Cermet composite

Abstract

The present disclosure aims to provide a new cermet composite material having an antibacterial effect, in which a ceramic phase containing silicon carbide and a metal phase containing Cu and Si are dispersed and mixed with each other. Disclosed is a cermet composite material containing a ceramic phase of silicon carbide and a metal phase of an alloy and / or intermetallic compound containing Cu and Si in a dispersed state, the metal phase containing at least one metal additive element M other than Cu or Si, the silicon carbide occupying more than half of the total mass of the constituent materials of the ceramic phase, the area ratio A / B of the ceramic phase / metal phase being 2 or more and 60 or less when an image of an area of 256 μm x 192 μm is obtained at a magnification of 500 times using a scanning electron microscope (SEM), and the following relationships being satisfied when the mass percentage (%) of Si in the metal phase is set as a and the mass percentage (%) of the additive element M is set as m: 0.01 ≤ m / a ≤ 1.4 and 0.3 ≤ m ≤ 20.

Description

Technical Field

[0001] This invention relates to a metal-ceramic composite material. More specifically, this invention relates to a metal-ceramic composite material in which a ceramic phase containing silicon carbide and a metallic phase containing Cu and Si are dispersed and mixed together, resulting in an antibacterial effect. Background Technology

[0002] Ceramic materials formed from silicon carbide (SiC) are lightweight and exhibit excellent wear resistance, high-temperature mechanical strength, and corrosion resistance. On the other hand, since silicon carbide is a brittle material with low toughness, combining it with copper (Cu) or copper alloys, which are highly thermally conductive, has advanced the development of composite materials with an excellent balance of toughness and thermal conductivity. Such composite materials containing silicon carbide and copper are known to be used in a wide range of applications, including heat-sealing materials, packaging materials, semiconductor substrates, and brake discs in electronic devices and semiconductor devices (see, for example, Patent Document 1).

[0003] For example, Patent Document 2 discloses a metal-ceramic composite material containing a Si-Cu alloy and SiC ceramic, wherein the Si:Cu content of the Si-Cu alloy is 60–30% by mass: 40–70% by mass. According to this document, it is reported that by having such a Si:Cu content, a composite material with improved toughness and suppressing the decrease in Young's modulus and the increase in density can be provided.

[0004] Furthermore, Patent Document 3 discloses a high thermal conductivity composite material in which Cu is melt-infiltrated into a porous SiC preform forming a framework structure, and an anti-reaction layer is formed between the two. According to this document, a composite material with high thermal conductivity and a low coefficient of thermal expansion, suitable for use as a heat-diffusing material in electronic devices and semiconductor devices, is reported.

[0005] However, from the perspective of promoting human and animal health and hygiene, and preventing infectious diseases, there has been ongoing effort to develop materials with improved antibacterial and antiviral properties for various building materials, including panel components, structural materials for buildings, bridges, ships, railways, roads, and ports, as well as flooring, wall materials, and ceilings. Furthermore, given the recent surge in the prevalence of severe colds and infectious diseases, this demand has increased significantly. For example, in livestock sheds for cattle, pigs, and birds, improving hygiene by preventing bacterial growth is crucial for preventing infectious diseases and ensuring a stable supply of products. For livestock shed flooring, attempts have been made to improve durability and antibacterial properties using concrete or cast-in-place grid flooring. However, these concrete or cast-in-place grid flooring materials do not provide sufficient antibacterial and antiviral properties.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2003-165787

[0009] Patent Document 2: Japanese Patent Application Publication No. 2004-035307

[0010] Patent Document 3: Japanese Patent Application Publication No. 2003-002770 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] To date, no silicon carbide and copper-containing composite materials have been reported to possess sufficient antibacterial properties. The inventors conducted research and found that due to the difficulty in impregnating copper or copper alloys, especially metal phases containing Cu and Si, into the silicon carbide ceramic phase, the impregnation is low. Therefore, it is difficult to achieve a balance between mechanical properties such as strength and hardness and antibacterial properties in such composite materials, and internal cracking may occur depending on the situation. Therefore, it is desirable to develop silicon carbide and copper-containing composite materials that possess good mechanical properties such as strength and hardness, and also exhibit excellent antibacterial properties.

[0013] Therefore, the first problem that this invention aims to solve is to provide a novel metal-ceramic composite material that is not found in the prior art, in which a silicon carbide ceramic phase and a Cu and Si metal phase are dispersed and mixed together, and which has an antibacterial effect.

[0014] In addition, another problem that this invention aims to solve is to provide a novel metal-ceramic composite material in which a silicon carbide ceramic phase and a Cu and Si metallic phase are dispersed and mixed together, exhibiting good mechanical properties such as strength and hardness and excellent antibacterial properties.

[0015] Methods for solving problems

[0016] The inventors conducted in-depth research and discovered that when impregnating silicon carbide ceramics with alloys and / or intermetallic compounds containing Cu and Si, by adjusting the alloys and / or intermetallic compounds to contain at least one metal additive element other than Cu or Si in a specified amount, and by making the ceramic phase and metal phase in the resulting metal-ceramic composite material have a specified area ratio, a metal-ceramic composite material with a significantly improved impregnation state and excellent antibacterial effect is formed, thus completing the present invention.

[0017] That is, the main solution of the present invention, which is a means of solving the above-mentioned problems, is as follows.

[0018] A metal-ceramic composite material comprising a ceramic phase and a metallic phase in a mutually dispersed state, wherein the ceramic phase contains silicon carbide, and the metallic phase contains an alloy and / or intermetallic compound comprising Cu and Si.

[0019] The aforementioned metallic phase contains at least one metallic additive element M other than Cu or Si, and

[0020] The aforementioned silicon carbide constitutes more than half of the total mass of the constituent materials of the aforementioned ceramic phase.

[0021] Here,

[0022] For the aforementioned metal-ceramic composite material, when obtaining an image with an area of ​​256 μm × 192 μm at 500x magnification using a scanning electron microscope (SEM), if, relative to the overall area of ​​the image, the percentage (%) of the total area of ​​the ceramic phase is set as A, and the percentage (%) of the total area of ​​the metal phase is set as B, and the area ratio of the ceramic phase to the metal phase (A / B) is 2 or more and 60 or less, and...

[0023] In the aforementioned metallic phase, when the mass percentage (%) of Si relative to its total mass is set as a and the mass percentage (%) of the added element M is set as m, the following relationship is satisfied:

[0024] 0.01≤m / a≤1.4, and

[0025] 0.3≤m≤20.

[0026] Invention Effects

[0027] According to the present invention, a novel metal-ceramic composite material, which is not found in the prior art, is provided, in which a ceramic phase containing silicon carbide and a metal phase containing Cu and Si are dispersed and mixed together, and which has antibacterial and antiviral effects.

[0028] According to a preferred embodiment of the metal-ceramic composite material of the present invention, the presence of a specified amount of additive element M in the metal phase containing Cu and Si results in a good infiltration state of the metal-ceramic composite material. Furthermore, due to this good infiltration state, while exhibiting excellent mechanical properties such as strength and hardness, it can also exhibit excellent antibacterial and antiviral properties brought by copper.

[0029] In another preferred embodiment of the metal-ceramic composite material according to the present invention, by adjusting the area ratio of the silicon carbide-containing ceramic phase to the metal phase containing Cu and Si, the mass ratio of the added element M in the metal phase relative to Si, and the mass ratio of Cu in the metal phase relative to Si to a specified range, the impregnation state of the metal-ceramic composite material is improved, and it is possible to achieve a good balance of improved mechanical properties, especially porosity (density of sintered body), flexural strength and hardness (e.g., Vickers hardness: indentation hardness), as well as excellent antibacterial and antiviral effects. Attached Figure Description

[0030] Figure 1 This is an example of an image of a metal-ceramic composite material obtained using a 500x scanning electron microscope (SEM) based on an embodiment of the present invention. Detailed Implementation

[0031] 1. Metal-ceramic composite materials

[0032] The metal-ceramic composite material of the present invention is formed by containing a ceramic phase and a metal phase in a mutually dispersed state. The ceramic phase contains silicon carbide (SiC), and the metal phase contains an alloy and / or intermetallic compound comprising Cu and Si. The metal phase contains at least one metal additive element M other than Cu or Si, and the silicon carbide accounts for more than half of the total mass of the constituent materials of the ceramic phase.

[0033] The amounts (mass%) of silicon carbide, free carbon, Cu and Si constituting the metallic phase, additive element M, and unavoidable impurities in metal-ceramic composites can be identified using XRF (fluorescence X-ray diffraction), ICP emission spectroscopy, and carbon analysis (combustion-infrared absorption spectrometry).

