the porosity of the preform of the porous ceramic sintered body obtained in this first step is not particularly limited, but may be, for example, 10% to 70%.
  • the metal phase-forming material containing the alloy and/or intermetallic compound of Cu and Si and the additive element M may be melted in advance at a high temperature of usually over 1000°C, preferably over 1200°C. can.
  • the metal phase-forming material containing the alloy and/or intermetallic compound of Cu and Si melted at a high temperature and the additive element M is usually heated in a high-pressure container under a pressure of more than 1 MPa, preferably 3 MPa or more, as described above. It can be impregnated into the preform of the porous ceramic sintered body obtained in the first step.
  • Another method is to form a preform as a precursor of a ceramic sintered body from a ceramic phase-forming material containing a majority of silicon carbide (SiC), and to sinter this preform and form a ceramic phase-forming material containing a majority of silicon carbide (SiC). Impregnation of the preform with a metal phase-forming material containing the alloy and/or intermetallic compound and the additive element M can also be carried out simultaneously.
  • the alloy and/or intermetallic compound consisting of Cu and Si is not particularly limited, but may be any known alloy and/or intermetallic compound. For example, Cu 3 Si, Cu 5 Si, Cu 6 Si, Cu 7 Si, etc. may be used as the alloy.
  • porous ceramics are formed in a metal phase-forming material containing an alloy and/or intermetallic compound of Cu and Si melted at a high temperature and an additive element M for a predetermined period of time (for example, 10 seconds to 200 seconds).
  • the sintered preform is held in an immersed state, and then the immersed preform is placed under pressure for a predetermined period of time (for example, 30 seconds to 300 seconds) to progress impregnation to the entire preform. be able to.
  • the preform Prior to immersing the preform of the porous ceramic sintered body in the metal phase forming material melted at a high temperature, the preform may also be heated in advance, separately from the heating and melting of the metal phase forming material.
  • Cooling can be quickly performed by introducing and circulating cooling gas into the high-pressure container in which melt impregnation has been performed. Alternatively, cooling can also be performed by contacting the preform after melt impregnation with a cooling metal.
  • Example 1 The metal-ceramic composite material of Example 1 was manufactured as follows. ⁇ First step> 70% by mass of commercially available SiC powder fine particles (manufactured by Saint-Gobain, average particle size 3 ⁇ m) and 30% by mass of coarse particles (manufactured by Shinano Electric Refining Co., Ltd., average particle size 20 ⁇ m) were mixed with 10% by mass (10% by mass) of phenolic resin as an organic binder. After mixing (3% by mass in terms of carbon) and press molding, heat treatment was performed at a temperature of 1000° C. for 3 hours in a nitrogen atmosphere to form a preform having a filling rate of 75% by volume in which the phenol resin was carbonized.
  • the mass ratio of the ceramic phase forming material used in the first step and the metal phase forming material used in the second step is set to 1:1, and among the metal phase forming materials, copper (Cu) and silicon ( The ratio of Si) was 7:3, and the mass ratio of the additional element Ni to the total mass of the metal phase forming material was 0.5% by mass.
  • a metal-ceramic composite material was produced by infiltrating the preform obtained in the first step with a Cu--Si--Ni alloy that was melted by holding it at a temperature of 1500° C. for 3 hours in an argon atmosphere.
  • the ceramic phase/metal phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 3.5, and the mass ratio b/a of Cu to Si in the metal phase (measurement method described later) is 4. It was .0.
  • the mass proportion of Si was 19.8 mass%
  • the mass proportion of Cu was 79.6 mass%
  • the mass proportion of additional element Ni was 0.5 mass% with respect to the total mass of the metal phase forming material (Measurement method described below).
  • Example 2 A metal-ceramic composite material was produced in the same manner as in Example 1, except that the mass ratio of the additional element Ni to the total mass of the metal phase forming material was changed to 5.0 mass%.
  • the ceramic phase/metallic phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 3.6, and the mass ratio b/a of Cu to Si in the metal phase (measurement method described later) is 4. It was .2.
  • the mass proportion of Si is 18.0 mass%
  • the mass proportion of Cu is 76.0 mass%
  • the mass proportion of the additional element Ni is 5.0 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material. % by mass (measurement method will be described later).
  • Example 3 A metal-ceramic composite material was produced in the same manner as in Example 1, except that the mass ratio of the additional element Ni to the total mass of the metal phase forming material was changed to 16.0 mass%.
  • the ceramic phase/metal phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 4.7, and the mass ratio b/a of Cu to Si in the metal phase (measurement method described later) is 5. It was .7.
