CN108640522A - A kind of devitrified glass solder and the method using solder welding porous silicon nitride and compact silicon nitride - Google Patents
A kind of devitrified glass solder and the method using solder welding porous silicon nitride and compact silicon nitride Download PDFInfo
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- CN108640522A CN108640522A CN201810602753.8A CN201810602753A CN108640522A CN 108640522 A CN108640522 A CN 108640522A CN 201810602753 A CN201810602753 A CN 201810602753A CN 108640522 A CN108640522 A CN 108640522A
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 93
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 77
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000003466 welding Methods 0.000 title claims abstract description 40
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 28
- 239000000919 ceramic Substances 0.000 claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000280 densification Methods 0.000 claims abstract description 24
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims description 78
- 238000000498 ball milling Methods 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000012634 fragment Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000005498 polishing Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000005219 brazing Methods 0.000 claims description 5
- 230000009172 bursting Effects 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000005476 soldering Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052661 anorthite Inorganic materials 0.000 abstract description 3
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052642 spodumene Inorganic materials 0.000 abstract description 3
- 230000004927 fusion Effects 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 19
- 239000010432 diamond Substances 0.000 description 8
- 229910003460 diamond Inorganic materials 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000007571 dilatometry Methods 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Structural Engineering (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Products (AREA)
- Glass Compositions (AREA)
Abstract
A kind of devitrified glass solder and method using solder welding porous silicon nitride and compact silicon nitride are related to a kind of solder and utilize solder welding densification Si3N4Ceramic and porous Si3N4The method of ceramics.It is to solve the problems, such as that the coefficient of thermal expansion of existing Ordinary microcrystalline glass solder and porous silicon nitride ceramic and compact silicon nitride ceramics is unmatched.The devitrified glass solder is by CaO, Al2O3、SiO2And Li2O is made.Method：One, the preparation of devitrified glass solder；Two, welding densification Si3N4Ceramic and porous Si3N4Ceramics.CaO Al of the anorthite as principal crystalline phase is precipitated2O3‑SiO2Li is added in system thereto2O reduces its fusion temperature, and reduces its coefficient of thermal expansion by the way that the spodumene of low thermal coefficient of expansion is precipitated, and reaches and matches with the coefficient of thermal expansion of base material.Applied to fine and close Si3N4Ceramic and porous Si3N4The connection of ceramics.
Description
Technical field
Densification Si is welded the present invention relates to a kind of solder and using the solder3N4Ceramic and porous Si3N4The method of ceramics.
Background technology
Si3N4Ceramic material has high hardness, high intensity, high wear-resistant, good corrosion-resistant and thermal-shock resistance
And the advantages that low dielectric constant.With compact silicon nitride ceramic phase ratio, porous silicon nitride ceramic is in addition to compact silicon nitride
Outside the fundamental characteristics such as ceramic high-temperature resistant, wear-resistant, corrosion-resistant and good thermal shock resistance, also there is high porosity, low-density
The features such as, and its permittivity ε can be adjusted by changing the porosity of silicon nitride ceramics, it is more in line with high-speed missile day
The requirement of irdome is a kind of ideal missile antenna cover material.So realizing that porous silicon nitride and the reliable of compact silicon nitride connect
It connects with important engineering significance.
Currently, devitrified glass connection has good applied at elevated temperature performance, and there is lower dielectric loss.And more often
Ag-Cu-Ti systems isoreactivity solder cannot meet applied at elevated temperature requirement since fusing point is low, and dielectric loss is higher, oxygen nitrogen
Glass connects the higher stability that can influence porous base material of temperature.
Invention content
The present invention is to solve existing Ordinary microcrystalline glass solders and porous silicon nitride ceramic and compact silicon nitride ceramics
The unmatched problem of coefficient of thermal expansion, a kind of devitrified glass solder is provided and utilizes solder welding porous silicon nitride and densification
The method of silicon nitride.
Devitrified glass solder of the present invention is by weight percentage by 20%~22% CaO, 18%~22% Al2O3, 50%
~60% SiO2With the Li of surplus2O is made.
