CN109776086A - A kind of glass and ceramic composite zero-expansion material and preparation method thereof - Google Patents
A kind of glass and ceramic composite zero-expansion material and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000174 eucryptite Inorganic materials 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims description 92
- 238000000498 ball milling Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 18
- 239000012634 fragment Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 5
- 239000002241 glass-ceramic Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims 2
- 229910018068 Li 2 O Inorganic materials 0.000 claims 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 229910014230 BO 3 Inorganic materials 0.000 claims 1
- 239000006004 Quartz sand Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 16
- 239000000377 silicon dioxide Substances 0.000 abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 abstract description 16
- 238000013461 design Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 229960000935 dehydrated alcohol Drugs 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005245 sintering Methods 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- -1 polyethylene Polymers 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 10
- 239000004576 sand Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- 238000000748 compression moulding Methods 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000156 glass melt Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910052845 zircon Inorganic materials 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a kind of glass and Ceramic Composite Zero-expansion material and preparation method thereof.The group of glass and ceramic composite becomes xBBZSL- (1-x) LiAlSiO4, wherein BBZSL includes the Bi of 30~45mol%2O3, 20~30 mol% B2O3, the ZnO of 15~30mol%, 0~15mol% SiO2And the Li of 0~10mol%2The wt% of O, 10 wt%≤x≤40.According to the present invention, by BBZSL glass and LAS Ceramic Composite, the thermal expansion coefficient of composite material can carry out macro adjustments and controls by adjusting its ratio, so as to design to obtain composite material, such as available zero expansion composite material according to actual needs.
Description
Technical field
The present invention relates to a kind of composite material BBZSL glass with zero thermal expansion characteristic and LAS ceramics and its preparation sides
Method belongs to fine ceramics material technical field.
Background technique
With the Miniature precision system in the fields such as microelectronics, optics and micromechanics and the development of aeronautical and space technology, to pottery
The requirement of the structural stability and security reliability of ceramic material is higher and higher.But some ceramic materials are due to higher
Thermal expansion coefficient often changes with the varying dimensions of operating ambient temperature, causes the performance of device unstable even
Failure.Therefore, performance stabilization, service life and the application range of thermal expansivity confrontation ceramic material will have unusual meaning.
Not noticeable variation or even stress fracture in mechanical fatigue, creep caused by thermal stress, pattern and micro-structure etc. will be serious
The variation of material property is caused even to be failed.Negative thermal expansion material such issues that be found to be solution provides possibility, Ke Yitong
It crosses and carries out the material with negative expansion coefficient and positive thermal expansion coefficient compound, prepare various low thermal coefficient of expansion or even zero
The composite material of the coefficient of expansion.Therefore, it develops negative thermal expansion material to be concerned, such as LAS (beta-eucryptite), ZrW2O8,
ZrO2/ZrW2O8, ZrW2O8/ZrSiO4Equal negative thermal expansion materials are found in succession.Wherein, LAS has in very big temperature range
Very strong negative heat expansion characteristics, negative expansion coefficient are up to -6.2 × 10-6/℃.But LAS ceramics thermal expansion coefficient is respectively to different
The characteristic of property, thermal stress is excessive after so that it is there are problems that multiple heat shock cycling causes material matrix to crack.In addition, due to
Li oxide in LAS ceramic systems containing low melting point causes the ceramic systems to be burnt so easily occurring liquid phase at a lower temperature
It is small and be difficult to obtain the ceramics sample of high densification between interface, to limit its practical application.Bi2O3-B2O3-ZnO
(BBZ)、Bi2O3-B2O3-SiO2(BBS)、Bi2O3-B2O3-SiO2The bismuth-containing glass such as-ZnO (BBSZ) have been obtained as seal glass
Research extensively.It was found that it is 460-600 DEG C that BBZ system, which has lower sealed knot temperature, thermal expansion coefficient is (6.8-9) × 10-6/℃。
BBSZ low-melting point sealing glass sealing temperature is (450~650) DEG C, and the coefficient of expansion is (7~1.3) × 10-6/℃。
Summary of the invention
It in view of the problems of the existing technology, can be zero thermal expansion and thermal expansion system the purpose of the present invention is to provide one kind
Adjustable glass ceramic composite of number and preparation method thereof.The material is applicable to aerospace, electronic material, optical information and propagates
The fields such as device and construction material.