  • the mass proportion of Si is 11.8 mass%
  • the mass proportion of Cu is 67.2 mass%
  • the mass proportion of the additive element Ni is 16.0 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material. % by mass (measurement method will be described later).
  • Example 4 Except that Mg powder (manufactured by Kojundo Kagaku Kenkyusho, particle size 180 ⁇ m or less) was used instead of Ni powder as the additive element, and the mass ratio of the additive element Mg to the total mass of the metal phase forming material was changed to 5.0% by mass. produced a metal-ceramic composite material in the same manner as in Example 1.
  • the ceramic phase/metallic phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 3.6, and the mass ratio b/a of Cu to Si in the metal phase (measurement method described later) is 4. It was .3.
  • the mass ratio of Si to the total mass of the metal phase of the obtained metal-ceramic composite material was 17.8% by mass
  • the mass ratio of Cu was 76.0% by mass
  • the mass ratio of the additive element Mg was 5.0%. % by mass (measurement method will be described later).
  • Example 5 Except that Zn powder (manufactured by Kojundo Kagaku Kenkyusho, particle size 75 ⁇ m or less) was used instead of Ni powder as the additive element, and the mass ratio of the additive element Zn to the total mass of the metal phase forming material was changed to 5.0% by mass. produced a metal-ceramic composite material in the same manner as in Example 1.
  • the ceramic phase/metallic phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 3.9, and the mass ratio b/a of Cu to Si in the metal phase (measurement method described later) is 4. It was .2.
  • the mass proportion of Si was 18.0 mass%
  • the mass proportion of Cu was 76.0 mass%
  • the mass proportion of the additive element Zn was 5.0 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material. % by mass (measurement method will be described later).
  • Example 6 Except that Ti powder (manufactured by Kojundo Kagaku Kenkyusho, particle size 45 ⁇ m or less) was used instead of Ni powder as the additive element, and the mass ratio of the additive element Ti to the total mass of the metal phase forming material was changed to 5.0% by mass. produced a metal-ceramic composite material in the same manner as in Example 1.
  • the ceramic phase/metallic phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 3.6, and the mass ratio b/a of Cu to Si in the metal phase (measurement method described later) is 4. It was .1.
  • the mass proportion of Si is 18.7 mass%
  • the mass proportion of Cu is 76.0 mass%
  • the mass proportion of the additive element Ti is 5.0 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material. % by mass (measurement method will be described later).
  • Example 7 A mixture of Ni/Ti powder (mass ratio 2:1) was used instead of Ni powder as the additive element, and the mass ratio of the Ni/Ti mixture to the total mass of the metal phase forming material was changed to 6.0% by mass.
  • a metal-ceramic composite material was produced in the same manner as in Example 1 except for this.
  • the ceramic phase/metal phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 3.7, and the mass ratio b/a of Cu to Si in the metal phase (measurement method described later) is 4. It was .8.
  • the mass ratio of Si was 15.8% by mass
  • the mass ratio of Cu was 75.2% by mass
  • the mass ratio of additional elements Ni/Ti was 6% by mass with respect to the total mass of the metal phase of the obtained metal-ceramic composite material. .0% by mass (measurement method will be described later).
  • Example 8 Except that the ratio of copper (Cu) to silicon (Si) in the metal phase forming material was changed to 6:4, and the mass ratio of the added element Ni to the total mass of the metal phase forming material was changed to 5.0% by mass.
  • a metal-ceramic composite material was produced in the same manner as in Example 1.
  • the ceramic phase/metal phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 3.5
  • the mass ratio b/a of Cu to Si in the metal phase is 2. It was .7.
  • the mass proportion of Si is 25.1 mass%
  • the mass proportion of Cu is 67.9 mass%
  • the mass proportion of the additive element Ni is 5.0 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material. % by mass (measurement method will be described later).
  • Example 9 Except that the ratio of copper (Cu) and silicon (Si) in the metal phase forming material was changed to 8:2, and the mass ratio of the added element Ni to the total mass of the metal phase forming material was changed to 5.0% by mass.
  • a metal-ceramic composite material was produced in the same manner as in Example 1.
  • the ceramic phase/metal phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 3.7, and the mass ratio b/a of Cu to Si (measurement method described later) in the metal phase is 13. It was .2.
  • the mass proportion of Si is 6.5 mass%
  • the mass proportion of Cu is 85.5 mass%
  • the mass proportion of additional element Ni is 5.0 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material. % by mass (measurement method will be described later).
  • Comparative example 1 The mass ratio of the ceramic phase forming material used in the first step and the metal phase forming material used in the second step and the mass ratio of the additional element Ni to the total mass of the metal phase forming material were changed to 23% by mass.
