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] The present invention relates to glass-metal composites. [Background technology]

[0002] Materials having functions such as heat resistance and nitridation resistance are preferably used for various members that are used under high temperature and nitrogen-containing atmospheres, such as heater members exposed to nitrogen and ammonia, automobile exhaust gas purification members exposed to NOx, and solid oxide fuel cell members that use ammonia as fuel. One example of a material having such functions is alumina (Al 2 O 3 ) and zirconia (ZrO 2 For example, Patent Document 1 listed below discloses a ceramic heater element including a plate-shaped ceramic body made of alumina and a heating element (metal member) embedded inside the ceramic body. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 3935166 Summary of the Invention [Problem to be solved by the invention]

[0004] Meanwhile, according to the study by the present inventors, it was found that a ceramic body made of alumina or the like is difficult to densify (i.e., only one with a reduced relative density can be obtained) at a temperature lower than the heat resistance temperature (typically 900 to 1000°C) of a general-purpose metal member such as stainless steel. This leads to a decrease in the gas barrier property of the ceramic body, and the metal member is easily corroded. In contrast, for example, it is said that a glass member with a high relative density can be obtained by firing a glass material at typically about 800 to 900°C. However, from the viewpoint of use in various applications, it is required to have a higher heat resistance temperature (for example, 1000°C or higher) than conventional glass members, and there is still room for improvement.

[0005] The present invention has been made in view of the above circumstances, and a main object of the present invention is to provide a composite in which a metal member is covered with a glass member, and which can suitably achieve both heat resistance of at least 1000°C (preferably 1100°C or higher) and nitridation resistance. [Means for solving the problem]

[0006] In order to achieve this object, the present invention provides a glass-metal composite comprising a metal member and a glass member covering at least a part of the metal member. In the glass member, crystallized portions are mixed in an amorphous matrix. The glass member is a sintered body made of a compact of glass powder, and the sintered body is subjected to the following conditions: Temperature: 1000℃ (in air); Time: 100 hours; When left at 200° C., the rate of change in thermal expansion coefficient before and after the storage is 10% or less (hereinafter, an embodiment that satisfies this condition is also simply referred to as "having heat resistance of at least 1000° C.").

[0007] As described above, since glass materials are relatively easily densified, the glass member obtained by firing the glass material can realize excellent relative density. This makes it possible to preferably realize nitridation resistance. In addition, since the glass member has a structure in which crystallized portions are mixed in an amorphous matrix and has heat resistance of at least 1000°C, it can realize excellent heat resistance.

[0008] In a 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. A glass-metal composite having such a configuration can more suitably achieve both heat resistance and nitridation resistance. In addition, a glass-metal composite having at least a portion of the other wide surface of the metal member covered by a member mainly composed of ceramic is preferred because it can be used in various industrial products.

[0009] In a preferred embodiment of the glass-metal composite disclosed herein, the glass member has the following composition in terms of oxide molar ratios: MgO: 4 to 30 mol %, CaO: 4 to 25 mol %, BaO: 0 to 45 mol %, ZnO: 0 to 10 mol %, Al 2 O 3 : 0.1 to 5 mol%, SiO 2 : 35 to 55 mol%, La 2 O 3 : Contains 0 to 5 mol%. A glass member having such a composition can more suitably achieve both heat resistance and nitridation resistance.

[0010] In a preferred embodiment of the glass-metal composite disclosed herein, the glass member has a relative density based on Archimedes' method of 95% or more. When the glass member has a high relative density as described above, a glass-metal composite having superior resistance to nitridation can be obtained. The method for calculating the relative density will be described in detail 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 having a glass member of such a configuration is preferable because it can prevent the production of substances that may have adverse effects on the human body and the environment during firing.

[0012] In a preferred embodiment of the glass-metal composite disclosed herein, the thermal expansion coefficient 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 thermal expansion coefficient of the glass member is close to the thermal expansion coefficient of the metal member to be coated. A glass-metal composite including a glass member having such a thermal expansion coefficient 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 preferably used because it has excellent heat resistance, for example, to 1000° C. or higher. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is an exploded perspective view illustrating a glass-metal composite according to one embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Preferred embodiments of the present invention will be described below. Matters other than those specifically mentioned in this specification and necessary for carrying out the present invention can be understood as design matters for a person skilled in the art based on the prior art in the relevant field. The present invention can be carried out based on the contents disclosed in this specification and the technical common sense in the relevant field. The following embodiments are not intended to limit the technology disclosed herein. In addition, in the drawings shown in this specification, the same reference numerals are used to describe members and parts that perform the same function. The dimensional relationships (length, width, thickness, etc.) in each drawing do not reflect the actual dimensional relationships. In this specification and claims, when a certain 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, the case where it is more than A and less than B is also included.

