CN113732565B - Solder, preparation method and application thereof, welding method and ceramic component - Google Patents

Solder, preparation method and application thereof, welding method and ceramic component Download PDF

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CN113732565B
CN113732565B CN202111110235.2A CN202111110235A CN113732565B CN 113732565 B CN113732565 B CN 113732565B CN 202111110235 A CN202111110235 A CN 202111110235A CN 113732565 B CN113732565 B CN 113732565B
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solder
ceramic
welding
powder
ceramics
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CN113732565A (en
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郑开宏
王娟
何晨杰
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Institute of New Materials of Guangdong Academy of Sciences
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Institute of New Materials of Guangdong Academy of Sciences
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40—Making wire or rods for soldering or welding

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  • Mechanical Engineering (AREA)
  • Ceramic Products (AREA)

Abstract

The invention discloses a welding flux, a preparation method and application thereof, a welding method and a ceramic component, and belongs to the technical field of ceramic welding. The solder comprises 5-15% of SiO as main component 2 40-50% of B 2 O 3 15-25% of Al 2 O 3 15-30% of MgO, and the solder containing the components can form MgAl at high temperature 2 O 4 And Al 18 B 4 O 33 The microcrystalline glass not only can enhance the connection reliability of the welding joint, but also can be connected with Al 2 O 3 The ceramic base material realizes good wetting, reduces the difference of the thermal expansion coefficients of the base material and the solder, reduces the residual stress of the joint and realizes Al 2 O 3 Reliable connection between ceramic substrates. The corresponding welding method has the advantages of safe process, environmental protection, reliability, simple and convenient operation, important application value and suitability for wide popularization and use.

Description

Solder, preparation method and application thereof, welding method and ceramic component
Technical Field
The invention relates to the technical field of ceramic welding, in particular to a solder, a preparation method and application thereof, a welding method and a ceramic component.
Background
Al 2 O 3 Ceramics are widely concerned about their excellent comprehensive mechanical and physical properties, such as good high temperature resistance, oxidation resistance, corrosion resistance, etc., and are more and more concerned about in the fields of microelectronics, aerospace, chemical engineering, etc., but their inherent high brittleness and low impact toughness cause Al 2 O 3 The poor processability of ceramics greatly limits the large-scale Al 2 O 3 Production and use of ceramic components and complex components.
At present, there is no effective method for realizing Al 2 O 3 Ceramic parts (especially large and complex shaped Al) 2 O 3 Ceramic component) to itself.
In view of this, the invention is particularly proposed.
Disclosure of Invention
It is an object of the present invention to provide a solder which can realize two Al 2 O 3 Reliable connection between ceramic substrates.
The second purpose of the invention is to provide a preparation method of the solder.
The invention also aims to provide application of the solder.
The fourth purpose of the present invention is to provide a method for soldering using the above solder.
The fifth object of the present invention is to provide a ceramic member having a welded joint welded by the above-described welding method.
The application can be realized as follows:
in a first aspect, the present application provides a solder, the main component of which comprises 5-15% by mass of SiO 2 40-50% of B 2 O 3 15-25% of Al 2 O 3 And 15-30% MgO.
In a preferred embodiment, the main component comprises 8-15% SiO 2 42-48% of B 2 O 3 18-22% of Al 2 O 3 And 15-26% MgO.
In a more preferred embodiment, the main component comprises 15% SiO 2 45% of B 2 O 3 20% of Al 2 O 3 And 20% MgO.
In an alternative embodiment, the solder further comprises water and a binder.
In an alternative embodiment, the mass ratio of the main component to water and binder is from 2.8 to 1.2.
In a preferred embodiment, the mass ratio of the main component to water and binder is 2.
In an alternative embodiment, the binder is a sodium silicate sol.
In a second aspect, the present application provides a method of making a solder as in any one of the preceding embodiments, comprising the steps of: mixing the main components according to the proportion.
In an alternative embodiment, the main ingredients are mixed using a three-dimensional mixer.
In an alternative embodiment, the mixing time is 1.5 to 3 hours, more preferably 2 hours.