  • a metal-ceramic composite material was produced in the same manner as in Example 1 except for the following.
  • the ceramic phase/metal phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 15.0
  • the mass ratio b/a of Cu to Si in the metal phase is 5. It was .7.
  • the mass proportion of Si was 15 mass%
  • the mass proportion of Cu was 85 mass%
  • the mass proportion of the additive element Ni was 23 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material (Measurement method described below).
  • Comparative example 2 The same process as in Example 1 was carried out except that the mass ratio of the ceramic phase forming material used in the first step and the metal phase forming material used in the second step was changed and the additive element M was not added.
  • a ceramic composite material was manufactured.
  • the ceramic phase/metal phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material is 1.5
  • the mass ratio b/a of Cu to Si in the metal phase is 4. It was .0.
  • the mass proportion of Si was 20 mass% and the mass proportion of Cu was 80 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material (measurement method described later).
  • Comparative example 3 The same process as in Example 1 was carried out except that the mass ratio of the ceramic phase forming material used in the first step and the metal phase forming material used in the second step was changed and the additive element M was not added.
  • a ceramic composite material was manufactured.
  • the ceramic phase/metal phase area ratio A/B (measurement method described later) of the obtained metal-ceramic composite material was 63.3, and the mass ratio b/a of Cu to Si in the metal phase (measurement method described later) was 4. It was .0.
  • the mass proportion of Si was 20 mass% and the mass proportion of Cu was 80 mass% with respect to the total mass of the metal phase of the obtained metal-ceramic composite material (measurement method described later).
  • Comparative example 4 A silicon carbide (SiC) sintered body was manufactured from the ceramic phase forming material by the same procedure as in Example 1. The characteristics were measured and evaluated for comparison without impregnating this with the metal phase forming material.
  • Measurement of various properties of composite materials (1) Measurement and calculation of area ratio A/B of ceramic phase/metal phase Example 1 9 and Comparative Examples 1 to 3, images with an area of 256 ⁇ m ⁇ 192 ⁇ m were obtained at a magnification of 500. With respect to the area of the entire image, the percentage (%) of the total area of the ceramic phase (gray area) is defined as A, and the percentage (%) of the total area of the metal phase (white area) is defined as B. The area ratio A/B was calculated. In principle, the total area percentage of each of both phases was measured from an image of one field of view, and the area ratio was calculated.
  • An optional additional step is to acquire images in any two or more fields of view and calculate the average value of the area ratio A/B in those images, which is the same as that obtained from the images of said one field of view. It may be confirmed that the area ratio is substantially the same.
  • Table 1 shows the ceramic phase/metal phase area ratio A/B for each of the metal-ceramic composite materials of Examples 1 to 9 and Comparative Examples 1 to 3.
  • XRF X-ray fluorescence spectrometry
  • X-ray fluorescence spectrometry is used to identify the main components and impurity elements contained in the sample, such as ceramics, copper, silicon, and additive metals, by placing the sample after crushing in a cup holder dedicated to powder analysis.
  • fluorescent X-ray analyzer "Supermini 20" manufactured by Rigaku Co., Ltd. was used.
  • ICP emission spectrometry is a quantitative analysis of elements measured by XRF by adding hydrochloric acid to the crushed sample, decomposing the components at room temperature, and measuring the emission intensity of each element using an ICP emission spectrometer. was carried out.
  • the ICP emission spectrometer used was "Agilent 5110" manufactured by Agilent Technologies.
  • Free carbon and silicon carbide were measured using a carbon/sulfur analyzer (combustion-infrared absorption method). The measurements were conducted in accordance with JIS R 2011:2007 "Chemical analysis method for refractories containing carbon and silicon carbide.” Note that silicon carbide (SiC) was measured using an indirect method (total carbon and free carbon are measured, and the difference in carbon is converted to silicon carbide).
  • the carbon/sulfur analyzer used was ⁇ EMIA-810W'' manufactured by Horiba, Ltd., which utilizes combustion in an oxygen stream (tubular electric furnace method) and infrared absorption method.
  • the amount of metal in the metal phase-forming material prepared as a powder mixture before impregnation is greater than the amount of metal impregnated into the preform of the ceramic phase-forming material, and Since each metal type including the additive element M constituting the forming material may not be mixed completely uniformly, the mass percentage of the additive element M in the metal phase forming material and the actually produced metal-ceramic composite material may be different. It is considered theoretically possible that the mass percentage of the additive element M in the metal phase does not completely match. In each of Examples 1 to 9 and Comparative Example 1 above, the mass percentage of the additive element M in the metal phase forming material and the mass percentage of the additive element M in the metal phase of the metal-ceramic composite material actually manufactured are It was a match.
