CN106699136A - Method for manufacturing sealing material - Google Patents

Method for manufacturing sealing material Download PDF

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Publication number
CN106699136A
CN106699136A CN201611225683.6A CN201611225683A CN106699136A CN 106699136 A CN106699136 A CN 106699136A CN 201611225683 A CN201611225683 A CN 201611225683A CN 106699136 A CN106699136 A CN 106699136A
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China
Prior art keywords
encapsulant
sealing material
glass
preparation
ball
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CN201611225683.6A
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Inventor
李箭
姚巍
蒲健
池波
贾礼超
颜冬
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Huazhong University of Science and Technology
Shenzhen Huazhong University of Science and Technology Research Institute
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Huazhong University of Science and Technology
Shenzhen Huazhong University of Science and Technology Research Institute
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Priority to CN201611225683.6A priority Critical patent/CN106699136A/en
Publication of CN106699136A publication Critical patent/CN106699136A/en
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/6261Milling
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/62625Wet mixtures
    • C04B35/6264Mixing media, e.g. organic solvents
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • C04B35/63404Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/6342Polyvinylacetals, e.g. polyvinylbutyral [PVB]
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36Glass starting materials for making ceramics, e.g. silica glass
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38Non-oxide ceramic constituents or additives
    • C04B2235/3852Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/386Boron nitrides

Abstract

The invention discloses a method for manufacturing a sealing material. The method comprises the following steps that after a solvent, a dispersing agent and powder are mixed and ball-milled for 12 h, an adhesive, a plasticizer and a defoaming agent are added, the materials are mixed, ball milling is carried out for 3 h during use, then a certain amount of solvent is added, and ball milling continues to be carried out for 24 h; then vacuum degassing is carried out, a precision casting machine is used for casting, a white blank is formed, standing and airing are carried out, and the sealing material is obtained. By means of the ingredient design and structural adjustment and control of the sealing material, DT4 glass with relatively low softening temperature is added into a Al2O3-based sealing material, a Al2O3 framework is filled with the melted glass, and the ceramic-based composite sealing material is obtained. On the basis of keeping the structural strength of the sealing material, the sealing performance of the sealing material is effectively improved, a structure compounding technology of the SOFC sealing material is provided, and manufacturing and popularization of the high-performance SOFC sealing material can be achieved.

Description

A kind of preparation method of encapsulant
Technical field
The present invention relates to a kind of preparation method of encapsulant.
Background technology
In terms of encapsulant, the good Al of pliability is prepared for using casting technology2O3- Al base encapsulants, and into Work(is applied to pile assembling, and when plus load is 30Psi (200kPa), its leak rate is about 0.02sccmcm-1, undergo near Performance still keeps stabilization after 100 thermal cycles.In addition, laboratory also developed various Al2O3The compound seal of-glass base Material, also obtains relatively good sealing effectiveness.But these encapsulants are remained in improvements, Al2O3- Al base composite sealings The interface leak rate of material is higher;Al2O3There is glass transition temperature crystallization high and easy, SOFC in-glass based composite material In During Process of Long-term Operation, the structural instability of encapsulant, so as to influence Performance data.
The content of the invention
Based on above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of high treating effect The preparation method of encapsulant, the encapsulant selects the glass material that a kind of softening temperature is relatively low, be difficult crystallization, with Al2O3 Ceramic base composite sealing material is constituted, so, can not only keep the advantage of Al2O3 base encapsulants can also improve its property Energy.
In order to solve the above-mentioned technical problem, the preparation method of a kind of encapsulant of the invention, it is characterised in that including as follows Step:
After solvent, dispersant and pulvis mixing and ball milling 12h, make after adding the mixing of binding agent, plasticizer and defrother With adding a certain amount of solvent to continue ball milling 24h after middle ball milling 3h again, then vacuum degassing is cast shape using accurate casting machine Into plain embryo, standing dry both the encapsulant.
Used as the preferred embodiment of above-mentioned technical proposal, the preparation method of encapsulant provided in an embodiment of the present invention is entered One step includes the part or all of of following technical characteristic:
As the improvement of above-mentioned technical proposal, in one embodiment of the invention, the material, ball, the mass ratio of solvent It is 1:1.5-2.0:0.8-1.2.
Used as the improvement of above-mentioned technical proposal, in one embodiment of the invention, the solvent is ethanol and dimethylbenzene 30-90 in mass ratio:The mixed liquor of 10-70.
Used as the improvement of above-mentioned technical proposal, in one embodiment of the invention, the pulvis is Al2O3Micro mist and DT4 Glass dust is according to mass ratio 50-90:The mixture of 10-50.
Used as the improvement of above-mentioned technical proposal, in one embodiment of the invention, the pulvis is by G glass dust and six Square boron nitride shines mass ratio 50-90:The mixture of 10-50.
Used as the improvement of above-mentioned technical proposal, in one embodiment of the invention, the binding agent contracts for polyvinyl alcohol Butyraldehyde.
Used as the improvement of above-mentioned technical proposal, in one embodiment of the invention, the plasticizer is poly- alkyl second two One or two mixtures in alcohol and butyl benzyl.
Used as the improvement of above-mentioned technical proposal, in one embodiment of the invention, the defrother is cyclohexanone.
As the improvement of above-mentioned technical proposal, in one embodiment of the invention, with Z in the mechanical milling processrO2Ball is Ball-milling medium, ball is about 3 with the ratio for adding powder:1.
Compared with prior art, technical scheme has the advantages that:.
Described above is only the general introduction of technical solution of the present invention, in order to better understand technological means of the invention, And can be practiced according to the content of specification, and in order to allow the above and other objects, features and advantages of the invention can Become apparent, below in conjunction with preferred embodiment, describe in detail as follows.
Brief description of the drawings
Fig. 1, AD40 and AD30 are cast carry sample thermogravimetric curve;
The temperature increasing schedule of Fig. 2, encapsulant leak rate and thermal cycle test;
Fig. 3, Al2O3Corresponding relation curve (on-load pressure between-glass sealing material leak rate and venting pressure 0.17Mpa, test temperature);
Al under Fig. 4, different temperatures2O3The sealing schematic diagram of mechanism of-glass sealing material;
Leak rate (on-load pressure 0.17MPa) of Fig. 5, h-BN encapsulant under different venting pressures and test temperature;
H-BN seals the schematic diagram of mechanism under Fig. 6, different temperatures;
Fig. 7, h-BN-G30 and h-BN-G50 encapsulant thermogravimetric curve;
The leak rate of Fig. 8, h-BN- glass composite seal with venting pressure change curve (on-load pressure 0.17Mpa, operating temperature)
The stress strain curve of Fig. 9, sealing casting belt when test is not heated up;
The leak rate of Figure 10, h-BN-G50 encapsulant varies with temperature curve, and (venting pressure is in 3.4kPa to 20.4kPa Change);
The leak rate of Figure 11, h-BN-G50 encapsulant with times of thermal cycle change curve (venting pressure from 3.4kPa to 20.4kPa, on-load pressure 0.17MPa, 750 DEG C of test temperature);
Specific embodiment
The following detailed description of specific embodiment of the invention, its as part of this specification, by embodiment come Principle of the invention is illustrated, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
As shown in figure 1, the structural representation of the preparation method for preferred embodiment of the present invention encapsulant, present invention sealing The preparation method of material, it is characterised in that comprise the following steps:
After solvent, dispersant and pulvis mixing and ball milling 12h, make after adding the mixing of binding agent, plasticizer and defrother With adding a certain amount of solvent to continue ball milling 24h after middle ball milling 3h again, then vacuum degassing is cast shape using accurate casting machine Into plain embryo, standing dry both the encapsulant.
The material, ball, the mass ratio of solvent are 1:1.5-2.0:0.8-1.2.
The solvent is ethanol and dimethylbenzene 30-90 in mass ratio:The mixed liquor of 10-70.
The pulvis is Al2O3Micro mist and DT4 glass dust are according to mass ratio 50-90:The mixture of 10-50.
The pulvis is to shine mass ratio 50-90 by G glass dust and hexagonal boron nitride:The mixture of 10-50.
The binding agent is polyvinyl butyral resin.
The plasticizer is one or two mixtures in poly- alkyl glycol and butyl benzyl.
The defrother is cyclohexanone.
With Z in the mechanical milling processrO2Ball is ball-milling medium, and ball is about 3 with the ratio for adding powder:1.
Embodiment:
Al2O3- glass base encapsulant, according to Al2O3The mass ratio 50 added with DT4 powders:50,60:40,70:30, 80:20,90:10.Ethanol and dimethylbenzene are hybridly prepared into mixed liquor for preparing Al2O3- glass powder streams by a certain percentage Prolong slurry.To ensure that slurry has the viscosity of stabilization to be cast, according to Al2O3- glass powders mass ratio and diameter of particle Difference, the quality of ethanol and dimethylbenzene is than scope value in 30-90:10-70, is named as AD50, AD40 by casting belt respectively, AD30, AD20, AD10.In h-BN (hexagonal boron nitride) base encapsulant, the casting belt of h-BN powders is only added to be named as h-BN Encapsulant.According to the mass ratio 50 that h-BN and G glass powders are added:50,70:30,90:Casting belt is named as h- by 10 respectively BN-G50, h-BN-G30, h-BN-G10.
Al2O31.2 μm of micro mist average grain diameter, thermal coefficient of expansion existsShi Yuewei 7.6 × 10-6K-1, DT4 glass is micro- Powder average grain diameter is 16 μm, and thermal coefficient of expansion existsWhen be 9.2 × 10-6K-1.Wherein glass constitutes the ratio of oxide It is SiO2:64.74mol%, Al2O3:3.4mol%, TiO2:6.66mol%, K2O3:9.8mol%, Na2O:11.45mol%, MnO2:3.95mol%.
Al is molded using casting technique2O3- glass base composite sealing material.In view of the encapsulant of heterogeneity ratio has Machine thing content is essentially identical, therefore, the encapsulant that glass content is 30% and 40% is selected in thermal analysis curve as reference, As shown in Figure 1.As seen from Figure 1, from 200 toSample quality is gradually reduced, main cause be sealing casting belt in Some organic additives volatilize.Therefore heating rate is reduced in the temperature range, it is to avoid quickly volatilization forms hole to organic matter Hole.Encapsulant leak rate test temperature increasing schedule curve is formulated according to this thermal analysis curve, as shown in Figure 2.From room temperature toThe rate of heat addition isAndShi Baowen 90min, then withHeating rate fromIt is heated to Shi Baowen 90min, then further withIt is heated to test temperatureInsulation 120min.In order to assess the thermal cycling stability of encapsulant, sample is cooled toHeat is carried out to follow Ring, then withThe rate of heat addition it is rapid fromIt is heated to Shi Baowen 120min.
Gas pressure changes with throughput during real pile use, is the reliability of enhancing sealing, early stage Different Al have been inquired into research work2O3The encapsulant of-glass ingredient in 0.17MPa on-load pressures,Under, gas leakage Rate is with the change of venting pressure, and test result is as shown in Figure 3.As can be seen that venting pressure increases to 20.4kPa by 3.4kPa When, the leak rate of encapsulant becomes larger.Mainly venting pressure is bigger, and pressure difference is bigger inside and outside encapsulant, and gas is let out Leakage is more obvious.With increasing for glass content, the leak rate of encapsulant is gradually reduced.When venting pressure is 3.4kPa, AD10 The initial leak rate of encapsulant is 0.02sccmcm-1, less than the limit leak rate value 0.04sccm that SECA standards specify cm-1.When glass content reaches 30wt% (AD30 encapsulants), the leak rate of encapsulant is down to 0.01sccmcm-1, with The leak rate rule of AD40, AD50 composite seal is similar.As venting pressure increases to 20.4kPa from 10.2kPa, The leak rate of AD10, AD20 and AD30 encapsulant is higher than 0.04sccmcm-1But, the leakage of AD40 and AD50 encapsulants Gas rate still is below 0.03sccmcm-1.Therefore, it follows that the presence of DT4 glass dust can be with REINFORCED Al2O3- glass is combined The air-tightness of encapsulant, when its running temperature is higher than glass softening point, glass can penetrate into Al by infiltration2O3Powder Body piles up the hole to be formed, so as to eliminate the leakage path of encapsulant inside and interface.The sealing of this composite seal Mechanism can be illustrated by schematic diagram 4, with Al2O3It is ceramic skeleton, by granularity relative to Al2O3The thinner DT4 glass dust of particle For filler is dispersed in Al2O3In particle.As T of the temperature less than glassg, glass dust and Al2O3Particle is to separate and scattered, works as temperature Degree rises to TgMore than, the viscosity of glass particle declines, mobility enhancing, Al2O3Particle is connected to each other by softening glass, so that Seal internal porosity is set to diminish.When SOFC reaches operating temperature, glass is wettable and is bonded and sealed Interface, eliminates gas leak path.Al2O3Feature with the composite seal of glass has high flexibility, can reduce in pile The thermal stress in portion, improves long-term thermal cycling stability.
H-BN encapsulants are under different test temperatures and venting pressure, and leak rate variation tendency is as shown in Figure 5.Test knot Fruit shows that, with the increase of venting pressure, its leak rate becomes larger.As test temperature is raised, its leak rate is gradually reduced, When especially temperature is higher than 700 DEG C, leak rate is maintained at than relatively low value.By taking the common gas pressure 6.8kPa of SOFC as an example, H-BN encapsulants are respectively 0.01sccmcm in 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C of leak rate-1、0.006sccm· cm-1、0.005sccm·cm-1、0.0045sccm·cm-1, far below the leak rate 0.04sccm of U.S.'s SECA organization prescribeds cm-1
Under other venting pressures, also there is similar variation tendency between its leak rate and temperature.It is worth noting that, Less than 700 DEG C, released gas rate and Al of the h-BN encapsulants in venting pressure 20.4kPa2O3Base encapsulant substantially close to, Leak rate is close to 0.04sccmcm-1, the sealing property of this explanation h-BN material is also by ceramic powder geometry bulk density institute Determine.And more than 700 DEG C, leak rate is less than 0.02sccmcm-1, it can be seen that the air-tightness of h-BN encapsulants improves In the presence of a critical-temperature.Suitable operating temperature is selected, h-BN surfaces will form high-viscosity B2O3Liquid phase film, suppresses B2O3 Volatilization then can guarantee that the structural integrity of liquid film.B2O3Liquid film is by infiltrating metal connector, or interface is realized on monocell surface It is coupled and seals, so as to improves the air-tightness of h-BN encapsulants.The sealing mechanism of h-BN encapsulants can be illustrated to say with Fig. 6 Bright, sheet h-BN geometry is piled up to form layer structure in h-BN encapsulants at normal temperatures, when temperature is higher than certain critical-temperature (Tc), h-BN surfaces begin with the B of a small amount of liquid2O3Formed so that the combination between h-BN encapsulants and interface becomes tight It is close.When being increased to SOFC running temperatures with temperature, glass phase B2O3It is present in the adjacent interfaces of encapsulant with liquid form, Eliminate interfacial gases leakage paths.
In h-BN- glass composite seal heat analysis, selection glass content is the encapsulant of 30wt% and 50wt% Used as reference, thermal analysis curve is as shown in Figure 7.As can be seen that fromExtremelyThe quality of sample is gradually reduced.
The encapsulant of different h-BN- glass ingredients 0.13MPa on-load pressures,Under carry out leak rate test. Leak rate is as shown in Figure 8 with the result that venting pressure changes.When venting pressure increases to 20.4kPa by 3.4kPa, sealing material The leak rate of material becomes larger.With the increase of glass content, leak rate is tapered into.Wherein h-BN-G50 encapsulants are initial Leak rate is less than 0.005sccmcm-1, 0.025sccmcm still is below when venting pressure reaches 20.4kPa its leak rate-1, show excellent sealing property.Relative to h-BN base encapsulants, when glass addition is less than 30wt%, h-BN- glass The leak rate of component encapsulant is larger, and main cause is probably that the presence of glass dust hinders h-BN layer growths, layer and layer Between combine defective tightness;And glass content, when reaching 50wt%, h-BN interconnects with glass dust, considerably reduces gas Leakage path.
Fig. 9 is the stress strain curve of different h-BN base composite sealings casting belt biscuits.It can be seen that sealing curtain coating biscuit with Tension becomes big, is broken after different displacements are plastically deformed.It is 15mm that curtain coating sealant band width is chosen in experiment, due to Thickness difference causes each casting belt cross-sectional area different, so different glass content encapsulant can not intuitively be reflected Tensile strength.
The tensile strength of various sample, maximum pull and thickness parameter are as shown in table 5.1.It can be seen that as glass contains The increase of amount, tensile strength is improved constantly.H-BN-G50 tensile strength is about 2 times of h-BN, and shows the position of maximum Shifting amount, illustrates that its plastic deformation ability is preferable.The addition of a certain amount of glass powder can strengthen the lamella knot of h-BN encapsulants With joint efforts.
The tensile strength of casting belt is sealed under the different glass content of table 1
As glass content increases, h-BN-G encapsulants are more and more finer and close.Being primarily due to h-BN layer structures has one Divide hole formation, a small amount of glass can hinder stratiform build stack fine and close, and glass is more or less the same with h-BN contents, and h-BN is in G glass Increase around glass and become big, the glass of flowing can fill up the hole that h-BN stacks formation in itself;The presence of h-BN has beneficial to glass Mechanical performance is kept during softening.Therefore, the air-tightness being added with beneficial to improvement h-BN encapsulants of glass.