[0016] <Glass-metal composite 1> FIG. 1 is an exploded perspective view for explaining a glass-metal composite 1 (specifically, a ceramic heater element) according to one embodiment. Roughly speaking, the glass-metal composite 1 according to this 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 FIG. 1, the metal member 4 according to this embodiment is a rectangular plate, and includes two metal leads 5 (corresponding to heating element leads) on one short side. Each component will be described in detail below.

[0017] <Glass material 2> The glass member 2 according to the present embodiment is characterized by having a heat resistance of at least 1000°C and having a crystallized portion mixed in an amorphous matrix. The presence of the crystallized portion makes it possible to realize high heat resistance. The ratio of the crystallized portion present in the amorphous matrix (i.e., the degree of crystallization) is not particularly limited as long as the effect of the technology disclosed herein is exhibited, but it may typically be 40 to 99% (for example, 50 to 95%). In this specification, the term "degree of crystallization" refers to a value calculated by the formula (area of ​​the peak derived from the crystalline component) x 100 / (area of ​​the peak derived from the crystalline component + area of ​​the peak derived from the amorphous component) (%) after calculating the peak (diffracted line) derived from the crystalline component and the peak (halo peak, i.e., broad scattered line) derived from the amorphous component in an XRD pattern obtained by XRD measurement. Such a measurement can be performed based on a conventionally known method for this type of measurement.

[0018] The glass member 2 is a member containing a glass component (i.e., a glass composition). The content of the glass component contained in the glass member 2 is not particularly limited as long as the effects of the technology disclosed herein are exhibited, but when the entire glass member is taken as 100% by weight, the content can be typically 70% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more. In addition, the upper limit of the glass component contained in the glass member 2 is not particularly limited, but may be, for example, 100% by weight, 99% by weight or less, or 95% by weight or less.

[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 for the glass member 2 to contain, for example, the following components. It is more preferable for the components to be contained in the following molar ratios calculated as oxides. When the entire glass components contained in the glass member 2 are taken as 100 mol %, the following components can be contained in an amount of, for example, 95 mol % or more, preferably 97 mol % or more, and more preferably 99 mol % or more (it can also be contained in an amount of 100 mol %). MgO: 4 to 30 mol%, CaO: 4 to 25 mol%, BaO: 0 to 45 mol% ZnO: 0 to 10 mol% Al 2 O 3 : 0.1 to 5 mol% SiO 2 : 35 to 55 mol% La 2 O 3 : 0 to 5 mol% Each component will be described below.

[0020] The above alkaline earth metal oxides (MgO, CaO, BaO) are components that can contribute to adjusting the thermal expansion coefficient and improving the heat resistance of the glass member. MgO (magnesium oxide; magnesia) is preferably contained in the range of 4 to 30 mol %. CaO (calcium oxide) is preferably contained in the range of 4 to 25 mol %. BaO (barium oxide) is preferably contained in the range of 0 to 45 mol %. BaO does not have to be contained (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 facilitate adjustment of the viscosity of the glass slurry (including ink-like and paste-like substances) used during firing and can also function to improve the airtightness and stability of the glass member. ZnO is preferably contained in the range of 0 to 10 mol %. ZnO does not have to be contained (i.e., 0 mol %), and if it is contained, it is preferably contained in an amount of 10 mol % or less.

[0022] Al 2 O 3 Aluminum oxide (alumina) is a component that controls the fluidity of the glass slurry and is involved in adhesion stability. 2 O 3 is preferably contained in the range of 0.1 to 5 mol % (for example, 2.0 to 2.5 mol %).

[0023] SiO2 (Silicon dioxide) is a component that constitutes the framework of glass components. SiO 2 If the SiO content is too high, the melting point (softening point) becomes too high, which is undesirable. 2 is preferably contained in the range of 35 to 55 mol % (for example, 36 to 51 mol %).

[0024] La 2 O 3 (Lanthanum oxide) is a component that can have the function of improving the stability of glass members. 2 O 3 is preferably contained in the range of 0 to 5 mol %. 2 O 3 may not be contained (that is, 0 mol %), and if contained, it is preferably contained in an amount of 5 mol % or less (for example, 3.0 mol % or less).

[0025] In addition, the glass member 2 may contain optional components other than the seven components described above as glass components, as long as the effects of the technology disclosed herein are not significantly impaired. 2 O 3 , Cu 2 O, Fe 2 O 3 , NiO, ZrO 2 , TiO 2 , Nb 2 O 5 , FeO, Fe 3 O 4 , CuO, SnO, SnO 2 , CEO 2 , Bi 2 O 3 , Y 2 O 3(yttria), etc. By adding one or more of these optional components to form a multi-component glass material, the physical stability of the glass member can be improved. From the viewpoints of workability, cost, etc., the ratio of the optional components to the entire glass member is preferably 0.01 to 5.0 mol % or less, more preferably 0.05 to 2.0 mol %, and even more preferably 0.1 to 1.0 mol % or less.

[0026] It is preferable that the glass member 2 does not contain alkali metal elements, lead, arsenic, cadmium, etc. Examples of such alkali metal elements include Li, Na, K, Rb, Cs, Fr, etc. If these alkali metal elements (particularly Na and K) are not contained, it is preferable because it is possible to prevent the generation of substances that may have a negative effect on the environment during firing. In addition, it is preferable that the glass member 2 does not contain lead (Pb), arsenic (As), or cadmium (Cd), because it is possible to prevent the generation of substances that may have a negative effect on the human body and the environment. In this specification and claims, "does not contain" means that the above-mentioned components are not intentionally added. Therefore, it does not strictly exclude unavoidable components that may be contained in small amounts due to raw materials, manufacturing processes, etc.

[0027] The glass member 2 may contain components other than the glass components as long as the effects of the technology disclosed herein are not significantly impeded. The content of such components other than the glass components is not particularly limited as long as the effects of the technology disclosed herein are exhibited, but can be approximately 30% by weight or less, for example 10% by weight or less, 5% by weight or less, when the entire glass member 2 is taken as 100% by weight. Examples of such components include inorganic fillers. Examples of such inorganic fillers include Al. 2 O 3 , ZrO 2 , Y 2 O 3 , BeO, MgO, La 2 O 3 , TiO 2 , Mullite (Al 6 O 13S 2 ), Forsterite (Mg 2 SiO 4 ), steatite (MgO SiO 2 These may be used alone or in combination of two or more.

[0028] The relative density of the glass member 2 is not particularly limited as long as the effect of the technology disclosed herein can be obtained, but is typically 80% or more, and from the viewpoint of improving nitridation resistance, it may be preferably 85% or more, more preferably 90% or more, even more preferably 95% or more, 97% or more, and particularly preferably 99% or more (however, the upper limit is 100%). When the glass member 2 has a high relative density (i.e., has excellent gas barrier properties), it is preferable because a glass-metal composite 1 having better nitridation resistance can be obtained. In addition, in the present specification and claims, "relative density" refers to the bulk density calculated based on the Archimedes method divided by the true density measured by the pycnometer method. Specifically, first, the dry weight W of the glass member is 1 and the weight W of the glass member when immersed in water (e.g., distilled water). 2 and the weight of water contained in the glass member when it is taken out of the water and the water droplets on its surface are removed. 3 Then, the weight in water W 2 Water density σ at the water temperature at the time of measurement w The bulk density is calculated based on the following formula (I) using the above. (bulk density) = W 1 σ w / (W 3 -W 2 ) · · · (I) Next, the relative density is calculated based on the true density of the sample calculated by the pycnometer method and on the basis of the following formula (II). (Relative density) = (bulk density) / (true density) (II) The series of measurements as described above can be carried out based on a conventionally known measurement method for this type of measurement.

[0029] The thermal expansion coefficient of the glass member 2 is not particularly limited as long as the effects of the technology disclosed herein can be obtained, but from the viewpoint of suitably preventing damage to the covered portion, it is preferable that the thermal expansion coefficient of the glass member is close to that of the metal member to be covered. The thermal expansion coefficient of such a glass member is, for example, 8.0×10 -6 K -1 ~13.0×10 -6 K -1 (Preferably 8.7 x 10 -6 K -1 ~12.3×10 -6 K -1 In this specification, the term "thermal expansion coefficient" refers to the average expansion coefficient (average linear expansion coefficient) measured using a thermomechanical analysis (TMA) in the temperature range from 30°C to 500°C, and refers to the value obtained by dividing the amount of change in sample length relative to the initial length of the sample by the temperature difference. The thermal expansion coefficient can be measured, for example, in accordance with JIS R3102:1995 or the like.

[0030] <Ceramic component 3> The ceramic member 3 according to the present embodiment is a member mainly composed of ceramic. In this specification and claims, "ceramic" (hereinafter also referred to as "ceramic component") refers to an inorganic compound not limited to oxide, and may be an inorganic compound not corresponding to glass (amorphous structure). In addition, the above-mentioned "mainly composed of ceramic" means that the component that is contained most in weight of the components constituting the ceramic member 3 is the ceramic component. Such a ceramic member may preferably contain 95% by weight or more, 97% by weight or more, or 99% by weight or more of the ceramic component. In addition, components other than the ceramic component may be, for example, various metal elements and nonmetal elements as unavoidable impurities. Examples of such ceramic components include Al2O3, MgO, BeO, ZrO2, TiO 2 , Y 2 O 3Examples of such materials include mullite, forsterite, steatite, boron nitride (BN), aluminum nitride (AlN), silicon nitride (Si3N4), and boehmite (AlOOH). These materials may be used alone or in combination of two or more.

[0031] <Metal material 4> As shown in FIG. 1, the metal member 4 according to this embodiment is a rectangular plate-like member. The metal member 4 is not particularly limited as long as the effect of the technology disclosed herein can be exhibited, but for example, one containing Fe, Cr and Al as constituent elements can be preferably used. Examples of such metal members include stainless steel containing Fe, Al, Cr, Ti and Si in a predetermined ratio, stainless steel containing Fe, Al, Cr and Ti in a predetermined ratio, and stainless steel containing Fe, Cr and Al in a predetermined ratio. Metal members having such a configuration are excellent in heat resistance at 1000° C. or more, and therefore can be preferably used. When stainless steel containing Al is used as the metal member 4, an alumina layer or a chromium oxide layer (Cr 2 O 3 ) etc. can be formed.

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

[0033] <Lead 5> The lead 5 according to this embodiment is a lead made of metal. As shown in Fig. 1, the lead 5 has a rectangular plate shape and is provided on one short side of the metal member 4. The material constituting the lead 5 is not particularly limited as long as it can exert the effects of the technology disclosed herein, and for example, a material exemplified in the description of the metal member 4 can be used.

[0034] <Production method of 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 manufacturing method of the glass-metal composite disclosed herein. Also, the steps described below can be carried out in an appropriate order.

[0035] First, prepare the glass material that constitutes the glass member 2. Specifically, prepare industrial products, reagents, or various mineral raw materials containing oxides, carbonates, nitrates, composite oxides, etc. of the various components that constitute the glass material, and mix them to obtain the desired composition ratio. Such mixing can be performed, 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 under a predetermined temperature condition (typically 1300°C to 1500°C) to melt the raw material powder. The molten raw material powder is then cooled (preferably quenched) to obtain a desired glass body. The obtained glass body is crushed and classified (sieved) until it has a desired size (particle size), to obtain a glass material in the form of cullets or powder. The average particle size of such a glass material can typically be 0.5 to 50 μm (for example, 1 to 40 μm or 2 to 30 μm). In this specification, the term "average particle size" refers to the particle size (D) corresponding to 50% of the cumulative value from the smallest particle size side in a volume-based particle size distribution based on a laser diffraction / scattering method. 50 This measurement can be carried out, for example, using a Mastersizer 3000 manufactured by Malvern Instruments.

[0036] The glass material prepared as described above, a solvent, and optionally a binder, etc., are stirred and mixed by a conventionally known method using a rotary mixer equipped with an agitator, a roll mill, a ball mill, etc., to obtain a glass slurry. The viscosity of the glass slurry is preferably adjusted appropriately, but can typically be 0.1 to 20 [Pa·s] (e.g., 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). The viscosity can be measured, for example, using a commercially available viscometer, based on the manual accompanying the viscometer. Here, the content of the above glass material is not particularly limited as long as the effects of the technology disclosed herein are exhibited. For example, when the weight of the glass slurry is 100% by weight, the content can be set to about 90% by weight or less, typically 40 to 85% by weight, for example, in the range of 60 to 80% by weight.

[0037] The content of the solvent is not particularly limited, but may be, for example, within the range of about 60% by weight or less, typically 15 to 50% by weight, for example 20 to 40% by weight, when the weight of the glass slurry is 100% by weight. As the solvent, those usually used in glass slurries can be used, and examples thereof include 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 may be, for example, within the range of about 20% by weight or less, typically 1 to 15% by weight, for example 2 to 10% by weight, when the weight of the glass slurry is 100% by weight. In addition, as the binder, those usually used in glass slurries can be used, and examples thereof include cellulose-based resins such as ethyl cellulose, methyl cellulose, nitrocellulose, cellulose acetate, cellulose propionate, and cellulose butyrate, or acrylic resins made of polymers or copolymers such as methyl (meth)acrylate, ethyl (meth)acrylate, normal 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 phthalic acid esters, and one or more of these can be appropriately selected and used.

[0039] The glass slurry may contain additive components such as inorganic filler, color pigment, thixotropy imparting agent, dispersant, plasticizer, antioxidant, defoamer, leveling agent, etc., as necessary. As the above components, those usually used in glass slurries can be used. For example, as the above inorganic filler, one or more of those described in the explanation of the components other than the glass components that may be contained in the glass member 2 can be used in combination. When the glass slurry contains an inorganic filler, the content of the inorganic filler is not particularly limited as long as the effect of the technology disclosed herein is exhibited, but can be set to about 30% by weight or less, typically 1 to 25% by weight, for example, within the range of 2 to 20% by weight, when the weight of the glass slurry is 100% by weight.

[0040] The glass slurry prepared as described above is applied onto a carrier sheet having a predetermined thickness and dried to obtain a glass green sheet. Such application can be carried out, for example, by a doctor blade method or the like. Next, a ceramic member (ceramic sintered body) is prepared. Here, a commercially available ceramic member is used, but of course a ceramic member produced based on a conventionally known method may also be used. Then, a metal member having two leads is sandwiched between the glass green sheet and the ceramic member produced as described above, and integrated with an adhesive or the like. Here, the metal member may be one that has been heat-treated in advance in an oxidizing atmosphere at a predetermined temperature (for example, 1000°C to 1100°C) for several hours (for example, about 1 to 2 hours) in order to ensure heat resistance. Examples of such adhesives include acrylic resins such as polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polybutyl acrylate, and cyanoacrylate. The thus integrated product is placed on an alumina setter, degreased at a prescribed temperature (e.g., 200°C to 600°C) for several hours (e.g., about 2 to 3 hours), and fired at a prescribed 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] In the above manufacturing method, a manufacturing method using a glass green sheet has been described, but the method is not limited thereto, and the glass-metal member 1 can also be obtained by placing a metal member 4 on a ceramic member 3, coating the metal member with a glass slurry so as to cover it, drying it, and then firing it. In the above manufacturing method, the integrated members are placed on an alumina setter and fired, but the method is not limited thereto, and firing by hanging or in sand, for example, is also possible.

[0042] <Modification> Although specific examples of the glass-metal composite (and the manufacturing method of the glass-metal composite) disclosed herein have been described in detail above, the glass-metal composite disclosed herein is not limited to such specific examples. The glass-metal composite disclosed herein includes various modifications of the above-mentioned specific examples as long as the purpose of the glass-metal composite is not changed.

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

[0044] The glass-metal composite according to the above embodiment includes the glass member 2 and the ceramic member 3, but is not limited thereto. For example, the glass-metal composite may have the ceramic member 3 changed to the glass member 2, or the ceramic member 3 changed to a glass member having a composition different from that of the glass member 2. A glass-metal composite in which the ceramic member 3 is changed to 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 the two, and then firing, etc. Also, a glass-metal composite in which the ceramic member 3 is changed to a glass member having a composition different from that of 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 the two, and then firing, etc.

[0045] Furthermore, for example, when the metal member is cylindrical, the glass member may cover the outside and / or inside of the cylindrical metal member. Such a covering may be a part or the entire outside, or a part or the entire inside.

[0046] In the above embodiment, both the glass member 2 and the ceramic member 3 are hexahedral in shape, but this is not limiting, and for example, glass members and / or ceramic members that do not have four corners may be used.

[0047] In the above embodiment, the metal member 4 is provided with two leads 5, but it is not limited thereto, and the metal member in the glass-metal member disclosed herein may not have leads. That is, the glass-metal member disclosed herein may have a configuration in which the metal member is sandwiched between a composite of a glass member and a ceramic member. In such a glass-metal component, the metal component may be in a form that protrudes from one short side of the composite of the glass component and the ceramic component, or in addition to a part of the short side of the metal component, a part of the metal component may also protrude from the short side corresponding to the opposite side of the one short side. Also, the entire metal component may be covered (embedded) by the composite. Note that, even when the glass-metal component is in such a form, the modified examples described in paragraphs 0043 to 0046 can be applied.

[0048] [Example] Examples of the glass-metal composite disclosed herein are described below, but it is not intended that the present invention be limited to such examples.

[0049] 1. Preparation of Glass-Metal Composites In this example, 22 types of glass-metal composites (samples 1 to 22) were produced. The production method of each sample will be described below.

[0050] 1-1. Preparation of glass materials A to I and green sheets containing each glass material First, each raw material powder was prepared and mixed so as to obtain the composition (mol%) shown in the corresponding column of Table 1. Then, a glass body was obtained by melting at 1300°C to 1500°C for 1 hour and quenching. The glass body was crushed and classified to obtain glass materials A to I. Here, the average particle size of glass materials A to I was about 10 μm. Next, the glass material prepared as above was mixed with a commercially available acrylic resin, a phthalate ester, and xylene, and stirred to obtain a glass slurry. Here, the blending amounts of the above components were such that, when the weight of the above glass slurry was 100% by weight, the glass material was 60% by weight, the acrylic resin was 10% by weight, the phthalate ester was 5% by weight, and the remainder was xylene. Then, the glass slurry prepared as above was applied onto a carrier sheet by a doctor blade method, dried, and cut into a size of 60 mm long x 40 mm wide, and the carrier sheet was peeled off to produce a green sheet containing glass materials A to I with a thickness of about 1.5 mm.

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

[0052] 1-3.Preparation of metal materials Heat-resistant ferritic stainless steel foils (specifically, NCA-1 and NCA-2 manufactured by Nippon Steel Corporation, and JFE20-5USR and JFE18-3USR manufactured by JFE Steel Corporation) were prepared, each having a length of 80 mm and a width of 15 mm (35 mm and 15 mm were also prepared for evaluation in 4-2 described later) and a thickness of 30 to 100 μm. NCA-1 was used for samples 1 to 10, 14 to 16, and 18 to 22, NCA-2 for sample 11, JFE20-5USR for sample 12, and JFE18-3USR for sample 13. Each metal foil was previously heat-treated at 1100°C for 1 hour in an oxidizing atmosphere in order to ensure heat resistance. For sample 17, SUS430 (thickness 50 μm) manufactured by Nilaco Corporation was used as is.

[0053] 1-4. Preparation of samples 1-9, 11-13, 17-22 A 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 by uniaxial pressing (press pressure: 50 MPa) to integrate them. Here, two types of samples were prepared for each sample: one in which a portion of one short side of the metal foil protruded from the two green sheets, which was used in the evaluation of 4-1 described below, and one in which the entire metal foil was buried between the two green sheets, which was used in the evaluation of 4-2 described below. At this stage, for samples in which the thickness of each of the two layers formed from the green sheets was thicker than 1.0 mm, multiple green sheets were appropriately stacked before pressing. The thus integrated product was placed on an alumina setter, degreased at 200°C to 600°C for 2 hours, and fired in an air atmosphere for 2 hours at the firing temperature shown in the corresponding column of Tables 2 to 4 to produce a glass-metal composite for each sample. The two layers formed from the two green sheets were then polished with a diamond polishing pad to a size of 50 mm long x 30 mm wide, and adjusted to a thickness shown in the corresponding column of Tables 2 to 4.

[0054] 1-5. Preparation of sample 10 A glass-metal composite according to Sample 10 was prepared in the same manner as Sample 6, except that two green sheets made of glass slurry to which ceramic material J was added as an inorganic filler in addition to glass material E were used. Here, the glass slurry was prepared so that, when the weight of the glass slurry was taken as 100% by weight, the glass material E was 45% by weight, the acrylic resin was 10% by weight, the phthalic acid ester was 5% by weight, the ceramic material J was 15% by weight, and the remainder was xylene. Then, the glass slurry prepared as described above was applied onto a carrier sheet by a doctor blade method, dried, and cut into a size of 60 mm long x 40 mm wide, and the carrier sheet was peeled off to prepare a glass green sheet of about 1.5 mm thick according to Sample 10.

