JP2015205800A - High thermal expansion filler composition and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-free high thermal expansion filler composition containing no alkali metal component.SOLUTION: The filler composition disclosed herein is added as a filler to a glass bonding material. The filler composition contains a compound represented by general formula (1): AMSiO(where A is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and M is at least one element selected from the group consisting of Fe, Ni and Co). The filler composition contains substantially no alkali metal component. In a preferred embodiment, the coefficient of linear thermal expansion at 25 to 500°C is 20-30 ppm/K.

Description

  The present invention relates to a filler composition. Specifically, the present invention relates to an alkali-less high thermal expansion filler composition added as a filler (filler) to a glass bonding material.

  Metal materials and ceramic materials are widely used in various devices, devices, apparatuses and the like in various industrial fields. For joining between members made of such materials (for example, joining between metal members or joining between a metal member and a ceramic member), various joining materials are used depending on the use of the member. For example, when joining parts that can be exposed to a high temperature range (for example, a temperature range of 500 ° C. or higher), (1) the coefficient of thermal expansion is the same as or slightly lower than that of the member to be joined (metal member or ceramic member). ) A bonding material having excellent heat resistance and durability in a high temperature range (for example, 500 ° C. to 1000 ° C.) is selected and used.

Patent Documents 1 and 2 and Non-Patent Document 1 are cited as prior art documents related to (1) above. In these documents, a technique using a leucite crystal (KAlSi ₂ O ₆ or 4SiO ₂ · Al ₂ O ₃ · K ₂ O) for adjusting the thermal expansion coefficient of the base material is disclosed. The leucite crystal is said to have a thermal expansion coefficient of about 20 ppm / K to 30 ppm / K, and is known for its high thermal expansion coefficient. For example, in Patent Documents 1 and 2, a high thermal expansion coefficient leucite crystal is precipitated in a glass matrix to achieve a thermal expansion coefficient comparable to that of the member to be joined, and has the above conditions (1) and (2). Realized glass bonding material.

JP 2009-195864 A JP 2009-199970 A

Takeshi Hoshikawa, “Low-fusible leucite glass ceramics for aesthetic restoration crowns”, Journal of High Temperature Society, November 2007, Vol. 33, No. 6, p. 293-299

  By the way, in recent years, the industry has been making efforts to use inexpensive metal materials (for example, stainless steel, copper, aluminum, etc.) without coating treatment due to cost reduction or the like. In connection with this, the alkali metal component (for example, potassium (K) contained in a leucite crystal) contained in a glass bonding material may become a problem. Specifically, when a glass bonding material containing an alkali metal component is used for bonding the inexpensive metal material, the metal material and the alkali metal component react at a high temperature range of 500 ° C. or higher, thereby stabilizing the joint. Deterioration (for example, adhesiveness and durability) may be caused. Under such circumstances, a highly thermally expandable filler that does not contain an alkali metal component (no alkali) is required.

  The present invention has been made in view of the above problems, and the object thereof is a filler composition that is added as a high thermal expansion filler (filler) to a glass bonding material for bonding and sealing metal members and ceramic members. Then, it is providing the filler composition which does not contain an alkali metal component. Another related object is to provide a method for easily producing such a filler composition.

As a result of intensive studies on various fillers, the present inventor has found a means that can solve the above-mentioned problems, and has completed the present invention.
The filler composition disclosed here is added as a filler to the glass bonding material. Such a filler composition has the following general formula (1): AMSi ₂ O ₆ (where A is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and M is Fe, And at least one element selected from the group consisting of Ni and Co.)). And it is characterized by not containing an alkali metal component substantially.