[0034] In this specification, the portion of the total analytical elements (each mass %) obtained in this way after removing silicon carbide and free carbon is regarded as a metallic phase containing unavoidable impurities, and the ratio of elements in the metallic phase is calculated.

[0035] In the metal-ceramic composite material, silicon carbide accounts for more than half of the total mass of the ceramic phase, i.e., more than 50% by mass, and there are no other limitations.

[0036] The ceramic phase of a metal-ceramic composite may contain less than 50% by mass of ceramic materials other than silicon carbide. Examples of such ceramic materials other than silicon carbide are not particularly limited, but include silicon nitride (Si3N4), aluminum nitride (AlN), boron nitride (BN), titanium nitride (TiN), zirconium nitride (ZrN), boron carbide (B4C), tantalum carbide (TaC), niobium carbide (NbC), titanium carbide (TiC), zirconium carbide (ZrC), chromium carbide (Cr3C2), molybdenum carbide (Mo2C), and tungsten carbide (WC).

[0037] The proportion of silicon carbide in the ceramic phase of the metal-ceramic composite material can more preferably be 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 or more, 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. In one embodiment, the ceramic phase may be formed solely of silicon carbide (excluding other ceramic materials) except for a small amount of free carbon. The higher the proportion of silicon carbide in the ceramic phase within the range exceeding 50% by mass, the more effectively the wear resistance, corrosion resistance, and strength characteristic of silicon carbide can be expressed in the metal-ceramic composite material.

[0038] The ceramic phase of a metal-ceramic composite may contain a small amount of free carbon. Free carbon refers to carbon atoms that exist independently in the ceramic phase or near the interface between the ceramic phase and the metal phase, without forming chemical bonds with silicon or other metal atoms. There is no particular limit to the content of free carbon in the ceramic phase; for example, it is typically less than 5% by mass relative to the total weight of the ceramic phase, and typically less than 3% by mass.

[0039] The proportion of Cu in the cermet composite material relative to the total mass of the metal phase is typically 60% by mass or more to 95% by mass or less, preferably 65% ​​by mass or more to 90% by mass or less. Furthermore, the proportion of Si in the cermet composite material relative to the total mass of the metal phase is typically 3% by mass or more to 35% by mass or less, preferably 5% by mass or more to 30% by mass or less.

[0040] The proportion of Cu and Si alloys and / or intermetallic compounds in the metal-ceramic composite material relative to the total mass of the metallic phase is typically greater than 70% by mass, preferably 71% by mass or more, 72% by mass or more, 73% by mass or more, 74% by mass or more, 75% by mass or more, 76% by mass or more, or 77% by mass or more. Alternatively, this proportion is typically 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, 94% by mass or less, 93% by mass or less, 92% by mass or less, 91% by mass or less, 90% by mass or less, 88% by mass or less, 86% by mass or less, or 84% by mass or less. By maintaining the proportion of Cu and Si alloys and / or intermetallic compounds in the metallic phase within the above ranges, the strength, thermal conductivity, antibacterial, and antiviral properties characteristic of copper in the metal-ceramic composite material can be more effectively expressed.

[0041] The proportion of Cu and Si alloys and / or intermetallic compounds in a metal-ceramic composite material relative to the total mass of the metallic phase is typically greater than 70% by mass and less than 99.7% by mass, preferably greater than 70% by mass and less than 99.5% by mass, greater than 70% by mass and less than 99% by mass, greater than 70% by mass and less than 98% by mass, greater than 70% by mass and less than 97% by mass, greater than 70% by mass and less than 96% by mass, greater than 70% by mass and less than 95% by mass, greater than 70% by mass and less than 94% by mass, greater than 70% by mass and less than 93% by mass, and less than 70% by mass. Quantity % or more to 92% or less; 70% or more to 91% or less; 70% or more to 90% or less; 70% or more to 88% or less; 70% or more to 86% or less; 70% or more to 84% or less; 71% or more to less than 99.7%; 71% or more to 99.5% or less; 71% or more to 99% or less; 71% or more to 98% or less; 71% or more to 97% or less; 71% or more to 96% or less; 71% or more to 95% or less. Below 71% of mass, 71% to 94% of mass, 71% to 93% of mass, 71% to 92% of mass, 71% to 91% of mass, 71% to 90% of mass, 71% to 88% of mass, 71% to 86% of mass, 71% to 84% of mass, 72% to less than 99.7% of mass, 72% to 99.5% of mass, 72% to 99% of mass, 72% to 98% of mass, 7 2% to 97% by mass, 72% to 96% by mass, 72% to 95% by mass, 72% to 94% by mass, 72% to 93% by mass, 72% to 92% by mass, 72% to 91% by mass, 72% to 90% by mass, 72% to 88% by mass, 72% to 86% by mass, 72% to 84% by mass, 73% to less than 99.7% by mass, 73% to 99.7% by mass.Below 5% by mass, 73% to 99% by mass, 73% to 98% by mass, 73% to 97% by mass, 73% to 96% by mass, 73% to 95% by mass, 73% to 94% by mass, 73% to 93% by mass, 73% to 92% by mass, 73% to 91% by mass, 73% to 90% by mass, 73% to 88% by mass, 73% to 86% by mass, 73% to 84% by mass, 74% to less than 99.7% by mass, and 74% to 99% by mass. Less than 5% by mass, 74% to 99% by mass, 74% to 98% by mass, 74% to 97% by mass, 74% to 96% by mass, 74% to 95% by mass, 74% to 94% by mass, 74% to 93% by mass, 74% to 92% by mass, 74% to 91% by mass, 74% to 90% by mass, 74% to 88% by mass, 74% to 86% by mass, 74% to 84% by mass, 75% to less than 99.7% by mass, and 75% to 99% by mass. Below 5% by mass, 75% to 99% by mass, 75% to 98% by mass, 75% to 97% by mass, 75% to 96% by mass, 75% to 95% by mass, 75% to 94% by mass, 75% to 93% by mass, 75% to 92% by mass, 75% to 91% by mass, 75% to 90% by mass, 75% to 88% by mass, 75% to 86% by mass, 75% to 84% by mass, 76% by mass to less than 99.7% by mass, and 76% by mass to 99% by mass. Below 5% by mass, 76% to 99% by mass, 76% to 98% by mass, 76% to 97% by mass, 76% to 96% by mass, 76% to 95% by mass, 76% to 94% by mass, 76% to 93% by mass, 76% to 92% by mass, 76% to 91% by mass, 76% to 90% by mass, 76% to 88% by mass, 76% to 86% by mass, 76% to 84% by mass, 77% to less than 99.7% by mass, and 77% to 99% by mass.Below 5% by mass, 77% to 99% by mass, 77% to 98% by mass, 77% to 97% by mass, 77% to 96% by mass, 77% to 95% by mass, 77% to 94% by mass, 77% to 93% by mass, 77% to 92% by mass, 77% to 91% by mass, 77% to 90% by mass, 77% to 88% by mass, 77% to 86% by mass, or 77% to 84% by mass.

[0042] In the metal phase of the cermet composite material, at least one metallic additive element M, other than Cu or Si, is not particularly limited to any other element. It may contain at least one element selected from the group consisting of Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y. Preferably, additive element M may contain at least one element selected from the group consisting of Ni, Mg, Zn, and Ti. More preferably, additive element M contains Ni.

[0043] The added element M can be a combination of two or more elements selected from Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y, as exemplified above. Preferably, the added element M can be a combination of two or more elements selected from Ni, Mg, Zn, and Ti. When the added element M contains a combination of two elements, for example, this combination can be Ni / Mg, Ni / Zn, Ni / Ti, Mg / Zn, Mg / Ti, or Zn / Ti. When the added element M contains a combination of three elements, for example, this combination can be Ni / Mg / Zn, Ni / Mg / Ti, or Mg / Zn / Ti.

[0044] In one embodiment, the added element M is at least one element selected from the group consisting of Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y, and does not contain any other elements. In a preferred embodiment, the added element M is at least one element selected from the group consisting of Ni, Mg, Zn, and Ti, and does not contain any other elements. In another embodiment, the added element M is a combination of two elements selected from Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y, and does not contain any other elements; or it is a combination of two elements Ni / Mg, Ni / Zn, Ni / Ti, Mg / Zn, Mg / Ti, or Zn / Ti, and does not contain any other elements. In another embodiment, the added element M is a combination of three elements selected from Ni, Pd, Mg, Ca, Zn, Ti, Zr, S, Mo, W, Fe, Mn, V, Nb, Ta, and Y, excluding other elements; or a combination of three elements selected from Ni / Mg / Zn, Ni / Mg / Ti, or Mg / Zn / Ti, excluding other elements.