[0055] 1-6. Preparation of samples 14 to 16 The metal foil shown in the corresponding column in Table 3 was sandwiched between a glass green sheet made of glass material E and a ceramic sintered body shown in the corresponding column in Table 3, and then integrated with a cyanoacrylate adhesive. Here, the 8% yttria-stabilized zirconia sintered body was prepared by molding ceramic material J by uniaxial pressing (pressing pressure: 50 MPa), firing at 1500°C for 4 hours, and polishing with a diamond polishing pad to obtain a size of 50 mm length x 30 mm width x 1.0 mm thickness. The forsterite sintered body was prepared by molding forsterite powder manufactured by Marusu Glaze Co., Ltd. by uniaxial pressing (pressing pressure: 50 MPa), firing at 1300°C for 4 hours, and polishing with a diamond polishing pad to obtain a size of 50 mm length x 30 mm width x 1.0 mm thickness. The magnesia sintered body was prepared by polishing with a diamond polishing pad to obtain a size of 50 mm length x 30 mm width x 1.0 mm thickness. The relative density of each sintered body was 99% or more based on the true density calculated by the pycnometer method and the bulk density calculated by the Archimedes method. Other than this, glass-metal composites according to Samples 14 to 16 were produced in the same manner as Sample 7.

[0056] 2. Preparation of ceramic-metal composite (preparation of sample 23) 5% by weight of methylcellulose was added to ceramic material J, and the mixture was mixed using a mortar and pestle to obtain granulated powder. Two pieces of the powder were molded using a uniaxial press (pressing pressure: 50 MPa) to measure 60 mm in length, 40 mm in width, and 1.5 mm in thickness. The ceramic-metal composite of Sample 23 was produced in the same manner as Sample 8, except that the firing temperature was set to 1100°C.

[0057] 3. Evaluation tests of glass materials A to I and ceramic material J The thermal expansion coefficients and heat resistance of the glass materials A to I and the ceramic material J prepared as described above were evaluated. Each evaluation will be described below.

[0058] 3-1.Evaluation of thermal expansion coefficient Glass materials A to I and ceramic material J were pressed at a pressure of 50 MPa to produce green compacts with a diameter of 20 mm and a thickness of 7 mm. 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 air atmosphere to obtain fired bodies. Then, the samples were cut into cylindrical shapes with a diameter of 15 mm and a thickness of 5 mm using a diamond cutter, and the thermal expansion coefficients were measured using a thermomechanical analyzer (TMA8310, manufactured by Rigaku Corporation). Specifically, the thermal expansion coefficients were 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. Note that, unlike the other samples, the thermal expansion coefficient of glass material H was calculated from the average linear expansion between 30°C and 300°C. The results are shown in the corresponding columns of Table 1.

[0059] 3-2.Evaluation of heat resistance The fired bodies of the glass materials A to I and the ceramic material J obtained in 3-1 above were subjected to heat exposure (heating time: 100 hours) at heating temperatures varying in 50°C increments in the air atmosphere at 400°C to 1100°C, and the thermal expansion coefficients after the heat exposure were measured. For the measurements, a thermomechanical analyzer (TMA8310, manufactured by Rigaku Corporation) was used. The highest temperature among the temperatures at which it was confirmed that the rate of change in the thermal expansion coefficient before and after the heat exposure was 10% or less was determined as the "material heat resistance temperature." The results are shown in the corresponding columns in Table 1.

[0060] 3-3. Evaluation of relative density The glass materials A to I and ceramic material J obtained in 3-1 above were heat-treated at about 1000°C for 2 hours to obtain fired products, which were then subjected to relative density measurement based on the Archimedes method. 1 Next, each glass product was immersed in distilled water and then placed in a desiccator equipped with a vacuum pump. After 45 minutes of vacuuming, the weight of each product in water W 2 and the water content W 3 The weight in water W 2 Water density σ at the temperature at which the measurement was performedw The bulk density was calculated based on the following formula (I). (bulk density) = W 1 σ w / (W 3 -W 2 ) · · · (I) Each of the sintered bodies was thoroughly crushed in an agate mortar, and the true density was measured using a pycnometer (AccuPycII1340, manufactured by Micromeritics). The relative density was calculated based on the bulk density and true density according to the following formula (II). (Relative density) = (bulk density) / (true density) (II) The results are shown in the corresponding columns in Table 1. Note that glass material H is shown as "-" because it melted during the above heat treatment.

[0061] 3-4. Evaluation of the presence or absence of crystallized areas The glass materials A to I and ceramic material J were evaluated for the presence or absence of crystallized parts. Specifically, the compacts of glass materials A to I and ceramic material J obtained in 3-1 above were heat-treated at about 1000°C for 2 hours, and then the obtained glass bodies and ceramic bodies were crushed to obtain powdered samples. Then, the powdered samples were subjected to powder X-ray crystal diffraction (XRD) to confirm the presence or absence of crystal precipitation. For this measurement, an X-ray diffractometer (Rigaku Corporation, RINT-TTRIII) was used. At this time, the samples in which no crystals were confirmed were marked as "absent," and the samples in which crystals were confirmed were marked as "present." The results are shown in the corresponding columns in Table 1. Note that glass material H was marked as "-" because it melted during the heat treatment.