  • antibacterial effect R For each of the metal-ceramic composite materials of Examples 1 to 9 and Comparative Examples 1 to 4, yellow grape vine was used as a test bacterium in accordance with JIS Z2801:2012 and JIS R1752:2020. Using cocci, the antibacterial effect R was measured in the dark at an action temperature of 25°C and an action time of 6 hours.
  • the specific conditions for measuring the antibacterial effect R were as follows.
  • antiviral effect R The metal-ceramic composite materials of Examples 1 to 9 and Comparative Examples 1 to 4 were tested as test viruses in accordance with ISO18071:2016 and JIS R 1756:2020.
  • the antiviral effect R was measured using macrophage Q ⁇ at an action temperature of 25° C. and an action time of 6 hours in the dark.
  • the specific conditions for measuring the antiviral effect R were as follows.
  • the preferred metal-ceramic composite material according to the present invention provides a good impregnated state and has excellent mechanical properties such as strength and hardness, as well as excellent mechanical properties due to copper.
  • porosity density of the sintered body
  • bending strength and hardness e.g. Vickers hardness: indentation hardness
  • antibacterial and antiviral effects are exhibited. Everything was well balanced and at a high level.
  • Comparative Example 1 in which the additive element M is excessively contained in the metal phase
  • Comparative Example 2 in which the ceramic phase has a smaller area ratio than the predetermined area ratio with respect to the metal phase
  • Comparative Example 2 in which the ceramic phase has a larger area ratio than the predetermined area ratio with respect to the metal phase.
  • a ceramic phase containing silicon carbide, and A metal-ceramic composite material comprising an alloy consisting of Cu and Si and/or a metal phase containing an intermetallic compound in a mutually dispersed state
  • the metal phase contains an additive element M that is at least one metal other than Cu or Si
  • the silicon carbide accounts for the majority of the total mass of the constituent materials of the ceramic phase, here,
  • SEM scanning electron microscope
  • the metal-ceramic composite material according to item 1 above which satisfies the following. [3].
  • the area ratio A/B of the ceramic phase/metal phase is 5 or less, and m/a ⁇ 1, and b/a ⁇ 3.
  • the metal-ceramic composite material according to any one of items 1 to 4 above which has an antibacterial effect R of 2.0 or more as measured under conditions using Staphylococcus aureus as a test bacterium in accordance with JIS Z2801:2012. [6].
  • the metal-ceramic composite material according to any one of items 1 to 5 above which is used as an anti-pathogen material. [7].
  • the relative density [D1/D2]*100 of the bulk density D1 of the metal-ceramic composite material to the true density D2 of the metal phase of the metal-ceramic composite material is 90% or more.
  • the metal-ceramic composite material according to any one of items 1 to 9 above which has a Vickers hardness of 25 GPa or more as measured at a five-point average in a one-point load test according to JIS R1610:2003. [11].

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CN117923950A (zh) * 2023-12-28 2024-04-26 国投陶瓷基复合材料研究院(西安)有限公司 一种陶瓷基复合材料散热基板及制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49116109A (enrdf_load_stackoverflow) * 1973-03-12 1974-11-06
JPH10219368A (ja) * 1996-12-06 1998-08-18 Nippon Cement Co Ltd 金属−セラミックス複合材料の製造方法
JP2001261469A (ja) * 2000-03-23 2001-09-26 Ngk Insulators Ltd 焼結体及びその製造方法並びに複合材料及びその製造方法
JP2003165787A (ja) * 2001-09-19 2003-06-10 Ngk Insulators Ltd 複合材料
JP2004035307A (ja) * 2002-07-02 2004-02-05 Taiheiyo Cement Corp 金属−セラミックス複合材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49116109A (enrdf_load_stackoverflow) * 1973-03-12 1974-11-06
JPH10219368A (ja) * 1996-12-06 1998-08-18 Nippon Cement Co Ltd 金属−セラミックス複合材料の製造方法
JP2001261469A (ja) * 2000-03-23 2001-09-26 Ngk Insulators Ltd 焼結体及びその製造方法並びに複合材料及びその製造方法
JP2003165787A (ja) * 2001-09-19 2003-06-10 Ngk Insulators Ltd 複合材料
JP2004035307A (ja) * 2002-07-02 2004-02-05 Taiheiyo Cement Corp 金属−セラミックス複合材料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117923950A (zh) * 2023-12-28 2024-04-26 国投陶瓷基复合材料研究院(西安)有限公司 一种陶瓷基复合材料散热基板及制备方法和应用

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