CN116178038B - Method for connecting transparent spinel and transparent sapphire ceramic by adopting double-layer glass solder - Google Patents
Method for connecting transparent spinel and transparent sapphire ceramic by adopting double-layer glass solder Download PDFInfo
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- CN116178038B CN116178038B CN202310146647.4A CN202310146647A CN116178038B CN 116178038 B CN116178038 B CN 116178038B CN 202310146647 A CN202310146647 A CN 202310146647A CN 116178038 B CN116178038 B CN 116178038B
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 103
- 239000000919 ceramic Substances 0.000 title claims abstract description 70
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 52
- 239000011029 spinel Substances 0.000 title claims abstract description 52
- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 50
- 239000010980 sapphire Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 238000003466 welding Methods 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012634 fragment Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005304 joining Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000010431 corundum Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 5
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000000156 glass melt Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000007517 polishing process Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 2
- 238000002834 transmittance Methods 0.000 abstract description 19
- 230000007704 transition Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005452 bending Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/10—Glass interlayers, e.g. frit or flux
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/52—Pre-treatment of the joining surfaces, e.g. cleaning, machining
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/55—Pre-treatments of a coated or not coated substrate other than oxidation treatment in order to form an active joining layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Structural Engineering (AREA)
- Glass Compositions (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a method for connecting transparent spinel and transparent sapphire ceramic by adopting double-layer glass solder, and belongs to the technical field of welding. The method utilizes double-layer glass solder to connect dissimilar ceramics step by step and inhibits interface reaction, thereby obtaining the joint with high strength and high light transmittance. The method comprises the following steps: the two glass solder powders are prepared into slurry and then are respectively and uniformly coated on the surfaces of transparent spinel ceramic and transparent sapphire ceramic; firstly, placing sapphire coated with glass slurry and spinel coated with the glass slurry in a muffle furnace for first-step connection; and then assembling according to the sequence of the sapphire/glass layer/spinel, applying a certain pressure, and placing in a muffle furnace for second-step connection. The double-layer glass solder prepared by the invention carries out gradient transition on the thermal expansion coefficient and the refractive index of heterogeneous ceramics, thereby improving the joint strength and ensuring the light transmittance of the joint.
Description
Technical Field
The invention relates to the technical field of welding, in particular to a method for connecting transparent spinel and transparent sapphire ceramic by double-layer glass solder.
Background
Transparent magnesia-alumina spinel ceramics (MgAl 2O4) and transparent sapphire ceramics (Al 2O3 in a single crystal state) are commonly used infrared transparent ceramics, and have wide application prospects in the fields of infrared detector windows and the like. Of course, there is a certain difference in the properties of these two transparent ceramics. For example, magnesia-alumina spinel ceramics have a broad light transmission wavelength range, relatively low manufacturing cost, but low mechanical properties. The sapphire ceramic has high strength, but is a single crystal material, so that the preparation cost is high. Thus, joining the two transparent ceramics together can take advantage of their respective advantages, thereby avoiding their respective disadvantages.
The glass solder has excellent light transmittance and good chemical compatibility with ceramic materials, and the physicochemical properties such as the thermal expansion coefficient, the refractive index and the like of the glass solder can be regulated and controlled by designing the components of the glass solder. Therefore, glass solder is an ideal material for joining transparent ceramics.
However, in order to obtain a joint with good light transmittance, it is necessary to avoid an interface reaction between the glass solder and the ceramic base material, preventing the formation of a new phase at the interface. When a single-layer glass solder is used for connecting heterogeneous transparent ceramics, interface reaction between the glass solder and two ceramic materials must be avoided at the same time, and the implementation is difficult.
Disclosure of Invention
The invention aims to provide a method for connecting transparent spinel and transparent sapphire ceramic, which can obtain a heterogeneous ceramic joint with high strength and high light transmittance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A method for connecting transparent spinel and transparent sapphire ceramic by adopting double-layer glass solder is characterized by comprising the following steps: the method utilizes two kinds of glass solders (glass solder I and glass solder II) to connect dissimilar ceramics step by step to prepare the sapphire/glass solder I/glass solder II/spinel joint.