[0062] [Table 1]

[0063] 4. Evaluation test of glass-metal composite (or ceramic-metal composite) Heat resistance and corrosion resistance were evaluated for Samples 1 to 23 prepared as described above. Each evaluation will be described below.

[0064] 4-1.Evaluation of heat resistance Each glass-metal composite was obtained by firing a portion of one short side of the metal foil protruding from the green sheet, and was subjected to a heat treatment at 1000°C for 2 hours. At this time, samples in which a crack had occurred in either one of the two layers, the two layers had peeled off, or the glass material had melted and adhered to the alumina setter, and other samples in which the shape could not be maintained, were marked with an "X". After the above heat treatment, the metal foil of the samples that had maintained the shape before the heat treatment was folded 90° in the plane direction. At this time, the oxide coating (specifically, Al 2 O 3 Or Cr 2 O 3 The results are shown in the corresponding columns of Tables 2 to 4.

[0065] 4-2.Evaluation of corrosion resistance For the samples that were evaluated as "good" in the heat resistance evaluation, the glass-metal composite obtained by firing the metal foil in which the entirety was embedded in the glass layer (or ceramic layer) was 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. The composite after such exposure was filled with resin and cut with a diamond cutter to expose the cross section of the glass layer (or ceramic layer) and the metal foil. Then, the cross section was analyzed with EDX (Energy Dispersive X-ray) to measure the thickness of the nitride layer, which is a layer in which nitrogen and chromium coexist. It is considered that the above-mentioned nitride layer is preferably detected with a thickness of 2 μm or less, and more preferably is not detected (i.e., ND). Based on this, the nitride layer confirmed to be more than 2 μm was marked as "x", the nitride layer confirmed but was 2 μm or less was marked as "△", and the nitride layer not confirmed to be "good". The results are shown in the corresponding columns of Tables 2 to 4.

[0066] 4-3. Overall evaluation Based on the results of the above evaluations, the evaluations of both heat resistance and corrosion resistance were marked as "good", those of heat resistance and / or corrosion resistance were marked as "good", and those of heat resistance and / or corrosion resistance were marked as "bad", and those of heat resistance and / or corrosion resistance were marked as "bad". The results are shown in the corresponding columns in Tables 2 to 4.

[0067] [Table 2]

[0068] [Table 3]

[0069] [Table 4]

[0070] From the above results, it was confirmed that the glass-metal composites according to Samples 1 to 13, which are glass-metal composites comprising a metal foil (i.e., a metal member) and a glass member covering at least a part of the metal foil, in which the glass member has a crystallized portion in an amorphous matrix and a material heat resistance temperature of 1000°C or higher, suitably achieve both heat resistance (specifically, about 1000°C to 1100°C) and nitridation resistance. It was also confirmed that the glass-metal composites according to Samples 14 to 16, in which one layer is a glass member and the other layer is a ceramic sintered body (i.e., a member mainly made of ceramic), suitably achieve both. On the other hand, it was confirmed that Sample 23, in which both layers are ceramic members, does not have sufficient nitridation resistance. Thus, the glass-metal composite disclosed herein can provide a composite that favorably achieves both heat resistance and nitridation resistance. [Explanation of symbols]

[0071] 1. Glass-metal composite 2 Glass components 3 Ceramic components 4 Metallic parts 5 Lead S Thickness of metal part 4 T thickness of glass member 2

Claims

1. A metal member; a glass member covering at least a portion of the metal member; A glass-metal composite comprising: In the glass member, a crystallized portion is mixed in an amorphous matrix, and a sintered body made of a compact of glass powder constituting the glass member is subjected to the following conditions: Temperature: 1000° C. (in air); Time: 100 hours; The glass-metal composite has a thermal expansion coefficient that changes by 10% or less when the glass-metal composite is left at room temperature.

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

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

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

5. 5. The glass-metal composite according to claim 1, wherein the glass member has a relative density based on Archimedes' method of 95% or more.

6. 6. The glass-metal composite according to claim 1, wherein the glass member does not contain any alkali metal element, lead, arsenic, or cadmium.

7. The thermal expansion coefficient of the glass member from 30° C. to 500° C. is 8.0×10 －６ K －１ ~13.0 x 10 －６ K －１ 7. The glass-metal composite of claim 1, wherein

8. 8. The glass-metal composite according to claim 1, wherein the metal member contains Fe, Cr and Al as constituent elements.

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