Solder, preparation method and application thereof, welding method and ceramic component
阅读说明：本技术 一种焊料及其制备方法与应用、焊接方法及陶瓷构件 (Solder, preparation method and application thereof, welding method and ceramic component ) 是由 郑开宏 王娟 何晨杰 于 2021-09-23 设计创作，主要内容包括：本发明公开了一种焊料及其制备方法与应用、焊接方法及陶瓷构件,属于陶瓷焊接技术领域。该焊料的主要成分包括5-15％的SiO-(2)、40-50％的B-(2)O-(3)、15-25％的Al-(2)O-(3)以及15-30％的MgO,含有上述成分的焊料在高温下可形成含MgAl-(2)O-(4)及Al-(18)B-(4)O-(33)的微晶玻璃,不仅能够增强焊接接头的连接可靠程度,而且能与Al-(2)O-(3)陶瓷母材实现良好的润湿,降低母材与焊料的热膨胀系数差异,减小接头的残余应力,实现Al-(2)O-(3)陶瓷基体之间的可靠连接。相应的焊接方法工艺安全,环保可靠,操作简便,具有重要的应用价值,适合被广泛推广和使用。(The invention discloses a solder, 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.)
1. The solder is characterized in that the main component of the solder comprises 5-15% of SiO by mass percent240-50% of B2O315-25% of Al2O3And 15-30% MgO.
2. The solder according to claim 1, wherein the main component comprises 8-15% SiO242-48% of B2O3、18-22% of Al2O3And 15-26% MgO;
preferably, the main component comprises 15% SiO245% of B2O320% of Al2O3And 20% MgO.
3. The solder according to claim 1, wherein the solder further comprises water and a binder;
preferably, the mass ratio of the main component to the water and the binder is 2:0.8-1.2: 0.8-1.2;
preferably, the mass ratio of the main component to the water and the binder is 2:1: 1;
preferably, the binder is a sodium silicate sol.
4. A method for preparing a solder according to any one of claims 1 to 3, comprising the steps of: mixing the main components according to the proportion;
preferably, the main components are mixed by a three-dimensional mixer;
preferably, the mixing time is 1.5-3h, more preferably 2 h;
preferably, when the solder further includes a binder, the preparation method further includes: and mixing the mixed main components with water and the binder according to a ratio.
5. Use of a solder according to any of claims 1 to 3 for Al2O3Ceramics or Al2O3Connecting ceramic particles;
preferably, when the solder is used to coat two Al's to be soldered2O3At least one Al in the ceramic2O3At least one of said Al being present at the surface of the ceramic weld2O3Al in ceramics2O3The content of (A) is not less than 95%.
6. A welding method characterized by comprising the following stepsThe method comprises the following steps: applying the solder according to any one of claims 1 to 3 to Al to be joined before soldering2O3Ceramic and/or Al2O3The connecting surface of the ceramic particles.
7. The soldering method according to claim 6, wherein when the solder is used for soldering Al2O3In the case of ceramics, at least one of the soldering surfaces is coated with two Al's of the solder2O3Heating the ceramic welding surface after the ceramic welding surface is attached;
wherein the heating treatment is carried out by raising the temperature to 1150-1200 ℃ at the rate of 3-5 ℃/min and keeping the temperature for 90-150 min;
preferably, the heating treatment is carried out at the rate of 3 ℃/min to 1150 ℃ and the temperature is kept for 120 min;
preferably, the heat treatment is carried out in an air oven;
preferably, in the heating treatment process, two bonded Al are subjected to heat treatment2O3The ceramic gives pressure to make two of the Al2O3The width of the weld between the ceramics does not exceed 160 μm.
8. The welding method according to claim 7, wherein the two bonded Al are subjected to the heat treatment2O3The ceramic gives pressure to make two of the Al2O3The width of the weld between the ceramics does not exceed 1 mm.
9. The soldering method according to claim 6, further comprising, before coating the solder, the Al to be soldered2O3Cleaning and drying the ceramic;
preferably, the cleaning is carried out by taking absolute ethyl alcohol as a cleaning reagent and carrying out ultrasonic cleaning for 10-15 min.
10. A ceramic member having a welded joint welded by the welding method according to any one of claims 6 to 9.
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
Al2O3Ceramics are of great interest for their excellent combination of mechanical and physical properties, such as good resistance to high temperaturesThe temperature, oxidation resistance, corrosion resistance and the like are more and more concerned in the fields of microelectronics, aerospace, chemical industry and the like, but the inherent high brittleness and low impact toughness of the alloy lead to Al2O3The poor processability of ceramics greatly limits the large-scale Al2O3Production and use of ceramic components and complex components.
