JPS58151375A - Adhesive for ceramics and adhesion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive for ceramics and a method for bonding the same, and particularly relates to a non-oxidized #I adhesive such as electrified silicon, silicon carbide, sialon, etc.
IJ-type Sera (Tsukusu Sangyo wo 9 is this and other seven Rikku X
OK and suitable adhesives used for bonding with #family and 0!
I Regarding the method of wearing.

Non-oxide thread ceramics such as silicon carbide, silicon carbide, and sialon are excellent in strength, thermal shock resistance, and chemical resistance, especially at high temperatures. 'fi--As a new high-temperature heat-resistant material, it has been in the spotlight in recent years, and the development of its application fields has been encouraged by woodcutter.For example, these materials include silver II & ware, Gaosho mechanical parts, heat exchangers, etc. Then, the temperature becomes about FCil [i temperature a (transition)]
The development of its use as a special high-temperature insulator in parts is being considered.

In order to use these non-oxide ceramics and fully develop their properties, it is necessary to intermix these non-oxide ceramics with each other during the manufacturing process of various *organs and other parts. Since it is necessary to bond tIt with other materials, it is essential to develop bonding techniques for non-oxide ceramics formed into various shapes.

However, non-oxide No. 7 Foxes generally have very poor affinity for melts, and metal oxides such as Madanesia have strong covalent bonds (unlike Tux materials). The reactivity with other compounds is also very low, and the coefficient of thermal expansion is less than half that of Al.
l The adhesion is extremely difficult. Conventionally, the only known method for adhering 72-layer adhesives is a hot press method under high temperature and high pressure, and the hot press method requires operation under high temperature and high pressure. However, it is extremely difficult to bond materials with large amplitudes and complex irregular shapes, and even if they can be bonded, the bonding strength is still insufficient.

The present inventor has developed a new adhesive that can easily bond materials with large and irregular shapes with sufficient adhesive strength without using the bridge-like F-brazing method and hot pressing method under very mild conditions. We have conducted various research with the aim of providing a bonding method. However, it goes without saying that the above-mentioned non-contributed material adhesive for construction of ceramics has the feature of adhesion with sufficient force, and in addition to this, the adhesive layer itself to be st-g is It is chemically stable, 6υ, and has extremely excellent heat resistance, heat shock resistance S4 & etc. that does not impair the properties of the above-mentioned non-oxide-based ceramics (Tuxus), and Kaede is known for its adhesive properties. The active ingredients of ``Kurenogo'' did not meet the above requirements.The inventors of the present invention found that sodium heptaphide and/or calcium heptaphide in particular met the above requirements. It has been found that these materials are suitable for adhesion not only of non-enemy-based sexics but also of oxide-based ceramics, and a separate patent application is currently being applied for. We found that alkali metal heptadides and/or alkaline earth metal fufluorides had similar effects, and this book!
i! If! The one that completed A is Ruru.

That is, the present invention provides an alkali metal fluoride and an alkaline earth metal fluoride (provided that sodium fluoride and/or
At least 11111.<o) excluding calcium heptadide. Or use a mixture of this and kaolin as an active ingredient as an adhesive for shaking and the above-mentioned mm agent between non-oxide-based selan-tux or oxide-based seran-tux or #FIm, chemical-based rc9 is a method for adhering ceramics, which is characterized in that 7-fox and oxide-based ceramics are fused together and heated to a temperature higher than m degrees for the decomposition of 7-fox.

'4 Example bonded steel is simply a non-saponifiable type of ceramic bonded steel, or an oxide type of ceramic type bonded steel. Usually about 1000-1500℃, preferably about 106
0 N By simply heating to 1,400°C, it is possible to bond ceramics to a container without applying pressure to any part. At this time, as the proportion of alkali gold@7) in the adhesive increases, it becomes possible to bond at a lower temperature within the above heating temperature range.

The IJa adhesive of the present invention has a great advantage in that it can sometimes bond non-oxide ceramics, and in this case, the bonding rate is 5.1 degrees.
'F/- is also 6, and the ri is about 80 using a known method.
0 ``I/- or - Good and rarely more than 80% of the time
I pray for the improvement of t-p. Furthermore, the adhesive of the present invention can be effectively applied to bonding large xm*es irregularly shaped non-metallic ceramic materials that cannot be bonded by known methods, and can also strongly bond second grade materials. In addition, the adhesive layer of the present invention is chemically stable and has heat resistance and thermal shock resistance almost comparable to non-oxide-based SEXXX.