On the one hand, the present invention provides a kind of glass and ceramic composite, and the group of the composite material becomes xBBZSL-
(1-x)LiAlSiO4, wherein BBZSL includes the Bi of 30~45mol%2O3, 20~30mol% B2O3, 15~30mol%
The SiO of ZnO, 0~15mol%2And the Li of 0~10mol%2O, 10wt%≤x≤40wt%.
According to the present invention, by BBZSL glass and LAS Ceramic Composite, the thermal expansion coefficient of composite material can be by adjusting it
Ratio carries out macro adjustments and controls, so as to design to obtain composite material, such as available zero thermal expansion composite wood according to actual needs
Material；BBZSL glass in composite material can not only be used for the regulator of Thermal expansion coefficient of composites, its mass percent is adjusted
Play the role of reducing the sintering of composite material but also as sintering aid and binder to coefficient of expansion progress macro adjustments and controls
Temperature and the densification for improving composite material.
Preferably, 10wt%≤x≤20wt%, it is highly preferred that x=20wt%.
Thermal expansion coefficient of composite material within the temperature range of 30~100 DEG C can be -0.657 × 10-6~1.240
×10-6/ DEG C, preferably 0.022 × 10-6/℃。
On the other hand, the present invention provides the preparation method of above-mentioned glass and ceramic composite, which is characterized in that will
BBZSL glass powder and LiAlSiO4Ceramic powder stoichiometrically mixes, and is sintered at 900~1250 DEG C, the composite wood is made
Material.
Preferably, the average grain diameter D of the BBZSL glass powder50≈ 1.1 ± 0.1um, the LiAlSiO4Ceramic powder is put down
Equal partial size D50≈2±0.5um。
Preferably, the BBZSL glass powder is prepared via a method which:
By Bi2O3、B2O3And/or H3BO3、ZnO、SiO2、Li2O and/or Li2CO3950~1050 after stoichiometrically mixing
DEG C be melted 1~1.5 hour, then quenching, obtains glass specimen；
By gained glass specimen ball milling, glass powder is obtained, it is preferable that the average grain diameter of the glass powder is D50≈2.0±
0.5um；By gained glass powdery sand mill, BBZSL glass powder is obtained.
Preferably, the good glass powder slurry of ball milling is placed at 100~120 DEG C of dryings 2~4 hours after the ball milling, it is dry
60 meshes are crossed after the completion.
Preferably, the LiAlSiO4Ceramic powder is prepared via a method which:
The source Li, the source Al, the source Si are stoichiometrically mixed, ball milling obtains powder, it is preferable that the average grain diameter of the powder
For D50≈2±0.5um；
By gained powder in 950~1000 DEG C pre-burning 3~5 hours, obtain LiAlSiO4Ceramic powder.
Preferably, the source Li is selected from Li2CO3At least one of with Li (OH), the source Al is selected from Al2O3And Al
(OH)3At least one of, the source Si is selected from SiO2At least one of with silicon powder.
Preferably, after the ball milling, the good original slurry material of ball milling is 6~12 hours dry in 130~180 DEG C, it does
20 meshes are crossed after dry.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the BBZSL/LAS composite material material of Examples 1 to 4 preparation, and wherein Examples 1 to 4 is distinguished
Corresponding a~d；
Fig. 2 is the relative length variation with temperature of BBZSL/LAS composite material prepared by Examples 1 to 4 and comparative example 1~2
Curve, wherein Examples 1 to 4 and comparative example 1~2 corresponding A~F；
Fig. 3 is the cross-section morphology figure of BBZSL/LAS composite material prepared by Examples 1 to 4 and comparative example 1.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
BBZSL(Bi2O3-B2O3-ZnO-SiO2-Li2O) coefficient of expansion of devitrified glass is (5~8) × 10-6/ DEG C, sealing-in
Temperature is 480~600 DEG C.In the present invention, using positive coefficient of expansion low temperature sealing glass BBZSL and LAS Ceramic Composite preparation zero
Expansion material, and the sintering temperature of LAS ceramics can be reduced by glass low melting point and sealing characteristic and improve composite wood
The densification of material.