The filler composition disclosed herein is substantially free of alkali metal components (for example, Li, Na, K, Rb, Cs, Fr. In particular, Li, Na, K.). For this reason, for example, even when the filler composition is used for a glass bonding material for bonding an inexpensive metal material (for example, stainless steel) that has not been coated, the above-described problems can be prevented in advance. Can do. Moreover, although this filler composition contains the compound shown by the said General formula (1), it can implement | achieve a high thermal expansion coefficient in spite of being alkali-less (alkali free). For this reason, in the glass bonding material containing the filler composition, for example, a high thermal expansion coefficient can be realized that is approximately the same as that of a metal member or ceramic member having a large thermal expansion coefficient.
In the present specification, “substantially does not contain an alkali metal component” means that an alkali metal component (element) is not added at least actively. In other words, it is acceptable that an alkali metal component (an alkali metal element or a compound containing the element) is mixed as an inevitable impurity. Specifically, it is acceptable that the alkali metal component is mixed in a proportion of 1% by mass or less (preferably 0.5% by mass or less, more preferably 0.1% by mass or less) of the whole filler composition.

In one preferred embodiment of the filler composition disclosed herein, the linear thermal expansion coefficient of 500 ° C. from 25 ° C. is 20ppm / K~30ppm / K (20 × 10 -6 / K~30 × 10 -6 / K) It is. Thereby, the linear thermal expansion coefficient of the glass bonding material containing the filler composition can be suitably adjusted to about 10 ppm / K to 20 ppm / K, which is substantially the same as that of a metal member or ceramic member having a large thermal expansion coefficient. .
In this specification, “linear thermal expansion coefficient” is an average linear expansion coefficient measured in a temperature range from 25 ° C. to 500 ° C. using a general thermomechanical analyzer (TMA). The value obtained by dividing the amount of change in the sample length relative to the initial length of the sample by the temperature difference. The linear thermal expansion coefficient can be measured according to JIS R 3102 (1995).

  In a preferred embodiment of the filler composition disclosed herein, the compound represented by the general formula (1) accounts for 80% by mass or more (for example, 80% by mass to 100% by mass) of the whole filler composition. Thereby, a high thermal expansion coefficient can be realized stably. Therefore, the effect of the present invention can be exhibited at a higher level.

  In a preferred embodiment of the filler composition disclosed herein, the compound represented by the general formula (1) is present as a crystal. A glass bonding material including such a crystal body (crystalline filler) can exhibit more excellent durability in a high temperature range, for example. Therefore, the effect of the present invention can be exhibited at a higher level.

  In a preferred embodiment of the filler composition disclosed herein, the glass bonding material is a glass bonding material for sealing and bonding one metal member and one other member. The metal material constituting the metal member generally has a large thermal expansion coefficient, for example, stainless steel (SUS) is approximately 10 ppm / K to 15 ppm / K, copper is approximately 17 ppm / K, and aluminum is approximately 23 ppm / K. For this reason, by including the filler composition disclosed herein in the glass bonding material, it is possible to match the thermal expansion coefficient with the metal member having a large thermal expansion coefficient, and it is preferable to use a joint portion having excellent airtightness. Can be realized.

This invention provides the manufacturing method of the filler composition added as a filler to a glass joining material as another side surface. Such a production method has the following general formula (1): AMSi ₂ O ₆ (where A is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and M is Fe, Ni). And at least one selected from the group consisting of Co.). Then, the preparation is performed by the following sub-process: A element source, M element source and silica are mixed at a predetermined ratio to prepare a mixture, wherein the mixture substantially contains an alkali metal component. And firing the mixture that does not contain the alkali metal component. According to such a production method, the alkali-less filler composition disclosed herein can be suitably produced.

  Hereinafter, preferred embodiments of the present invention will be described. Note that matters necessary for the implementation of the present invention other than matters specifically mentioned in the present specification (for example, characteristics of the composition and physical properties of the filler composition) are based on conventional technology in the field. It can be grasped as a design item of the trader. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.

≪Filler composition≫
The filler composition disclosed here is typically added to the glass bonding material as a filler in order to improve the thermal expansion coefficient. Such a filler composition contains a compound represented by the following general formula: AMSi ₂ O ₆ (1);
In the general formula (1), A is a Group 2 element, that is, at least one element of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). M is at least one element selected from so-called iron group elements, that is, iron (Fe), nickel (Ni), and cobalt (Co).