The reason why each of the above-mentioned extremely outstanding effects can be achieved by using the adhesive of the present invention is not clear at present, but it is thought to be as follows. That is, the alkali metal heptaphide or Fi (and) alkaline earth metal fluoride constituting the adhesive of the present invention can be used as a non-oxidation-based cefix interlayer, as a metalloid yarn cefix interrelationship, or as a non-saponifiable substance. When heated to a temperature higher than the decomposition temperature of the oxides intervening between the Cefix and the oxide ceramics, it decomposes and generates 7 bulk gas, and the fluorine gas decomposes the ceramic material.
! While it erodes the surface, the alkali metal or (
and) an alkaline earth metal, or a reaction product of this metal and p-olin, penetrates into the material that has been eroded by the above method, and forms an adhesive layer having excellent adhesive strength between the adhered materials. considered to be a thing. In the case of the adhesive of the present invention in which kaolin is used in combination, the kaolin activates the alkali metals and/or alkaline earth metals produced by the heating, further promoting their penetration into the ceramic material. It seems to be. In any case, the present invention provides a new adhesion technology for Ceraix,69 and in particular it establishes a new adhesion technology for non-oxidized Celaix, for which no effective bonding method has been available in the past. This will not only expand the fields of use for non-oxide ceramics, but also contribute to the further development of various fields that require high-temperature heat-resistant materials.

The non-enemy type Selantux to which this adhesion is applied is:
Examples of friends include expanded silicon, silicon nitride, and sialoa. r@suiaguchi/ means electrification of cum in silicon and aluminum. Examples of adhesion between these non-oxide materials include silicon carbide-silicon carbide, silicon nitride-silicon nitride, silicon nitride-silicon carbide, silicon carbide-silicon, silicon carbide-sialoa, and sialon-sialon. An example is adhesion.

The adhesive of the present invention can also be used to combine the above-mentioned non-oxide ceramics with oxide ceramics such as arunna, mullite ceramics, ladder ratio shea, zirconia, cordierite, etc.
It can also be suitably used for adhesion with beryllia or the like or between the above-mentioned oxide ceramics.

It is also possible to form an image layer with a metal on the non-oxide ceramics via the above-mentioned oxide ceramics. In this case, the coefficient of expansion of the non-thickened sex and the metal is ! Since the input voltage is different, there is a cough compound type hexalyx that exists between them. If the thickness of this oxide-based ceramic is 6 or less, only -y111 class ceramics may be used as the skeleton oxide ceramics, but if the thickness is larger than b-type, then the oxide-based ceramics (two or more types of ceramics) can be used. 11!
It is preferable to use a combination of those with different l coefficients1
0 The shape of the bones of the family ↑ There is no fixed size for the bones of large species, and they can have any shape such as plate-like, column-like, pieg-like, block-like, etc., and they can also be glued together. It can also be a shape.

Alkali used as an active ingredient in this @Hata adhesive*Jl1
As heptadium, lithium fluoride, potassium heptadide,
Examples of the alkaline earth metal fluorides include berylicum fluoride, magnesium fluoride, stro/thium heptatide, and palicium heptatide. For rounding to increase adhesive strength, it is preferable that the purity is as high as possible. Of these alkali metal heptadides and alkaline earth metal fluorides, which are advantageously used in the shaded line, any one of them can be used depending on the purpose, and when used as a mixture of two or more types. Depending on the purpose, add any heptadide in any ratio (usually 288 to 8:2).
) should be mixed. Among the alkali metal fluorides, when lithium heptadide and potassium heptadide are used, it is desirable to use them together with kaolin or (and) alkaline earth gold @ heptadide.

The above alkali metal fluorides or (and) alkaline earths! I
Any commercially available kaolin can be used in combination with the I4 Kinpeng fluoride, and especially if it is
Class I), not affected by crystal size, history, etc. Its composition is mainly SjO, Aj, O, and Fe.
Ordinary adhesives containing some amount of WO, T108, CaO1K, 0, etc. may be used, but those with higher purity tend to improve the adhesive strength when used. can improve the physical properties of Adhesion of cough alkali metal heptaphide or alkaline earth metal fluoride is achieved by adding about 1 weight or more to the Kaori hepta-alkali metal fluoride or (and) alkaline earth metal fluoride. It can have the function of increasing the effect and/or educating the physical properties of the II adhesion layer, and this effect gradually improves as the amount of kaolin O is increased. If so, excess kaolin may partially remain in the adhesive layer, reducing the adhesive effect. Value is usually alkaline gold @7
It is preferable to use the above-mentioned alkali metal fluoride or (and) alkaline earth metal in an amount of up to about 901 to 96 per fluoride or (and) alkaline earth metal. It can also be used in the form of a simple powder mixture of metal tsutsukaji or kaori/kaori, and it can also be used by blending kunosei with a normal vehicle (organic sticky substance such as palsam or this and an organic solvent). The thus obtained adhesive can be used in the form of a paste. Heated above the decomposition temperature of metal fluorides* or alkaline earth metal fluorides. The application of adhesive between materials depends on the form of the adhesive. For example, if it is in powder form, it is enough to sprinkle it on the surface to be adhered, or if it is in paste form, it can be applied to the surface to be bonded. It can be applied in the same way as the agent. The usual amount is the composition of the adhesive used, especially the amount of kaolin used, heating conditions after applying the cough adhesive, and the material fDIM to be bonded.
It can be determined as appropriate depending on the size, shape, especially thickness 1, etc., and is not determined by the title, but this is the original! [In terms of one amount of active ingredient, it is preferable that the surface structure to be adhered is 1-mDK, 1lJO,ol ~ 6F, preferably 0.1-l11!1 degree.
The heating after application of the adhesive as described above is carried out at a temperature at which the alkali metal difluoride and alkaline earth metal heptafluoride decompose and release fluorine. Fi, especially when heating the above, do not use any pressure handle 1m
Although it is not necessary to apply a slight pressure to the surface to be adhered, it is possible to apply a slight pressure to ensure adhesion of the surface to be adhered. (9) The above heating can generally be easily carried out in air, but if there is a risk of linearization of the material to be coated due to heating, it can also be carried out under a nitrogen atmosphere. .