In an alternative embodiment, when the solder further includes a bonding agent, the preparation method further includes: mixing the main components with water and adhesive in certain proportion.
In a third aspect, the present application provides the use of a solder as in any of the preceding embodiments, for example for Al 2 O 3 Ceramics or Al 2 O 3 And (4) connecting the ceramic particles.
In an alternative embodiment, when solder is used to coat both of the Al's to be soldered 2 O 3 At least one Al in the ceramic 2 O 3 At least one Al component in the welded surface of the ceramic 2 O 3 Al in ceramics 2 O 3 The content of (A) is not less than 95%.
In a fourth aspect, the present application provides a welding method comprising the steps of: applying the solder of any of the previous embodiments to the Al to be soldered prior to soldering 2 O 3 Ceramic and/or Al 2 O 3 The connecting surface of the ceramic particles.
In an alternative embodiment, when solder is used to solder Al 2 O 3 In the case of ceramics, two Al's, at least one of which is coated with solder 2 O 3 Heating the ceramic welding surface after the ceramic welding surface is attached;
wherein the heating treatment is carried out by heating to 1150-1200 ℃ at a speed of 3-5 ℃/min and keeping the temperature for 90-150min.
In a preferred embodiment, the heat treatment is carried out at a rate of 3 ℃/min up to 1150 ℃ and at a temperature of 120min.
In an alternative embodiment, the heating process is performed in an air oven.
In an alternative embodiment, the two bonded Al are subjected to a heat treatment 2 O 3 The ceramic gives pressure to make two of the Al 2 O 3 The width of the weld between the ceramics does not exceed 160 μm.
In an alternative embodiment, the two bonded Al layers are treated before the heat treatment 2 O 3 The ceramic is pressurized to make two Al 2 O 3 The width of the weld between the ceramics does not exceed 1mm.
In an alternative embodiment, before coating the solder, the method further comprises the step of coating Al to be soldered 2 O 3 The ceramic is washed and dried.
In an optional embodiment, the cleaning is performed by taking absolute ethyl alcohol as a cleaning reagent and performing ultrasonic cleaning for 10-15min.
In a fifth aspect, the present application provides a ceramic member having a welded joint welded by the welding method of any one of the foregoing embodiments.
The beneficial effect of this application includes:
in the solder used in this application, al 2 O 3 Can have good compatibility with a welding base material, and is also compatible with B 2 O 3 Al can be formed during high temperature heat treatment (1125-1175 deg.C) 18 B 4 O 33 A whisker. MgO may be mixed with Al in the matrix of the parent material 2 O 3 React to form MgAl on the welding surface (welding interface) of the base material 2 O 4 And (3) a reaction layer. SiO 2 2 The method is mainly used for forming the microcrystalline glass, has good fluidity in the high-temperature heat treatment process, and plays a good role in wetting the parent metal.
The components are matched according to the proportion provided by the application, so that the corresponding solder and Al can be mixed 2 O 3 The ceramic substrates have good wettability and low thermal expansion coefficient difference, so that the residual stress of a welding joint is small, the connection strength is high, and Al is effectively realized 2 O 3 Reliable connection between ceramic substrates. The corresponding welding method has the advantages of safe process, environmental protection, reliability, simple and convenient operation, important application value and suitability for wide popularization and use.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 shows Al provided in example 1 2 O 3 Micrographs of ceramic jointsSlicing;
FIG. 2 shows Al provided in example 3 2 O 3 Photomicrographs of the ceramic joints.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The solder, the preparation method and application thereof, the welding method and the ceramic member provided by the application are specifically described below.
The application provides a solder, which comprises 5-15% of SiO as the main component by mass percent 2 40-50% of B 2 O 3 15-25% of Al 2 O 3 And 15-30% MgO.
In an alternative embodiment, the primary ingredient is in powder form. Wherein, siO 2 The purity of the powder is analytically pure, and the powder is colorless fine crystal particles or white powder; b is 2 O 3 The purity of the powder is analytically pure; al (Al) 2 O 3 The purity of the powder is analytically pure, and the powder is white powder; the purity of MgO powder is analytically pure, and the MgO powder is white ultrafine powder.