At present, there is no effective method for realizing Al2O3Ceramic parts (especially large and complex shaped Al)2O3Ceramic 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 Al2O3Reliable 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.
It is a fifth object of the present invention 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 SiO240-50% of B2O315-25% of Al2O3And 15-30% MgO.
In a preferred embodiment, the main component comprises 8-15% SiO242-48% of B2O318-22% of Al2O3And 15-26% MgO.
In a more preferred embodiment, the main component comprises 15% SiO245% of B2O320% of Al2O3And 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 the water and the binder is 2:0.8 to 1.2.
In a preferred embodiment, the mass ratio of the main component to the water and the binder is 2:1:1.
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 Al2O3Ceramics or Al2O3And (4) connecting the ceramic particles.
In an alternative embodiment, when solder is used to coat both of the Al's to be soldered2O3At least one Al in the ceramic2O3At least one Al component in the welded surface of the ceramic2O3Al in ceramics2O3The 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 soldering2O3Ceramic and/or Al2O3The connecting surface of the ceramic particles.
In an alternative embodiment, when solder is used to solder Al2O3In the case of ceramics, two Al's, at least one of which is coated with solder2O3Welding of ceramicsHeating treatment is carried out after the surfaces are attached;
wherein the heating treatment is carried out by raising the temperature to 1150-1200 ℃ at the rate of 3-5 ℃/min and keeping the temperature for 90-150 min.
In a preferred embodiment, the heat treatment is carried out at a rate of 3 ℃/min up to 1150 ℃ and at a temperature of 120 min.
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 treatment2O3The ceramic gives pressure to make two of the Al2O3The 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 treatment2O3The ceramic is pressurized to make two Al2O3The width of the weld between the ceramics does not exceed 1 mm.
In an alternative embodiment, before coating the solder, the method further comprises the step of coating Al to be soldered2O3The 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 10-15 min.
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, Al2O3Can have good compatibility with a welding base material, and is also compatible with B2O3Al can be formed in the high temperature heat treatment process (1125-18B4O33A whisker. MgO may be mixed with Al in the matrix of the parent material2O3React to form MgAl on the welding surface (welding interface) of the base material2O4And (3) a reaction layer. SiO 22The 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 the above-mentioned formationAccording to the proportion provided by the application, the corresponding solder and Al can be matched2O3The 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 realized2O3Reliable 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 needed to be used 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 for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows Al provided in example 12O3Photomicrographs of the ceramic joints;
FIG. 2 shows Al provided in example 32O3Photomicrographs 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 percent240-50% of B2O315-25% of Al2O3And 15-30% MgO.
In an alternative embodiment, the major component is a powderIn the form of a powder. Wherein, SiO2The purity of the powder is analytically pure, and the powder is colorless fine crystal particles or white powder; b is2O3The purity of the powder is analytically pure; al (Al)2O3The 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, SiO2The content of (b) may be 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, etc., may also be 5.5 wt%, 6.5 wt%, 7.5 wt%, 8.5 wt%, 9.5 wt%, 10.5 wt%, 11.5 wt%, 12.5 wt%, 13.5 wt%, 14.5 wt%, etc., and may also be any other value within the range of 5 to 15 wt%.
B2O3The content of (b) may be 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt% or 50 wt%, may also be 40.5 wt%, 41.5 wt%, 42.5 wt%, 43.5 wt%, 44.5 wt%, 45.5 wt%, 46.5 wt%, 47.5 wt%, 48.5 wt% or 49.5 wt%, etc., and may also be any other value within the range of 40 to 50 wt%.
Al2O3The content of (B) may be 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, etc., may also be 15.5 wt%, 16.5 wt%, 17.5 wt%, 18.5 wt%, 19.5 wt%, 20.5 wt%, 21.5 wt%, 22.5 wt%, 23.5 wt%, 24.5 wt%, etc., and may also be any other value within the range of 15 to 25 wt%.
The MgO content may be 15 wt%, 18 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, or 30 wt%, or may be 20.5 wt%, 21.5 wt%, 22.5 wt%, 23.5 wt%, 24.5 wt%, 25.5 wt%, 26.5 wt%, 27.5 wt%, 28.5 wt%, or 29.5 wt%, etc., or may be any other value within the range of 15 to 30 wt%.