Examples will be given below to further explain the present invention.

Example A mixed powder consisting of 40% by weight of lithium fluoride and 60% by weight of kaolin was placed between a silicon nitride plate and a mullite ceramics plate (manufactured by Nippon Kayuto Co., Ltd.).
．． Sprinkle it in an amount that will reach 6F, and add mullite precious cera (
Place a steel plate on top of a steel plate and heat it in an electric f
Dei! Heated for 0 minutes.

The adhesive strength of the obtained bonded body sample was determined at three points according to the standard method under conditions of a span of 205 W and a loading rate of 0.6 wa/min, and it was found to be 4S! I was disappointed with 01/-. 9) When the fractured surface after the above-mentioned test was examined, it was found that the outside of the adhesive part was 1i1 (base material silicon nitride).
After being immersed at 0° C. for 60 hours, no abnormalities were observed in the bonded area to test the chemical resistance.

The thermal shock resistance Vtl111 was determined by a rapid cooling test in which the above bonded body sample was heated to 1100°C for hours and then rapidly cooled in air.
There are no abnormalities in the adhesive or glued parts.

Example 2 A mixed powder consisting of lithium heptadide 2o1 lid and kaolin 80 wt. was placed between a silicon nitride plate and a mullite negative seven fox plate [manufactured by Nippon Kagaku Tougyo Co., Ltd.] with the adhesive surface being cross-blown.
This was then heated in an electric furnace at 1860°C.
Heat for 10 minutes to remove the zygote.

The adhesive strength of the combined sample after death was measured and found to be 806/d. In addition, the II resistance and thermal shock resistance, which were conducted in the same manner as the actual inversion test, were 6.9 with no abnormalities.

11Ali118 Magnesium heptadide powder was sprinkled between two silicon nitride plates and between a silicon nitride plate and a mullite ceramic plate (Nihon Kagaku Togyo Co., Ltd.) in an amount of 0.6 f. This was heated in an electric furnace at 1800'C for 20 minutes to obtain a bonded body.

The adhesive strength of each of the obtained bonded body samples was measured and was found to be 6, which was equal to or higher than that of the case of the dead body. Further, electrical resistance and thermal shock resistance were tested in the same manner as in Example 1, with no abnormalities observed for any of the samples.

*Example 4 A mixed powder consisting of 40wt of magnesium fluoride and 60wt 11s of lithium heptadide was bonded between a silicon nitride plate and a mullite ceramics plate [manufactured by Nippon Kagaku Togyo Co., Ltd.] for an area of 1
A copper plate was placed on top of a ceramic plate, and this was heated in an electric furnace for 2 hours.
Example 1 The adhesive strength of the postmortem coalesced sample obtained after heating at 00°C for 20 minutes was measured.
It was rarely equal to or better than the case of . Furthermore, the chemical resistance and thermal shock resistance tests conducted in the same manner as in Example 1 were passed without any abnormality.

(that's all)

Claims (1)

[Scope of Claims] ■ At least one plant of alkali gold @ heptathide and alkaline earth metal fluoride (excluding edashi, sodium heptafluoride and/or calcium heptafluoride), or this and kaolin Se2ix bonding adhesive whose active ingredient is a mixture of Φ At least 9 MQ of alkali metal fluoride.
! Kiyoshi's adhesive on the mall. ψ The adhesive according to the eighth product of claim a, in which the oxidation and oxidation material has a volume of at least 1 ml. (2) The adhesive according to item #1 of the patent claim, wherein the adhesive is oxide-based. ■ At least 4 to 119 of alkali gold @7) oxides and alkaline earth metal heptides, excluding sodium heptadide and/or calcium heptaphide. ), or a mixture of this and kaolin. A method for adhering ceramics, which is characterized by intervening with 1-series ceramics and heating it above the decomposition temperature of fluoride. Large 111 nt of Liao Zhang Bao from 7 fixes and a clearing material type celatics
112fl No. 6 bonding method, characterized in that the above-mentioned adhesive is interposed between them and laminated outside of the layer. (2) A bonding method according to claim 7, wherein another oxidation-based ceramic having the above-mentioned expansion coefficient has a metal bonded to one surface in advance to form a round shape.