An embodiment of the present invention provides a kind of BBZSL glass and LAS Ceramic Composite Zero-expansion material, consisting of x
BBZSL-(1-x)LiAlSiO4.Wherein 10wt%≤x≤40wt%.For example, x=10,20,30,40wt%.Preferably,
10wt%≤x < 40wt%, it is highly preferred that 10wt%≤x≤20wt%, it is further preferred that x=20wt%.If x <
10wt%, the then too small (< 1 × 10 of thermal expansion coefficient-6/℃)；If x > 40wt%, the excessive (> 1 × 10 of thermal expansion coefficient-6/
℃).BBZSL glass ingredient can be the Bi of 30~45mol%2O3, 20~30mol% B2O3, 15~30mol% ZnO, 0~
The SiO of 15mol%2And the Li of 0~10mol%2O, it is preferable that BBZSL glass ingredient is 35mol%Bi2O3- 25mol%
B2O3- 20mol%ZnO-12.5mol%SiO2- 7.5mol%Li2O。
By adjusting the mass percent of BBZSL glass in composite material, Thermal expansion coefficient of composites can be regulated and controled, most
Zero-expansion material is obtained eventually.For example, the composite material 30~100 DEG C thermal expansion coefficient (- 0.657~1.240) ×
10-6/ DEG C between it is adjustable.When the mass percent of BBZSL glass is 20% (i.e. x=20wt%), the composite material is zero
Expansion.The composite material is in 30~150 DEG C of thermal expansion coefficient in (- 0.414~1.905) × 10-6/ DEG C between it is adjustable.Institute
Composite material is stated in 30~200 DEG C of thermal expansion coefficient in (- 0.089~2.598) × 10-6/ DEG C between it is adjustable.The composite wood
Expect in 30~250 DEG C of thermal expansion coefficient in (0.248~2.764) × 10-6/ DEG C between it is adjustable.The composite material 30~
300 DEG C of thermal expansion coefficient is in (0.426~2.820) × 10-6/ DEG C between it is adjustable.Heat of the composite material at 30~350 DEG C
The coefficient of expansion is in (0.575~2.884) × 10-6/ DEG C between it is adjustable.
In addition, the BBZSL glass in composite material is alternatively arranged as sintering aid and binder, the sintering of composite material is reduced
Temperature and the densification for improving composite material.For example, the sintering temperature of the composite material can be 900~1250 DEG C.
Hereinafter, illustrating the preparation method of the composite material.
In an embodiment of the present invention, by BBZSL glass powder and LiAlSiO4Ceramic powder stoichiometrically mixes,
900~1250 DEG C of sintering, are made the composite material.
In one example, BBZSL glass powder is made by traditional glass smelting method.
The weight of various raw materials (source Bi, the source B, the source Zn, the source Si, the source Li) needed for being calculated by BBZSL glass proportion (mol%)
(wt%) ingredient is carried out.The source Bi can be Bi2O3, the source B can be B2O3And/or H3BO3, the source Zn can be that the source ZnO, Si can be SiO2、Li
Source can be Li2O and/or Li2CO3.The purity of raw material can be greater than 99.9%.Raw material powder is carried out after mixing melted.It is melted
Device can be platinum crucible.Glass melting temperature can be 950~1050 DEG C.Melting time can be 1~1.5 hour.Then, it then will be melted
Good glass melt quenching, such as quenching in deionized water is directly poured into, obtain glass specimen (glass fragment).
By glass fragment ball milling, glass powder is obtained.The average grain diameter D of glass powder50≈2.0±0.5um.In one example,
Using wet ball grinding.For example, in material: ball: dehydrated alcohol=1:4:1 ratio 1~2h of planetary ball mill obtains glass powder slurry.
Ball-milling device can be aluminium oxide ceramics tank.
The good glass powder slurry of wet ball grinding can be placed in 100~120 DEG C of (such as 110 DEG C) thermostatic drying chambers, dry 2~
4h.60 meshes can be crossed after the completion of drying, and it is spare to obtain glass powder.