Referenced to ground, siO 2 The content of (B) may be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, etc., may also be 5.5wt%, 6.5wt%, 7.5wt%, 8.5wt%, 9.5wt%, 10.5wt%, 11.5wt%, 12.5wt%, 13.5wt%, 14.5wt%, etc., and may also be any other value within the range of 5 to 15 wt%.
B 2 O 3 The content of (B) may be 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt% or 50wt%, may be 40.5wt%, 41.5wt%, 42.5wt%, 43.5wt%, 44.5wt%, 45.5wt%, 46.5wt%, 47.5wt%, 48.5wt% or 49.5wt%, etc., and may be 40 to 50wt%Any other value within the range.
Al 2 O 3 The content of (B) may be 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, etc., may also be 15.5wt%, 16.5wt%, 17.5wt%, 18.5wt%, 19.5wt%, 20.5wt%, 21.5wt%, 22.5wt%, 23.5wt%, 24.5wt%, etc., and may also be any other value within the range of 15 to 25 wt%.
The MgO content may be 15wt%, 18wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, or 30wt%, or may be 20.5wt%, 21.5wt%, 22.5wt%, 23.5wt%, 24.5wt%, 25.5wt%, 26.5wt%, 27.5wt%, 28.5wt%, or 29.5wt%, etc., or may be any other value within the range of 15 to 30 wt%.
Wherein, al 2 O 3 Can have good compatibility with a welding base material, and is also compatible with B 2 O 3 Al can be formed during high temperature heat treatment (1125-1175 deg.C) 18 B 4 O 33 A whisker.
MgO may be mixed with Al in the matrix of the parent material 2 O 3 React to form MgAl on the welding surface (welding interface) of the base material 2 O 4 And (3) a reaction layer.
SiO 2 The method is mainly used for forming the microcrystalline glass, has good fluidity in the high-temperature heat treatment process, and plays a good role in wetting the parent metal.
By compounding the above components, the corresponding solder can be mixed with Al 2 O 3 The ceramic substrates have good wettability and low thermal expansion coefficient difference, so that the residual stress of the welding joint is small, and the connection strength is high.
It is worth mentioning that if SiO 2 The content of (b) is less than 5wt%, which easily causes a decrease in the fluidity of the brazing filler metal; more than 15wt% tends to cause an imbalance in borosilicate ratio, which affects whisker formation. If B is 2 O 3 Less than 40wt% may result in Al formation 18 B 4 O 33 The number of whiskers is small, so that the strength of a joint obtained by welding is greatly reduced; if highAt 50wt%, the high temperature resistance of the joint is liable to deteriorate. If Al is present 2 O 3 The content of (b) is less than 15wt%, which easily causes insufficient solder reaction and decreases the number of whiskers; if it exceeds 25wt%, the melting temperature of the solder tends to increase, and the softening degree at the set temperature tends to be poor. If the MgO content is less than 15wt%, the reaction tends to be insufficient, and the reaction layer tends to be thin or disappear; if the amount is more than 30wt%, the reaction layer tends to have an excessively large thickness and a high interface brittleness.
In a preferred embodiment, the main component in the solder comprises 8-15% SiO 2 42-48% of B 2 O 3 18-22% of Al 2 O 3 And 15-26% MgO.
In a more preferred embodiment, the main component comprises 15% SiO 2 45% of B 2 O 3 20% of Al 2 O 3 And 20% MgO.
At the above preferred or more preferred ratios, the corresponding solder can be mixed with Al 2 O 3 The ceramic substrates have better wettability and smaller difference of thermal expansion coefficients, so that the residual stress of the welding joint is smaller, and the connection strength is higher.
Further, the solder also comprises water and a bonding agent.
By reference, the mass ratio of the main component to water and the binder can be 2. Wherein the binder may be, for example and without limitation, a sodium silicate sol.
