CN108585508A - The high boron sealing glass ceramic and its preparation and application that a kind of nickel oxide and iron oxide are co-doped with - Google Patents
The high boron sealing glass ceramic and its preparation and application that a kind of nickel oxide and iron oxide are co-doped with Download PDFInfo
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- CN108585508A CN108585508A CN201810421734.5A CN201810421734A CN108585508A CN 108585508 A CN108585508 A CN 108585508A CN 201810421734 A CN201810421734 A CN 201810421734A CN 108585508 A CN108585508 A CN 108585508A
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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- 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
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Abstract
The invention discloses a kind of NiO and Fe2O3The high boron sealing glass ceramic and its preparation and application being co-doped with, are to be with molar ratio（12~30）：（0~5）：（13~36）：（12~20）：（12~20）：（5~20）：（0~15）B2O3、Al2O3、SiO2, CaO, SrO, NiO and Fe2O3It is made of raw material.The B of high-content in the present invention2O3It is remarkably improved the mobility of seal glass；NiO and Fe2O3Be co-doped with can reinforcing glass network structure, improve the thermal stability of seal glass and its chemical compatibility with cathode；In addition, due to Fe2O3Incorporation fine and close hercynite can be generated in the seal interface with metal base, improve the chemical stability of seal interface.Raw material of the present invention is simple and easy to get, stable preparation process, has reached practical and industrialized condition.
Description
Technical field
The invention belongs to field of solid oxide fuel, and in particular to a kind of NiO with high high-temp stability and
Fe2O3The high boron sealing glass ceramic being co-doped with and its preparation and use.
Background technology
Solid oxide fuel cell（SOFC）It is a kind of novel power generator for converting chemical energy to electric energy.With biography
System energy utilization patterns are compared, and SOFC has generating efficiency high, and the cost of material is low, fuel（As methane, coal gas, methanol, alcohol,
Oil liquefied gas etc.）The advantages that adaptable.But due to battery operating temperature height（700~750 DEG C）, how at high temperature will
Fuel gas and oxic gas carry out effectively isolation and sealing-in and inhibit harmful anti-between seal, sealing materials and SOFC other components
The main problem in SOFC research process should be become, wherein it is the pass of planar SOFC development to select suitable seal, sealing materials
Key.Seal, sealing materials of the borosilicate glass as intermediate temperature solid oxide fuel cell easily pass through since its sealing property is good
It composition regulation performance and prepares the advantages that simple and receives significant attention.
Improve B in glass2O3Content the sealing-in ability between seal glass and base material can be improved.However some researches show that,
In the borosilicate glass of alkaline including earth metal oxide, B2O3Content increase to 20mol% from 2mol%, seal glass is in SOFC
Mass loss in operational process is from 0.03mg/cm2It improves to 0.16mg/cm2(Zhang T, Fahrenholtz W G,
Reis S T, et al. Borate Volatility from SOFC Sealing Glasses[J]. Journal of
the American Ceramic Society, 2010, 91(8):2564-2569).Containing boron substance in borosilicate glass
Volatilization can cause to generate a large amount of holes in seal glass, influence the air-tightness of seal, sealing materials, the thermal stability of glass can also decline.
Meanwhile acutely volatilize containing boron substance then on cathode deposit and chemically reacted with it, such as with lanthanum-strontium ferro-cobalt（LSCF）
Its product of cathode reaction is LaBO3, deep fades (the Fuel cells. 2013, Volume of cathode catalysis performance can be caused
12, Issue 6, PF1101-1108；J. Electrochem. Soc. 2013, Volume 160, Issue 3,
PF301-F308) 。
Invention content
The purpose of the present invention is to provide one kind containing NiO and Fe2O3High boron sealing glass ceramic and its preparation and user
Method.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of NiO and Fe2O3The high boron sealing glass ceramic being co-doped with, is to be with molar ratio（12~30）：（0~5）：（13~36）：
（12~20）：（12~20）：（5~20）：（0~15）B2O3、Al2O3、SiO2, CaO, SrO, NiO and Fe2O3It is made of raw material.It is excellent
Selection of land, raw materials used B2O3、Al2O3、SiO2, CaO, SrO, NiO and Fe2O3Molar ratio be（15~20）：（0~3）：（24~30）：
（16~18）：（16~18）：（10~15）：（5~10）.