By glass powdery sand mill, BBZSL glass powder is obtained.The partial size of gained BBZSL glass powder can be D50≈1.1±0.1um。
In one example, by resulting glass powder in material: ball: dehydrated alcohol=1:4:1.5 ratio is put into sand mill (such as Horizontal sand
Grinding machine), 2-4h is sanded.
In one example, LiAlSiO4Ceramic powder is obtained by solid reaction process.
By LiAlSiO4Chemical formula carries out ingredient.Raw material may include the source Li, the source Al, the source Si.The source Li can be selected from Li2CO3And Li
At least one of (OH).The source Al can be selected from Al2O3With Al (OH)3At least one of.The source Si is selected from SiO2And silicon powder
At least one of.The purity of raw material can be greater than 99.9%.
By each raw material mixing and ball milling, mixed powder is obtained.The partial size of mixed powder can be D50≈2±0.5um.One example
In, using wet ball grinding.Such as with material: ball: 1~2h of deionized water=1:3:2 ratio planetary ball mill.It can be ball milling material
It is added in polyethylene tetrachloro tank, in planetary ball mill ball milling.
The good original slurry material of wet ball grinding can be put into thermostatic drying chamber, dry 6~12h in 130~180 DEG C.It is dry
20 meshes can be crossed after dry, obtain uniformly mixed powder.
By mixed powder in 950-1000 DEG C 3~5h of pre-burning (such as 4h), obtain LiAlSiO4Ceramic powder is for future use.
Pre-burning device can be Muffle furnace.
By BBZSL glass powder and LiAlSiO4Ceramic powder presses xBBZSL- (1-x) LiAlSiO4(10wt%≤x≤40wt%)
Mass ratio mixing, ball milling.In one example, using wet ball grinding.Such as by material: ball: dehydrated alcohol=1:3:2 ratio is customary
Celestial body grinds 1~2h.It can be and ball milling material is added in polyethylene tetrachloro tank, in planetary ball mill ball milling.It dries, makes after ball milling
Grain, such as added weight percentage is that the PVB solution of 6~8wt% is granulated as binder in powder.It can mistake after granulation
Sieve, such as cross 20 meshes.By gained grain forming, such as compression molding, biscuit is obtained.
Biscuit before sintering can be in 300~500 DEG C (such as 400 DEG C) row 3~5h of element (such as 4h).Sintering atmosphere can be
Air atmosphere.Sintering temperature can be 900~1250 DEG C, preferably 1000~1100 DEG C.Sintering time can be 1~4h, such as 2h.
In one example, the preparation step of the compound Zero-expansion material of BBZSL/LAS is as follows:
(1) weight (wt%) of various raw materials needed for calculating by BBZSL glass proportion (mol%) carries out ingredient, by powder craft
It is uniformly mixed to be placed in platinum crucible and be melted, melting system is 950~1050 DEG C/1-1.5h, the glass that then will be melted again
Glass melt directly pours into quenching in deionized water, obtains glass specimen；
(2) will obtain glass fragment in material in step (1): ball: dehydrated alcohol=1:4:1 ratio is put into aluminium oxide ceramics tank,
Planetary ball mill 1~2h, D50≈2±0.5um；
(3) the good glass powder slurry of ball milling in step (2) is placed in 110 DEG C of thermostatic drying chambers, dry 2~4h is dry to complete
60 meshes are crossed afterwards, and it is spare to obtain glass powder；
(4) will obtain glass powder in material in step (3): ball: dehydrated alcohol=1:4:1.5 ratio is put into horizontal sand mill, sand
Grind 2-4h, D50≈1.1±0.1um；
(5) LiAlSiO is pressed4Chemical formula carries out ingredient, and with material: ball: polyethylene tetrachloro is added in deionized water=1:3:2 ratio
In tank, in planetary ball mill ball milling 1~2h, D50≈2±0.5um；
(6) the good original slurry material of step (5) ball milling is put into thermostatic drying chamber, dry 6~12h in 130~180 DEG C,
20 meshes are crossed after drying, obtain uniformly mixed powder；
(7) powder after the excessively complete sieve of step (6) is placed in Muffle furnace, pre-burning 4h, obtains LiAlSiO in 980 DEG C4Ceramic powder
For future use；
(8) the BBZSL glass powder and LiAlSiO that will be obtained in step (4) and step (7)4Ceramic powder presses xBBZSL- (1-x)
LiAlSiO4The mixing of (10wt%≤x≤40wt%) mass ratio, in material: ball: poly- second is added in dehydrated alcohol=1:3:2 ratio
In alkene tetrachloro tank, in 1~2h of planetary ball mill ball milling；After drying in the powder mixed added weight percentage be 6~
The PVB solution of 8wt% is granulated as binder, crosses 20 meshes, then compression molding；
(9) step (8) sample is placed in Muffle furnace, in 400 DEG C of row element 4h, is being burnt between 900-1100 DEG C in air atmosphere
2h is tied, composite material is made.