Wherein, Al2O3Can have good compatibility with a welding base material, and is also compatible with B2O3Al can be formed in the high temperature heat treatment process (1125-18B4O33A whisker.
MgO may be mixed with Al in the matrix of the parent material2O3React to form MgAl on the welding surface (welding interface) of the base material2O4And (3) a reaction layer.
SiO2The 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 Al2O3The 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 SiO2The content of (b) is less than 5 wt%, which easily causes a decrease in the fluidity of the brazing filler metal; above 15 wt% it is liable to cause an unbalance in borosilicate ratio, affecting whisker formation. If B is2O3Less than 40 wt% may result in Al formation18B4O33The number of whiskers is small, so that the strength of a joint obtained by welding is greatly reduced; if the amount is more than 50 wt%, the high temperature resistance of the joint tends to be lowered. If Al is present2O3The content of (b) is less than 15 wt%, which easily causes insufficient solder reaction and decreases the number of whiskers; if it exceeds 25 wt%, 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 15 wt%, the reaction tends to be insufficient, and the reaction layer tends to be thin or disappear; if the amount is more than 30 wt%, 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% SiO242-48% of B2O318-22% of Al2O3And 15-26% MgO.
In a more preferred embodiment, the main component comprises 15% SiO245% of B2O320% of Al2O3And 20% MgO.
At the above preferred or more preferred ratios, the corresponding solder can be mixed with Al2O3Better wettability between ceramic matrices and smallerThe residual stress of the welded joint is smaller and the connection strength is higher due to the difference of the thermal expansion coefficients.
Further, the solder also comprises water and a bonding agent.
The mass ratio of the main component to water and binder may, by reference, be 2:0.8-1.2:0.8-1.2, such as 2:0.8:0.8, 2:1:1, 2:1.2:1.2, 2:1:0.8, 2:1:1.2, 2:0.8:1 or 2:0.8:1.2, etc., preferably 2:1:1. 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 solder2O3The 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 2 h.
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 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 Al2O3Ceramic and/or Al2O3And (4) connecting the ceramic particles. When used for Al2O3In joining ceramics, solder is applied to two Al to be welded2O3At least one Al in the ceramic2O3The welding surface of the ceramic. When used for Al2O3When the ceramic particles are connected, the solder is uniformly coated on all the surfaces of the ceramic particles.
Referably, when both base metals to be welded are Al2O3In 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 are2O3In the ceramic, at least one Al2O3Al in ceramics2O3The 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 connected2O3Ceramics or Al2O3The connecting surface of the ceramic particles.
The following main pairs of Al2O3The welding process of ceramics as a base material, Al is used as the welding base material2O3The welding process and parameters of the ceramic particles can be referred toAl2O3The description of the ceramic is not repeated herein.
With respect to Al2O3With ceramic as the base material, the solder is applied to two Al to be soldered2O3At least one Al in the ceramic2O3The welding surface of the ceramic.
In an alternative embodiment, at least one Al2O3Al in ceramics2O3The content of (B) is not less than 95 wt%.
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/cm2E.g. 0.3g/cm2、0.35g/cm2Or 0.4g/cm2。
Subsequently, two Al coated with solder (at least one of the bonding surfaces coated with solder) are applied2O3And (4) performing heating treatment after the welding surfaces of the ceramics are attached. In the application, the heating treatment is carried out by raising the temperature to 1150-1200 ℃ at the rate of 3-5 ℃/min and keeping the temperature for 90-150 min.
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 any other value within the range of 1150-.
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 90-150 min.
In a preferred embodiment, the heat treatment is carried out at a rate of 3 ℃/min up to 1150 ℃ and at a temperature of 120 min.
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 temperature2O4And Al18B4O33The microcrystalline glass of the crystal whisker not only enhances the connection reliability of the joint, but also is connected with Al2O3Ceramic nutThe 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 Al2O3Reliable 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; higher than 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 softening is likely to occur, the phenomenon of flooding is severe and whiskers in the joint are subject to coalescence 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 layers2O3The ceramic is pressurized to make two Al2O3The width of the weld between the ceramics is about 1 mm. In the process, air bubbles in the solder can be discharged, so that the solder is compact, and the defects of the welding seam are reduced.
Further, during the heating process, two Al can be added2O3The ceramic is again extruded to make two Al2O3The 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 included2O3The ceramic is washed and dried.