[0045] When the added element M includes Ni, the mass percentage of Ni relative to the total mass of the added element M can be 5% to 100% (i.e., only Ni) or less, preferably 10% to 100%, 20% to 100%, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100%, 70% to 100%, 80% to 100%, or 90% to 100%.

[0046] The metallic phase of the metal-ceramic composite material contains Cu, Si, and at least one metallic additive element M other than Cu or Si, as well as impurities that are inevitably mixed in without active addition operations, namely, unavoidable impurities.

[0047] Unavoidable impurities may include any impurity known to be present in known metal-ceramic composites. There are no particular limitations on unavoidable impurities; examples include Mn, Sr, Sn, P, and Cr. The content of unavoidable impurities in the metallic phase is not particularly limited, but may be less than 5% by mass relative to the total mass of the metallic phase.

[0048] When a scanning electron microscope (SEM) is used to obtain an image with an area of ​​256 μm × 192 μm at 500 magnification for the metal-ceramic composite material of the present invention, and the percentage (%) of the total area of ​​the ceramic phase relative to the total area of ​​the image is set as A and the percentage (%) of the total area of ​​the metal phase is set as B, the area ratio of the ceramic phase to the metal phase A / B is 2 or more and 60 or less.

[0049] In addition, in the metal phase of the metal-ceramic composite material of the present invention, when the mass percentage (%) of Si is set as a and the mass percentage (%) of the added element M is set as m relative to its total mass, the following relationship holds.

[0050] 0.01≤m / a≤1.4, and

[0051] 0.3≤m≤20.

[0052] According to the present invention, the metal-ceramic composite material, by fully satisfying the area ratio A / B of the ceramic phase / metal phase within the aforementioned specific range and the aforementioned two relationships, facilitates the formation of a well-infiltrated state in which the silicon carbide-containing ceramic phase and the Cu and Si-containing metal phases are sufficiently dispersed and mixed. Because the metal phase exhibits a good infiltration state into the ceramic phase, the inherent properties of silicon carbide in the ceramic phase—namely, wear resistance, corrosion resistance, and strength—and the inherent properties of copper in the copper alloy contained in the metal phase—namely, strength, thermal conductivity, and antibacterial and antiviral properties—can be more effectively utilized. Therefore, in the present invention, by fully satisfying the area ratio A / B of the ceramic phase / metal phase within the aforementioned specific range and the aforementioned two relationships, preferably, the metal phase exhibits a good infiltration state into the ceramic phase, thereby obtaining a metal-ceramic composite material with improved mechanical properties, particularly porosity (density of the sintered body), flexural strength and hardness (e.g., Vickers hardness: indentation hardness), and a balance between antibacterial and antiviral effects.

[0053] The metal-ceramic composite material of the present invention comprises a ceramic phase and a metallic phase in a mutually dispersed state. The ceramic phase contains silicon carbide, and the metallic phase contains an alloy and / or intermetallic compound comprising Cu and Si, i.e., forming a state in which the ceramic phase and the metallic phase are mutually dispersed and mixed. Therefore, when obtaining an image of the metal-ceramic composite material with an area of ​​256 μm × 192 μm at 500x magnification using a scanning electron microscope (SEM), due to this dispersed and mixed state of the ceramic and metallic phases, the calculated reproducibility of the area ratio A / B (the percentage of the total area of ​​the ceramic phase A (%) / the percentage of the total area of ​​the metallic phase B (%)) in the image is generally high. Therefore, it is usually sufficient to use only one field of view to obtain the image. From the viewpoint of further improving the accuracy of the calculated reproducibility of A / B, images can also be obtained using any two or more fields of view, the average value of the area ratio A / B in these images can be calculated, and this average value can be regarded as the area ratio A / B for the material.

[0054] exist Figure 1 The image shows an example of a metal-ceramic composite material according to an embodiment of the present invention, obtained using a 500x scanning electron microscope (SEM). The embodiment in which Ni is added as an additive element M at a ratio of 5% by mass relative to the total mass of the metallic phase of the composite material is shown. In the image, the white areas represent the metallic phase containing copper alloy and the additive element Ni, while the gray areas represent the ceramic phase, primarily composed of SiC. The two phases are observed to be dispersed and mixed together.

[0055] When a scanning electron microscope (SEM) is used to obtain an image with an area of ​​256 μm × 192 μm at 500x magnification for the metal-ceramic composite material of the present invention, the area ratio A / B of the ceramic phase / metal phase relative to the overall area of ​​the image is 2 or more and 60 or less, preferably 2.5 or more and 50 or less, more preferably 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 and 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, 3.5 or more and 4.5 or less, or 3.7 or more and 4.5 or less.

[0056] By ensuring that the area ratio A / B of the ceramic phase / metal phase relative to the overall area of ​​the scanning electron microscope (SEM) image is within the aforementioned range, the metal phase is preferably well impregnated into the ceramic phase. This results in a metal-ceramic composite material in which the reduction of any of the following is effectively suppressed: porosity (density of the sintered body), flexural strength and hardness (e.g., Vickers hardness: indentation hardness), as well as antibacterial and antiviral effects, and a good balance of properties is obtained.

[0057] In the metallic phase of the metal-ceramic composite material of the present invention, when the mass percentage (%) of the added element M relative to its total mass is set as m, 0.3 ≤ m ≤ 20 holds true. In another embodiment, the range of m is not particularly limited, and can be selected from, for example, the ranges of 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.

[0058] Furthermore, in the metallic phase of the metal-ceramic composite material of the present invention, when the mass percentage (%) of Si relative to its total mass is set as a and the mass percentage (%) of the added element M is set as m, the relationship 0.01≤m / a≤1.4 holds true, preferably 0.05≤m / a≤1.2, more preferably 0.1≤m / a≤1, 0.15≤m / a≤1, 0.2≤m / a≤1, 0.25≤m / a≤1, 0.3≤m / a≤1, 0.35≤m / a≤1, 0.4≤m / a≤1, 0.45≤m / a≤1, 0.5≤m / a≤1, 0.1≤m / a<1, 0.15≤m / a<1, 0.2≤m / a<1, 0.25≤m / a<1, 0.3≤m / a<1, 0.35≤m / a <1, 0.4≤m / a<1, 0.45≤m / a<1, 0.5≤m / a<1, 0.1≤m / a≤0.9, 0.15≤m / a≤0.9, 0.2≤m / a≤0.9, 0.25≤m / a≤0.9, 0.3≤m / a≤0.9, 0.35≤m / a≤0.9, 0.4≤m / a≤0.9, 0.45≤m / a ≤0.9, 0.5≤m / a≤0.9, 0.1≤m / a≤0.8, 0.15≤m / a≤0.8, 0.2≤m / a≤0.8, 0.25≤m / a≤0.8, 0.3≤m / a≤0.8, 0.35≤m / a≤0.8, 0.4≤m / a≤0.8, 0.45≤m / a≤0.8, or 0.5≤m / a≤0.8.

[0059] By keeping the ratio m / a of the mass percentage of Si a (%) to the mass percentage of added element M m (%) within the above range, the metal phase is preferably well impregnated into the ceramic phase, thereby maintaining the porosity (density of the sintered body) at a suitable value, which results in a further improvement in the good balance of flexural strength and hardness (e.g., Vickers hardness: indentation hardness).

[0060] In another embodiment, in the metal-ceramic composite material of the present invention, when the area ratio A / B of the ceramic phase / metal phase relative to the overall area of ​​the scanning electron microscope (SEM) image is greater than 5 (and less than 60), the ratio of the mass percentage m (%) of added element M to the mass percentage a (%) of Si is preferably m / a < 1. Furthermore, when the area ratio A / B is greater than 5 (and less than 60), it is more preferable to have a ratio of 0.1 ≤ m / a < 1, 0.15 ≤ m / a < 1, 0.2 ≤ m / a < 1, 0.25 ≤ m / a < 1, 0.3 ≤ m / a < 1, 0.35 ≤ m / a < 1, 0.4 ≤ m / a < 1, 0.45 ≤ m / a < 1, 0.5 ≤ m / a < 1, 0.1 ≤ m / a ≤ 0.9, 0.15 ≤ m / a ≤ 0.9, 0.2 ≤ m / a ≤ 0.9, or 0.25 ≤ m / a ≤ 0.9. 0.3≤m / a≤0.9, 0.35≤m / a≤0.9, 0.4≤m / a≤0.9, 0.45≤m / a≤0.9, 0.5≤m / a≤0.9, 0.1≤m / a≤0.8, 0.15≤m / a≤0.8, 0.2≤m / a≤0.8, 0.25≤m / a≤0.8, 0.3≤m / a≤0.8, 0.35≤m / a≤0.8, 0.4≤m / a≤0.8, 0.45≤m / a≤0.8, or 0.5≤m / a≤0.8.