Advantages of the present invention is as follows:
1, BBZSL glass powder and LiAlSiO required for the present invention is prepared using traditional glass smelting method and solid reaction process4
Ceramic powder, compound Zero-expansion material sintering are also sintered using simple Muffle furnace, and preparation process is simple, is not necessarily to special sintering work
Skill；
2, the thermal expansion coefficient of BBZSL/LAS composite material can carry out macro adjustments and controls by adjusting its ratio, so as to according to reality
Border, which needs to design, obtains composite material；
3, the BBZSL glass in composite material can not only be used for the regulator of Thermal expansion coefficient of composites, its quality hundred is adjusted
Dividing reduces composite material but also as sintering aid and binder compared with to the effect for carrying out macro adjustments and controls to the coefficient of expansion
Sintering temperature and the intensity for improving composite material；
4, present invention process is simple, and pollution-free, at low cost, is easy to industrialize.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Test method:
(1) material phase analysis (XRD): composite sample is ground into the thinner powder of particle in the agate mortar, then in German cloth Shandong
It is tested on the D8ADVANCE high-resolution powder x-ray diffraction of gram company manufacture, obtains XRD diffracting spectrum.Using copper
K alpha ray, test voltage 40Kv, electric current 40mA, scanning range are 10~80 °, and scanning speed is 10 °/min；
(2) thermal expansion coefficient: thermal expansion coefficient is measured using Germany Netzsch DIL 402C type thermal dilatometer, specimen size is about
For 5 × 5 × 25mm, Range of measuring temp is room temperature to 350 DEG C, and the rate of heat addition is 10 DEG C/min, test in air atmosphere into
Row, reference material Al2O3；
(3) cross-section morphology (SEM): Japan's Hitachi TM3030 type scanning electron microscope (voltage 20kV) is used to observe sample
The cross-section morphology of product.
Embodiment 1:
(1) by BBZSL glass proportion (mol%), 365.81g Bi is weighed2O3、68.72g H3BO3、36.34g ZnO、16.69g
SiO2With 12.43g Li2CO3, the material prepared is poured into mortar, addition appropriate amount of deionized water, which stirs evenly, is placed on 1000 DEG C
1.5h is kept the temperature in platinum crucible, the glass melt water quenching that then will be melted again obtains glass specimen；
(2) by glass fragment is obtained in step (1) with expect+ball+dehydrated alcohol=400g+1600g+400g ratio is added to oxygen
Change in aluminium ceramic pot, planetary ball mill 1h；
(3) the good glass powder slurry of ball milling in step (2) is placed in 110 DEG C of thermostatic drying chambers, dry 4h, mistake after the completion of drying
60 meshes, it is spare to obtain glass powder；
(4) glass powder will be obtained in step (3) be put into Horizontal sand in material+ball+dehydrated alcohol=300g+1200g+450g ratio
Grinding machine is sanded 4h, obtains BBZSL glass powder, D50≈1.1±0.1um；
(5) LiAlSiO is pressed4Chemical formula carries out ingredient, claims 125.05g Li2CO3、172.6g Al2O3With 202.35g SiO2Match
Material, total 500g；And be added in polyethylene tetrachloro tank with material+ball+deionized water=500g+1500g+1000g, in planetary ball mill
Machine ball milling 1h；
(6) the good original slurry material of step (5) ball milling is put into thermostatic drying chamber, dry 12h, mistake after drying in 150 DEG C
20 meshes obtain uniformly mixed powder；
(7) powder after the excessively complete sieve of step (6) is placed in Muffle furnace, pre-burning 4h, obtains LiAlSiO in 980 DEG C4Ceramics
Powder, D50≈2±0.5um；
(8) the 10g BBZSL glass powder and 90g LiAlSiO that will be obtained in step (4) and step (7)4Ceramic powder mixing, altogether
100g；It is added in polyethylene tetrachloro tank with material+ball+dehydrated alcohol=100g+300g+200g, in planetary ball mill ball milling 1h；It dries
Added weight percentage is that the PVB solution of 6~8wt% is granulated as binder in the powder mixed after dry, crosses 20
Mesh, then compression molding；
(9) step (8) sample is placed in Muffle furnace, in 400 DEG C of row element 4h, in 1200 DEG C of heat preservation 2h, system in air atmosphere
At composite material.Its thermal expansion coefficient is shown in Table 1.