Wherein, the cleaning can be carried out by taking absolute ethyl alcohol as a cleaning reagent and carrying out ultrasonic cleaning for 10-15min, and specifically can be carried out in an ultrasonic cleaning machine.
In some embodiments, the preparation of the solder and the Al2O3The welding method of ceramics can be referred to as followsThe process is as follows:
1) proportioning SiO by using a three-dimensional mixer2、B2O3、Al2O3And 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 welded2O3Processing the ceramic into a sample with a target specification;
4) subjecting the Al to be welded in the step 3)2O3Putting 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 connected2O3At least one surface to be connected in the ceramic sample (coating thickness is 1-2mm), the surfaces to be connected of the two samples to be connected are opposite, and proper pressure is given to ensure that the two Al surfaces are opposite2O3The 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 air furnace is cooled to room temperature along with the furnace after the temperature is kept, so that Al is realized2O3And (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 Al2O3Ceramic parts (especially large and complex shaped Al)2O3Ceramic 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 Al2O3The ceramic connection solder comprises the following components: 10 wt% SiO2Powder, 45 wt% of B2O3Powder, 20 wt% Al2O3Powder and 25 wt% MgO powder.
Wherein, SiO2The purity of the powder is analytically pure, and the powder is colorless fine crystal particles or white powder; b is2O3The purity of the powder is analytically pure; al (Al)2O3The 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.
Preparation method of the solder and realization of Al by using the solder2O3The method of ceramic joining comprises the steps of:
1) weighing SiO according to mass percentage2Powder, B2O3Powder, Al2O3Mixing 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 brazed2O3Ceramic (Al)2O3Content 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 2mm) on two Al to be connected2O3Opposite surfaces to be connected of ceramic samplesThe connecting surfaces of two connected samples are opposite, and proper pressure is applied until two Al2O3The width of the weld between the ceramic samples was about 1 mm;
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 Al2O3And (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 Al2O3The results of the observation of the ceramic joint structure are shown in FIG. 2. In FIG. 2, the middle part is Al18B4O33Whisker with MgAl as upper and lower boundary2O4Proves that the solder provided by the application indeed forms MgAl-containing solder at high temperature2O4And Al18B4O33The microcrystalline glass of (4).
Example 4
This example is substantially the same as example 2 except that the solder has the following components: 8 wt% SiO2Powder, 48 wt% of B2O3Powder, 18 wt% Al2O3Powder and 26 wt% MgO powder.
Example 5
This example is substantially the same as example 2 except that the solder has the following components: 11 wt% SiO2Powder, 44 wt% of B2O3Powder, 21 wt% Al2O3Powder and 24 wt% MgO powder.
Example 6
This example is substantially the same as example 2 except that the solder has the following components: 5 wt% SiO2Powder, 50 wt% of B2O3Powder, 15 wt% Al2O3Powder and 30 wt% MgO powder.
Example 7
This example is substantially the same as example 2 except that the solder has the following components: 15 wt% SiO2Powder, 45 wt% of B2O3Powder, 20 wt% Al2O3Powder and 20 wt% 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 soldered2O3One Al in the ceramic2O3The 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 approximately the same as example 2, except that the temperature was raised to 1100 ℃ in step 6).
Comparative example 3
This comparative example is approximately the same as example 2, except that the temperature in step 6) was raised to 1125 ℃.
Comparative example 4
This comparative example is substantially the same as example 2, except that the temperature in step 6) is raised to 1250 ℃.
Comparative example 5
This comparative example is substantially the same as example 2, differing only byThe solder comprises the following components: 20% by weight of SiO2Powder, 35 wt% of B2O3Powder, 30 wt% Al2O3Powder and 15 wt% 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 wt% SiO2Powder, 55 wt% of B2O3Powder, 10 wt% Al2O3Powder and 32 wt% MgO powder.
Comparative example 7
This comparative example is approximately the same as example 2, differing only by SiO in step 1)2Powder, B2O3Powder, Al2O3The powder and MgO powder are mixed by a common mixer.
Test examples
The soldered joints obtained in the above examples 1 to 7 and comparative examples 1 to 7 were tested for shear strength 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, SiO2Powder, B2O3Powder, Al2O3The 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 SiO2Powder, B2O3Powder, Al2O3Mixing 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 temperature2O4And Al18B4O33The microcrystalline glass not only can enhance the connection reliability of the welding joint, but also can be connected with Al2O3The 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 Al2O3Reliable 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.
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.
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