The method for welding porous silicon nitride and compact silicon nitride using above-mentioned solder, includes the following steps：
One, the preparation of devitrified glass solder：
1. CaO by weight percentage:20%~22%, Al2O3：18%~22%, SiO2：50%~60%, surplus
Li2O weighs CaO, Al respectively2O3、SiO2And Li2O is as solder；
2. solder is carried out ball milling, then solder is dried, obtains mixed-powder；
3. mixed-powder is carried out melting, then melt is directly poured into distilled water, obtains the glass for bursting into fritter
Fragment；
4. glass fragment is carried out ball milling, glass powder is obtained, 300 mesh sieve is crossed after drying, it is spare；
Two, welding densification Si3N4Ceramic and porous Si3N4Ceramics：
1. by fine and close Si3N4Ceramic and porous Si3N4Ceramic manufacturing is to weld size, by fine and close Si3N4Ceramic base material waits for
It is smooth that the face of weld is polishing to surface；
2. by the fine and close Si after polishing3N4Ceramic material immerses in acetone, is cleaned by ultrasonic, is then rinsed, blown with absolute ethyl alcohol
It is dry to be welded；By porous Si3N4Ceramics, which are put into acetone, to be impregnated, and is then dried to be welded；
3. glass powder prepared by step 1 is pressed into sheet in tablet press machine, with glue by the glass powder cementation of sheet
In porous Si3N4Ceramics and densification Si3N4Between ceramics, it is assembled into porous Si3N4Ceramic material/devitrified glass solder/densification
Si3N4Structural member；
4. structural member is placed in vacuum brazing stove, and in structural member upper ends pressure block, the pressure of pressure block is 1 ×
103~1 × 104Then soldering furnace is evacuated to 1.0 × 10 by Pa-3~6.0 × 10-3Pa, with the rate of heat addition liter of 10 DEG C/min
Temperature keeps the temperature 10~20min to 300~350 DEG C；Then beginning recrystallization temperature is warming up to the heating speed of 5 DEG C/min, then after
The continuous heating rate with 10 DEG C/min is warming up to 1080 DEG C~1220 DEG C, and keeps the temperature 10~30min；It is cooled to after the completion of welding
300~350 DEG C, close power supply furnace cooling.
Further, step 1 2. in by solder carry out ball milling specific method be：
Solder is put into agate jar, ZrO is then placed in2(99.9%) ball, addition absolute ethyl alcohol, 2~4h of ball milling,
Rotating speed is 200~300r/min.
Further, 2. middle dry specific method is step 1：Solder is put into drying box and is heated to 80~85 DEG C,
Dry 3~5h, removes the absolute ethyl alcohol in solder.
Further, step 1 3. in the specific method of melting be：
Mixed-powder is put into corundum crucible, crucible is put into glass melting stove, is heated with the rate of 10 DEG C/min
To 1500~1550 DEG C, 1~2h of heat preservation keeps glass melting uniform, obtains melt.
Further, step 1 4. in by glass fragment carry out ball milling specific method be：
Glass fragment is put into agate jar, 4~5h of ball milling, rotating speed are afterwards for addition alcohol and agate ball (99.9%)
400~450r/min.
Further, 1. the middle specific method polished is step 2：Using the diamond disk of 800# by fine and close Si3N4Pottery
The surface to be welded of porcelain base material is polishing to surfacing, is then polishing to table using the diamond paste that granularity is W2.5 and W1 successively
Face is smooth.
Further, 2. the middle time being cleaned by ultrasonic is 3~5min to step 2.
Further, step 2 3. in glass powder be pressed into the technological parameter of sheet in tablet press machine be：Pressure 7~
9MPa, 3~5min of pressurize.
Further, 4. middle cooling rate is 5 DEG C/min~50 DEG C/min to step 2.
Further, step 2 4. in temperature-fall period in be additionally added heat treatment process, in recrystallization temperature (in such as Fig. 1
T1 and T2) under keep the temperature 0.5h~1h, be then cooled back to 300~350 DEG C, close power supply furnace cooling.Increase heat treatment process
It can promote the precipitation of crystal in glass, form devitrified glass.Pure glassy state passes through addition there are a lower softening temperature
Crystallization technique, further promotes crystallization, can improve the softening temperature of devitrified glass, improves the applied at elevated temperature performance of connector.
Beneficial effects of the present invention：
The present invention proposes the CaO-Al anorthite is precipitated as principal crystalline phase2O3-SiO2Li is added in system thereto2O drops
Its low fusion temperature, and its coefficient of thermal expansion is reduced by the way that the spodumene of low thermal coefficient of expansion is precipitated, reach the heat with base material
Matched expansion coefficient.Such as raw material is weight percentage CaO:20%, Al2O3：18%, SiO2：57%, Li2O：5% it is micro-
Crystal glass, by different temperatures crystallization from the coefficient of thermal expansion 8.4 × 10 of original glass-6/ DEG C, most preferably reach 3.5 by crystallization
×10-6/ DEG C, the base material densification Si used3N4Coefficient of thermal expansion be 3.2 × 10-6/ DEG C, the coefficient of thermal expansion of the two differs only by
9.4%.Show that the glass system can reach the coefficient of thermal expansion to match with base material, realizes preferable connection application.
Relative to other devitrified glasses, CaO-Al of the invention2O3-SiO2Base microcrystal glass and silicon nitride ceramics have compared with
For close coefficient of thermal expansion, fusing point is low, and has preferable crystallization ability.Therefore CaO-Al is used2O3-SiO2Base microcrystal glass
Porous silicon nitride ceramic and compact silicon nitride ceramics are connected, and a small amount of modifer L i is added on basic composition2O, to optimize it
Connect temperature and crystallization characteristic.
Description of the drawings
Fig. 1 is that the DSC heat scans of 1 solder of embodiment analyze curve；
Fig. 2 is 1 glass solder of the embodiment devitrified glass that crystallization is formed at different temperatures and densification Si3N4Thermal expansion
Coefficient；
Fig. 3 is that the DSC heat scans of 6 solder of embodiment analyze curve；
Fig. 4 dissipates for the Typical Joints tissue of 1 devitrified glass solder connection compact silicon nitride of the embodiment and porous silicon nitride back of the body
Penetrate photo.
Specific implementation mode
Technical solution of the present invention is not limited to act specific implementation mode set forth below, further includes between each specific implementation mode
Arbitrary combination.
Specific implementation mode one：Present embodiment devitrified glass solder by weight percentage by 20%~22% CaO,
18%~22% Al2O3, 50%~60% SiO2With the Li of surplus2O is made.
Specific implementation mode two：Present embodiment utilizes devitrified glass solder welding porous silicon nitride and compact silicon nitride
Method includes the following steps：
One, the preparation of devitrified glass solder：
1. CaO by weight percentage:20%~22%, Al2O3：18%~22%, SiO2：50%~60%, surplus
Li2O weighs CaO, Al respectively2O3、SiO2And Li2O is as solder；
2. solder is carried out ball milling, then solder is dried, obtains mixed-powder；
3. mixed-powder is carried out melting, then melt is directly poured into distilled water, obtains the glass for bursting into fritter
Fragment；
4. glass fragment is carried out ball milling, glass powder is obtained, 300 mesh sieve is crossed after drying, it is spare；
Two, welding densification Si3N4Ceramic and porous Si3N4Ceramics：
1. by fine and close Si3N4Ceramic and porous Si3N4Ceramic manufacturing is to weld size, by fine and close Si3N4Ceramic base material waits for
It is smooth that the face of weld is polishing to surface；
2. by the fine and close Si after polishing3N4Ceramic material immerses in acetone, is cleaned by ultrasonic, is then rinsed, blown with absolute ethyl alcohol
It is dry to be welded；By porous Si3N4Ceramics, which are put into acetone, to be impregnated, and is then dried to be welded；
3. glass powder prepared by step 1 is pressed into sheet in tablet press machine, with glue by the glass powder cementation of sheet
In porous Si3N4Ceramics and densification Si3N4Between ceramics, it is assembled into porous Si3N4Ceramic material/devitrified glass solder/densification
Si3N4Structural member；
4. structural member is placed in vacuum brazing stove, and in structural member upper ends pressure block, the pressure of pressure block is 1 ×
103~1 × 104Then soldering furnace is evacuated to 1.0 × 10 by Pa-3~6.0 × 10-3Pa, with the rate of heat addition liter of 10 DEG C/min
Temperature keeps the temperature 10~20min to 300~350 DEG C；Then beginning recrystallization temperature is warming up to the heating speed of 5 DEG C/min, then after
The continuous heating rate with 10 DEG C/min is warming up to 1080 DEG C~1220 DEG C, and keeps the temperature 10~30min；It is cooled to after the completion of welding
300~350 DEG C, close power supply furnace cooling.