The compound represented by the general formula (1) can achieve a high thermal expansion coefficient without containing an alkali metal element. Specifically, a high thermal expansion coefficient can be realized by including the A element and the M element. Among these, the selection of the M element can greatly affect the thermal expansion coefficient. According to the inventor's study, if the element A is the same, the coefficient of thermal expansion is highest when cobalt is included in the element M, and the coefficient of thermal expansion is then increased when nickel is included. Moreover, when iron is contained in the M element, the coefficient of thermal expansion is relatively lowest.
Silicon (Si) is an element constituting the skeleton of the general formula (1). By including silicon, excellent high temperature durability, chemical resistance, thermal shock resistance and the like can be realized. Moreover, the compound shown by the said General formula (1) can implement | achieve the outstanding physical stability and thermal stability by containing A element. Moreover, the compound shown by the said General formula (1) can implement | achieve high heat resistance and durability in a high temperature range by containing M element. Further, it is possible to match the physicochemical properties with the member to be joined (for example, a metal member).

  The filler composition disclosed here contains substantially no alkali metal component. Specifically, an alkali metal element (typically Li, Na, K, Rb, Cs, Fr, particularly Li, Na, K) and a compound containing the element are not included. Thereby, the stability fall of a glass bonding material can be prevented beforehand.

The filler composition disclosed herein may be substantially composed of only the compound represented by the general formula (1), or a secondary component other than the compound having the compound as a main component. (Compound) may be contained in a proportion of less than 50% by mass (typically 30% by mass or less, for example, 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less). Further, it goes without saying that a minute amount of a component (compound) due to inevitable impurities or the like is allowed.
Examples of secondary components include oxide forms such as magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), barium oxide (BaO), iron oxide (FeO, Fe ₂ O). ₃ , Fe ₃ O ₄ ), nickel oxide (NiO, Ni ₂ O ₃ ), cobalt oxide (CoO, Co ₂ O ₃ , Co ₃ O ₄ ) and the like.

In a preferred embodiment, the compound represented by the general formula (1) is 80% by mass or more (typically 80% by mass to 100% by mass, preferably 90% by mass to 100% by mass) of the entire filler composition, More preferably 95% to 100% by mass). Thereby, a high thermal expansion coefficient can be realized stably.
Or even if the compound shown by the said General formula (1) is 80 mass% or more (for example, 85 mass% or more) of the whole filler composition, and occupies 95 mass% or less (for example, 90 mass% or less). Good. Thereby, productivity and workability can be improved, and further cost reduction can be realized.

  In a preferred embodiment, the filler composition disclosed herein substantially contains one or more components of a boron (B) component, an arsenic (As) component, and a lead (Pb) component in addition to the alkali metal component. Not included. For example, the boron component is likely to be scattered in a high temperature range (for example, a temperature range of 700 ° C. or higher), which may change the thermal expansion coefficient or reduce the mechanical strength of the joint. For this reason, when considering use in such a high temperature range, it is not preferable from the viewpoint of maintaining long-term durability (particularly long-term high-temperature durability). Moreover, since an arsenic component and a lead component may have a bad influence with respect to a human body and an environment, it is preferable to set it as minimum use from a viewpoint of environmental property, workability | operativity, and safety.

In the filler composition disclosed herein, almost all (for example, 90% by mass or more of the whole filler composition) may be present as a crystal (crystalline filler), or only a part is present as a crystal. Or almost all may exist as an amorphous material (amorphous, ie, an amorphous filler).
In a preferred embodiment, the composition represented by the general formula (1) is present as a crystal. For example, by depositing the crystalline filler in an alkali-less amorphous glass matrix, it is possible to realize an alkali-free glass bonding material that is highly thermally expandable and that is further superior in heat resistance and durability in a high temperature range. Can do.