The NiO and Fe2O3The preparation method for the high boron sealing glass ceramic being co-doped with, includes the following steps：
（1）Raw material is uniformly mixed according to a ratio, 1300 DEG C of -1350 DEG C of melted 0.5-1h；Then the glass metal melted is carried out
Chilling obtains glass frit；Glass frit is crushed again, obtains glass powder after sieving；
（2）Glass powder and sealing-in agent, dispersant and solvent are mixed into slurry, ball milling keeps its evenly dispersed in the ball mill,
Then tape casting spontaneously dries, then is cut into the idiosome of required shape, that is, is made containing NiO and Fe2O3Glass sealing material.
The sealing-in agent is epoxy resin, methylcellulose, polyvinyl butyral, one kind in polyvinyl alcohol or several
Kind.
The dispersant is one or more of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
The solvent is one or more of water, ethyl alcohol, isopropanol, n-butanol, toluene, dimethylbenzene, acetone.
The NiO and Fe2O3The application method for the high boron sealing glass ceramic being co-doped with is by the high boron sealing glass ceramic
It is placed in and waits for sealing-in position, first 600 DEG C are warming up to the rate of 5 DEG C/min in electric furnace, be then warming up to the rate of 2 DEG C/min
750 DEG C, Crystallizing treatment 2h, finally 600 DEG C are cooled to the rate of 2 DEG C/min and complete sealing-in.
The remarkable advantage of the present invention is：
（1）The B that the present invention passes through addition high-content2O3, the mobility of seal glass is significantly improved, improves it between base material
Sealing-in ability；
（2）The present invention is by being co-doped with suitable NiO and Fe2O3The network structure of glass is not only increased, and is effectively inhibited
The fracture of Si-O-B keys in glass network, improves the stability of boron atom in glass network, to significantly reduce sealing-in glass
In glass the thermal stability of seal glass itself and its chemically compatible with cathode is improved in the volatilization of military service process containing boron substance
Property；
（3）NiO and Fe2O3When the glass being co-doped with is with stainless steel substrate sealing-in, it is brilliant that fine and close iron point can be precipitated in seal interface
Stone restrained effectively the elements diffusion at seal interface, to improve the chemical stability of seal interface；
（4）Raw material of the present invention is simple and easy to get, stable preparation process, has reached practical and industrialized condition.
Description of the drawings
Fig. 1 is the infrared spectrogram of seal glass, wherein (a) is to be not added with NiO and Fe2O3Glass, (b) be addition 5
The glass of mol.% NiO (c) is addition 20 mol.%NiO and 15 mol.%Fe2O3Glass.
Fig. 2 is seal glass and cathode（LSCF）Interfacial microstructure figure after being handled 2000 hours at 700 DEG C, wherein
(a) it is to be not added with NiO and Fe2O3Glass, (b) be addition 20 mol.%NiO and 15 mol.%Fe2O3Glass.
Fig. 3 is the seal interface figure that seal glass works long hours under hot environment under different atmosphere, wherein（a）Oxidation
Atmosphere（Air）,（b）Reducing atmosphere（10%H2+90%N2）.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, further illustrated the present invention with the following example, but
Protection scope of the present invention is not limited to this.
Table 1 is the component proportion of sealing glass ceramic in embodiment 1-4.
The component table of sealing glass ceramic in 1 embodiment 1-4 of table（Mole percent）
Embodiment 1
According to each group distribution ratio of table 1, a certain amount of analysis pure raw material is weighed（CaO、SrO、SiO2、Al2O3、B2O3、NiO、
Fe2O3）, for 24 hours it is uniformly mixed it with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in chamber type electric resistance furnace
In, 1300 DEG C are heated to 2 DEG C/min in air atmosphere, keeps the temperature 0.5h；Crucible is then taken out, melt is poured into deionized water
Middle chilling, it is dry to obtain glass frit；Glass frit is ground, is sieved with 100 mesh sieve, glass powder is obtained.By glass powder and gather
Vinyl alcohol, fish oil, ethyl alcohol and toluene by weight percentage 80:2:1:10:7 are mixed into slurry, and ball milling makes it in the ball mill
Even dispersion；Then tape casting spontaneously dries, then is cut into the idiosome of required shape.Idiosome is placed in and waits for sealing-in position, in electricity
600 DEG C first are warming up to the rate of 5 DEG C/min in stove, is then warming up to 750 DEG C, Crystallizing treatment 2h with the rate of 2 DEG C/min, most
600 DEG C are cooled to the rate of 2 DEG C/min complete sealing-in afterwards.
Embodiment 2
According to each group distribution ratio of table 1, a certain amount of analysis pure raw material is weighed（CaO、SrO、SiO2、Al2O3、B2O3、NiO、
Fe2O3）, for 24 hours it is uniformly mixed it with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in chamber type electric resistance furnace
In, 1330 DEG C are heated to 2 DEG C/min in air atmosphere, keeps the temperature 1h；Crucible is then taken out, melt is poured into deionized water
Chilling, it is dry to obtain glass frit；Glass frit is ground, is sieved with 100 mesh sieve, glass powder is obtained.By glass powder and methyl
Cellulose, polyvinyl alcohol, n-butanol and acetone by weight percentage 82:2:2:8:6 are mixed into slurry, and ball milling makes in the ball mill
Its is evenly dispersed；Then tape casting spontaneously dries, then is cut into the idiosome of required shape.Idiosome is placed in and waits for sealing-in position,
600 DEG C first are warming up to the rate of 5 DEG C/min in electric furnace, is then warming up to 750 DEG C with the rate of 2 DEG C/min, Crystallizing treatment
2h is finally cooled to 600 DEG C with the rate of 2 DEG C/min and completes sealing-in.The example is to preferably constitute.
Embodiment 3
According to each group distribution ratio of table 1, a certain amount of analysis pure raw material is weighed（CaO、SrO、SiO2、Al2O3、B2O3、NiO、
Fe2O3）, for 24 hours it is uniformly mixed it with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in chamber type electric resistance furnace
In, 1350 DEG C are heated to 3 DEG C/min in air atmosphere, keeps the temperature 1h；Crucible is then taken out, melt is poured into deionized water
Chilling, it is dry to obtain glass frit；Glass frit is ground, is sieved with 100 mesh sieve, glass powder is obtained.By glass powder and epoxy
Resin, polyacrylamide, isopropanol and toluene by weight percentage 84:1.5:0.5:9:5 are mixed into slurry, in the ball mill ball
Mill keeps its evenly dispersed；Then tape casting spontaneously dries, then is cut into the idiosome of required shape.Idiosome is placed in and waits for sealing-in
Position is first warming up to 600 DEG C in electric furnace with the rate of 5 DEG C/min, is then warming up to 750 DEG C with the rate of 2 DEG C/min, crystallization
2h is handled, being finally cooled to 600 DEG C with the rate of 2 DEG C/min completes sealing-in.The example is to preferably constitute.
Embodiment 4
According to each group distribution ratio of table 1, a certain amount of analysis pure raw material is weighed（CaO、SrO、SiO2、Al2O3、B2O3、NiO、
Fe2O3）, for 24 hours it is uniformly mixed it with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in chamber type electric resistance furnace
In, 1350 DEG C are heated to 3 DEG C/min in air atmosphere, keeps the temperature 1h；Crucible is then taken out, melt is poured into deionized water
Chilling, it is dry to obtain glass frit；Glass frit is ground, is sieved with 100 mesh sieve, glass powder is obtained.By glass powder and epoxy
Resin, polyacrylamide, isopropanol and toluene by weight percentage 84:1.5:0.5:9:5 are mixed into slurry, in the ball mill ball
Mill keeps its evenly dispersed；Then tape casting spontaneously dries, then is cut into the idiosome of required shape.Idiosome is placed in and waits for sealing-in
Position is first warming up to 600 DEG C in electric furnace with the rate of 5 DEG C/min, is then warming up to 750 DEG C with the rate of 2 DEG C/min, crystallization
2h is handled, being finally cooled to 600 DEG C with the rate of 2 DEG C/min completes sealing-in.
By glass powder obtained by 1.5mg embodiments 1-4 respectively with suitable KBr with 1/150（By weight）Ratio it is mixed
Combined pressure piece as a contrast with traditional glass passes through infrared Fourier spectrometer（FT-IR, model Mattson Galaxy S-
7000, USA）Obtain the infrared spectrum of sample.Melt after heat preservation is poured into the stainless steel grinding tool after preheating, acquisition Φ=
The glass cylinder of 10mm, d=25mm are tested on NETZSCH DIL 402EP thermal dilatometers with the rate of heat addition of 10 DEG C/min,
Obtain glass transition point and softening point.Pass through x-ray photoelectron spectroscopy（ESCALAB 250, Thermo scientific,
Inc）, use the monochromatic sources Al K α（10mA, 15kV）The B1s spectrums for obtaining sample, are as a result shown in Fig. 1 and table 2-3 respectively.
Fig. 1 is the infrared spectrogram of seal glass, wherein (a) is to be not added with NiO and Fe2O3Glass, (b) be addition 5
The glass of mol.% NiO (c) is addition 20 mol.%NiO and 15 mol.%Fe2O3Glass.As seen from Figure 1, it is not added with NiO
And Fe2O3Glass network in B-O-Si keys in entire B-O-Shared ratio is 0.318 in network, is added to 20 mol.%
NiO and 15 mol.%Fe2O3Glass network in B-O-Si keys in entire B-O-Shared ratio is 0.186 in network, thus
It can be seen that NiO and Fe2O3Addition obviously inhibit the dissociation of B-O-Si keys, this may be the bond energy ratio B- due to B-O-Si keys
The bond energy of O-B keys is high, thus improves stability of the B in glass network.
Table 2 adds different content NiO and Fe2O3Seal glass XPS B1s combination energy
As can be seen from Table 2, the B1s combinations of the seal glass of 5 mol.% NiO of addition can be 190.5 eV.Add 10 mol.% NiO
With 5 mol.%Fe2O3Seal glass B1s combination can be 190.8 eV.Add 15 mol.% NiO and 10 mol.%Fe2O3
Seal glass B1s combination can be 191.1 eV.Add 20 mol.% NiO and 15 mol.%Fe2O3Seal glass B1s
In conjunction with can be 191.2 eV.I.e. with NiO and Fe2O3The increase of content, the B1s of seal glass is combined can be also in rising trend, by
This is as it can be seen that NiO and Fe2O3Addition have inhibiting effect to the volatilization of boron to a certain extent.
Table 3 adds different content NiO and Fe2O3Seal glass coefficient of thermal expansion
As can be seen from Table 3, NiO and Fe2O3The glass being co-doped with, glass transition temperature and softening temperature have larger carry
Height, the coefficient of thermal expansion of glass is with NiO and Fe2O3The increase of content and be gradually reduced, illustrate NiO and Fe2O3Enhance glass
Network structure further improves the thermodynamic stability of glass, it is made to be more suitable as seal, sealing materials.
Fig. 2 is seal glass and cathode（LSCF）Interfacial microstructure figure after being handled 2000 hours at 700 DEG C, wherein
(a) it is to be not added with NiO and Fe2O3Glass, (b) be addition 20 mol.%NiO and 15 mol.%Fe2O3Glass.It can by Fig. 2
With, it is evident that being not added with NiO and Fe2O3Seal glass in there is a large amount of B substance to volatilize, so as to cause in LSCF containing big
Measure LaBO3The presence of substance, and add 20 mol.%NiO and 15mol.%Fe2O3Seal glass in, only exist a small amount of
LaBO3Substance illustrates to add 20 mol.%NiO and 15mol.%Fe2O3Seal glass and cathode (LSCF) have preferable chemistry
Compatibility.
Fig. 3 be seal glass aoxidize and reducing atmosphere under, the seal interface of 700 DEG C of hot operation 100h, wherein（a）For
Oxidizing atmosphere（Air）,（b）For reducing atmosphere（10%H2+90%Ar）.As we can clearly see from the figure, NiO and Fe2O3It is co-doped with
When glass is with stainless steel substrate sealing-in, is aoxidizing and still having preferable seal interface under reducing atmosphere, interface is complete, without more
Remaining stomata and crackle generate, meanwhile, interface is precipitated fine and close hercynite and effectively inhibits the chemical reaction between interface, from
And further improve the chemical stability of seal interface.
It is proved present invention obtains the seal glass used under suitable intermediate temperature SOFC working environment by above-described embodiment,
Significant effect embodies a concentrated reflection of the thermal stability of seal, sealing materials and its raising aspect with the chemical compatibility of cathode.With tradition
Borosilicate system seal glass（Without NiO）It compares, is added to NiO and Fe2O3Borosilicate system seal glass inhibit in glass network
The fracture of B-O-Si keys improves stability of the B in glass network, improve seal glass itself thermal stability and its with
The chemical compatibility of cathode significantly improves the sealing property of seal, sealing materials.