The composition of the glass solder I is ：La2O3：50-58％,SiO2：18-25％,B2O3：12-18％,Nb2O5：4-8％,Ta2O5：2-8％;, and the composition of the glass solder II is that MgO is added on the basis of the component of the glass solder I, and the added MgO accounts for 4-8% of the weight of the glass solder I.
The connection method specifically comprises the following steps:
(1) Material preparation: carrying out ultrasonic cleaning on spinel ceramic and sapphire ceramic by taking acetone as a medium, removing greasy dirt, carrying out ultrasonic treatment for 5-20min, and then drying for later use;
(2) Preparing glass solder: oxide raw materials are respectively weighed according to chemical components of the glass solder I and the glass solder II, and after being uniformly mixed, the glass solder I powder and the glass solder II powder are prepared by adopting a melting-water quenching method;
(3) The first step is connected: preparing glass slurry I and glass slurry II from glass solder I powder and glass solder II powder respectively, coating the glass slurry I on the surface of sapphire ceramic, coating the glass slurry II on the surface of spinel ceramic, and then placing the spinel ceramic into a muffle furnace in air atmosphere for heating and heat preservation treatment; after the heat preservation is finished, rapidly cooling to room temperature; respectively obtaining a glass layer I and a glass layer II on the surfaces of the sapphire ceramic and the spinel ceramic;
(4) Surface treatment: respectively grinding and polishing a glass layer I and a glass layer II on the surfaces of the sapphire and spinel ceramics;
(5) And the second step is connected: assembling according to the sequence of 'sapphire/glass layer I/glass layer II/spinel', and simultaneously applying a certain pressure to the joint by adopting a weight placing mode (placing an object on the upper surface of the joint to apply vertical downward pressure); placing the assembled and pressurized sample into a muffle furnace in air atmosphere for heating and heat preservation treatment; and after the heat preservation is finished, cooling to room temperature along with a furnace to obtain the sapphire/glass solder I/glass solder II/spinel joint, so that double-layer glass solder connection between dissimilar ceramics is realized.
In the step (2), the melting-water quenching method comprises the following steps: putting the weighed oxide raw material powder for preparing the glass solder I or the glass solder II into a ball milling tank, and performing ball milling by taking alcohol or deionized water as a ball milling medium and taking ZrO 2 as a grinding ball, wherein the ball milling speed is 400-500 r/min, and the ball milling time is 2-5h; drying the obtained mixed powder after ball milling, pouring the dried material into a platinum crucible or a corundum crucible, heating to 1500-1600 ℃ in a muffle furnace in air atmosphere, preserving heat for 1-3h, and rapidly pouring the obtained glass melt into deionized water to obtain glass fragments; putting the glass fragments into an agate ball milling tank, and performing ball milling by taking agate as a grinding ball, wherein the ball milling rotating speed is 400-500 r/min, and the ball milling time is 2-5h; and (3) screening the mixture of the glass fragments and the glass powder obtained after ball milling, separating the glass fragments, and drying the glass powder remained after screening to obtain glass solder powder I or glass solder powder II.
In the step (3), the process of preparing the slurry from the glass solder powder I and the glass solder powder II comprises the following steps: adding 3-6% of absolute ethyl alcohol and 3-5% of ethyl cellulose into the glass solder powder I or the glass solder powder II, and then rapidly stirring with a glass rod to uniformly mix the materials to obtain glass slurry I or glass slurry II.
In the step (3), the heating and heat preservation processes are as follows: heating to 1350-1450 ℃ at 10-20 ℃/min, and preserving heat for 10-30min; in order to inhibit crystallization of glass, the rapid cooling process requires a cooling rate higher than 40 ℃/min, which can be achieved by introducing inert gas into a muffle furnace, or directly taking out a sample from the furnace and cooling in air.