Preferably, the powdered solder may be mixed with deionized water prior to mixing with the water glass. In addition, B in the solder 2 O 3 The reaction can occur when meeting water and release heat in a large amount, and if the sodium silicate sol is mixed into the water, the heat can aggravate the reaction between the sodium silicate and the carbon dioxide in the air so as to quickly solidify the sizing agent, which is not beneficial to coating the sizing agent. This application is through mixing powder and water earlier, and sodium silicate sol adds, can make thick liquids keep softening, easily coating.
Through mixing the main components with water and sodium silicate sol according to the proportion, the solder can be quickly condensed at normal temperature, the base material matrix with the solder coated on the surface has certain strength before heating, the support is not required to be provided by the outside, the connecting piece is convenient to fix at room temperature, and the precise matching of the connecting surface is ensured.
Correspondingly, the application also provides a preparation method of the solder, which comprises the following steps: mixing the main components according to the proportion to correspondingly obtain the powder solder.
Preferably, the main components are mixed by a three-dimensional mixer. The mixing time may, by reference, be 1.5-3h, such as 1.5h, 2h, 2.5h or 3h, etc., preferably 2h.
It is worth to be noted that the three-dimensional mixing instrument adopted by the application is set based on the adopted main components in a targeted manner, part of the main components used by the application is lighter in specific weight and heavier in specific weight, and the phenomenon of heavy sinking and light floating can occur during mixing, and the material can be mixed unevenly and layered by adopting a common stirring mode (even if stirring is accompanied in the mixing process); and the three-dimensional mixing appearance that this application adopted mixes can make the material constantly stir and roll at the mixing process to effectively overcome the different problem of proportion, make the material obtain the homogeneous mixing.
Further, still include: and mixing the mixed main components with water and a binder according to a ratio to obtain the mixed slurry. In some alternative embodiments, the mixing time of the main component with water and the binder may be 5-10min, and in other embodiments, the mixing time may be adjusted according to actual conditions to achieve uniform mixing without visible large particles.
Furthermore, the application also provides the use of the above-mentioned solder, for example for Al 2 O 3 Ceramic and/or Al 2 O 3 And (4) connecting the ceramic particles. When used for Al 2 O 3 In joining ceramics, solder is applied to two Al to be welded 2 O 3 At least one Al in the ceramic 2 O 3 A ceramic weld face. When used for Al 2 O 3 When the ceramic particles are connected,the solder is uniformly coated on all surfaces of the ceramic particles.
Referably, when both base metals to be welded are Al 2 O 3 In the case of ceramics, the solder may be applied to the bonding surface of only one of the base materials, or may be applied to the bonding surfaces of both base materials at the same time (preferably).
In an alternative embodiment, the two Al are 2 O 3 In the ceramic, at least one Al 2 O 3 Al in ceramics 2 O 3 The content of (b) is not less than 95%, for example, but not limited to, 95% or 98%.
In addition, the application also provides a welding method, which comprises the following steps: before welding, the welding flux is coated on Al to be connected 2 O 3 Ceramics or Al 2 O 3 The connecting surface of the ceramic particles.
The following main pairs of Al 2 O 3 The welding process of ceramics as a base material, al is used as the welding base material 2 O 3 The welding process and parameters of the ceramic particles can be referred to Al 2 O 3 Ceramics, not described in detail herein.
With respect to Al 2 O 3 With ceramic as the base material, the solder is applied to two Al to be soldered 2 O 3 At least one Al in the ceramic 2 O 3 A ceramic weld face.
In an alternative embodiment, at least one Al 2 O 3 Al in ceramics 2 O 3 The content of (B) is not less than 95wt%.
The amount of solder to be applied is preferably (1 to 2 mm). Times.the area of the soldering surface, and may be, for example, specifically 0.3 to 0.4g/cm 2 E.g. 0.3g/cm 2 、0.35g/cm 2 Or 0.4g/cm 2 。
Subsequently, two Al coated with solder (at least one of the soldering surfaces is coated with solder) 2 O 3 And (4) performing heating treatment after the welding surfaces of the ceramics are attached. In the application, the heating treatment is carried out at a rate of 3-5 ℃/min to 1150-1200 ℃, and the temperature is kept for 90-150min.
For reference, the temperature rise rate can be 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, or the like, or can be any other value within the range of 3-5 ℃/min.
The heating temperature may be 1150 deg.C, 1155 deg.C, 1160 deg.C, 1165 deg.C, 1170 deg.C, 1175 deg.C, 1180 deg.C, 1185 deg.C, 1190 deg.C, 1195 deg.C, 1200 deg.C, etc., or may be any other value within the range of 1150-1200 deg.C.
The heat preservation time can be 90min, 100min, 110min, 120min, 130min, 140min or 150min, and the like, and can also be any other value within the range of 90-150min.
In a preferred embodiment, the heat treatment is carried out at a rate of 3 ℃/min up to 1150 ℃ and at a temperature of 120min.
The above-mentioned heating treatment may be carried out in an air furnace.
By performing the heat treatment under the above-mentioned conditions, the MgAl-containing solder can be formed at a high temperature 2 O 4 And Al 18 B 4 O 33 The microcrystalline glass of the crystal whisker not only enhances the connection reliability of the joint, but also is connected with Al 2 O 3 The ceramic base material realizes good wetting, reduces the difference of the thermal expansion coefficients of the base material and the solder, reduces the residual stress of the joint, and realizes two Al 2 O 3 Reliable connection of the ceramic base body.
It is worth mentioning that when the temperature rise rate is lower than 3 ℃/min, a large amount of overflow flow of the solder at high temperature is easily caused; above 3 ℃/min, the internal reaction of the solder is liable to be insufficient. Heating temperatures below 1150 ℃ tend to result in insufficient melting of the solder, and unmelted solder powder is present in the joint; above 1200 c, solder is prone to excessive softening, flooding is severe and whiskers in the joint are subject to engulfment and agglomeration. The heat preservation time is shorter than 90min, so that insufficient solder reaction is easily caused, the heat preservation time is longer than 150min, crystal grains in the joint are easily grown, and the strengthening effect is reduced.
In an alternative embodiment, the method further comprises, before the heat treatment, attaching two Al layers 2 O 3 The ceramic imparts pressure to the two Al 2 O 3 The width of the weld between the ceramics is about 1mm. In the process, the solder can be dischargedThe air bubbles enable the welding flux to be compact, and the defects of welding seams are reduced.
Further, during the heating process, two Al can be added 2 O 3 The ceramic is again extruded to make two Al 2 O 3 The width of the weld between the ceramics does not exceed 160 μm. The pressure can be determined according to the quality of the connecting sample, so that after the solder is melted at high temperature, the connecting sample can extrude part of the solder under the action of gravity, on one hand, the solder can be fully contacted with the substrate, on the other hand, the requirement that the width of a welding seam does not exceed 160 mu m can be met, and good bonding strength can be obtained.
In an alternative embodiment, before coating the solder, al to be soldered may be further included 2 O 3 The ceramic is washed and dried.
Wherein, the cleaning can be carried out by taking absolute ethyl alcohol as a cleaning reagent for 10-15min by ultrasonic cleaning, and specifically can be carried out in an ultrasonic cleaning machine.
In some embodiments, the preparation of the solder and the Al 2 O 3 The welding method of ceramics can be referred to the following processes:
1) Proportioning SiO by using a three-dimensional mixer 2 、B 2 O 3 、Al 2 O 3 And MgO powder are mixed for 1.5 to 3 hours to prepare powder solder;
2) Mixing the powder solder with deionized water, and then mixing the powder solder with sodium silicate sol until no large visible particles exist, wherein the mass ratio of the powder solder to the deionized water to the sodium silicate sol is 2:1:1, obtaining mixed slurry;
3) Al to be welded 2 O 3 Processing the ceramic into a sample with a target specification;
4) Subjecting the Al to be welded in the step 3) 2 O 3 Putting the ceramic into an ultrasonic cleaning machine, ultrasonically cleaning the ceramic for 10-15min by using absolute ethyl alcohol, and placing the ceramic in a drying oven for drying;
5) Evenly coating the slurry in the step 2) on two Al to be connected 2 O 3 At least one surface to be connected (coating thickness is 1-2 mm) in the ceramic sample, making the surfaces to be connected of the two samples to be connected face to face, and applying proper pressure to make the two samples to be connectedAl (B) in 2 O 3 The width of a welding seam between the ceramic samples is about 1mm, in the process, slurry is solidified, and the connecting piece has weak connection strength;
6) Putting the connection sample into an air furnace, and applying proper pressure in the whole heating process to control the width of a welding seam not to exceed 160 mu m;
7) The air furnace starts to heat up to 1150-1200 ℃ at the rate of 3-5 ℃/min, the temperature is kept for 90-150min, and the furnace is cooled to room temperature after the temperature is kept, so that Al is realized 2 O 3 And (4) connecting the ceramic samples.
In the technical scheme, the microcrystalline glass is formed at high temperature through the solder, so that the mismatch of the thermal expansion coefficients of the solder and the ceramic substrate is reduced, the residual stress is reduced, the strength of the glass is improved by the dispersion strengthening effect of the microcrystalline glass, and the reliability of the joint is improved.
Correspondingly, the application also provides a welding joint which is obtained by welding through the welding method. The obtained welding joint has stronger shearing strength, and effectively realizes Al 2 O 3 Ceramic parts (especially large and complex shaped Al) 2 O 3 Ceramic component) to itself.
Accordingly, the present application also provides a ceramic member having a welded joint welded by the above welding method.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a method for preparing Al 2 O 3 The ceramic connection solder comprises the following components: 10wt% SiO 2 Powder, 45wt% of B 2 O 3 Powder, 20wt% Al 2 O 3 Powder and 25wt% MgO powder.
Wherein, siO 2 The purity of the powder is analytically pure, and the powder is colorless fine crystal particles or white powder; b is 2 O 3 The purity of the powder is analytically pure; al (aluminum) 2 O 3 The purity of the powder is analytically pure, and the powder is white powder; the purity of MgO powder is analytically pure, and the character is whiteA fine powder.
Preparation method of the solder and realization of Al by using the solder 2 O 3 The method of ceramic joining comprises the steps of:
1) Weighing SiO according to mass percentage 2 Powder, B 2 O 3 Powder, al 2 O 3 Mixing the powder and MgO powder for 2h by using a three-dimensional mixer to prepare powder solder;
2) Mixing the powder solder with deionized water, and then mixing the powder solder with sodium silicate sol until no large visible particles exist, wherein the mass ratio of the powder solder to the deionized water to the sodium silicate is 2:1:1, obtaining mixed slurry;
3) Processing to target specification of Al to be brazed 2 O 3 Ceramic (Al) 2 O 3 Content of 98 wt%) in an ultrasonic cleaning machine, ultrasonically cleaning with anhydrous ethanol for 15min, and drying in a drying oven;
4) Respectively coating the uniformly stirred mixed slurry (coating thickness is 2 mm) on two Al to be connected 2 O 3 The opposite surfaces to be connected of the ceramic samples are opposite, the surfaces to be connected of the two samples are opposite, and proper pressure is applied until two Al layers are formed 2 O 3 The width of the weld between the ceramic samples was about 1mm;
5) Ceramic welding is carried out in an air furnace, a sample to be connected is placed in the air furnace, and proper pressure is given so that the width of a welding seam does not exceed 160 mu m;
6) Heating the air furnace to 1150 ℃ at the speed of 3 ℃/min, preserving heat for 120 minutes, cooling the air furnace to room temperature along with the furnace after heat preservation is finished, and finishing two Al 2 O 3 And (4) connecting the ceramic samples.
A micrograph of the resulting linker is shown in FIG. 1. As can be seen from fig. 1: the welding seam is complete and has no defect, the wetting condition of the solder and the substrate is good, and part of the solder permeates into the substrate along the defect of the substrate.
Example 2
This example is substantially the same as example 1, except that the temperature in step 6) was raised to 1175 ℃.
Example 3
This example is substantially the same as example 1, except that the temperature in step 6) was raised to 1200 ℃.
For the obtained Al 2 O 3 The results of the observation of the ceramic joint structure are shown in FIG. 2. In FIG. 2, the middle part is Al 18 B 4 O 33 Whisker with MgAl as upper and lower boundary 2 O 4 Proves that the solder provided by the application indeed forms MgAl-containing solder at high temperature 2 O 4 And Al 18 B 4 O 33 The microcrystalline glass of (4).
Example 4
This example is substantially the same as example 2 except that the solder has the following components: 8% by weight of SiO 2 Powder, 48wt% of B 2 O 3 Powder, 18wt% Al 2 O 3 Powder and 26wt% MgO powder.
Example 5
This example is substantially the same as example 2 except that the solder has the following components: 11wt% SiO 2 Powder, 44wt% of B 2 O 3 Powder, 21wt% Al 2 O 3 Powder and 24wt% MgO powder.
Example 6
This example is substantially the same as example 2 except that the solder has the following components: 5wt% SiO 2 Powder, 50wt% of B 2 O 3 Powder, 15wt% Al 2 O 3 Powder and 30wt% MgO powder.
Example 7
This example is substantially the same as example 2 except that the solder has the following components: 15wt% SiO 2 Powder, 45wt% of B 2 O 3 Powder, 20wt% Al 2 O 3 Powder and 20wt% MgO powder.
Example 8
This example is substantially the same as example 2 except that the temperature increase rate in step 6) was 4 ℃/min.
Example 9
This example is substantially the same as example 2 except that the temperature increase rate in step 6) was 5 ℃/min.
Example 10
This example is substantially the same as example 2 except that the solder is applied to only two Al to be soldered 2 O 3 One Al in the ceramic 2 O 3 The welding surface of the ceramic.
Comparative example 1
This comparative example is approximately the same as example 2, except that the temperature is raised to 1050 ℃ in step 6).
Comparative example 2
This comparative example is substantially the same as example 2, except that the temperature is raised to 1100 ℃ in step 6).
Comparative example 3
This comparative example is about the same as example 2, except that the temperature is raised to 1125 ℃ in step 6).
Comparative example 4
This comparative example is substantially the same as example 2, except that the temperature is raised to 1250 ℃ in step 6).
Comparative example 5
This comparative example is substantially the same as example 2 except that the solder has the following composition of components: 20% by weight of SiO 2 Powder, 35wt% of B 2 O 3 Powder, 30wt% Al 2 O 3 Powder and 15wt% MgO powder.
Comparative example 6
This comparative example is substantially the same as example 2 except that the solder has the following composition of components: 3% by weight of SiO 2 Powder, 55wt% of B 2 O 3 Powder, 10wt% Al 2 O 3 Powder and 32wt% MgO powder.
Comparative example 7
This comparative example is approximately the same as example 2, differing only by SiO in step 1) 2 Powder, B 2 O 3 Powder, al 2 O 3 The powder and MgO powder are mixed by a common mixer.
Test examples
The soldered joints obtained in examples 1 to 7 and comparative examples 1 to 7 were subjected to a shear strength test in a universal testing machine according to GB/T11363-2008, and the results are shown in Table 1:
TABLE 1 shear strength of brazed joints
Shear strength (MPa)
Example 1 45.971
Example 2 42.858
Example 3 38.430
Example 4 44.533
Example 5 41.500
Example 6 37.240
Example 7 79.570
Comparative example 1 12.049
Comparative example 2 28.918
Comparative example 3 31.359
Comparative example 4 35.511
Comparative example 5 30.686
Comparative example 6 28.400
Comparative example 7 14.551
It can be seen by comparing examples 1-7 that the formulation and process conditions provided in example 7 result in a weld joint with the best performance.
As can be seen by comparing examples 1-7 with comparative examples 1-7, siO 2 Powder, B 2 O 3 Powder, al 2 O 3 The proportion of the powder and the MgO powder is set outside the range of the application, so that the shearing strength of the welding joint is obviously reduced; setting the heating process conditions outside the scope of the present application can also cause the shear strength of the weld joint to be significantly reduced; by using common mixing equipment to SiO 2 Powder, B 2 O 3 Powder, al 2 O 3 Mixing the powder with the MgO powder also reduces the shear strength of the welded joint.
In summary, the solder provided by the present application can form MgAl-containing solder at high temperature 2 O 4 And Al 18 B 4 O 33 The microcrystalline glass not only can enhance the connection reliability of the welding joint, but also can be connected with Al 2 O 3 The ceramic base material realizes good wetting, reduces the difference of the thermal expansion coefficients of the base material and the solder, reduces the residual stress of the joint and realizes Al 2 O 3 Method for manufacturing semiconductor deviceA reliable connection between them. The corresponding welding method has the advantages of safe process, environmental protection, reliability, simple and convenient operation, important application value and suitability for wide popularization and use.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (21)

1. A solder material, characterized in that the solder material consists of main components and water and a binder according to mass percent, wherein the main components comprise 5-15% of SiO 2 40-50% of B 2 O 3 15-25% of Al 2 O 3 15-30% of MgO;
the mass ratio of the main component to the water and the binder is 2.8-1.2;
the solder is used for Al 2 O 3 And (5) connecting the ceramics.
2. The solder according to claim 1, wherein the main component is composed of 8-15% of SiO 2 42-48% of B 2 O 3 18-22% of Al 2 O 3 And 15-26% of MgO.
3. Solder according to claim 2, characterised in that the main component consists of 15% SiO 2 45% of B 2 O 3 20% of Al 2 O 3 And 20% MgO.
4. The solder according to claim 1, wherein the mass ratio of the main component to water and the binder is 2.
5. The solder of claim 1, wherein the binder is a sodium silicate sol.
6. The method for preparing a solder according to any one of claims 1 to 5, comprising the steps of: mixing the main components according to the proportion.
7. The production method according to claim 6, wherein the main components are mixed using a three-dimensional mixer.
8. The method of claim 7, wherein the mixing time is 1.5 to 3 hours.
9. The method of claim 8, wherein the mixing time is 2 hours.
10. The method according to claim 6, wherein when the solder further includes an adhesive, the method further comprises: and mixing the mixed main components with water and the binder according to a ratio.
11. Use of a solder according to any of claims 1 to 5 for Al 2 O 3 And (5) connecting the ceramics.
12. Use according to claim 11, when the solder is used to coat two Al's to be soldered 2 O 3 At least one Al in the ceramic 2 O 3 At least one Al at the welded surface of ceramics 2 O 3 Al in ceramics 2 O 3 The content of (A) is not less than 95%.
13. A method of welding, comprising the steps of: applying the solder according to any one of claims 1 to 5 to Al to be joined before soldering 2 O 3 A connecting surface of a ceramic.
14. The method of claim 13A soldering method characterized in that when said solder is used for soldering Al 2 O 3 In the case of ceramics, at least one of the soldering surfaces is coated with two Al's of the solder 2 O 3 Heating the ceramic welding surface after the ceramic welding surface is attached;
wherein the heating treatment is carried out by heating to 1150-1200 ℃ at a speed of 3-5 ℃/min and keeping the temperature for 90-150min.
15. The welding method according to claim 14, wherein the heating process is carried out at a rate of 3 ℃/min up to 1150 ℃ and for 120min.
16. The welding method according to claim 13, wherein the heating treatment is performed in an air furnace.
17. The welding method according to claim 14, wherein the two bonded Al are subjected to a heating treatment 2 O 3 The ceramic gives pressure to make two of the Al 2 O 3 The width of the weld between the ceramics does not exceed 160 μm.
18. The welding method according to claim 14, wherein the two bonded Al are subjected to the heat treatment before the heat treatment 2 O 3 The ceramic gives pressure to make two of the Al 2 O 3 The width of the weld between the ceramics does not exceed 1mm.
19. The soldering method according to claim 13, wherein before the solder is applied, further comprising the Al to be soldered 2 O 3 The ceramic is washed and dried.
20. The welding method of claim 19, wherein the cleaning is performed by ultrasonically cleaning with absolute ethanol as a cleaning agent for 10-15min.
21. A ceramic member having a welded joint obtained by welding by the welding method according to any one of claims 13 to 20.
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