As described above, the filler composition disclosed herein is highly thermally expandable. That is, it is alkali-free (alkali-free) and has a high thermal expansion coefficient. In a preferred embodiment, the linear thermal expansion coefficient from 25 ° C. to 500 ° C. is 18 ppm / K or more (typically 20 ppm / K or more, for example, 22 ppm / K or more, dare to say 23 ppm / K or more), and 40 ppm / K or less (typically 30 ppm / K or less, for example, 28 ppm / K or less). Thereby, it is possible to match the thermal expansion coefficient at a high level with a member to be joined (for example, a metal member) having a large thermal expansion coefficient, and it is possible to realize an airtight and favorable bonding.
In addition, as a filler which does not contain an alkali metal component (alkali metal element) and can exhibit relatively high thermal expansion and heat resistance, magnesium oxide (MgO), lanthanum strontium iron oxide (LaSrFeO ₃ ), yttrium-based superconductor (YBCO, YBa ₂ Cu ₃ O ₇ ) and the like are already known. However, since these fillers have a thermal expansion coefficient of about 15 ppm / K at the maximum, which is lower than the filler composition disclosed here, a large amount of these fillers are added to the glass bonding material in order to achieve a high thermal expansion coefficient. There is a need. Therefore, the original functionality (for example, durability and chemical stability) of the glass can be reduced.

The shape of the filler disclosed here is not particularly limited, and may be, for example, a plate shape, a small piece shape, a particle shape (powder shape, powder shape), a needle shape, or the like. In a preferred embodiment, it has a generally spherical shape, a slightly distorted spherical shape or the like. Specifically, the ratio (so-called aspect ratio) of the longest side length to the shortest side length (typically thickness) of the particles is 1 or more and 5 or less (typically 2 Or less, preferably 1.5 or less). The “particle shape” can be measured by a general particle image analyzer, for example, a flow type particle image analyzer.
The average particle size of the filler particles is not particularly limited, but is usually about 0.1 μm to 10 μm (typically 1 μm to 5 μm). Thereby, it can disperse | distribute uniformly in a glass bonding | jointing material, and can realize a still higher airtight and high quality bonded part. In the present specification, the “average particle size” means a particle size corresponding to 50% cumulative from the fine particle side in a volume-based particle size distribution measured by a particle size distribution measurement based on a general laser diffraction / light scattering method. (D ₅₀ particle diameter, also called median diameter).

≪Method for producing filler composition≫
Such an alkali-less filler composition can be produced using a method similar to the conventional one (for example, a solid phase reaction method). In a preferred embodiment, the method includes preparing the compound represented by the general formula (1). And for the production, the following sub-steps:
(S10: Preparation of mixture) A element source, M element source and silica are mixed at a predetermined ratio, wherein the mixture is substantially free of alkali metal elements;
(S20: Firing of the mixture) Firing the mixture containing no alkali metal element;
Is included. Specifically, the following procedure can be used.

(S10: Preparation of mixture)
First, an A element supply source, an M element supply source, and silica (SiO ₂ ) as raw materials are prepared.
As the A element supply source, a salt or a complex containing the A element can be preferably used. As the salt containing A element, sulfate, carbonate, nitrate, oxide, hydroxide, halide, sulfide, etc. of A element can be used. Moreover, as an A element-containing complex, an A element-containing ammine complex, hydroxy complex, cyano complex, halogeno complex, or the like can be used.
As the M element supply source, a salt containing M element can be preferably used. As the salt containing M element, sulfate, carbonate, nitrate, oxalate, perchlorate, oxide, hydroxide, halide, sulfide, etc. of M element can be used. In a preferred embodiment, the hydrate form is used.

  Next, these raw materials are weighed and prepared so that the ratio of the A element, the M element, and the Si element is 1: 1: 2, and an additive or the like is added as necessary. This is homogeneously mixed by a conventionally known stirring / mixing means (for example, a ball mill) to obtain a raw material mixture.

(S20: Firing of the mixture)
And after drying the obtained raw material mixture, after heating to suitable temperature (for example, 1400 degreeC-1600 degreeC) with a melting furnace etc., it cools. Thereby, the compound (filler composition) represented by the general formula (1) can be obtained. The firing may be performed once, for example, it may be repeated twice or more with cooling (cooling) interposed therebetween.
In a preferred embodiment, the composition obtained above is prepared into a cullet or powder form by pulverization or sieving (classification). Thereby, an even higher airtight and high quality joint can be realized.

  In another preferred embodiment, the fired product after heating is cooled to room temperature and then pulverized to an appropriate particle size (typically 1 μm to 10 μm). This pulverized product is again subjected to heat treatment (crystallization treatment) at an appropriate temperature (for example, 1000 ° C. to 1200 ° C.). Thereby, a crystal body (crystalline filler) can be suitably obtained.