Embodiment 2:
(1) by BBZSL glass proportion (mol%), 365.81g Bi is weighed2O3、68.72g H3BO3、36.34g ZnO、16.69g
SiO2With 12.43g Li2CO3, the material prepared is poured into mortar, addition appropriate amount of deionized water, which stirs evenly, is placed on 1000 DEG C
1.5h is kept the temperature in platinum crucible, the glass melt water quenching that then will be melted again obtains glass specimen；
(2) by glass fragment is obtained in step (1) with expect+ball+dehydrated alcohol=400g+1600g+400g ratio is added to oxygen
Change in aluminium ceramic pot, planetary ball mill 1h；
(3) the good glass powder slurry of ball milling in step (2) is placed in 110 DEG C of thermostatic drying chambers, dry 4h, mistake after the completion of drying
60 meshes, it is spare to obtain glass powder；
(4) glass powder will be obtained in step (3) be put into Horizontal sand in material+ball+dehydrated alcohol=300g+1200g+450g ratio
Grinding machine is sanded 4h, obtains BBZSL glass powder, D50≈1.1±0.1um；
(5) LiAlSiO is pressed4Chemical formula carries out ingredient, claims 125.05g Li2CO3、172.6g Al2O3With 202.35g SiO2Match
Material, total 500g；And be added in polyethylene tetrachloro tank with material+ball+deionized water=500g+1500g+1000g, in planetary ball mill
Machine ball milling 1h；
(6) the good original slurry material of step (5) ball milling is put into thermostatic drying chamber, dry 12h, mistake after drying in 150 DEG C
20 meshes obtain uniformly mixed powder；
(7) powder after the excessively complete sieve of step (6) is placed in Muffle furnace, pre-burning 4h, obtains LiAlSiO in 980 DEG C4Ceramics
Powder, D50≈2.0±0.5um；
(8) the 20g BBZSL glass powder and 80g LiAlSiO that will be obtained in step (4) and step (7)4Ceramic powder mixing, altogether
100g；It is added in polyethylene tetrachloro tank with material+ball+dehydrated alcohol=100g+300g+200g, in planetary ball mill ball milling 1h；It dries
Added weight percentage is that the PVB solution of 6~8wt% is granulated as binder in the powder mixed after dry, crosses 20
Mesh, then compression molding；
(9) step (8) sample is placed in Muffle furnace, in 400 DEG C of row element 4h, in 1050 DEG C of heat preservation 2h, system in air atmosphere
At composite material.Its thermal expansion coefficient is shown in Table 1.