In the step (4), grinding is carried out by adopting grinding liquid, wherein the grinding liquid is obtained by adding corundum powder with the diameter of 7-14 mu m into water; polishing by adopting a polishing solution, wherein the polishing solution is obtained by adding cerium oxide powder with the diameter of 0.65-0.95 mu m into water; in the grinding and polishing process, the thickness of the glass layer on the surface of the transparent ceramic is controlled to be 20-50 mu m.
In the step (5), the pressure applied to the welding joint is 0.5-3KPa.
In the step (5), the heating and heat preservation processes are as follows: heating to 850-950 ℃ at a heating rate of 5-15 ℃/min, and preserving heat for 30-60min.
The invention has the following advantages and beneficial effects:
(1) According to the invention, the transparent spinel and the transparent sapphire ceramic are connected by using double-layer glass solder, so that the occurrence of interface reaction can be restrained, and the light transmittance of the joint is ensured.
(2) The thermal expansion coefficient and the refractive index of the double-layer glass solder prepared by the invention are between those of the sapphire and the spinel, and the thermal expansion coefficient and the refractive index of the glass solder I are both larger than those of the glass solder II, so that the thermal expansion coefficient and the refractive index of the joint are gradient transition, and the mechanical property and the optical property of the joint are further improved.
(3) The bending strength of the joint obtained by the invention is more than 200MPa, and the straight line transmittance of the joint at the wavelength of 1000nm is more than 85%.
Drawings
FIG. 1 is a schematic illustration of the preparation of a sapphire/spinel joint according to example 1; wherein: (a) For mechanical property testing joints, (b) for optical property testing joints.
FIG. 2 is a photograph of the microstructure of the sapphire/spinel joint prepared in example 1.
Fig. 3 is a photograph of the microstructure of the sapphire/spinel joint prepared in comparative example 1.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
In this embodiment, two kinds of glass solders are melted and then connected with heterogeneous transparent ceramics to obtain a sapphire/glass solder i/glass solder ii/spinel joint, and the implementation process of this embodiment refers to fig. 1, and specifically includes the following steps:
(1) Material preparation: preparing two ceramics with the size of 3 multiplied by 4 multiplied by 18mm for mechanical property test, preparing two ceramics with the size of 8 multiplied by 1.5mm for transmittance test, ultrasonically cleaning spinel ceramics and sapphire ceramics to be connected by taking acetone as a medium, removing greasy dirt, ultrasonically treating for 10min, and drying for later use.
(2) Preparing glass solder: the oxide raw materials were weighed according to the following weight composition. Glass solder i composition (wt.％)：La2O3：55％,SiO2：20％,B2O3：15％,Nb2O5：7％,Ta2O5：3％; glass solder ii composition (wt.%); mgO is added on the basis of the composition of the glass solder I, and the addition amount of MgO is 5% of the weight of the glass solder I. Putting the weighed oxide raw material powder into a ball milling tank, performing ball milling by taking alcohol or deionized water as a ball milling medium and taking ZrO 2 as a grinding ball, wherein the ball milling rotating speed is 450 r/min, and the ball milling time is 2h; drying the mixed powder after ball milling, pouring the dried material into a platinum crucible or a corundum crucible, heating to 1550 ℃ in a muffle furnace in air atmosphere, and rapidly pouring the obtained glass melt into deionized water after heat preservation for 2 hours to obtain glass fragments; putting the glass fragments into an agate ball milling tank, and performing ball milling by taking agate as a grinding ball, wherein the ball milling rotating speed is 450 r/min, and the ball milling time is 2h. Screening the obtained glass fragments and mixed powder after ball milling is completed to obtain the glass fragments; and drying the mixed powder to obtain the glass powder.