≪Glass bonding material≫
The filler composition produced as described above can be used in the same manner as conventional fillers. For example, it can be prepared by adding the filler composition to various conventionally known amorphous glasses and used as a glass bonding material.
Amorphous glass can be appropriately selected from alkali-free ones. As a specific example, glass powder mainly composed of various oxides, for example, RO—SiO ₂ —Al ₂ O ₃ —TiO ₂ glass (herein, RO refers to an oxide of a Group 2 element). hereinafter the _{same.), RO-SiO 2 -Al} 2 O 3 -B 2 O 3 based _{glass, RO-SiO 2 -Al 2 O} 3 -Bi 2 O 3 based _{glass, RO-SiO 2 -Al 2 O} 3 -TiO ₂ -B ₂ O ₃ based _{glass, RO-SiO 2 -Al 2 O} 3 -ZnO-SnO type _{glass, RO-SiO 2 -Al 2 O} 3 -PbO based _{glass, SnO-P 2 O 5 -SiO} 2 -Al ₂ O ₃ glass, B ₂ O ₃ —SiO ₂ —ZnO glass, B ₂ O ₃ —SiO ₂ —Bi ₂ O ₃ glass, Bi ₂ O ₃ —B ₂ O ₃ —ZnO glass, PbO—SiO _2- B ₂ O ₃ series glass And SiO ₂ —B ₂ O ₃ —PbO—Li ₂ O-based glass. Of these, the alkali component, boron component, arsenic component, glass that does not contain any lead component (e.g., the _{RO-SiO 2 -Al 2 O 3} -TiO 2 -based glass and _{SnO-P 2 O 5 -SiO 2} -Al ₂ O ₃ glass) can be preferably used.

One in the case of using the _{RO-SiO 2 -Al 2 O 3} -TiO 2 based glass as a preferred example, at a weight ratio of oxide basis, the total of the components shown below than 90% by weight of the total glass (e.g. 95 (Mass% or more) may be prepared.
At least one of MgO, CaO, and BaO 60-80% by mass (for example, 70-75% by mass)
SiO ₂ 10 to 25 wt% (e.g. 15 to 20% by weight)
Al ₂ O ₃ 1~15 wt% (e.g., 5 to 10% by weight)
TiO ₂ 1-5% by mass (eg, 1-3% by mass)
The RO—SiO ₂ —Al ₂ O ₃ —TiO ₂ -based glass may be composed of the main constituent components described above, or may include any component other than those described above. Examples of such additive components include oxides such as ZnO, ZrO ₂ , V ₂ O ₅ , Nb ₂ O ₅ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CuO, Cu ₂ O, and SnO. SnO ₂ , P ₂ O ₅ , La ₂ O ₃ , CeO _{2 and the} like. The ratio of these constituent components is preferably about 5% by mass or less (typically 3% by mass or less, for example, 2% by mass or less) of the whole glass powder in terms of mass ratio in terms of oxide. The same applies to other glass types.

  Moreover, the addition amount of a filler composition is good to set it as 5 mass%-30 mass% (for example, 5 mass%-15 mass%) with respect to the total sum total of a filler composition and amorphous glass, for example. The filler composition disclosed herein has a high coefficient of thermal expansion while being alkali-less. For this reason, the thermal expansion coefficient of the glass bonding material can be improved with a small addition amount. Thereby, for example, a glass bonding material having a thermal expansion coefficient of about 10 ppm / K to 20 ppm / K (typically 10 ppm / K to 15 ppm / K) can be suitably realized. The glass bonding material having such properties can be preferably used for sealing and bonding a member to be bonded (for example, a metal member) having a large thermal expansion coefficient.

  In a preferred embodiment, the filler composition and the amorphous glass are mixed at a predetermined ratio, and then fired at an appropriate temperature and cooled to precipitate the filler composition as a crystal in the amorphous glass. Thereby, the junction part which can be maintained for a long time in a high temperature range can be suitably realized.