[0061] In metal-ceramic composites, when the area ratio A / B of the ceramic phase / metal phase is greater than 5 (and less than 60), that is, even when the proportion of the metal phase impregnated in the ceramic phase is relatively small, the impregnation of the two phases becomes easier by m / a < 1, or by satisfying the more preferred ratio described above, and the balance of properties such as porosity (density of the sintered body), flexural strength and hardness (e.g., Vickers hardness: indentation hardness) and antibacterial and antiviral effects can be adequately maintained.

[0062] In the metal phase of the metal-ceramic composite material of the present invention, it is preferable that the relationship b / a ≥ 2.5 holds true when the mass percentage (%) of Cu relative to its total mass is set as b and the mass percentage (%) of Si is set as a as described above. By ensuring that the mass ratio of Cu to Si in the metal phase satisfies this relationship, a metal-ceramic composite material in which the balance of porosity (density of the sintered body), flexural strength and hardness, as well as antibacterial and antiviral effects can be further improved.

[0063] From the perspective of balancing the above-mentioned properties, a more preferred relationship between the mass percentage (%) b of Cu and the mass percentage (%) a of Si in the metallic phase is b / a ≥ 3, further preferred is b / a ≥ 3.5, and even more preferred is b / a ≥ 4. In particular, from the perspective of improving porosity (density of the sintered body) and flexural strength, a more preferred relationship between the mass percentage (%) b of Cu and the mass percentage (%) a of Si in the metallic phase is b / a ≥ 4.5, and even more preferred is b / a ≥ 5.

[0064] There is no particular upper limit to the ratio b / a of the mass percentage of Cu (%)b to the mass percentage of Si (%)a in the metallic phase. However, from the viewpoint of fully obtaining the effect of improving hardness (e.g., Vickers hardness: indentation hardness), it is preferable that the relationship b / a≤20 holds, and more preferably b / a≤18, b / a≤16, or b / a≤14.

[0065] In another embodiment, the ratio b / a of the mass percentage (%) of Cu in the metal phase to the mass percentage (%) of Si in the metal phase can preferably be 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.

[0066] As described above, the metallic phase of the metal-ceramic composite material contains Cu, Si, and additive element M. In addition, it contains unavoidable impurities such as Mn, Sr, Sn, P, and Cr. Therefore, the sum of the mass percentages of Si (a%), Cu (b%), and M (m%) in the metallic phase is not 100% by mass. From the viewpoint of forming a well-dispersed and mixed state of the silicon carbide ceramic phase and the Cu and Si metallic phases in the metallic phase of the metal-ceramic composite material, and effectively utilizing the inherent properties of silicon carbide (wear resistance, corrosion resistance, and strength) and the inherent properties of copper (strength, thermal conductivity, and antibacterial and antiviral properties), a+b+m ≥ 95% by mass is preferred, more preferably a+b+m ≥ 96% by mass, and even more preferably a+b+m ≥ 97%, a+b+m ≥ 98%, or a+b+m ≥ 99% by mass.

[0067] From the viewpoint of further improving the infiltration state of the metal phase into the ceramic phase and further improving the balance of the resulting porosity (density of the sintered body), flexural strength and hardness (e.g., Vickers hardness: indentation hardness), as well as antibacterial and antiviral effects, it is more preferable that: in the metal-ceramic composite material of the present invention, the area ratio A / B of the ceramic phase / metal phase relative to the area of ​​the entire scanning electron microscope (SEM) image is 5 or less (and 2 or more), and the ratio of the mass percentage m (%) of element M added to the metal phase to the mass percentage a (%) of Si is m / a < 1 (and 0.01 or more), and the ratio of the mass percentage b (%) of Cu to the mass percentage a (%) of Si is b / a ≥ 3.

[0068] Further preferably, in the metal-ceramic composite material, 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 added element M to the mass percentage a (%) of Si is m / 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. Even more preferably, in the metal-ceramic composite material, 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 added element M to the mass percentage a (%) of Si is m / a ≤ 0.8, and the ratio of the mass percentage b (%) of Cu to the mass percentage a (%) of Si is b / a ≥ 4.

[0069] In a preferred embodiment, the metal-ceramic composite material of the present invention can be used as an antipathogenic material that exerts antibacterial and antiviral effects, that is, it can be used as an antibacterial and antiviral material.

[0070] Examples of bacteria that can be targeted include Staphylococcus aureus, Klebsiella pneumoniae, Pseudomonas aeruginosa, Escherichia coli, Moraxella osloensis, and methicillin-resistant Staphylococcus aureus.

[0071] In addition, viruses that could be targeted include bacteriophage Qβ, bacteriophage Φ6, influenza virus, coronavirus, and human immunodeficiency virus.

[0072] The antibacterial and antiviral effects can be specifically evaluated using the tests described later.

[0073] In a preferred embodiment, the antibacterial effect R obtained by measuring Staphylococcus aureus as the test bacteria in the metal-ceramic composite material of the present invention according to JIS Z2801:2012 and JIS R1752:2020 (which references thereto) can be 2.0 or higher. It should be noted that, as for the culture conditions of the test piece inoculated with the test bacterial solution in the determination of antibacterial effect, JIS Z2801:2012 specifies an action temperature of 35±1°C and an action time of 24±1 hours; however, in this case, the culture and determination are carried out in the dark at an action temperature of 25°C and an action time of 6 hours. Furthermore, JIS R1752:2020 specifies a light irradiation time of 8 hours for the test piece inoculated with the test bacterial solution; however, in this case, the culture and determination are carried out in the dark without light irradiation and with an action time of 6 hours.

[0074] The specific conditions for determining antibacterial effects can typically be set as follows.

[0075] Unprocessed product name: SLG glass

[0076] • Sample size: 50mm × 50mm × 5mm

[0077] ·N number: n=2

[0078] • Test bacteria: Staphylococcus aureus (NBRC12732)

[0079] • Aseptic treatment of test samples: Heating was performed using a dry sterilizer (80°C, 15 minutes).

[0080] • Conditions for application: Temperature: 25℃, Application time: 6 hours, Dark environment

[0081] • Bacterial count measurement using agar medium

[0082] The antibacterial effect R is more preferably 2.5 or higher, further preferably 3.0 or higher, even more preferably 3.5 or higher, still more preferably 3.9 or higher, even more preferably 4.2 or higher, and most preferably 4.5 or higher. There is no particular upper limit to the antibacterial effect R; in practice, approximately 5.5 to 6 can be considered the upper limit.

[0083] By making the antibacterial effect R of the metal-ceramic composite material of the present invention 2.0 or higher, or preferably within the above range, the composite material is more suitable for use as an antibacterial material in a wide range of applications.

[0084] In a preferred embodiment, the antiviral efficacy R obtained by measuring the metal-ceramic composite material of the present invention using bacteriophage Qβ or bacteriophage Φ6 as the test bacteriophage according to ISO 18071:2016 and JIS R 1756:2020 can be 2.5 or higher. It should be noted that, in the determination of antiviral efficacy, the culture conditions for the test specimens inoculated with the test solution, as specified in ISO 18071:2016 and JIS R 1756:2020, stipulate an exposure time of 4 hours under visible light irradiation. However, in this case, the culture and measurement are performed in the dark under conditions of 6 hours without light irradiation.

[0085] The specific conditions for measuring antiviral efficacy can typically be set as follows.

[0086] Unprocessed product name: SLG glass

[0087] • Sample size: 50mm × 50mm × 4mm

[0088] ·N number: n=2

[0089] • Test bacteriophage: Bacteriophage Qβ (NBRC20012) or Bacteriophage Φ6 (NBRC105899)

[0090] • Aseptic treatment of test samples: Heating was performed using a dry sterilizer (80°C, 15 minutes).

[0091] • Conditions for application: Temperature: 25℃, Application time: 6 hours, Dark environment

[0092] • Infection value measurement using agar medium

[0093] The antiviral efficacy R is more preferably 3.0 or higher, further preferably 3.5 or higher, even more preferably 4.0 or higher, still more preferably 4.5 or higher, even more preferably 4.6 or higher, and most preferably 4.7 or higher. There is no particular upper limit to the antiviral efficacy R; in practice, approximately 6.5 to 7 can be considered the upper limit.

[0094] By making the antiviral effect R of the metal-ceramic composite material of the present invention 2.5 or more, or preferably within the above range, the composite material can be more suitable as an antiviral material for a wide range of applications.

[0095] In another embodiment, the aforementioned temperature and duration of the culture conditions used to determine the antibacterial and antiviral effects can be varied depending on the bacteria or virus used. The temperature can be appropriately selected within the range of 10°C to 40°C. For example, in the case of testing with *E. coli*, the temperature can be set to 37°C, where its growth and reproduction are most active. Furthermore, the culture time can be appropriately set within the range of 2 hours to 72 hours or longer, depending on the growth and reproduction rate of the bacteria or virus used. For example, in the case of a virus with a slow growth and reproduction rate, the culture time can be set to 96 hours.

[0096] A significant advantage is that the metal-ceramic composite material of the preferred embodiment of the present invention can be used as an antipathogenic material that exerts sufficient antibacterial and antiviral effects even in the dark. That is, the metal-ceramic composite material according to the preferred embodiment can provide an antipathogenic material that exerts antibacterial and antiviral effects regardless of the illuminance.

[0097] In a preferred embodiment, the porosity of the metal-ceramic composite material of the present invention, as determined by Archimedes' method according to JIS R1634:1998, can be 10% or less. More preferably, this porosity is 9% or less, even more preferably 8% or less, even more preferably 7% or less, still more preferably 6% or less, even more preferably 5% or less, and most preferably 4% or less. The lower limit of this porosity (as long as it is 0% or more) is not particularly limited; in practice, about 2-3% can be considered the lower limit.

[0098] By making the porosity of the metal-ceramic composite material of the present invention less than 10%, or preferably within the above range, it is easy to obtain a composite material with further improved compactness of the sintered body and higher hardness.

[0099] In a preferred embodiment, when the metal-ceramic composite material of the present invention is measured according to JIS R1634:1998 using the Archimedes method, the relative density [D1 / D2]×100 of the bulk density D1 of the metal-ceramic composite material relative to the true density D2 of the metallic phase of the metal-ceramic composite material can be 90% or more. More preferably, this relative density is 91% or more, further preferably 92% or more, even more preferably 93% or more, still more preferably 94% or more, and most preferably 95% or more.

[0100] By making the relative density of the metal-ceramic composite material of the present invention 90% or more, or preferably within the above range, it is as easy as in the case where the porosity is below the specified upper limit to obtain a composite material with further improved compactness of the sintered body and higher hardness.

[0101] In a preferred embodiment, the flexural strength of the metal-ceramic composite material of the present invention, as determined by a three-point flexural strength test according to JIS R1601:2008, can be 230 MPa or higher. More preferably, this flexural strength is 250 MPa or higher, even more preferably 270 MPa or higher, even more preferably 280 MPa or higher, still even more preferably 290 MPa or higher, and most preferably 300 MPa or higher.

[0102] By making the flexural strength of the metal-ceramic composite material of the present invention 230 MPa or more, or preferably within the above range, the mechanical strength for bending operations is further improved, making it more suitable for a wide range of applications requiring high bending resistance.

[0103] In a preferred embodiment, the Vickers hardness of the metal-ceramic composite material of the present invention, measured by averaging five points using a one-point load test according to JIS R1610:2003, can be 25 GPa or higher. More preferably, this Vickers hardness is 26 GPa or higher, even more preferably 26.5 GPa or higher, even more preferably 27 GPa or higher, still more preferably 27.5 GPa or higher, and most preferably 28 GPa or higher.

[0104] By making the Vickers hardness of the metal-ceramic composite material of the present invention 25 GPa or higher, or preferably within the above range, the robustness of the compression operation is further improved, making it more suitable for a wide range of applications requiring high rigidity.

[0105] The metal-ceramic composite material of the present invention can be processed into various shapes for use. Its shape is not particularly limited and can be a film, sheet, thin plate, thick plate, approximately prism, approximately cylinder, etc.

[0106] Furthermore, the metal-ceramic composite material of the present invention can be applied to a wide range of applications requiring antibacterial and antiviral properties. For example, this composite material is suitable for use as components of various articles, structural materials for buildings, bridges, ships, railways, roads, ports, etc., flooring materials for buildings including livestock sheds, wall materials, ceilings, and other building materials.

[0107] 2. Manufacturing methods for metal-ceramic composite materials

[0108] The method for manufacturing the metal-ceramic composite material of the present invention is not particularly limited as long as it results in a metal-ceramic composite material having the above-described structure and properties. The metal-ceramic composite material of the present invention can be manufactured, for example, as described below.

[0109] For example, as a first step, a preform of a porous ceramic sintered body is formed from a ceramic phase forming material containing more than half silicon carbide (SiC). As a subsequent second step, a metal-ceramic composite material of the present invention can be manufactured by impregnating the preform with a metal phase forming material under pressure. The metal phase forming material contains an alloy and / or intermetallic compound containing Cu and Si molten at high temperature, as well as an additive element M. The types of other substances besides silicon carbide that may be included in the ceramic phase forming material, the additive element M contained in the metal phase forming material, and the types of unavoidable impurities are as described above for the metal-ceramic composite material.

[0110] By appropriately adjusting the mass ratio of the ceramic phase forming material used in the first step to the metal phase forming material used in the second step, the mass ratio of Cu and Si in the alloy and / or intermetallic compound, the mass ratio of the Cu and / or intermetallic compound containing Cu and Si in the metal phase forming material, and the mass ratio of the added element M, the metal-ceramic composite material of the present invention can be obtained that satisfies the specified range of the ceramic phase / metal phase area ratio A / B, the specified range of the mass percentage m (%) of the added element M, the specified range of the mass percentage m (%) of the added element M / the mass percentage a (%) of Si, and preferably the specified range of the mass percentage b (%) of Cu / the mass percentage a (%) of Si.

[0111] In the first step described above, the silicon carbide contained as the main component in the ceramic phase forming material can be commercially available high-purity silicon carbide raw material powder. Preforms of porous ceramic sintered bodies can be manufactured, for example, by a so-called recrystallization method. This recrystallization method refers to molding a ceramic phase forming material containing more than half silicon carbide using a molding method such as die forming, and then holding it at a high temperature typically above 2000°C, preferably above 2200°C.

[0112] Alternatively, a mixture containing high-purity silicon (Si) particles and carbon (C) particles can be heated at a temperature above 1400°C to induce reaction sintering, thereby obtaining a preform of a porous ceramic sintered body containing silicon carbide. In the case of reaction sintering, from the viewpoint of formability and high density of the preform, it is preferable to use a binder (a substance carbonized by sintering) such as phenolic resin or asphalt simultaneously with high-purity carbon powder. Carbon fiber 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, and can be, for example, from 10% to 70%.

[0113] In the second step described above, the metal phase forming material containing Cu and Si alloys and / or intermetallic compounds and added element M can be pre-melted at a high temperature typically exceeding 1000°C, preferably exceeding 1200°C. This metal phase forming material, molten at such a high temperature, containing Cu and Si alloys and / or intermetallic compounds and added element M, can be impregnated into the preform of the porous ceramic sintered body obtained in the first step under a pressure typically exceeding 1 MPa, preferably exceeding 3 MPa, in a high-pressure vessel.

[0114] Alternatively, a preform can be formed from a ceramic phase-forming material containing more than half silicon carbide (SiC) as a precursor for a ceramic sintering body. Simultaneously, the preform is fired and infiltrated with a metallic phase-forming material containing molten Cu and Si alloys and / or intermetallic compounds and added element M.

[0115] There are no particular limitations on the alloys and / or intermetallic compounds containing Cu and Si; any known alloy and / or intermetallic compound may be used. For example, Cu3Si, Cu5Si, Cu6Si, Cu7Si, etc., may be used as alloys.

[0116] As an unrestricted specific example, the preform of the porous ceramic sintered body is held in a state where it is immersed in a metal phase forming material containing an alloy and / or intermetallic compound of Cu and Si molten at high temperature and an added element M for a specified time period (e.g., 10 seconds to 200 seconds). Then, the immersed preform is placed under pressure for a specified time period (e.g., 30 seconds to 300 seconds), thereby achieving infiltration throughout the preform. Before immersing the preform of the porous ceramic sintered body in the molten metal phase forming material, the preform may be preheated by heating and melting the metal phase forming material.

[0117] Preferably, in the second step described above, after the molten metal phase forming material is impregnated into the preform of the porous ceramic sintered body at high temperature, it is immediately cooled. Cooling can be carried out rapidly by introducing cooling gas into the high-pressure vessel where the molten impregnation is performed and circulating it. Alternatively, cooling can be achieved by bringing the molten-impregnated preform into contact with cooling metal.

[0118] The present invention has been described with reference to numerous embodiments regarding metal-ceramic composite materials and their manufacturing methods. However, it should be understood that the various components of these embodiments can be arbitrarily combined within the scope of the present invention. That is, it should be noted that the present invention is not limited to these embodiments, and the scope of the present invention is defined only by the appended claims.

[0119] Example

[0120] The present invention will be further illustrated below with reference to embodiments. The present invention is not limited to these embodiments in any way.

[0121] Example 1

[0122] The metal-ceramic composite material of Example 1 was manufactured in the following manner.

[0123] <Step 1>

[0124] 70% by mass of commercially available SiC powder microparticles (manufactured by Saint-Gobain, average particle size 3 μm) and 30% by mass of coarse particles (manufactured by Shinano Electric Refining Co., Ltd., average particle size 20 μm) were mixed with 10% by mass of phenolic resin (3% by mass of carbon) as an organic binder. After preforming, the mixture was heated at 1000°C for 3 hours in a nitrogen atmosphere to form a preform with a 75% by volume filling rate after carbonizing the phenolic resin.

[0125] <Step 2>

[0126] Commercially available copper powder (manufactured by the High Purity Chemical Research Institute, average particle size 3 μm), silicon powder (manufactured by the High Purity Chemical Research Institute, average particle size 100 μm), and nickel powder (manufactured by the High Purity Chemical Research Institute, average particle size 3 μm) were mixed in a crucible. The mass ratio of the ceramic phase-forming material used in step 1 to the metal phase-forming material used in step 2 was set to 1:1, the ratio of copper (Cu) to silicon (Si) in the metal phase-forming material was set to 7:3, and the mass ratio of the added element Ni relative to the total mass of the metal phase-forming material was set to 0.5% by mass. The mixture was held at 1500°C for 3 hours under an argon atmosphere to allow the molten Cu-Si-Ni alloy to permeate into the preform obtained in step 1, thus producing a metal-ceramic composite material.

[0127] The obtained metal-ceramic composite material has a ceramic phase / metal phase area ratio A / B (measured by a method described below) of 3.5, and a Cu / Si mass ratio b / a (measured by a method described below) of 4.0. Furthermore, relative to the total mass of the metal phase forming material, the mass percentages of Si are 19.8%, Cu is 79.6%, and Ni is 0.5% (measured by a method described below).

[0128] Example 2

[0129] Except that the mass ratio of the added element Ni relative to the total mass of the metal phase forming material was changed to 5.0% by mass, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The area ratio A / B of the ceramic phase / metal phase of the resulting metal-ceramic composite material (measured by a method described later) was 3.6, and the mass ratio b / a of Cu to Si in the metal phase (measured by a method described later) was 4.2. In addition, relative to the total mass of the metal phase of the resulting metal-ceramic composite material, the mass proportion of Si was 18.0% by mass, the mass proportion of Cu was 76.0% by mass, and the mass proportion of the added element Ni was 5.0% by mass (measured by a method described later).

[0130] Example 3

[0131] Except that the mass ratio of the added element Ni relative to the total mass of the metal phase forming material was changed to 16.0% by mass, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The resulting metal-ceramic composite material had a ceramic phase / metal phase area ratio A / B (measured by a method described later) of 4.7, and a Cu / Si mass ratio b / a (measured by a method described later) of 5.7 in the metal phase. In addition, relative to the total mass of the metal phase in the resulting metal-ceramic composite material, the mass proportion of Si was 11.8% by mass, the mass proportion of Cu was 67.2% by mass, and the mass proportion of the added element Ni was 16.0% by mass (measured by a method described later).

[0132] Example 4

[0133] As an additive element, Mg powder (prepared by the High Purity Chemical Research Institute, with a particle size of 180 μm or less) was used instead of Ni powder. The mass ratio of the additive element Mg relative to the total mass of the metal phase forming material was changed to 5.0% by mass. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The area ratio A / B of the ceramic phase / metal phase of the obtained metal-ceramic composite material (measured by the method described below) was 3.6, and the mass ratio b / a of Cu to Si in the metal phase (measured by the method described below) was 4.3. In addition, relative to the total mass of the metal phase of the obtained metal-ceramic composite material, the mass proportion of Si was 17.8% by mass, the mass proportion of Cu was 76.0% by mass, and the mass proportion of the additive element Mg was 5.0% by mass (measured by the method described below).

[0134] Example 5

[0135] As an additive element, Zn powder (prepared by the High Purity Chemical Research Institute, with a particle size of 75 μm or less) was used instead of Ni powder. The mass ratio of the additive element Zn relative to the total mass of the metal phase forming material was changed to 5.0% by mass. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The area ratio A / B of the ceramic phase / metal phase of the obtained metal-ceramic composite material (measured by the method described below) was 3.9, and the mass ratio b / a of Cu to Si in the metal phase (measured by the method described below) was 4.2. In addition, relative to the total mass of the metal phase of the obtained metal-ceramic composite material, the mass proportion of Si was 18.0% by mass, the mass proportion of Cu was 76.0% by mass, and the mass proportion of the additive element Zn was 5.0% by mass (measured by the method described below).

[0136] Example 6

[0137] As an additive element, Ti powder (prepared by the High Purity Chemical Research Institute, with a particle size of 45 μm or less) was used instead of Ni powder. The mass ratio of the additive element Ti relative to the total mass of the metal phase forming material was changed to 5.0% by mass. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The area ratio A / B of the ceramic phase / metal phase of the obtained metal-ceramic composite material (measured by the method described below) was 3.6, and the mass ratio b / a of Cu to Si in the metal phase (measured by the method described below) was 4.1. In addition, relative to the total mass of the metal phase of the obtained metal-ceramic composite material, the mass proportion of Si was 18.7% by mass, the mass proportion of Cu was 76.0% by mass, and the mass proportion of the additive element Ti was 5.0% by mass (measured by the method described below).

[0138] Example 7

[0139] As an additive element, a mixture of Ni / Ti powder (mass ratio 2:1) was used instead of Ni powder. The mass ratio of the Ni / Ti mixture relative to the total mass of the metal phase forming material was changed to 6.0% by mass. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The resulting metal-ceramic composite material had a ceramic phase / metal phase area ratio A / B (measured by a method described later) of 3.7, and a Cu / Si mass ratio b / a (measured by a method described later) of 4.8 in the metal phase. Furthermore, relative to the total mass of the metal phase in the resulting metal-ceramic composite material, the mass proportion of Si was 15.8% by mass, the mass proportion of Cu was 75.2% by mass, and the mass proportion of the additive element Ni / Ti was 6.0% by mass (measured by a method described later).

[0140] Example 8

[0141] The ratio of copper (Cu) to silicon (Si) in the metal phase forming material was set to 6:4, and the mass ratio of the added element Ni relative to the total mass of the metal phase forming material was changed to 5.0% by mass. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The resulting metal-ceramic composite material had a ceramic phase / metal phase area ratio A / B (measured by a method described later) of 3.5, and a Cu / Si mass ratio b / a (measured by a method described later) of 2.7. Furthermore, relative to the total mass of the metal phase in the resulting metal-ceramic composite material, the mass percentage of Si was 25.1% by mass, the mass percentage of Cu was 67.9% by mass, and the mass percentage of the added element Ni was 5.0% by mass (measured by a method described later).

[0142] Example 9

[0143] The ratio of copper (Cu) to silicon (Si) in the metal phase forming material was set to 8:2, and the mass ratio of the added element Ni relative to the total mass of the metal phase forming material was changed to 5.0% by mass. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The resulting metal-ceramic composite material had a ceramic phase / metal phase area ratio A / B (measured as described later) of 3.7, and a Cu / Si mass ratio b / a (measured as described later) of 13.2. Furthermore, relative to the total mass of the metal phase in the resulting metal-ceramic composite material, the mass percentage of Si was 6.5% by mass, the mass percentage of Cu was 85.5% by mass, and the mass percentage of the added element Ni was 5.0% by mass (measured as described later).

[0144] Comparative Example 1

[0145] The mass ratio of the ceramic phase forming material used in the first step to the metal phase forming material used in the second step was changed, and the mass ratio of the added element Ni relative to the total mass of the metal phase forming material was changed to 23% by mass. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The resulting metal-ceramic composite material had a ceramic phase / metal phase area ratio A / B (measured by a method described later) of 15.0, and a Cu / Si mass ratio b / a (measured by a method described later) of 5.7 in the metal phase. Furthermore, relative to the total mass of the metal phase in the resulting metal-ceramic composite material, the mass percentage of Si was 15% by mass, the mass percentage of Cu was 85% by mass, and the mass percentage of the added element Ni was 23% by mass (measured by a method described later).

[0146] Comparative Example 2

[0147] The mass ratio of the ceramic phase forming material used in the first step to the metal phase forming material used in the second step was changed, and no additive element M was added. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The resulting metal-ceramic composite material had a ceramic phase / metal phase area ratio A / B (measured by a method described later) of 1.5, and a Cu / Si mass ratio b / a (measured by a method described later) of 4.0. Furthermore, relative to the total mass of the metal phase in the resulting metal-ceramic composite material, the mass percentage of Si was 20% by mass, and the mass percentage of Cu was 80% by mass (measured by a method described later).

[0148] Comparative Example 3

[0149] The mass ratio of the ceramic phase forming material used in the first step to the metal phase forming material used in the second step was changed, and no additive element M was added. Otherwise, the metal-ceramic composite material was manufactured in the same manner as in Example 1. The resulting metal-ceramic composite material had a ceramic phase / metal phase area ratio A / B (measured by a method described later) of 63.3, and a Cu / Si mass ratio b / a (measured by a method described later) of 4.0. Furthermore, relative to the total mass of the metal phase in the resulting metal-ceramic composite material, the mass percentage of Si was 20% by mass, and the mass percentage of Cu was 80% by mass (measured by a method described later).

[0150] Comparative Example 4

[0151] Using the same steps as in Example 1, a silicon carbide (SiC) sintered body was manufactured from a ceramic phase forming material. For comparison purposes, its properties were measured and evaluated without impregnating it with a metal phase forming material.

[0152] Determination of various properties of composite materials

[0153] (1) Determination and calculation of the area ratio A / B of ceramic phase / metal phase

[0154] Using a scanning electron microscope (SEM) (JSM-IT200, manufactured by Nippon Electron Ltd.), images of the various metal-ceramic composite materials of Examples 1-9 and Comparative Examples 1-3 were obtained at 500x magnification, with an area of ​​256 μm × 192 μm. The percentage of the total area of ​​the ceramic phase (gray areas) relative to the overall area of ​​the image was set as A, and the percentage of the total area of ​​the metallic phase (white areas) was set as B. The area ratio A / B of the ceramic phase / metallic phase was calculated. In principle, the area ratio is calculated by measuring the percentage of the total area of ​​each phase from an image of a single field of view. As an optional additional step, images can be obtained from any two or more fields of view, and the average of the area ratios A / B in these images can be calculated. It is confirmed that this average is substantially the same as the area ratio obtained from an image of a single field of view. When an average is calculated in this way, if a difference of 0.1 or more exists between the former area ratio (one field of view) and the latter area ratio (average of multiple fields of view), the latter value is used as the area ratio.

[0155] The area ratio A / B of the ceramic phase / metal phase of each metal-ceramic composite material of Examples 1-9 and Comparative Examples 1-3 is shown in Table 1.

[0156] (2) Identification and determination of the composition of the metallic phase

[0157] The amounts (mass%) of silicon carbide, free carbon, Cu and Si constituting the metallic phase, additive element M, and unavoidable impurities in the various metal-ceramic composite materials of Examples 1-9 and Comparative Examples 1-3 were identified using XRF (X-ray fluorescence spectrometry), ICP emission spectroscopy, and a carbon / sulfur analysis apparatus (combustion-infrared absorption spectrometry). For the above three measurements, the metal-ceramic composite material samples were pulverized into powder before analysis.

[0158] XRF (X-ray fluorescence) analysis involves placing a pulverized sample in a special powder analysis cup to identify the main components and impurities, such as ceramics, copper, silicon, and added metals. The XRF analysis apparatus used is the "Supermini20" manufactured by Rigaku Corporation.

[0159] ICP emission spectroscopy involves adding hydrochloric acid to a pulverized sample, decomposing the components at room temperature, and then measuring the emission intensity of each element using an ICP emission spectrometer. This allows for quantitative analysis of elements previously analyzed using XRF. The ICP emission spectrometer used is the Agilent 5110 manufactured by Agilent Technologies, Inc.

[0160] Free carbon and silicon carbide (SiC) were determined using a carbon / sulfur analysis apparatus (combustion-infrared absorption method). The determination was performed according to JIS R 2011:2007, "Chemical analysis method for refractories containing carbon and silicon carbide." It should be noted that for silicon carbide (SiC), an indirect method (determining total carbon and free carbon, and converting the difference in carbon to silicon carbide) was used. The carbon / sulfur analysis apparatus used was the "EMIA-810W" manufactured by Horiba Manufacturing Co., Ltd., which utilizes combustion in an oxygen stream (tubular electric furnace method) - infrared absorption method.

[0161] In addition, based on these identification and measurement results, the ratio m / a of the mass percentage m (%) of the added element M in the metal phase of the metal ceramic composite material to the mass percentage a (%) of Si, and the ratio b / a of the mass percentage b (%) of Cu to the mass percentage a (%) of Si were calculated.

[0162] Table 1 shows the mass percentages of Si (a%), Cu (b%), added element M (m%), the ratio of added element M (m%) to Si (a%), and the ratio of Cu (b%) to Si (a%) in the metal phase of each metal-ceramic composite material of Examples 1-9 and Comparative Examples 1-3, along with the type of added element M.

[0163] It should be noted that in the manufacturing of metal-ceramic composites, the amount of metal in the metal phase forming material prepared as a powder mixture before impregnation is greater than the amount of metal in the preform impregnated with the ceramic phase forming material. Furthermore, there may be cases where the various metals, including the additive element M constituting the metal phase forming material, are not completely and uniformly mixed during impregnation. Therefore, it is theoretically possible that the mass percentage of the additive element M in the metal phase forming material may not be completely consistent with the mass percentage of the additive element M in the metal phase of the metal-ceramic composite material actually manufactured.

[0164] In each of the above Examples 1 to 9 and Comparative Example 1, the mass percentage of the added element M in the metal phase forming material is consistent with the mass percentage of the added element M in the metal phase of the metal ceramic composite material actually manufactured.

[0165] (3) Evaluation of infiltration status

[0166] The impregnation state of the various metal-ceramic composite materials of Examples 1-9 and Comparative Examples 1-3 was observed by examining their appearance after impregnation treatment. The evaluation criteria for the impregnation state are shown below. The evaluation results are presented in Table 2.

[0167] 〇 (Good): Overall permeation.

[0168] △ (Moderate): No localized infiltration.

[0169] × (Poor): Not impregnated.

[0170] (4) Whether there are internal cracks in the composite material

[0171] The presence or absence of internal cracks was confirmed in scanning electron microscope (SEM) images at magnifications of 250 and 500 for each of the metal-ceramic composite materials of Examples 1-9 and Comparative Examples 1-3, obtained in the same manner as described in (1) above. When no internal cracks were confirmed in the 250 magnification image, confirmation was also made in the 500 magnification image. The evaluation criteria are shown below. The evaluation results are shown in Table 2.

[0172] 〇 (Good): No internal cracks were observed even in images magnified to 500x.

[0173] × (Defective): Internal cracks appear in images at magnification of 250x or 500x.

[0174] (5) Determination of antibacterial activity (antibacterial effect R)

[0175] For each of the metal-ceramic composite materials in Examples 1-9 and Comparative Examples 1-4, the antibacterial effect R was determined using Staphylococcus aureus as the test bacterium in the dark at an operating temperature of 25°C for 6 hours, according to JIS Z2801:2012 and JIS R1752:2020. The specific conditions for determining the antibacterial effect R are as follows.

[0176] Unprocessed product name: SLG glass

[0177] • Sample size: 50mm × 50mm × 5mm

[0178] ·N number: n=2

[0179] • Test bacteria: Staphylococcus aureus (NBRC12732)

[0180] • Aseptic treatment of test samples: Heating was performed using a dry sterilizer (80°C, 15 minutes).

[0181] • Conditions for application: Temperature: 25℃, Application time: 6 hours, Dark environment

[0182] • Bacterial count measurement using agar medium

[0183] The results of the determination of antibacterial effect R are shown in Table 2.

[0184] (6) Determination of antiviral activity (antiviral effect R)

[0185] For each of the metal-ceramic composite materials in Examples 1-9 and Comparative Examples 1-4, the antiviral efficacy R was determined using bacteriophage Qβ as the test virus in the dark at an incubation temperature of 25°C for 6 hours, according to ISO 18071:2016 and JIS R 1756:2020. The specific conditions for determining the antiviral efficacy R are as follows.

[0186] Unprocessed product name: SLG glass

[0187] • Sample size: 50mm × 50mm × 4mm

[0188] ·N number: n=2

[0189] • Experimental bacteriophage: Bacteriophage Qβ (NBRC20012)

[0190] • Aseptic treatment of test samples: Heating was performed using a dry sterilizer (80°C, 15 minutes).

[0191] • Conditions for application: Temperature: 25℃, Application time: 6 hours, Dark environment

[0192] • Infection value measurement using agar medium

[0193] The results of the determination of the antiviral effect R are shown in Table 2.