(3) The first step is connected: preparing the glass powder obtained in the step (2) into slurry, respectively adding 5% of absolute ethyl alcohol and 3% of ethyl cellulose into the glass powder, and rapidly stirring with a glass rod to uniformly mix the absolute ethyl alcohol and the ethyl cellulose to obtain the slurry. And (3) coating the glass slurry I on the surface of the sapphire ceramic, coating the glass slurry II on the surface of the spinel ceramic, then putting the spinel ceramic into a muffle furnace in air atmosphere for heating, heating to 1350 ℃ at 20 ℃/min, preserving heat for 30min, directly taking out the sample from the furnace after the heat preservation is finished, and cooling in air.
(4) Surface treatment: the glass layers on the surfaces of the sapphire and the spinel are ground down by using a grinding liquid (obtained by adding corundum powder with the diameter of 7-14 μm into water), and the glass layers on the surfaces of the sapphire and the spinel are polished by using a polishing liquid (obtained by adding cerium oxide powder with the diameter of 0.65 μm into water). In the process of grinding and polishing, the thickness of the glass layer on the surface of the transparent ceramic is controlled to be 35 mu m.
(5) And the second step is connected: the assembly was performed in the order "sapphire/glass layer i/glass layer ii/spinel" while applying a pressure of 2KPa to the joint by placing a weight. After the sample is assembled, the sample is put into a muffle furnace in air atmosphere, the temperature is raised to 850 ℃ at 10 ℃ per minute, and the sample is kept for 30 minutes and then cooled to room temperature along with the furnace.
FIG. 3 is a photograph of the microstructure of the sapphire/spinel joint prepared in example 1. As can be seen from the figure, the whole joint has no defects such as air holes, cracks and the like. The glass solder and the ceramic base material are well bonded at the interface, and no interface reaction product is generated. In addition, the glass solder I and the glass solder II are well combined and can be clearly distinguished. The refractive index of spinel was 1.71, the refractive index of sapphire was 1.77, the refractive index of the glass solder i obtained in example 1 was 1.754, and the refractive index of the glass solder ii was 1.731. The refractive indexes of the two glass solders are just positioned between the refractive indexes of the two ceramic base materials, so that the refractive indexes of the joint can realize gradient transition, and the light transmittance of the joint is ensured. The joint obtained in example 1 had a bending strength of 221MPa and a linear transmittance of 85.5% at a wavelength of 1000 nm.
Example 2
The difference from example 1 is that: the composition of glass solder I in weight percent in step (2) was ：La2O3：55％,SiO2：20％,B2O3：15％,Nb2O5：7％,Ta2O5：8％, the same as in example 1. The refractive index of the glass solder I in example 2 was 1.763, the bending strength of the joint obtained in example 2 was 209MPa, and the transmittance of the joint at a wavelength of 1000nm was 85.4%.
Example 3
The difference from example 1 is that: in the step (2), mgO is added into the glass solder II on the basis of the composition of the glass solder I, and the weight percentage of MgO is as follows: 8%. The other steps were the same as in example 1. The refractive index of the glass solder II in example 3 was 1.726, the bending strength of the joint obtained in example 3 was 213MPa, and the transmittance of the joint at a wavelength of 1000nm was 85.3%.
Comparative example 1
The comparative example adopts glass solder 1 to directly connect sapphire ceramic and spinel ceramic, and the specific preparation steps are as follows:
(1) Material preparation: the method comprises the steps of preparing sapphire ceramics and spinel ceramics with the size of 8 multiplied by 1.5mm for transmittance test, performing ultrasonic cleaning on the spinel ceramics and the sapphire ceramics by taking acetone as a medium, removing greasy dirt, performing ultrasonic treatment for 10min, and then drying for later use.
(2) Preparing glass solder: the glass solder I is prepared by placing weighed oxide raw material powder into a ball milling tank according to the weight percentage of ：La2O3：55％,SiO2：20％,B2O3：15％,Nb2O5：7％,Ta2O5：3％., performing ball milling by taking alcohol or deionized water as a ball milling medium and taking ZrO 2 as a grinding ball, wherein the ball milling rotating speed is 450 r/min, and the ball milling time is 2h; drying the mixed powder after ball milling, pouring the dried material into a platinum crucible or a corundum crucible, heating to 1550 ℃ in a muffle furnace in air atmosphere, and rapidly pouring the obtained glass melt into deionized water after heat preservation for 2 hours to obtain glass fragments; putting the glass fragments into an agate ball milling tank, and performing ball milling by taking agate as a grinding ball, wherein the ball milling rotating speed is 450 r/min, and the ball milling time is 2h. Screening the obtained glass fragments and mixed powder after ball milling is completed to obtain the glass fragments; and drying the mixed powder to obtain the glass powder.
(3) And (3) joint connection: preparing the glass powder obtained in the step (2) into slurry, respectively adding 5% of absolute ethyl alcohol and 3% of ethyl cellulose into the glass powder, and rapidly stirring with a glass rod to uniformly mix the absolute ethyl alcohol and the ethyl cellulose to obtain glass slurry I. The glass paste i was coated on the surface of the sapphire ceramic, and then assembled in the order of "sapphire/glass solder i/spinel". Heating the assembled sample in a muffle furnace in air atmosphere, heating to 1350 ℃ at 20 ℃ per minute, preserving heat for 30min, directly taking the sample out of the furnace after the heat preservation is finished, and cooling in air.
Fig. 3 is a photograph of the microstructure of the sapphire/spinel joint prepared in comparative example 1. As can be seen from the figure, the reaction layer formed at both side interfaces, resulting in comparative example 1 having only 35.2% in-line transmittance at a wavelength of 1000 nm.
Comparative example 2
In the second step of connection process of the step (4), the temperature is increased to 830 ℃ in a muffle furnace at 10 ℃/min. The other steps were the same as in example 1. The joint obtained in comparative example 2 had a bending strength of 26MPa and a transmittance of 76.4% at a wavelength of 1000 nm. Due to the low connection temperature, the interdiffusion between the glass solder layers is insufficient, holes are generated in the welding lines, and the joint strength is obviously reduced.
Comparative example 3
In the second step of connection process of the step (4), the temperature is increased to 970 ℃ in a muffle furnace at 10 ℃ per minute. The other steps were the same as in example 1. The joint obtained in comparative example 3 had a bending strength of 214MPa and a transmittance of 21.7% at a wavelength of 1000 nm. The joining temperature increases and crystallization of the glass solder layer occurs, resulting in a decrease in joint transmittance.
The joint strength and the linear transmittance of each of the above examples and comparative examples are shown in table 1.
Table 1 joint strength and in-line transmittance at 1000nm for examples and comparative examples
Claims (6)
1. A method for connecting transparent spinel and transparent sapphire ceramic by adopting double-layer glass solder is characterized by comprising the following steps: the method utilizes glass solder I and glass solder II to connect different ceramics step by step to prepare a ceramic joint;
The composition of the glass solder I is ：La2O3：50-58％,SiO2：18-25％,B2O3：12-18％,Nb2O5：4-8％,Ta2O5：2-8％;, and the composition of the glass solder II is that MgO is added on the basis of the component of the glass solder I, and the added MgO amount is 4-8% of the weight of the glass solder I;
the method for connecting the transparent spinel and the transparent sapphire ceramic by adopting double-layer glass solder specifically comprises the following steps:
(1) Material preparation: carrying out ultrasonic cleaning on spinel ceramic and sapphire ceramic by taking acetone as a medium, removing greasy dirt, carrying out ultrasonic treatment for 5-20min, and then drying for later use;
(2) Preparing glass solder: oxide raw materials are respectively weighed according to chemical components of the glass solder I and the glass solder II, and after being uniformly mixed, the glass solder I powder and the glass solder II powder are prepared by adopting a melting-water quenching method;
(3) The first step is connected: preparing glass slurry I and glass solder II from glass solder I powder and glass solder II powder respectively, coating the glass slurry I on the surface of sapphire ceramic, coating the glass slurry II on the surface of spinel ceramic, and then placing the spinel ceramic into a muffle furnace in air atmosphere for heating and heat preservation treatment; after the heat preservation is finished, rapidly cooling to room temperature; respectively obtaining a glass layer I and a glass layer II on the surfaces of the sapphire ceramic and the spinel ceramic;
(4) Surface treatment: respectively grinding and polishing a glass layer I and a glass layer II on the surfaces of the sapphire and spinel ceramics;
(5) And the second step is connected: assembling according to the sequence of the sapphire, the glass layer I, the glass layer II and the spinel, and simultaneously applying a certain pressure to the joint in a manner of placing a weight; putting the assembled and pressurized sample into a muffle furnace with air atmosphere for heating and heat preservation treatment, wherein the heating and heat preservation process is as follows: heating to 850-950 ℃ at a heating rate of 5-15 ℃/min, and preserving heat for 30-60min; and after the heat preservation is finished, cooling to room temperature along with a furnace to obtain the sapphire/glass solder I/glass solder II/spinel joint, so that double-layer glass solder connection between dissimilar ceramics is realized.