≪Members to be joined≫
As a member to be joined (joining target), a member having a thermal expansion coefficient relatively close to that of the glass joining material can be used. For example, a member made of a metal material or a ceramic material having a thermal expansion coefficient similar to or slightly higher than that of the glass bonding material can be suitably used. As a thermal expansion coefficient of such a member, a linear thermal expansion coefficient from 25 ° C. to 500 ° C. is about 10 ppm / K to 25 ppm / K as an approximate guide. Examples of such a metal material include stainless steel (SUS), copper (Cu), and aluminum (Al). Moreover, as a ceramic material, an alumina-based ceramic mainly composed of alumina (aluminum oxide: Al ₂ O ₃ ) can be given.

≪Join method≫
Such a glass bonding material can be widely used, for example, for bonding between one metal member and one other member (for example, bonding between metal members or bonding between a metal member and a ceramic member). Or it can use widely for joining (for example, joining of ceramic members and joining of a ceramic member and a metal member) of one ceramic member and one other member.

The joining of the members to be joined can be performed as follows, for example.
First, a glass bonding material containing the filler composition is prepared. In addition, a member to be joined having a large thermal expansion coefficient is prepared. Next, it arrange | positions so that to-be-joined members (for example, a metal member and a ceramic member) may contact and connect mutually, and the said glass joining material is provided (arrangement or application | coating) to a connection part. And after this composite is dried, it is fired in a temperature range (typically 600 ° C. or higher, for example, 1000 ° C. to 1200 ° C.) higher than the softening point of the glass bonding material. As a result, it is possible to form a joint portion that is excellent in air tightness and excellent in heat resistance and durability even in a high temperature region between the members to be joined having a large thermal expansion coefficient.

  EXAMPLES Examples relating to the present invention will be described below, but the present invention is not intended to be limited to those shown in the following examples.

[Preparation of filler]
First, a total of five types of fillers (S1 to S5) shown in Table 1 below were produced. Specifically, the raw materials shown in Table 1 were mixed so as to have the composition shown in the column of synthetic crystals, melted at 1500 ° C., and then cooled. This was pulverized to produce fillers (S1 to S5) having an average particle diameter of about 1 μm to 5 μm. Moreover, the commercially available filler (S6-S8) was prepared as a comparative example.

[Measurement of linear thermal expansion coefficient]
The prepared fillers (S1 to S5) and commercially available fillers (S6 to S8) were press-molded into prismatic shapes of 7 mm × 7 mm × 50 mm, respectively, and calcined at 1000 ° C. The calcined product after calcination was cut out into a cylindrical shape of about Φ5 mm × 10 to 20 mm with a diamond cutter to obtain a test specimen for measurement. And the linear expansion coefficient of this test piece was evaluated using the thermomechanical analyzer (Rigaku Corporation make, TMA8310). Specifically, the temperature was increased from room temperature (25 ° C.) to 500 ° C. at a constant rate of 10 ° C./min, and the linear thermal expansion coefficient was calculated from the difference in thermal expansion between the test piece and the standard sample. The obtained linear thermal expansion coefficient is shown in Table 1.

  As shown in Table 1, in the magnesium oxide of S7 and YSZ of S8, the linear thermal expansion coefficient showed a relatively low value of 14 ppm / K or less. On the other hand, the filler composition of S1 to S6 showed a relatively high value of linear thermal expansion coefficient of 20 ppm / K to 30 ppm / K. Especially, in the filler composition of S1 to S5 according to the invention disclosed herein, it is possible to realize high thermal expansion (for example, linear thermal expansion coefficient is 23 ppm / K to 28 ppm / K) without containing an alkali metal component. did it.

[Preparation of glass bonding material]
In this test, corresponding glass bonding materials (Examples 1 to 8) were prepared using the fillers (S1 to S8). Specifically, first, as an alkali-less amorphous glass, the following composition in terms of oxide:
BaO 75% by mass
SiO ₂ 17% by mass
Al ₂ O ₃ 7% by mass
TiO ₂ 3% by mass
A glass raw material powder (average particle size: 1 μm to 3 μm) was prepared.
Next, the glass composition and the filler were mixed and mixed so that the mass ratio was 90:10. This was melted at 1500 ° C. and then cooled. The obtained glass composition was pulverized to produce glass bonding materials (Examples 1 to 8) having an average particle diameter of about 1 μm to 5 μm.