The invention mainly relates to solid oxide fuel cell（SOFC）Field, but be not restricted to that SOFC, can also use
Sealing-in between metalloid and ceramics and ceramics and ceramics.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (7)
1. a kind of NiO and Fe2O3The high boron sealing glass ceramic being co-doped with, it is characterised in that：It is to be with molar ratio（12~30）：（0
~5）：（13~36）：（12~20）：（12~20）：（5~20）：（0~15）B2O3、Al2O3、SiO2, CaO, SrO, NiO and Fe2O3For
Raw material is made.
2. NiO according to claim 1 and Fe2O3The high boron sealing glass ceramic being co-doped with, it is characterised in that：It is raw materials used
B2O3、Al2O3、SiO2, CaO, SrO, NiO and Fe2O3Molar ratio be（15~20）：（0~3）：（24~30）：（16~18）：（16~
18）：（10~15）：（5~10）.
3. a kind of preparing NiO and Fe as described in claim 12O3The method for the high boron sealing glass ceramic being co-doped with, feature exist
In：Include the following steps：
（1）Raw material is uniformly mixed according to a ratio, 1300 DEG C of -1350 DEG C of melted 0.5-1h；Then the glass metal melted is carried out
Chilling obtains glass frit；Glass frit is crushed again, obtains glass powder after sieving；
（2）Glass powder and sealing-in agent, dispersant and solvent are mixed into slurry, ball milling keeps its evenly dispersed in the ball mill,
Then tape casting spontaneously dries, then is cut into the idiosome of required shape, that is, is made containing NiO and Fe2O3Glass sealing material.
4. NiO according to claim 3 and Fe2O3The preparation method for the high boron sealing glass ceramic being co-doped with, feature exist
In：The sealing-in agent is one or more of epoxy resin, methylcellulose, polyvinyl butyral, polyvinyl alcohol.
5. NiO according to claim 3 and Fe2O3The preparation method for the high boron sealing glass ceramic being co-doped with, feature exist
In：The dispersant is one or more of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
6. NiO according to claim 3 and Fe2O3The preparation method for the high boron sealing glass ceramic being co-doped with, feature exist
In：The solvent is one or more of water, ethyl alcohol, isopropanol, n-butanol, toluene, dimethylbenzene, acetone.
7. a kind of NiO as described in claim 1 and Fe2O3The application method for the high boron sealing glass ceramic being co-doped with, feature exist
In：The high boron sealing glass ceramic is placed in and waits for sealing-in position, first 600 DEG C are warming up to the rate of 5 DEG C/min in electric furnace,
Then 750 DEG C, Crystallizing treatment 2h are warming up to the rate of 2 DEG C/min, finally with the rate of 2 DEG C/min be cooled to 600 DEG C it is i.e. complete
At sealing-in.
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| CN201810421734.5A CN108585508A (en) | 2018-05-04 | 2018-05-04 | The high boron sealing glass ceramic and its preparation and application that a kind of nickel oxide and iron oxide are co-doped with |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810421734.5A CN108585508A (en) | 2018-05-04 | 2018-05-04 | The high boron sealing glass ceramic and its preparation and application that a kind of nickel oxide and iron oxide are co-doped with |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001049621A1 (en) * | 1999-12-30 | 2001-07-12 | Corning Incorporated | Copper alumino-silicate glasses |
| CN103030278A (en) * | 2013-01-08 | 2013-04-10 | 福州大学 | Glass sealing material, as well as preparation and using methods thereof |
| CN106746672A (en) * | 2016-11-24 | 2017-05-31 | 福州大学 | Anti-corrosion glass and its preparation and application that a kind of Fe Ni are co-doped with |
-
2018
- 2018-05-04 CN CN201810421734.5A patent/CN108585508A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001049621A1 (en) * | 1999-12-30 | 2001-07-12 | Corning Incorporated | Copper alumino-silicate glasses |
| CN103030278A (en) * | 2013-01-08 | 2013-04-10 | 福州大学 | Glass sealing material, as well as preparation and using methods thereof |
| CN106746672A (en) * | 2016-11-24 | 2017-05-31 | 福州大学 | Anti-corrosion glass and its preparation and application that a kind of Fe Ni are co-doped with |
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Application publication date: 20180928 |