Embodiment 3:
(1) by BBZSL glass proportion (mol%), 365.81g Bi is weighed2O3、68.72g H3BO3、36.34g ZnO、16.69g
SiO2With 12.43g Li2CO3, the material prepared is poured into mortar, addition appropriate amount of deionized water, which stirs evenly, is placed on 1000 DEG C
1.5h is kept the temperature in platinum crucible, the glass melt water quenching that then will be melted again obtains glass specimen；
(2) by glass fragment is obtained in step (1) with expect+ball+dehydrated alcohol=400g+1600g+400g ratio is added to oxygen
Change in aluminium ceramic pot, planetary ball mill 1h；
(3) the good glass powder slurry of ball milling in step (2) is placed in 110 DEG C of thermostatic drying chambers, dry 4h, mistake after the completion of drying
60 meshes, it is spare to obtain glass powder；
(4) glass powder will be obtained in step (3) be put into Horizontal sand in material+ball+dehydrated alcohol=300g+1200g+450g ratio
Grinding machine is sanded 4h, obtains BBZSL glass powder, D50≈1.1±0.1um；
(5) LiAlSiO is pressed4Chemical formula carries out ingredient, claims 125.05g Li2CO3、172.6g Al2O3With 202.35g SiO2Match
Material, total 500g；And be added in polyethylene tetrachloro tank with material+ball+deionized water=500g+1500g+1000g, in planetary ball mill
Machine ball milling 1h；
(6) the good original slurry material of step (5) ball milling is put into thermostatic drying chamber, dry 12h, mistake after drying in 150 DEG C
20 meshes obtain uniformly mixed powder；
(7) powder after the excessively complete sieve of step (6) is placed in Muffle furnace, pre-burning 4h, obtains LiAlSiO in 980 DEG C4Ceramics
Powder, D50≈2.0±0.5um；
(8) the 30g BBZSL glass powder and 70g LiAlSiO that will be obtained in step (4) and step (7)4Ceramic powder mixing, altogether
100g；It is added in polyethylene tetrachloro tank with material+ball+dehydrated alcohol=100g+300g+200g, in planetary ball mill ball milling 1h；It dries
Added weight percentage is that the PVB solution of 6~8wt% is granulated as binder in the powder mixed after dry, crosses 20
Mesh, then compression molding；
(9) it will be placed in Muffle furnace in step (8) sample, in 400 DEG C of row element 4h, in 975 DEG C of heat preservation 2h, system in air atmosphere
At composite material.Its thermal expansion coefficient is shown in Table 1.
Embodiment 4:
(1) by BBZSL glass proportion (mol%), 365.81g Bi is weighed2O3、68.72g H3BO3、36.34g ZnO、16.69g
SiO2With 12.43g Li2CO3, the material prepared is poured into mortar, addition appropriate amount of deionized water, which stirs evenly, is placed on 1000 DEG C
1.5h is kept the temperature in platinum crucible, the glass melt water quenching that then will be melted again obtains glass specimen；
(2) by glass fragment is obtained in step (1) with expect+ball+dehydrated alcohol=400g+1600g+400g ratio is added to oxygen
Change in aluminium ceramic pot, planetary ball mill 1h；
(3) the good glass powder slurry of ball milling in step (2) is placed in 110 DEG C of thermostatic drying chambers, dry 4h, mistake after the completion of drying
60 meshes, it is spare to obtain glass powder；
(4) glass powder will be obtained in step (3) be put into Horizontal sand in material+ball+dehydrated alcohol=300g+1200g+450g ratio
Grinding machine is sanded 4h, obtains BBZSL glass powder, D50≈1.1±0.1um；
(5) LiAlSiO is pressed4Chemical formula carries out ingredient, claims 125.05g Li2CO3、172.6g Al2O3With 202.35g SiO2Match
Material, total 500g；And be added in polyethylene tetrachloro tank with material+ball+deionized water=500g+1500g+1000g, in planetary ball mill
Machine ball milling 1h；
(6) the good original slurry material of step (5) ball milling is put into thermostatic drying chamber, dry 12h, mistake after drying in 150 DEG C
20 meshes obtain uniformly mixed powder；
(7) powder after the excessively complete sieve of step (6) is placed in Muffle furnace, pre-burning 4h, obtains LiAlSiO in 980 DEG C4Ceramics
Powder, D50≈2.0±0.5um；
(8) the 40g BBZSL glass powder and 60g LiAlSiO that will be obtained in step (4) and step (7)4Ceramic powder mixing, altogether
100g；It is added in polyethylene tetrachloro tank with material+ball+dehydrated alcohol=100g+300g+200g, in planetary ball mill ball milling 1h；It dries
Added weight percentage is that the PVB solution of 6~8wt% is granulated as binder in the powder mixed after dry, crosses 20
Mesh, then compression molding；
(9) it will be placed in Muffle furnace in step (8) sample, in 400 DEG C of row element 4h, in 900 DEG C of heat preservation 2h, system in air atmosphere
At composite material.Its thermal expansion coefficient is shown in Table 1.
The thermal expansion coefficient (× 10 of each embodiment of table 1 at different temperatures-6/℃)
| 30~100 DEG C | 30~150 DEG C | 30~200 DEG C | 30~250 DEG C | 30~300 DEG C | 30~350 DEG C | |
| Embodiment 1 | -0.657 | -0.414 | -0.089 | 0.248 | 0.426 | 0.575 |
| Embodiment 2 | 0.022 | 0.271 | 0.653 | 0.980 | 1.200 | 1.254 |
| Embodiment 3 | 0.178 | 0.623 | 1.211 | 1.598 | 1.760 | 1.877 |
| Embodiment 4 | 1.240 | 1.905 | 2.598 | 2.764 | 2.820 | 2.884 |
| Comparative example 1 | -8.574 | -7.827 | -7.464 | -7.562 | -7.784 | -8.052 |
| Comparative example 2 | -2.612 | -2.673 | -2.795 | -3.007 | -3.186 | -3.318 |
Fig. 1 shows the XRD spectrum of the BBZSL/LAS composite material material of Examples 1 to 4 preparation, it can be seen that composite material
Middle crystal phase includes LiAlSiO4(PDF card number No.26-0840) and unknown phase, wherein being mutually LiAlSiO4Principal crystalline phase.In addition, may be used also
With discovery with the increase of BBZSL glass, LiAlSiO in composite material4The diffraction peak intensity of phase reduces, and nearby occurs at 28 °
Faint steamed bun peak, this illustrates composite L iAlSiO4It is mutually reducing, BBZSL glass largely mutually exists with indefinite form.
The relative length of table 1 and the BBZSL/LAS composite material prepared Fig. 2 shows Examples 1 to 4 and comparative example 1~2 with
The change curve of temperature, it can be seen that BBZSL glass is added to the Thermal expansion coefficient of composites being prepared in LAS ceramics can
By negative thermal expansion coefficient (- 8 × 10-6/ DEG C) adjust and arrived positive thermal expansion coefficient (2 × 10-6/ DEG C), especially 1 He of embodiment
The thermal expansion coefficient of 2, BBZSL/LAS composite materials nearly zero.
Fig. 3 shows the cross-section morphology figure of BBZSL/LAS composite material prepared by Examples 1 to 4 and comparative example 1, can see
Out in composite material BBZSL glass increase, the pore amount and pore size in composite ceramics are all being reduced, and illustrate BBZSL
Glass facilitates the sintering of LAS ceramics.
Comparative example 1
(1) LiAlSiO is pressed4Chemical formula carries out ingredient, claims 125.05g Li2CO3、172.6g Al2O3With 202.35g SiO2Match
Material, total 500g；And be added in polyethylene tetrachloro tank with material+ball+deionized water=500g+1500g+1000g, in planetary ball mill
Machine ball milling 1h；
(2) the good original slurry material of step (1) ball milling is put into thermostatic drying chamber, dry 12h, mistake after drying in 150 DEG C
20 meshes obtain uniformly mixed powder；
(3) powder after the excessively complete sieve of step (2) is placed in Muffle furnace, pre-burning 4h, obtains LiAlSiO in 980 DEG C4Ceramics
Powder, D50=2.0 ± 0.5um；
(4) the 100g LiAlSiO for obtaining step (3)4Ceramic powder is added with material+ball+dehydrated alcohol=100g+300g+200g
Enter in polyethylene tetrachloro tank, in planetary ball mill ball milling 1h；After drying in the powder mixed added weight percentage be 6~
The PVB solution of 8wt% is granulated as binder, crosses 20 meshes, then compression molding；
(5) it will be placed in Muffle furnace in step (4) sample, in 400 DEG C of row element 4h, in 1350 DEG C of heat preservation 2h in air atmosphere,
LiAlSiO is made4Ceramics.Its thermal expansion coefficient is shown in Table 1.
Comparative example 2
Substantially with embodiment 1, the difference is that, the mass percent of BBZSL glass powder is 5wt%.
After tested, thermal expansion coefficient is shown in Table 1 to resulting composite material.
Claims (10)
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| CN113773071A (en) * | 2021-08-30 | 2021-12-10 | 潮州三环（集团）股份有限公司 | Ceramic material, ceramic slurry and multilayer chip ceramic capacitor |
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