[Measurement of linear thermal expansion coefficient]
About the produced glass joining material (Example 1- Example 8), it carried out similarly to the case of the said filler, and measured the thermal expansion coefficient. Table 2 shows the obtained linear thermal expansion coefficients.

As shown in Table 2, the glass bonding materials of Examples 7 and 8 had a relatively low linear thermal expansion coefficient of 7 ppm / K to 9 ppm / K.
On the other hand, in the glass bonding materials of Examples 1 to 6, the linear thermal expansion coefficient showed a relatively high value of 10 ppm / K to 20 ppm / K. In particular, in the glass bonding materials of Examples 1 to 5 according to the invention disclosed herein, an alkali metal component is not included (with no alkali), and high thermal expansion (for example, a linear thermal expansion coefficient of 11 ppm / K to 12 ppm / K) could be realized.

[Evaluation of bondability with stainless steel substrate]
The produced glass bonding materials (Examples 1 to 8) were each press-formed into a disk shape of Φ15 mm × 2.5 mm to prepare pellet-shaped samples. This was placed on a stainless steel (linear thermal expansion coefficient: 10 ppm / K to 15 ppm / K) substrate and baked at 1300 ° C. for about 5 minutes in the atmosphere, thereby attempting to join the pellet and the substrate.
Thereafter, for each laminate, it was confirmed whether or not bonding was realized, and if bonding was realized, it was an airtight bonding portion. Specifically, first, it was confirmed whether or not the pellet could be peeled off from the substrate using tweezers, and evaluated whether or not it was mechanically bonded. About the joined body which can confirm joining, the penetration flaw inspection was further performed and the presence or absence of the crack was confirmed.
The results are shown in Table 2. In Table 2, “◯” indicates that both were mechanically bonded and no crack was confirmed, and “×” indicates that both were not mechanically bonded, or in penetration inspection. This indicates that cracks were observed at the joint.

As shown in Table 2, in Example 7 in which magnesium oxide was added as a filler and Example 8 in which YSZ was added, cracks were observed at the joint with the stainless steel substrate. On the other hand, as a filler, the general formula: AMSi ₂ O ₆ (A is at least one element selected from Mg, Ca, Sr, Ba, and M is at least one element selected from Fe, Ni, Co) In Examples 1 to 5 in which the filler composition containing the element is added) and in Example 6 in which the leucite crystal is added as the filler, the airtightness of the joint is high, and good bonding to the substrate is realized. It was.
From the above, by using the filler composition disclosed herein, it does not contain an alkali metal component, has a thermal expansion coefficient comparable to that of a metal member (here, stainless steel), and It was found that a glass bonding material excellent in bondability could be realized.

  As mentioned above, although the specific example of this invention was demonstrated in detail, these are only illustrations and do not limit a claim. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

Claims (6)

A filler composition added as a filler to a glass bonding material,
The following general formula (1):
AMSi ₂ O ₆ (1)
(Here, A is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and M is at least one element selected from the group consisting of Fe, Ni and Co.) );
Including a compound represented by
A filler composition characterized by containing substantially no alkali metal component.   The filler composition according to claim 1, wherein the linear thermal expansion coefficient from 25 ° C to 500 ° C is from 20 ppm / K to 30 ppm / K.   The filler composition according to claim 1 or 2, wherein the compound represented by the general formula (1) accounts for 80% by mass or more of the entire filler composition.   The filler composition according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is present as a crystal.   The filler composition according to any one of claims 1 to 4, wherein the glass bonding material is a glass bonding material for sealing and bonding one metal member and one other member. A method for producing a filler composition added as a filler to a glass bonding material,
The following general formula (1):
AMSi ₂ O ₆ (1)
(Here, A is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and M is at least one element selected from the group consisting of Fe, Ni and Co);
Wherein the preparation comprises the following sub-steps:
Mixing an A element source, an M element source and silica in a predetermined ratio to prepare a mixture, wherein the mixture is substantially free of alkali metal components; and
Calcining the mixture containing no alkali metal component;
A method for producing an alkali-less filler composition comprising: