Glass-metal composite

Abstract

To provide a glass-metal composite capable of suitably achieving both of at least 1000°C heat resistance and nitriding resistance.SOLUTION: A glass-metal composite 1 includes a glass member 2, a ceramic member 3 and a metal member 4 sandwiched thereby. The metal member 4 includes two metal lead 5 on the side of one shorter side; in the glass member 2, a crystallized portion is mixed in an amorphous matrix; and when leaving a sintered body consisting of a glass powder green compact constituting the glass member on the following conditions: a temperature of 1000°C (in the atmospheric atmosphere) and a period of time of 100 hours, the rate of change of a thermal expansion coefficient before and after the leaving is 10% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a glass-metal composite. [Background technology]

[0002] For various components used in high-temperature and nitrogen-containing atmospheres, such as heater components exposed to nitrogen and ammonia, automotive exhaust gas purification components exposed to NOx, and solid oxide fuel cell components that use ammonia as fuel, materials with properties such as heat resistance and nitridation resistance are preferably used. Examples of materials with such properties include ceramic materials such as alumina (Al2O3) and zirconia (ZrO2). For example, Patent Document 1 below discloses a ceramic heater element comprising a plate-shaped ceramic body made of alumina and a heating element (metal component) embedded inside the ceramic body. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 3935166 [Overview of the project] [Problems that the invention aims to solve]

[0004] Incidentally, our inventors' research has shown that ceramic materials made of alumina and the like are difficult to densify at temperatures below the heat resistance temperature of general-purpose metal components such as stainless steel (typically 900-1000°C) (i.e., only materials with reduced relative density can be obtained). As a result, we have found that the gas barrier properties of the ceramic material decrease, making the metal component more susceptible to corrosion. In contrast, with glass materials, for example, it is said that glass components with high relative density can be obtained by firing them at a temperature of around 800-900°C. However, from the perspective of use in various applications, there is a requirement for materials with a higher heat resistance temperature (e.g., 1000°C or higher) compared to conventional glass components, and there is still room for improvement.

[0005] The present invention has been made in view of the above circumstances, and its main objective is to provide a composite in which a metal member is coated with a glass member, wherein heat resistance of at least 1000°C (preferably 1100°C or higher) and nitriding resistance can be suitably achieved simultaneously. [Means for solving the problem]

[0006] To achieve this objective, the present invention provides a glass-metal composite comprising a metal member and a glass member covering at least a portion of the metal member. In the glass member, crystalline portions are interspersed within the amorphous matrix. A fired body made from compacted glass powder constituting the glass member is subjected to the following conditions: Temperature: 1000℃ (in an atmospheric environment); Time: 100 hours; The rate of change in the coefficient of thermal expansion before and after leaving the product unattended is 10% or less (hereinafter, a form that satisfies this condition will also simply be referred to as "having heat resistance to at least 1000°C").

[0007] As mentioned above, glass materials are relatively easy to densify, so glass components obtained by firing these glass materials can achieve excellent relative density. This allows for desirable nitriding resistance. Furthermore, since the glass component has a structure in which crystalline portions are mixed within an amorphous matrix and has heat resistance of at least 1000°C, excellent heat resistance can be achieved.

[0008] In one preferred embodiment of the glass-metal composite disclosed herein, the metal member has a sheet-like or plate-like shape with a pair of wide surfaces, and the glass member covers at least a portion of at least one of the wide surfaces of the sheet-like or plate-like metal member. With a glass-metal composite of this configuration, both heat resistance and nitriding resistance can be more favorably achieved. Furthermore, a glass-metal composite in which at least a portion of the other wide surface of the metal member is covered with a member mainly composed of ceramic is preferred because it can be used in various industrial products.

[0009] In one preferred embodiment of the glass-metal composite disclosed herein, the glass component comprises the following composition in terms of oxide molar ratio: MgO: 4-30 mol%, CaO: 4-25 mol%, BaO: 0-45 mol%, ZnO: 0-10 mol%, Al2O3: 0.1-5 mol%, SiO2: 35-55 mol%, and La2O3: 0-5 mol%. Glass components with such a composition can more effectively achieve both heat resistance and nitriding resistance.

[0010] In one preferred embodiment of the glass-metal composite disclosed herein, the relative density of the glass component based on the Archimedes method is 95% or higher. Because the glass component has the high relative density described above, a glass-metal composite with superior nitriding resistance can be obtained. Details of the method for calculating this relative density will be described later.

[0011] In a preferred embodiment of the glass-metal composite disclosed herein, the glass member does not contain alkali metal elements, lead, arsenic, or cadmium. A glass-metal composite provided with a glass member having such a configuration is preferable because it can prevent in advance the generation of substances that may adversely affect the human body or the environment during firing.

[0012] In a preferred embodiment of the glass-metal composite disclosed herein, the coefficient of thermal expansion of the glass member from 30°C to 500°C is 8.0×10 -6 K -1 ~13.0×10 -6 K -1 . From the viewpoint of suitably preventing damage to the coated portion, it is preferable that the coefficient of thermal expansion of the glass member approximates that of the metal member to be coated. A glass-metal composite provided with a glass member having such a coefficient of thermal expansion is preferable because damage to the coated portion is suitably suppressed.

[0013] In a preferred embodiment of the glass-metal composite disclosed herein, the metal member contains Fe, Cr and Al as constituent elements. A metal member having such a configuration is excellent in heat resistance of, for example, 1000°C or higher, and therefore can be preferably used. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] [Figure 1] FIG. 1 is an exploded perspective view for explaining a glass-metal composite according to an embodiment. MODES FOR CARRYING OUT THE INVENTION

[0015] Hereinafter, preferred embodiments of the present invention will be described. Matters necessary for the practice of the present invention other than those specifically mentioned in the present specification can be understood as design matters for those skilled in the art based on prior art in the relevant field. The present invention can be implemented based on the content disclosed in the present specification and common technical knowledge in the relevant field. The following embodiments are not intended to limit the technology disclosed herein to such embodiments. In addition, in the drawings shown in the present specification, members and portions exhibiting the same function are denoted by the same reference numerals in the description. Further, dimensional relationships (length, width, thickness, etc.) in each drawing do not reflect actual dimensional relationships. In this specification and the claims, when a predetermined numerical range is described as A to B (A and B are arbitrary numerical values), it means A or more and B or less. Therefore, it includes the case of more than A and less than B.

[0016] <<Glass-Metal Composite 1>> Figure 1 is an exploded perspective view for explaining a glass-metal composite 1 (specifically, a ceramic heater element) according to one embodiment. Broadly speaking, the glass-metal composite 1 according to the present embodiment includes a glass member 2, a ceramic member 3, and a metal member 4 (corresponding to a heating element) sandwiched therebetween. As shown in Figure 1, the metal member 4 according to the present embodiment is in the shape of a rectangular plate, and is provided with two metal leads 5 (corresponding to heating element leads) on one short side thereof. Each component will be described in detail below.

[0017] <Glass Member 2> The glass member 2 according to this embodiment has a heat resistance of at least 1000°C and is characterized by the presence of crystalline portions mixed in the amorphous matrix. The presence of crystalline portions makes it possible to achieve high heat resistance. Furthermore, the percentage of crystalline portions present in the amorphous matrix (i.e., degree of crystallinity) is not particularly limited as long as the effects of the technology disclosed herein are achieved, but it is typically 40 to 99% (e.g., 50 to 95%). In this specification, "degree of crystallinity" refers to the value calculated by the formula (area of ​​peaks originating from crystalline components) × 100 / (area of ​​peaks originating from crystalline components + area of ​​peaks originating from amorphous components) (%) after calculating the peaks originating from crystalline components (diffraction lines) and peaks originating from amorphous components (halo peaks, i.e., broad scattered lines) in the XRD pattern obtained by X-ray diffraction (XRD) measurement. Such measurement can be performed based on conventionally known methods of this type of measurement.

[0018] The glass component 2 is a component containing glass components (i.e., a glass composition). The content of glass components in the glass component 2 is not particularly limited as long as the effects of the technology disclosed herein are achieved, but typically it can be 70% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more, when the entire glass component is considered to be 100% by weight. Furthermore, there is no particular upper limit to the amount of glass components in the glass component 2, but it may be, for example, 100% by weight, 99% by weight or less, 95% by weight or less, etc.

[0019] The composition of the glass components constituting the glass member 2 is not particularly limited as long as the effects of the technology disclosed herein are achieved, but it is preferable that it contains, for example, the following components. Furthermore, it is more preferable that the molar ratio of each component in terms of oxide is as follows. When the total amount of glass components contained in the glass member 2 is taken as 100 mol%, the following components can be contained in, for example, 95 mol% or more, preferably 97 mol% or more, and more preferably 99 mol% or more (it can also be contained in 100 mol%). MgO: 4-30 mol%, CaO: 4-25 mol%, BaO: 0-45 mol% ZnO: 0-10 mol% Al2O3: 0.1-5 mol% SiO2: 35-55 mol% La2O3: 0-5 mol% The following describes each component.

[0020] The above alkaline earth metal oxides (MgO, CaO, BaO) are components that can contribute to adjusting the coefficient of thermal expansion and improving the heat resistance of glass components. MgO (magnesium oxide; magnesia) is preferably contained in a range of 4 to 30 mol%. CaO (calcium oxide) is preferably contained in a range of 4 to 25 mol%. BaO (barium oxide) is preferably contained in a range of 0 to 45 mol%. BaO may not be contained at all (i.e., 0 mol%), and if it is contained, it is preferably contained in an amount of 45 mol% or less (for example, 16 to 38 mol%).

[0021] ZnO (zinc oxide) is a component that can help adjust the viscosity of the glass slurry (including ink-like and paste-like materials) used during firing, and can also improve the airtightness and stability of the glass components. It is preferable that ZnO be included in a range of 0 to 10 mol%. ZnO may not be included at all (i.e., 0 mol%), and if it is included, it is preferable that it be included in an amount of 10 mol% or less.

[0022] Al2O3 (aluminum oxide; alumina) is a component that can control the fluidity of glass slurry and contribute to its adhesion stability. It is preferable that Al2O3 be present in an amount ranging from 0.1 to 5 mol% (for example, 2.0 to 2.5 mol%).

[0023] SiO2 (silicon dioxide) is a component that makes up the framework of glass materials. However, if the SiO2 content is too high, the melting point (softening point) becomes too high, which is undesirable. It is preferable that the SiO2 content is in the range of 35 to 55 mol% (for example, 36 to 51 mol%).

[0024] La2O3 (lanthanum oxide) is a component that may have the function of improving the stability of glass components. It is preferable that La2O3 is included in the range of 0 to 5 mol%. La2O3 may not be included (i.e., 0 mol%), and if it is included, it is preferable that it is included in an amount of 5 mol% or less (for example, 3.0 mol% or less).

[0025] Furthermore, the glass member 2 may contain any components other than the seven components described above as glass components, as long as the effects of the technology disclosed herein are not significantly hindered. Examples of such optional components include B2O3, Cu2O, Fe2O3, NiO, ZrO2, TiO2, Nb2O5, FeO, Fe3O4, CuO, SnO, SnO2, CeO2, Bi2O3, Y2O3 (yttria), etc. By adding one or more of these optional components to constitute a multi-component glass material, the physical stability of the glass member can be improved. From the viewpoint of workability and cost, the proportion of optional components to the total glass member is preferably 0.01 to 5.0 mol%, more preferably 0.05 to 2.0 mol%, and even more preferably 0.1 to 1.0 mol%.

[0026] It is preferable that the glass component 2 does not contain alkali metal elements, lead, arsenic, cadmium, etc. Examples of such alkali metal elements include Li, Na, K, Rb, Cs, and Fr. It is preferable that the glass component 2 does not contain these alkali metal components (especially Na and K) because it is possible to prevent the generation of substances that may adversely affect the environment during firing. It is also preferable that the glass component 2 does not contain lead (Pb), arsenic (As), or cadmium (Cd) because it is possible to prevent the generation of substances that may adversely affect human health or the environment. In this specification and in the claims, "does not contain" means that the above-mentioned components have not been intentionally added. Therefore, it does not strictly exclude trace amounts of unavoidable substances that may be present due to raw materials or manufacturing processes.

[0027] Furthermore, the glass component 2 may contain components other than the glass component, as long as the effects of the technology disclosed herein are not significantly hindered. The content of such components other than the glass component is not particularly limited as long as the effects of the technology disclosed herein are achieved, but it can be approximately 30% by weight or less, for example, 10% by weight or less, or 5% by weight or less, when the total weight of the glass component 2 is 100% by weight. Examples of such components include inorganic fillers. Examples of such inorganic fillers include Al2O3, ZrO2, Y2O3, BeO, MgO, La2O3, TiO2, and mullite (Al6O 13 Examples include Si2, forsterite (Mg2SiO4), and steatite (MgO·SiO2). These can be used individually or in combination of two or more.

[0028] The relative density of the glass member 2 is not particularly limited as long as the effects of the technology disclosed herein can be obtained, and is typically 80% or more. From the viewpoint of improving nitriding resistance, it is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more, 97% or more, and particularly preferably 99% or more (provided that the upper limit is 100%). When the glass member 2 has a high relative density (that is, has excellent gas barrier properties), a glass-metal composite 1 with more excellent nitriding resistance can be obtained, which is preferable. In the present specification and claims, the term "relative density" refers to a value obtained by dividing the bulk density calculated based on the Archimedes method by the true density measured by the pycnometer method. Specifically, first, the dry weight W1 of the glass member, the weight W2 of the glass member in water when immersed in water (e.g., distilled water), and the wet weight W3 of the glass member after it is taken out of water and water droplets on the surface are removed, are measured. Then, the density of water σ at the water temperature when measuring the in-water weight W2 w is used to calculate the bulk density based on the following formula (I). (Bulk density)=W1σ w / (W3-W2) ··· (I) Subsequently, the relative density is calculated based on the following formula (II) using the true density of the sample calculated by the pycnometer method. (Relative density)=(Bulk density) / (True density) ··· (II) The series of measurements as described above can be performed based on conventionally known measurement methods for this type of measurement.

[0029] The coefficient of thermal expansion of the glass member 2 is not particularly limited as long as the effects of the technology disclosed herein can be obtained. From the viewpoint of suitably preventing damage to the coated portion, it is preferable to approximate the coefficient of thermal expansion of the glass member to the coefficient of thermal expansion of the metal member to be coated. The coefficient of thermal expansion of such a glass member is, for example, 8.0×10 -6 / K -1 to 13.0×10 -6 / K -1 (preferably 8.7×10 -6 / K -1 to 12.3×10 -6 / K -1It can be set to the extent of [a certain value]. In this specification, "thermal expansion coefficient" refers to the average expansion coefficient (average linear expansion coefficient) measured using a thermomechanical analyzer (TMA) in the temperature range of 30°C to 500°C, and is the value obtained by dividing the change in sample length relative to the initial length of the sample by the temperature difference. The thermal expansion coefficient can be measured in accordance with, for example, JIS R3102:1995.

[0030] <Ceramic component 3> The ceramic member 3 according to this embodiment is a member mainly composed of ceramic. In this specification and in the claims, "ceramic" (hereinafter also referred to as "ceramic component") refers to an inorganic compound not limited to oxides, and may be an inorganic compound that does not fall under the category of glass (amorphous structure). Furthermore, "mainly composed of ceramic" means that the ceramic component is the component that is present in the largest amount by weight among the components constituting the ceramic member 3. Such a ceramic member may preferably contain 95% or more by weight of the ceramic component, 97% or more by weight, or 99% or more by weight. Components other than the ceramic component may include, for example, various metallic and nonmetallic elements as unavoidable impurities. Examples of such ceramic components include Al2O3, MgO, BeO, ZrO2, TiO2, Y2O3, mullite, forsterite, steatite, boron nitride (BN), aluminum nitride (AlN), silicon nitride (Si3N4), boehmite (AlOOH), etc. These can be used individually or in combination of two or more types.

[0031] <Metal component 4> As shown in Figure 1, the metal member 4 according to this embodiment is a rectangular plate-shaped member. The metal member 4 is not particularly limited as long as the effects of the technology disclosed herein are achieved, but for example, one containing Fe, Cr, and Al as constituent elements can be preferably used. Examples of such a material include stainless steel containing Fe, Al, Cr, Ti, and Si in predetermined proportions, stainless steel containing Fe, Al, Cr, and Ti in predetermined proportions, and stainless steel containing Fe, Cr, and Al in predetermined proportions. Metal members with such a configuration can be preferably used because they have excellent heat resistance above 1000°C. When stainless steel containing Al is used as the metal member 4, an alumina layer or a chromium oxide layer (Cr2O3) may be formed on the surface of the metal member after firing.

[0032] The thickness of the metal material 4 (part S in Figure 1) is not particularly limited as long as the effects of the technology disclosed herein are achieved. However, from the viewpoint of suitably achieving nitriding resistance, for example, if the thickness of the glass member 2 (part T in Figure 1) is set to 100%, it can typically be 50% or less, preferably 30% or less, and more preferably 10% or less (for example, 1-5%).

[0033] <Lead 5> The lead 5 in this embodiment is a metal lead. As shown in Figure 1, the lead 5 is a rectangular plate and is provided on one of the short sides of the metal member 4. The material constituting the lead 5 is not particularly limited as long as the effects of the disclosed technology are achieved, but for example, materials exemplified in the description of the metal member 4 can be used.

[0034] ≪Method for manufacturing glass-metal composite 1≫ Next, an example of a method for manufacturing the glass-metal composite 1 will be described. Note that the following manufacturing method is not intended to limit the methods for manufacturing the glass-metal composite disclosed herein to this method. Furthermore, the steps described below can be carried out in any order as appropriate.

[0035] First, the glass material constituting the glass component 2 is prepared. Specifically, industrial products, reagents, or various mineral raw materials containing oxides, carbonates, nitrates, complex oxides, etc., of the various components that make up the glass material are prepared and mixed in the desired composition ratio. Such mixing can be carried out, for example, by putting each powder into a mixer such as a ball mill and mixing for several hours to several tens of hours. Next, the obtained raw material powder is dried and then heated at a predetermined temperature (typically 1300°C to 1500°C) to melt it. The molten raw material powder is then cooled (preferably rapidly cooled) to obtain the desired glass body. The obtained glass body is then crushed and classified (sieved) to the desired size (particle size) to obtain glass material in the form of cullet or powder. The average particle size of such glass material can typically be 0.5 to 50 μm (for example, 1 to 40 μm or 2 to 30 μm). In this specification, "average particle size" refers to the particle size corresponding to 50% of the cumulative value from the smallest particle size in the volume-based particle size distribution based on laser diffraction and scattering (D 50 This refers to particle size. Such measurements can be performed, for example, using a Malvern Mastersizer 3000.

[0036] A glass slurry can be obtained by stirring and mixing the glass material prepared as described above, a solvent, and, if necessary, a binder, etc., using a conventionally known method such as a rotary mixer equipped with a stirrer, a roll mill, or a ball mill. The viscosity of such a glass slurry is preferably adjusted as appropriate, but is typically 0.1 to 20 [Pa·s] (for example, 0.3 to 15 [Pa·s] or 0.5 to 10 [Pa·s]) (measured at a liquid temperature of 25°C and an E-type viscometer rotor rotation speed of 1 rpm). This viscosity can be measured, for example, using a commercially available viscometer and following the manual accompanying the viscometer. Here, the content of the glass material is not particularly limited insofar as the effects of the technology disclosed herein are achieved, but for example, when the weight of the glass slurry is taken as 100% by weight, it can be approximately 90% by weight or less, typically in the range of 40 to 85% by weight, for example, 60 to 80% by weight.

[0037] Furthermore, the content of the above solvent is not particularly limited, but for example, when the weight of the glass slurry is taken as 100% by weight, it can be approximately 60% by weight or less, typically 15 to 50% by weight, for example, in the range of 20 to 40% by weight. In addition, it is possible to use solvents that are normally used in glass slurries, such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, terpineol, tetrahydrofuran, dimethyl sulfoxide, γ-butyl lactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, xylene, ion-exchanged water, etc., and one or more of these can be appropriately selected and used.

[0038] The content of the binder is not particularly limited, but for example, when the weight of the glass slurry is 100% by weight, it can be approximately 20% by weight or less, typically 1 to 15% by weight, for example, in the range of 2 to 10% by weight. As such a binder, it is possible to use those that are normally used in glass slurries, and examples include cellulosic resins such as ethylcellulose, methylcellulose, nitrocellulose, cellulose acetate, cellulose propionate, and cellulose butyrate, or acrylic resins made from polymers or copolymers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethylmethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate, poly-α-methylsulfone, polyvinyl alcohol, polybutene, and phthalate esters, and one or more of these can be appropriately selected and used.

[0039] The glass slurry may contain additive components such as inorganic fillers, coloring pigments, thixotropy imparters, dispersants, plasticizers, antioxidants, defoamers, and leveling agents, as needed. These components are typically those used in glass slurries. For example, the inorganic filler can be one or more of those described in the description of components other than glass components that may be contained in the glass member 2. When the glass slurry contains an inorganic filler, the amount of the inorganic filler is not particularly limited as long as the effects of the disclosed technology are achieved. However, when the weight of the glass slurry is considered as 100% by weight, the amount of the inorganic filler can be approximately 30% by weight or less, typically 1 to 25% by weight, for example, within the range of 2 to 20% by weight.

[0040] A glass green sheet can be obtained by coating the glass slurry prepared as described above onto a carrier sheet having a predetermined thickness and drying it. Such coating can be carried out, for example, by the doctor blade method. Next, a ceramic component (ceramic sintered body) is prepared. A commercially available ceramic component is used here, but of course, a ceramic component manufactured according to conventionally known methods may also be used. Then, a metal component with two leads is sandwiched between the glass green sheet and the ceramic component prepared as described above, and integrated with an adhesive or the like. Here, as for the metal component, in order to ensure heat resistance, it may be used that has been heat-treated in an oxidizing atmosphere at a predetermined temperature (e.g., 1000°C to 1100°C) for several hours (e.g., about 1 to 2 hours). Examples of such adhesives include acrylic resins such as polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polybutyl acrylate, and cyanoacrylate. The resulting integrated material is placed on an alumina setter, degreased at a predetermined temperature (e.g., 200°C to 600°C) for several hours (e.g., about 2 to 3 hours), and then fired at a predetermined temperature (e.g., 1000°C to 1100°C) for several hours (e.g., about 2 to 3 hours) to obtain the glass-metal composite 1.

[0041] Although the above manufacturing method describes a method using a glass green sheet, it is not limited to this method. The glass-metal component 1 can also be obtained by placing the metal component 4 on top of the ceramic component 3, coating the metal component with a glass slurry, drying it, and then firing it. Furthermore, although the above manufacturing method describes firing the integrated component on an alumina setter, it is not limited to this method. For example, firing can also be performed by hanging or firing in sand.

[0042] <Variation> Although specific examples of glass-metal composites (and methods for manufacturing glass-metal composites) disclosed herein have been described in detail above, the glass-metal composites disclosed herein are not limited to these specific examples. The glass-metal composites disclosed herein include various modifications of the above-mentioned specific examples, as long as their purpose is not altered.

[0043] As shown in Figure 1, the metal member 4 according to the above embodiment is in the shape of a rectangular plate, but is not limited to this, and the metal member disclosed herein may be in the shape of a sheet (foil), an elliptical plate, or various other shapes.

[0044] The glass-metal composite according to the above embodiment comprises a glass member 2 and a ceramic member 3, but is not limited thereto. For example, the ceramic member 3 may be replaced with a glass member 2, or the ceramic member 3 may be replaced with a glass member having a different composition from the glass member 2. A glass-metal composite in which the ceramic member 3 is replaced with the glass member 2 can be obtained by sandwiching a metal member equipped with leads between two glass green sheets prepared as described above, integrating them, and then firing them. Furthermore, a glass-metal composite in which the ceramic member 3 is replaced with a glass member of a different composition than the glass member 2 can be obtained by sandwiching a metal member equipped with leads between two glass green sheets of two different types, integrating them, and then firing them.

[0045] Furthermore, for example, if the metal member is cylindrical, the glass member may be configured to cover the outside and / or inside of the cylindrical metal member. Such covering may be part or all of the outside, or part or all of the inside.

[0046] In the above embodiment, both the glass member 2 and the ceramic member 3 have a hexahedral shape, but the embodiment is not limited to this, and for example, glass members and / or ceramic members without four corners may be used.

[0047] In the above embodiment, the metal member 4 is described as having two leads 5, but it is naturally not limited to this, and the metal member in the glass-metal member disclosed herein does not have leads. That is, the glass-metal member disclosed herein may be in which the metal member is sandwiched between a composite of a glass member and a ceramic member. Furthermore, in such a glass-metal member, the metal member may protrude from one of the short sides of the composite of the glass member and the ceramic member, or a portion of the metal member may protrude not only from one of the short sides but also from the short side opposite to the short side. Alternatively, the entire metal member may be covered (embedded) by the composite. The modifications described in paragraphs 0043 to 0046 can also be applied when the glass-metal member is in such a configuration.

[0048] [Examples] The following describes examples relating to the glass-metal composite disclosed herein, but the present invention is not intended to be limited to such examples.

[0049] 1. Fabrication of glass-metal composites In this example, 22 types of glass-metal composites (Samples 1-22) were prepared. The preparation method for each sample is described below.

[0050] 1-1. Preparation of glass materials A to I and green sheets containing each glass material First, the raw material powders were prepared and mixed to achieve the composition (mol%) shown in the corresponding column of Table 1. Then, the mixture was melted at 1300°C to 1500°C for 1 hour and rapidly cooled to obtain a glass body. Glass materials A to I were obtained by crushing and classifying this glass body. The average particle size of glass materials A to I was approximately 10 μm. Next, the glass material prepared as described above was mixed with commercially available acrylic resin, phthalate ester, and xylene, and stirred to obtain a glass slurry. The proportions of each component were such that, when the weight of the glass slurry was considered to be 100% by weight, the glass material accounted for 60% by weight, the acrylic resin 10% by weight, the phthalate ester 5% by weight, and the remainder being xylene. The glass slurry prepared as described above was then coated onto a carrier sheet using the doctor blade method, dried, cut to a size of 60 mm x 40 mm, and the carrier sheet was peeled off to produce a green sheet with a thickness of approximately 1.5 mm containing glass materials A to I.

[0051] 1-2. Preparation of ceramic material J As ceramic material J, we used 8 mol% yttria-stabilized zirconia manufactured by Kyoritsu Material, with the composition (mol%) shown in the corresponding column of Table 1. The average particle size of ceramic material J was approximately 0.5 μm.

[0052] 1-3. Preparation of Metal Materials We prepared heat-resistant ferritic stainless steel foils measuring 80mm x 15mm (35mm x 15mm was also prepared for evaluation in section 4-2, described later) with a thickness of 30-100μm (specifically, NCA-1 and NCA-2 from Nippon Steel Corporation, and JFE20-5USR and JFE18-3USR from JFE Steel Corporation). NCA-1 was used for samples 1-10, 14-16, and 18-22; NCA-2 for sample 11; JFE20-5USR for sample 12; and JFE18-3USR for sample 13. To ensure heat resistance, each metal foil was pre-heat-treated at 1100°C for 1 hour in an oxidizing atmosphere. For sample 17, SUS430 (50μm thick) from Niraco Co., Ltd. was used as is.

[0053] 1-4. Preparation of samples 1-9, 11-13, and 17-22 The metal foil shown in the corresponding column of Tables 2 to 4 was sandwiched between two green sheets shown in the corresponding column of Tables 2 to 4, and then the two green sheets were pressed together using a uniaxial press (pressing pressure: 50 MPa) to form a single unit. For each sample, two types were prepared: one in which a portion of the short side of the metal foil protruded from the two green sheets, which was used for evaluation 4-1 described later, and another in which the entire metal foil was embedded in the two green sheets, which was used for evaluation 4-2 described later. At this stage, for samples where the thickness of each of the two layers formed from the green sheets was thicker than 1.0 mm, multiple green sheets were laminated as appropriate before pressing. The integrated material was placed on an alumina setter, degreased at 200°C to 600°C for 2 hours, and then fired in an air atmosphere for 2 hours at the firing temperatures shown in the corresponding columns of Tables 2 to 4 to produce glass-metal composites for each sample. The two layers formed from the two green sheets were then polished using a diamond polishing pad to adjust the dimensions to 50 mm in length and 30 mm in width, and the thickness to the thickness shown in the corresponding columns of Tables 2 to 4.

[0054] 1-5. Preparation of Sample 10 A glass-metal composite for Sample 10 was prepared in the same manner as for Sample 6, except that two green sheets were used, each consisting of a glass slurry to which ceramic material J was added as an inorganic filler in addition to glass material E. Here, the glass slurry was prepared so that, when the weight of the glass slurry is considered as 100% by weight, glass material E accounted for 45% by weight, acrylic resin 10% by weight, phthalate ester 5% by weight, ceramic material J 15% by weight, and the remainder being xylene. The glass slurry prepared as described above was then coated onto a carrier sheet using the doctor blade method, dried, cut to a size of 60 mm x 40 mm, and the carrier sheet was peeled off to produce a glass green sheet with a thickness of approximately 1.5 mm for Sample 10.

[0055] 1-6. Preparation of Samples 14-16 The metal foil shown in the corresponding column of Table 3 was sandwiched between a glass green sheet made of glass material E and a ceramic sintered body shown in the corresponding column of Table 3, and then integrated using a cyanoacrylate adhesive. Here, as the 8% yttria-stabilized zirconia sintered body, ceramic material J was formed by uniaxial pressing (press pressure: 50 MPa), fired at 1500°C for 4 hours, polished with a diamond polishing pad, and measured in dimensions of 50 mm (length) x 30 mm (width) x 1.0 mm (thickness). As the forsterite sintered body, forsterite powder manufactured by Marusu Yuyaku Co., Ltd. was formed by uniaxial pressing (press pressure: 50 MPa), fired at 1300°C for 4 hours, polished with a diamond polishing pad, and measured in dimensions of 50 mm (length) x 30 mm (width) x 1.0 mm (thickness). As the magnesia sintered body, magnesia manufactured by Nikkatoh Co., Ltd. was polished with a diamond polishing pad and measured in dimensions of 50 mm (length) x 30 mm (width) x 1.0 mm (thickness). The relative density of each sintered body was 99% or more, calculated from the true density calculated by the pycnometer method and the bulk density calculated by the Archimedes method. Aside from this, the glass-metal composites for samples 14-16 were fabricated in the same manner as for sample 7.

[0056] 2. Fabrication of ceramic-metal composites (fabrication of sample 23) A ceramic-metal composite for Sample 23 was fabricated in the same manner as Sample 8, except that 5% by weight of methylcellulose was added to ceramic material J, and the resulting granulated powder was mixed using a mortar and pestle. Two of these granulated powders were then molded to 60 mm in length, 40 mm in width, and 1.5 mm in thickness using a uniaxial press (press pressure: 50 MPa), and the firing temperature was set to 1100°C.

[0057] 3. Evaluation tests of glass materials A-I and ceramic material J The thermal expansion coefficient and heat resistance of the glass materials A-I and ceramic material J, which were prepared as described above, were evaluated. The evaluations are described below.

[0058] 3-1. Evaluation of the coefficient of thermal expansion For glass materials A-I and ceramic material J, compacts with a diameter of 20 mm and a thickness of 7 mm were prepared by press molding at a press pressure of 50 MPa. Then, glass materials A, D, and E were heat-treated at 1100°C, glass materials B, C, and G at 1000°C, glass materials F and I at 900°C, and glass material H at 450°C for 2 hours in an atmospheric environment to obtain fired bodies. These were then cut into cylindrical shapes with a diameter of 15 mm and a thickness of 5 mm using a diamond cutter, and the coefficient of thermal expansion was measured using a thermomechanical analyzer (Rigaku Corporation, TMA8310). Specifically, the coefficient of thermal expansion was calculated from the average linear expansion between 30°C and 500°C when the temperature was raised from room temperature (25°C) to 1000°C at a constant rate of 10°C / min. For glass material H, unlike the other samples, the coefficient of thermal expansion was calculated from the average linear expansion between 30°C and 300°C. The results are shown in the corresponding column of Table 1.

[0059] 3-2. Evaluation of heat resistance The fired glass materials A-I and ceramic material J obtained in 3-1 above were subjected to thermal exposure in an atmospheric environment at temperatures ranging from 400°C to 1100°C, with heating times varying in 50°C increments (heating time: 100 hours). The coefficient of thermal expansion after thermal exposure was measured. A thermomechanical analyzer (Rigaku Corporation, TMA8310) was used for this measurement. The highest temperature at which the rate of change in the coefficient of thermal expansion before and after thermal exposure was confirmed to be 10% or less was defined as the "material heat resistance temperature." The results are shown in the corresponding column of Table 1.

[0060] 3-3. Evaluation of Relative Density The compacted glass materials A-I and ceramic material J obtained in 3-1 above were heat-treated at approximately 1000°C for 2 hours to obtain fired products, and their relative density was measured using the Archimedes method. Specifically, first, the dry weight W1 of each fired product was measured. Next, each glass fired product was immersed in distilled water, placed in a desiccator with a vacuum pump, and vacuumed for 45 minutes. Then, the water weight W2 and water content weight W3 of each fired product were measured. Finally, the density σ of water at the water temperature at which the water weight W2 was measured was calculated. w Using the following formula (I), the bulk density was calculated. (Bulk density) = W1σ w / (W3-W2)···(I) After thoroughly grinding each of the above sintered bodies in an agate mortar, the true density was measured using a pycnometer (AccuPycII1340, Micromerities). Using the above bulk density and true density, the relative density was calculated based on the following formula (II). (Relative density) = (Bulk density) / (True density) ... (II) The results are shown in the corresponding column of Table 1. Note that glass material H melted during the heat treatment described above, so it is indicated with "-".

[0061] 3-4. Evaluation of the presence or absence of crystallized portions The presence or absence of crystallized portions was evaluated for glass materials A-I and ceramic material J. Specifically, the compacted glass materials A-I and ceramic material J obtained in 3-1 above were heat-treated at approximately 1000°C for 2 hours, and then the resulting glass and ceramic materials were pulverized to obtain powdered samples. Powder X-ray diffraction (XRD) was then performed on these powdered samples to confirm the presence or absence of crystal precipitation. An X-ray diffractometer (Rigaku Corporation, RINT-TTRIII) was used for this measurement. Samples in which no crystals were observed were marked "None," and samples in which crystals were observed were marked "Present." The results are shown in the corresponding columns in Table 1. Glass material H was marked "-" because it melted during the heat treatment described above.