Specific implementation mode three：Present embodiment is unlike specific implementation mode two：Step 1 2. in by solder into
The specific method of row ball milling is：Solder is put into agate jar, ZrO is then placed in2(99.9%) anhydrous second is added in ball
Alcohol, 2~4h of ball milling, rotating speed are 200~300r/min.It is other to be identical with embodiment two.
Specific implementation mode four：Present embodiment is unlike specific implementation mode two or three：Step 1 is 2. middle dry
Specific method be：Solder is put into drying box and is heated to 80~85 DEG C, dry 3~5h.Other and specific implementation mode two
Or three is identical.
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode two to four：Step 1 3. in
The specific method of melting is：Mixed-powder is put into corundum crucible, crucible is put into glass melting stove, with 10 DEG C/min's
Rate is heated to 1500~1550 DEG C, and 1~2h of heat preservation keeps glass melting uniform, obtains melt.Other and specific implementation mode two
It is identical to one of four.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode two to five：Step 1 4. in
By glass fragment carry out ball milling specific method be：Glass fragment is put into agate jar, after alcohol and agate ball is added
4~5h of ball milling, rotating speed are 400~450r/min.It is other identical as one of specific implementation mode two to five.
Specific implementation mode seven：Unlike one of present embodiment and specific implementation mode two to six：Step 2 1. in
The specific method of polishing is：Using the diamond disk of 800# by fine and close Si3N4It is flat that the surface to be welded of ceramic base material is polishing to surface
Whole, then using the diamond paste that granularity is W2.5 and W1, to be polishing to surface smooth successively.Other and specific implementation mode
One of two to six is identical.
Specific implementation mode eight：Unlike one of present embodiment and specific implementation mode two to seven：Step 2 2. in
The time of ultrasonic cleaning is 3~5min.It is other identical as one of specific implementation mode two to seven.
Specific implementation mode nine：Unlike one of present embodiment and specific implementation mode two to eight：Step 2 3. in
The technological parameter that glass powder is pressed into sheet in tablet press machine is：7~9MPa of pressure, 3~5min of pressurize.Other and specific reality
It is identical to apply one of mode two to eight.
Specific implementation mode ten：Unlike one of present embodiment and specific implementation mode two to nine：Step 2 4. in
Cooling rate is 5 DEG C/min~50 DEG C/min.It is other identical as one of specific implementation mode two to nine.
Specific implementation mode 11：Unlike one of present embodiment and specific implementation mode two to ten：In step 2
4. it is additionally added heat treatment process in temperature-fall period in, 0.5h~1h is kept the temperature under recrystallization temperature, then it is cooled back to 300~
350 DEG C, close power supply furnace cooling.It is other identical as one of specific implementation mode two to ten.
Elaborate below to the embodiment of the present invention, following embodiment under based on the technical solution of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1：
The method that the present embodiment welds porous silicon nitride and compact silicon nitride using devitrified glass solder, including following step
Suddenly：
One, the preparation of devitrified glass solder：
1. CaO by weight percentage:20%, Al2O3：18%, SiO2：57%, Li2O：5% weighs CaO, Al respectively2O3、
SiO2And Li2O is as solder；
2. solder is put into agate jar, it is put into ZrO2(99.9%) alcohol, ball milling 2h, rotating speed 200r/ is added in ball
Solder, is then put into drying box and is heated to 80 DEG C by min, and dry 5h removes the absolute ethyl alcohol in solder, obtains mixed powder
End；
3. mixed-powder is put into corundum crucible, crucible is put into glass melting stove, is added with the rate of 10 DEG C/min
For heat to 1500 DEG C, heat preservation 1h keeps glass melting uniform, then directly pours into distilled water melt, obtains the glass for bursting into fritter
Glass fragment；
4. glass fragment is put into agate pot, alcohol and agate ball (99.9%) ball milling 4h, rotating speed 400r/ afterwards is added
Min obtains glass powder, and 300 mesh sieve is crossed after drying, spare；
Two, welding densification Si3N4Ceramic and porous Si3N4Ceramics：
1. using ceramic inner circle cutting machine by fine and close Si3N4Ceramic and porous Si3N4Ceramic manufacturing will be caused to weld size
Close Si3N4The surface to be welded of ceramic base material is polishing to certain flatness using the diamond disk of 800#, is then using granularity successively
It is smooth that the diamond paste of W2.5 and W1 is polishing to surface；
2. by the fine and close Si after polishing3N4Ceramic material immerses in acetone, is cleaned by ultrasonic 5min, is then rushed with absolute ethyl alcohol
It washes, drying is to be welded；In order to not influence porous Si3N4Structure, by porous Si3N4Ceramics, which are put into acetone, impregnates removal cutting machine
In cooling oil, then dry to be welded；
3. glass powder prepared by step 1 is in tablet press machine, using the pressure of 8MPa, pressurize 4min is pressed into sheet,
The glass powder of sheet is adhered into porous Si with 502 glue3N4Ceramics and densification Si3N4Between ceramics, it is assembled into porous Si3N4
Ceramic material/devitrified glass solder/densification Si3N4Structural member；
4. structural member is placed in vacuum brazing stove, and in structural member upper ends pressure block, the pressure of pressure block is 1 ×
104Then soldering furnace is evacuated to 1.0 × 10 by Pa-3Pa is warming up to 300 DEG C, heat preservation with the rate of heat addition of 10 DEG C/min
10min makes 502 glue of fixed sample fully volatilize；Then beginning recrystallization temperature is warming up to the heating speed of 5 DEG C/min
It 750 DEG C, then continues to be warming up to 1080 DEG C of welding temperature with the heating rate of 10 DEG C/min, and keep the temperature 20min；After the completion of welding
300 DEG C are cooled to, cooling rate is 10 DEG C/min, closes power supply furnace cooling.
The DSC heat scans analysis curve of the present embodiment solder is as shown in Figure 1.From figure 1 it appears that being deposited at 625 DEG C
It is fluctuated at one, illustrates that glass has a glassy state to elastomeric state transition temperature here, i.e. the transition temperature Tg of glass is
625 DEG C, crystallization exothermic peak is 750 DEG C and 910 DEG C, illustrates occur crystallization at both temperatures, in 1061 DEG C and 1117 DEG C
There are an endothermic peak, illustrate that the crystal being precipitated at such a temperature is melted.There is crystallization peak from these results suggest that,
Illustrate that devitrified glass can be formed by crystallization, fusing endothermic peak can provide foundation for setting welding procedure.In addition, the glass
Only 1061 DEG C of the fusing point of solder, explanation can be achieved with connecting within 1200 DEG C.
The present embodiment glass solder devitrified glass that crystallization is formed at different temperatures and densification Si3N4Coefficient of thermal expansion
As shown in Fig. 2, wherein curve 1 is the thermal dilatometry of original glass, curve 2 is that glass is kept the temperature under first crystallization peak temperature
1h forms the thermal dilatometry of devitrified glass, and curve 3 is the crystallite glass that glass keeps the temperature 1h formation under second crystallization peak temperature
The thermal dilatometry of glass, curve 4 are densification Si3N4.The original glass and the non-isomorphous of glass solder are calculated by the result of Fig. 3
Coefficient of thermal expansion obtained glass is from room temperature to 500 DEG C after change processing, by different temperatures crystallization from original glass
Coefficient of thermal expansion 8.4 × 10-6/ DEG C, most preferably reach 3.5 × 10 by crystallization-6/ DEG C, the base material densification Si used3N4Heat it is swollen
Swollen coefficient is 3.2 × 10-6/ DEG C, the coefficient of thermal expansion of the two differs only by 9.4%.Show that the glass system can reach and base material phase
Matched coefficient of thermal expansion realizes preferable connection application.
Embodiment 2：
The present embodiment difference from example 1 is that：Step 2 4. in welding temperature be 1100 DEG C, cooling rate
For 5 DEG C/min, other steps and parameter are same as Example 1.
Embodiment 3：
The present embodiment difference from example 1 is that：Step 2 4. in welding temperature be 1100 DEG C, other steps
It is same as Example 1 with parameter.
Embodiment 4：
The present embodiment difference from example 1 is that：Step 2 4. in welding temperature be 1100 DEG C, cooling rate
For 50 DEG C/min, other steps and parameter are same as Example 1.
Embodiment 5：
The present embodiment difference from example 1 is that：Step 2 4. in welding temperature be 1120 DEG C, other steps
It is same as Example 1 with parameter.
Embodiment 6：
The method that the present embodiment welds porous silicon nitride and compact silicon nitride using devitrified glass solder, including following step
Suddenly：
One, the preparation of devitrified glass solder：
1. CaO by weight percentage:20%, Al2O3：18%, SiO2：59%, Li2O：3% weighs CaO, Al respectively2O3、
SiO2And Li2O is as solder；
2. solder is put into agate jar, it is put into ZrO2(99.9%) alcohol, ball milling 2h, rotating speed 200r/ is added in ball
Solder, is then put into drying box and is heated to 80 DEG C by min, and dry 5h removes the absolute ethyl alcohol in solder, obtains mixed powder
End；
3. mixed-powder is put into corundum crucible, crucible is put into glass melting stove, is added with the rate of 10 DEG C/min
For heat to 1500 DEG C, heat preservation 1h keeps glass melting uniform, then directly pours into distilled water melt, obtains the glass for bursting into fritter
Glass fragment；
4. glass fragment is put into agate pot, alcohol and agate ball (99.9%) ball milling 4h, rotating speed 400r/ afterwards is added
Min obtains glass powder, and 300 mesh sieve is crossed after drying, spare；
Two, welding densification Si3N4Ceramic and porous Si3N4Ceramics：
1. using ceramic inner circle cutting machine by fine and close Si3N4Ceramic and porous Si3N4Ceramic manufacturing will be caused to weld size
Close Si3N4The surface to be welded of ceramic base material is polishing to certain flatness using the diamond disk of 800#, is then using granularity successively
It is smooth that the diamond paste of W2.5 and W1 is polishing to surface；
2. by the fine and close Si after polishing3N4Ceramic material immerses in acetone, is cleaned by ultrasonic 5min, is then rushed with absolute ethyl alcohol
It washes, drying is to be welded；In order to not influence porous Si3N4Structure, by porous Si3N4Ceramics, which are put into acetone, impregnates removal cutting machine
In cooling oil, then dry to be welded；
3. glass powder prepared by step 1 is in tablet press machine, using the pressure of 8MPa, pressurize 4min is pressed into sheet,
The glass powder of sheet is adhered into porous Si with 502 glue3N4Ceramics and densification Si3N4Between ceramics, it is assembled into porous Si3N4
Ceramic material/devitrified glass solder/densification Si3N4Structural member；
4. structural member is placed in vacuum brazing stove, and in structural member upper ends pressure block, the pressure of pressure block is 1 ×
104Then soldering furnace is evacuated to 1.0 × 10 by Pa-3Pa is warming up to 300 DEG C, heat preservation with the rate of heat addition of 10 DEG C/min
10min makes 502 glue of fixed sample fully volatilize；Then beginning recrystallization temperature is warming up to the heating speed of 5 DEG C/min
It 807 DEG C, then continues to be warming up to 1140 DEG C of welding temperature with the heating rate of 10 DEG C/min, and keep the temperature 20min；After the completion of welding
300 DEG C are cooled to, cooling rate is 10 DEG C/min, closes power supply furnace cooling.
Embodiment 7：
The present embodiment and embodiment 6 the difference is that：Step 2 4. in welding temperature be 1160 DEG C, other steps
It is same as Example 6 with parameter.
Embodiment 8：
The present embodiment and embodiment 6 the difference is that：Step 2 4. in welding temperature be 1180 DEG C, other steps
It is same as Example 6 with parameter.
Embodiment 9：
The present embodiment and embodiment 6 the difference is that：Step 2 4. in welding temperature be 1200 DEG C, other steps
It is same as Example 6 with parameter.
Embodiment 10：
The present embodiment and embodiment 6 the difference is that：Step 2 4. in welding temperature be 1220 DEG C, other steps
It is same as Example 6 with parameter.
The DSC heat scans analysis curve of the present embodiment solder is as shown in Figure 3.From figure 3, it can be seen that being deposited at 683 DEG C
It is fluctuated at one, illustrates that glass has a glassy state to elastomeric state transition temperature here, i.e. the transition temperature Tg of glass is
683 DEG C, crystallization exothermic peak is 807 DEG C and 948 DEG C, illustrates occur crystallization at both temperatures, there are one at 1121 DEG C
Endothermic peak illustrates that the crystal being precipitated at such a temperature is melted.There is crystallization peak from these results suggest that, has illustrated to lead to
It crosses crystallization and forms devitrified glass, fusing endothermic peak can provide foundation for setting welding procedure.In addition, the glass solder is molten
Only 1121 DEG C of point, explanation can be achieved with connecting within 1200 DEG C, can reduce to porous Si3N4Damage, and glass is molten
Refining is easy, energy saving.
Joint mechanical property is evaluated using compression shear strength, different welding temperatures in embodiment 1-10, solder compositions and
Shown in the strength of joint table 1 obtained under the conditions of cooling velocity, the experimental results showed that, CaO-Al using the present invention2O3-SiO2-
Li2O devitrified glasses solder is to porous Si3N4With fine and close Si3N4It realizes and is successfully connected.
Table 1
As shown in figure 4, Fig. 4 is 1 devitrified glass solder connection compact silicon nitride of the embodiment of the present invention and porous silicon nitride
Typical Joints tissue back scattering photo.A is compact silicon nitride, and B is weld seam, and C is that glass solder penetrates into what porous silicon nitride was formed
Penetrating layer, D are porous silicon nitride.Glass solder and the good compatibility of base material are relied primarily on, connection is realized by penetrating into wrap up.
Then the thermally matched of realization and base material is separated out to adjust the crystal of intermediate weld by different cooling velocities and heat treatment, subtracted
Few residual stress, reaches preferable connection.Weld seam Oxford gray is spodumene, and light color is mutually anorthite.
Claims (10)
1. a kind of devitrified glass solder, it is characterised in that the devitrified glass solder by weight percentage by 20%~22% CaO,
18%~22% Al2O3, 50%~60% SiO2With the Li of surplus2O is made.
2. using the method for devitrified glass solder welding porous silicon nitride and compact silicon nitride described in claim 1, feature
It is that this approach includes the following steps：
One, the preparation of devitrified glass solder：
1. CaO by weight percentage:20%~22%, Al2O3：18%~22%, SiO2：50%~60%, the Li of surplus2O points
Also known as take CaO, Al2O3、SiO2And Li2O is as solder；
2. solder is carried out ball milling, then solder is dried, obtains mixed-powder；
3. mixed-powder is carried out melting, then melt is directly poured into distilled water, obtains the glass fragment for bursting into fritter；
4. glass fragment is carried out ball milling, glass powder is obtained, 300 mesh sieve is crossed after drying, it is spare；
Two, welding densification Si3N4Ceramic and porous Si3N4Ceramics：
1. by fine and close Si3N4Ceramic and porous Si3N4Ceramic manufacturing is to weld size, by fine and close Si3N4The surface to be welded of ceramic base material
It is smooth to be polishing to surface；
2. by the fine and close Si after polishing3N4Ceramic material immerses in acetone, is cleaned by ultrasonic, is then rinsed with absolute ethyl alcohol, drying waits for
Weldering；By porous Si3N4Ceramics, which are put into acetone, to be impregnated, and is then dried to be welded；
3. glass powder prepared by step 1 is pressed into sheet in tablet press machine, the glass powder of sheet adhered to glue more
Hole Si3N4Ceramics and densification Si3N4Between ceramics, it is assembled into porous Si3N4Ceramic material/devitrified glass solder/densification Si3N4's
Structural member；
4. structural member is placed in vacuum brazing stove, and in structural member upper ends pressure block, the pressure of pressure block is 1 × 103~
1×104Then soldering furnace is evacuated to 1.0 × 10 by Pa-3~6.0 × 10-3Pa is warming up to the rate of heat addition of 10 DEG C/min
300~350 DEG C, keep the temperature 10~20min；Then beginning recrystallization temperature is warming up to the heating speed of 5 DEG C/min, then continue to
The heating rate of 10 DEG C/min is warming up to 1080 DEG C~1220 DEG C, and keeps the temperature 10~30min；It is cooled to 300 after the completion of welding~
350 DEG C, close power supply furnace cooling.
3. the method for welding porous silicon nitride and compact silicon nitride according to claim 2, it is characterised in that：Step 1 is 2.
It is middle by solder carry out ball milling specific method be：Solder is put into agate jar, ZrO is then placed in2Anhydrous second is added in ball
Alcohol, 2~4h of ball milling, rotating speed are 200~300r/min.
4. the method for welding porous silicon nitride and compact silicon nitride according to claim 2 or 3, it is characterised in that：Step
One 2. in dry specific method be：Solder is put into drying box and is heated to 80~85 DEG C, dry 3~5h.
5. the method for welding porous silicon nitride and compact silicon nitride according to claim 4, it is characterised in that：Step 1 is 3.
The specific method of middle melting is：Mixed-powder is put into corundum crucible, crucible is put into glass melting stove, with 10 DEG C/min
Rate be heated to 1500~1550 DEG C, 1~2h of heat preservation keeps glass melting uniform, obtains melt.
6. the method for welding porous silicon nitride and compact silicon nitride according to claim 5, it is characterised in that：Step 1 is 4.
It is middle by glass fragment carry out ball milling specific method be：Glass fragment is put into agate jar, alcohol and agate ball is added
4~5h of ball milling afterwards, rotating speed are 400~450r/min.
7. the method for welding porous silicon nitride and compact silicon nitride according to claim 6, it is characterised in that：Step 2 is 2.
The time of middle ultrasonic cleaning is 3~5min.
8. the method for welding porous silicon nitride and compact silicon nitride according to claim 7, it is characterised in that：Step 2 is 3.
The middle technological parameter that glass powder is pressed into sheet in tablet press machine is：7~9MPa of pressure, 3~5min of pressurize.
9. the method for welding porous silicon nitride and compact silicon nitride according to claim 8, it is characterised in that：Step 2 is 4.
Middle cooling rate is 5 DEG C/min~50 DEG C/min.
10. the method for welding porous silicon nitride and compact silicon nitride according to claim 9, it is characterised in that：In step
Two 4. in temperature-fall period in be additionally added heat treatment process, 0.5h~1h is kept the temperature under recrystallization temperature, be then cooled back to 300~
350 DEG C, close power supply furnace cooling.
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