2. The method of joining transparent spinel and transparent sapphire ceramics using a double glass solder according to claim 1, wherein: in the step (2), the melting-water quenching method comprises the following steps: respectively placing weighed oxide raw material powder for preparing glass solder I or glass solder II into a ball milling tank, and performing ball milling by taking alcohol or deionized water as a ball milling medium and ZrO 2 as a grinding ball, wherein the ball milling speed is 400-500 r/min, and the ball milling time is 2-5h; drying the obtained mixed powder after ball milling, pouring the dried material into a platinum crucible or a corundum crucible, heating to 1500-1600 ℃ in a muffle furnace in air atmosphere, preserving heat for 1-3h, and rapidly pouring the obtained glass melt into deionized water to obtain glass fragments; putting the glass fragments into an agate ball milling tank, and performing ball milling by taking agate as a grinding ball, wherein the ball milling rotating speed is 400-500 r/min, and the ball milling time is 2-5h; and (3) screening the mixture of the glass fragments and the glass powder obtained after ball milling, separating the glass fragments, and drying the glass powder remained after screening to obtain glass solder powder I and glass solder powder II.
3. The method of joining transparent spinel and transparent sapphire ceramics using a double glass solder according to claim 1, wherein: in the step (3), the process of preparing the slurry from the glass solder powder I and the glass solder powder II comprises the following steps: and respectively adding 3-6% of absolute ethyl alcohol and 3-5% of ethyl cellulose into the glass solder powder I or the glass solder powder II, and then rapidly stirring with a glass rod to uniformly mix the materials to obtain glass slurry I and glass slurry II.
4. The method of joining transparent spinel and transparent sapphire ceramics using a double glass solder according to claim 1, wherein: in the step (3), the heating and heat preservation process is as follows: heating to 1350-1450 ℃ at 10-20 ℃/min, and preserving heat for 10-30min; in order to inhibit crystallization of glass, the cooling speed is required to be higher than 40 ℃/min in the rapid cooling process, wherein inert gas is introduced into a muffle furnace or a sample is directly taken out of the furnace, and the rapid cooling process is carried out in air.
5. The method of joining transparent spinel and transparent sapphire ceramics using a double glass solder according to claim 1, wherein: in the step (4), grinding is carried out by adopting grinding fluid, wherein the grinding fluid is obtained by adding corundum powder with the diameter of 7-14 mu m into water; polishing by adopting a polishing solution, wherein the polishing solution is obtained by adding cerium oxide powder with the diameter of 0.65-0.95 mu m into water; in the grinding and polishing process, the thickness of the glass layer on the surface of the transparent ceramic is controlled to be 20-50 mu m.
6. The method of joining transparent spinel and transparent sapphire ceramics using a double glass solder according to claim 1, wherein: in the step (5), the pressure applied to the welding joint is 0.5-3KPa.
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