[0194] (7) Determination of porosity

[0195] For each of the metal-ceramic composite materials in Examples 1-9 and Comparative Examples 1-4, the porosity was determined using the Archimedes method according to JIS R1634:1998. The results are shown in Table 2.

[0196] (8) Determination of true density and relative density

[0197] For each of the metal-ceramic composite materials in Examples 1-9 and Comparative Examples 1-4, the relative density [D1 / D2]×100 of the bulk density D1 of the composite material relative to the true density D2 of the metal phase (the theoretical density of the metal phase calculated based on the ratio of SiC to the metal phase) was determined using the Archimedes method according to JIS R1634:1998. The measurement results are shown in Table 2.

[0198] (9) Determination of bending strength

[0199] For each metal-ceramic composite material of Examples 1-9 and Comparative Examples 1-4, according to JIS R1601:2008, the distance between external supports was 30±0.1mm, the test fixture was 3p-30, the support type was rotary, the test piece was standard test piece I, and standard test piece I < total length (L) T The bending strength was determined using a three-point bending strength test under the conditions of a thickness greater than 36 mm but less than 45 mm, a width (w) of 4.0 ± 0.1 mm, and a thickness (t) of 3.0 ± 0.1 mm. The test results are shown in Table 2.

[0200] (10) Vickers hardness determination

[0201] For each of the metal-ceramic composite materials in Examples 1-9 and Comparative Examples 1-4, the Vickers hardness was determined by a 5-point average using a 1-point load test with a test force of 2.942 N (HV 0.3) according to JIS R1610:2003. The test results are shown in Table 2.

[0202]

[0203]

[0204] As can be seen from the results of Examples 1 to 9 above, the preferred metal-ceramic composite material according to the present invention provides a good impregnation state, thereby exhibiting excellent mechanical properties such as strength and hardness, as well as excellent antibacterial and antiviral properties brought by copper. In particularly preferred examples, the porosity (density of the sintered body), flexural strength and hardness (e.g., Vickers hardness: indentation hardness), as well as the antibacterial and antiviral effects are all well balanced and excellent at a high level.

[0205] On the other hand, according to Comparative Example 1, which contains an excessive amount of added element M in the metal phase, Comparative Example 2, which has a smaller area of ​​ceramic phase relative to the metal, and Comparative Example 3, which has a larger area of ​​ceramic phase relative to the metal, a good infiltration state cannot be obtained, the porosity becomes high and a dense sintered body cannot be obtained, or the desired level of antibacterial activity or antiviral activity cannot be obtained, resulting in results that are unsuitable for practical use.

[0206] It should be noted that the various solutions or implementation methods that may be included in this invention are summarized below.

[0207] [1]. A metal-ceramic composite material, comprising a ceramic phase and a metallic phase in a mutually dispersed state, wherein the ceramic phase contains silicon carbide, and the metallic phase contains an alloy and / or intermetallic compound comprising Cu and Si.

[0208] The aforementioned metallic phase contains at least one metallic additive element M other than Cu or Si, and

[0209] The aforementioned silicon carbide constitutes more than half of the total mass of the constituent materials of the aforementioned ceramic phase.

[0210] Here,

[0211] For the aforementioned metal-ceramic composite material, when obtaining an image with an area of ​​256 μm × 192 μm at 500x magnification using a scanning electron microscope (SEM), if, relative to the overall area of ​​the image, the percentage (%) of the total area of ​​the ceramic phase is set as A, and the percentage (%) of the total area of ​​the metal phase is set as B, and the area ratio of the ceramic phase to the metal phase (A / B) is 2 or more and 60 or less, and...

[0212] In the aforementioned metallic phase, when the mass percentage (%) of Si relative to its total mass is set as a and the mass percentage (%) of the added element M is set as m, the following relationship is satisfied:

[0213] 0.01≤m / a≤1.4, and

[0214] 0.3≤m≤20.

[0215] [2]. According to the metal-ceramic composite material described in Item 1 above, when the mass percentage (%) of Cu relative to its total mass in the metal phase is set as b and the mass percentage (%) of Si is set as a as described above, the following relationship is satisfied:

[0216] b / a≥2.5.

[0217] [3]. The metal-ceramic composite material according to Item 2 above, wherein the area ratio A / B of the ceramic phase / metal phase is less than 5, and m / a<1 and b / a≥3.

[0218] [4]. The metal-ceramic composite material according to any one of items 1 to 3 above, wherein the added element M comprises at least one selected from the group consisting of Ni, Mg, Zn and Ti.

[0219] [5]. The metal-ceramic composite material according to any one of items 1 to 4 above, wherein the antibacterial effect R obtained by measuring under the condition of using Staphylococcus aureus as the test bacteria according to JIS Z2801:2012 is 2.0 or higher.

[0220] [6]. The metal-ceramic composite material according to any one of items 1 to 5 above, characterized in that the metal-ceramic composite material is used as an anti-pathogen material.

[0221] [7]. The metal-ceramic composite material according to any one of items 1 to 6 above, wherein the porosity determined by Archimedes method according to JISR 1634:1998 is less than 10%.

[0222] [8]. The metal-ceramic composite material according to any one of items 1 to 7 above, wherein, when measured by Archimedes method according to JISR 1634:1998, the relative density [D1 / D2]×100 of the bulk density D1 of the metal-ceramic composite material relative to the true density D2 of the metal phase of the metal-ceramic composite material is 90% or more.

[0223] [9]. The metal-ceramic composite material according to any one of items 1 to 8 above, wherein the flexural strength obtained by the three-point flexural strength test according to JISR 1601:2008 is 230 MPa or more.

[0224]

[10] . The metal-ceramic composite material according to any one of items 1 to 9 above, wherein the Vickers hardness obtained by averaging 5 points using a 1-point load test according to JISR 1610:2003 is 25 GPa or higher.

[0225]

[11] . The metal-ceramic composite material according to any one of items 1 to 10 above, wherein the ceramic phase further contains free carbon.

Claims

1. A metal-ceramic composite material, comprising a ceramic phase and a metallic phase in a mutually dispersed state, wherein the ceramic phase contains silicon carbide, and the metallic phase contains an alloy and / or intermetallic compound comprising Cu and Si. The metallic phase contains at least one metallic additive element M other than Cu or Si, wherein the additive element M comprises at least one element selected from the group consisting of Ni, Mg, Zn, and Ti. The silicon carbide constitutes more than half of the total mass of the constituent materials of the ceramic phase. Here, When a scanning electron microscope (SEM) is used to obtain an image of the aforementioned metal-ceramic composite material at 500x magnification with an area of ​​256 μm × 192 μm, and the percentage (%) of the total area of ​​the ceramic phase relative to the overall area of ​​the image is defined as A, and the percentage (%) of the total area of ​​the metal phase is defined as B, the area ratio of the ceramic phase to the metal phase, A / B, is greater than 2 and less than 5. In the metallic phase, when the mass percentage (%) of Si is set as a, the mass percentage (%) of Cu is set as b, and the mass percentage (%) of added element M is set as m, relative to its total mass, the following relationship is satisfied: 0.01≤m / a≤1.4、 0.3≤m≤16, and b / a≥2.

5.

2. The metal-ceramic composite material according to claim 1, wherein, 0.01≤m / a<1, and b / a≥3.

3. The metal-ceramic composite material according to claim 1 or 2, wherein, According to JIS Z2801:2012, the antibacterial efficacy R obtained under the condition of using Staphylococcus aureus as the test bacteria was greater than 2.

0. The culture conditions for the test pieces inoculated with the test bacterial solution are specified in JIS Z2801:2012 as a temperature of 35±1℃ and a time of 24±1 hours. However, the culture and determination in this case were carried out in the dark at a temperature of 25℃ and a time of 6 hours.

4. The metal-ceramic composite material according to claim 1 or 2, characterized in that, The metal-ceramic composite material is used as an anti-pathogen material.

5. The metal-ceramic composite material according to claim 1 or 2, wherein, According to JIS R1634:1998, the porosity determined by the Archimedes method is less than 10%.

6. The metal-ceramic composite material according to claim 1 or 2, wherein, When measured using the Archimedes method according to JIS R1634:1998, the relative density [D1 / D2]×100 of the bulk density D1 of the metal-ceramic composite material relative to the true density D2 of the metallic phase of the metal-ceramic composite material is 90% or more.

7. The metal-ceramic composite material according to claim 1 or 2, wherein, The bending strength obtained by the three-point bending strength test according to JIS R1601:2008 is above 230 MPa.

8. The metal-ceramic composite material according to claim 1 or 2, wherein, According to JIS R1610:2003, the Vickers hardness obtained by averaging 5 points using a 1-point load test is above 25 GPa.

9. The metal-ceramic composite material according to claim 1 or 2, wherein, The ceramic phase also contains free carbon.

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