[0062] [Table 1]

[0063] 4. Evaluation tests of glass-metal composites (or ceramic-metal composites) Samples 1-23, prepared as described above, were evaluated for heat resistance and corrosion resistance. The evaluations are described below.

[0064] 4-1. Evaluation of heat resistance Each glass-metal composite obtained by firing a portion of the metal foil that extended beyond the green sheet on one of its shorter sides was subjected to heat treatment at 1000°C for 2 hours. Samples that failed to maintain their shape, such as those with cracks in either of the two layers, those where the two layers separated, or those where the glass material melted and solidified into the alumina setter, were marked with "×". After the heat treatment, samples that maintained their shape before heat treatment were bent 90° in the planar direction. Samples where the oxide film (specifically Al2O3 or Cr2O3) on the surface of the metal foil peeled off were marked with "×", and those where it did not peel off were marked with "〇". The results are shown in the corresponding columns of Tables 2 to 4.

[0065] 4-2. Evaluation of corrosion resistance For samples that received a "○" in the heat resistance evaluation, glass-metal composites obtained by firing metal foil embedded entirely in a glass layer (or ceramic layer) were placed in an electric furnace equipped with a mechanism for circulating ammonia gas and exposed to an ammonia atmosphere at 700°C for 2 hours. After this exposure, the composites were filled with resin and cut with a diamond cutter to expose the cross-sections of the glass layer (or ceramic layer) and metal foil. These cross-sections were then subjected to EDX (Energy Dispersive X-ray) analysis, and the coexisting nitrogen and chromium layer was identified as the nitride layer, and the thickness of this nitride layer was measured. It is preferable that the nitride layer be detected with a thickness of 2 μm or less, and more preferable that it is not detected (i.e., ND). Based on this, samples in which a nitride layer greater than 2 μm was confirmed were marked "×", samples in which a nitride layer was confirmed but less than 2 μm were marked "△", and samples in which no nitride layer was confirmed were marked "○". The results are shown in the corresponding columns of Tables 2 to 4.

[0066] 4-3. Overall Evaluation Based on the above evaluation results, we indicated "○" for those that received a "○" for both heat resistance and corrosion resistance evaluations, "△" for those that received a "△" for both heat resistance and / or corrosion resistance evaluations, and "×" for those that received a "×" for both heat resistance and / or corrosion resistance evaluations. The results are shown in the corresponding columns of Tables 2 to 4.

[0067] [Table 2]

[0068] [Table 3]

[0069] [Table 4]

[0070] Based on the above results, it was confirmed that in glass-metal composites comprising a metal foil (i.e., a metal member) and a glass member covering at least a portion of the metal foil, where the glass member has crystalline portions in its amorphous matrix and a material heat resistance temperature of 1000°C or higher, both heat resistance (specifically, around 1000°C to 1100°C) and nitriding resistance can be suitably achieved. Furthermore, it was confirmed that the same balance can be suitably achieved in glass-metal composites comprising samples 14 to 16, where one layer is a glass member and the other layer is a ceramic sintered body (i.e., a ceramic-based member). On the other hand, it was confirmed that the nitriding resistance was insufficient in sample 23, where both layers are ceramic members. Thus, the glass-metal composite disclosed herein provides a composite in which both heat resistance and nitriding resistance are suitably achieved. [Explanation of Symbols]

[0071] 1. Glass-metal composite 2 Glass components 3. Ceramic components 4 Metal components 5 Lead S Thickness of metal component 4 Thickness of glass component 2

Claims

1. Metal components and A glass member covering at least a portion of the metal member, A glass-metal composite comprising, Here, the fired body obtained by firing the compacted glass material constituting the glass member at 1000°C or 1100°C has the following characteristics: Temperature: 1000°C (in an atmospheric environment); Time: 100 hours; When left unattended, the rate of change in the coefficient of thermal expansion before and after said unattended period is 10% or less. Crystallized regions are interspersed within the amorphous matrix. The relative density based on the Archimedes method is over 95%. The coefficient of thermal expansion from 30°C to 500°C is 8.0 × 10⁻⁶. －６ K －１ ~13.0 x 10 －６ K －１ That is, Glass-metal composite.

2. The metal member has a sheet-like or plate-like shape with a pair of wide surfaces, The glass-metal composite according to claim 1, wherein the glass member covers at least a portion of at least one of the wide surfaces of the sheet-like or plate-like metal member.

3. The glass-metal composite according to claim 2, wherein at least a portion of the other wide surface of the metal member is covered with a member mainly composed of ceramic.

4. The glass component has the following composition in terms of oxide molar ratio: MgO: 4-30 mol% CaO: 4-25 mol% BaO: 0-45 mol% ZnO: 0-10 mol% Al ２ O ３ : 0.1-5 mol% SiO ２ : 35-55 mol% La ２ O ３ : 0 to 5 mol% A glass-metal composite according to any one of claims 1 to 3, including the glass-metal composite according to any one of claims 1 to 3.

5. The glass-metal composite according to any one of claims 1 to 4, wherein the glass member does not contain any alkali metal elements, lead, arsenic, or cadmium.

6. The glass-metal composite according to any one of claims 1 to 5, wherein the metal member comprises Fe, Cr, and Al as constituent elements.

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