Based on leak rate test, tensile strength and Analysis of Surface Topography, h-BN-G50 has relatively excellent comprehensive Can, therefore using h-BN-G50 as research object in subsequent experimental.In the running of pile, Temperature Distribution is simultaneously uneven It is even, therefore (650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C) the test h-BN-G50 in the case where on-load pressure is 0.13MPa, different temperatures Leak rate with venting pressure change, test result is as shown in Figure 10.As temperature is increased to 800 DEG C, leak rate drop by 650 DEG C Low about 0.002sccmcm-1, in venting pressure 6.8kPa, the leak rate of h-BN-G50 encapsulants is less than 0.01sccm cm-1;When venting pressure increases to 20.4kPa, the leak rate of h-BN-G50 encapsulants still is below 0.025sccmcm-1, this is far below the 0.04sccmcm that SECA standards specify-1.On the one hand it is because B aoxidizes the glass phase B to be formed in h-BN2O3 Adjacent interface enhancing interface binding power can be infiltrated;Another aspect is that the softening transform of G glass can dynamically absorb hot answering Combination inside power enhancing.
SOFC piles running may be needed repeatedly to start and close, and sealing material in true pile operation is simulated in experiment Material state carries out the circulation leak rate test of intensification cooling.Figure 11 shows h-BN-G50 encapsulant leak rates with thermal cycle Change, venting pressure from 3.4kPa to 20.4kPa, on-load pressure 0.13MPa, 750 DEG C of test temperature.As can be seen from the figure pass through The leak rate of the h-BN-G50 encapsulants crossed after 10 circulations changes little, is maintained at more stable state.Be probably by In the thermal coefficient of expansion and adjacent interfaces comparison match of h-BN-G50 encapsulants, except h-BN can be absorbed by dynamic sliding Outside thermal stress, G glass can also by softening transform relief of thermal stress;So that the thermal cycle of h-BN-G50 encapsulants Leak rate stabilization is than relatively low value.
The advantage of the invention is that:
By in Al2O3DT4 glass dust is added in powder, the sealing property of encapsulant can be effectively improved, and with Glass content increases air leakage rate and is gradually reduced, and when glass content is more than 40wt%, leak rate reaches stationary value, and its is microcosmic Pattern is displayed that and has been densified.After AD40 encapsulants are by 10 thermal cycles, air leakage rate is held essentially constant, sealing There was only a small amount of Al in material2SiO5With K (K, Na)3Al4Si4O16Mutually separate out, show stronger thermal stability.
It is lower that by 10 thermal cycle tests, there are not significant changes in the air-tightness of h-BN base encapsulants, This illustrates that it can meet to work long hours and seal demand with the SOFC under multiple thermal cycle conditions.
Innovative point of the invention is:By the composition design and structure regulating of encapsulant, by softening temperature relatively Low DT4 glass is added to Al2O3In base encapsulant, make the glass-filled of melting to Al2O3Skeleton, constitute ceramic base answer Close encapsulant.Its sealing property is effectively improved on the basis of encapsulant structural strength is kept, there is provided a kind of SOFC The structure composite technology of encapsulant.The h-BN of layer structure can meet the structural support and sealing need of SOFC encapsulants Ask, and the B that h-BN surfaces are formed in situ through high-temperature oxydation2O3Liquid film then undertakes the function of interfacial seal and dissipative stress, continuously B2O3Binding effect of the liquid film at interface will farthest eliminate gas leakage path.Help to realize that high-performance SOFC is sealed The making and popularization of material.
The above is the preferred embodiment of the present invention, can not limit the right model of the present invention with this certainly Enclose, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention, may be used also To make some improvement and variation, these are improved and variation is also considered as protection scope of the present invention.

Claims (9)

1. a kind of preparation method of encapsulant, it is characterised in that comprise the following steps:
After solvent, dispersant and pulvis mixing and ball milling 12h, after adding binding agent, plasticizer and defrother to mix in use Solvent is added to continue ball milling 24h after ball milling 3h again, then vacuum degassing is cast formin embryo, stands using accurate casting machine Dry both the encapsulant.
2. the preparation method of encapsulant as claimed in claim 1, it is characterised in that:The binding agent, plasticizer and de-bubble The total amount of agent, ball, the mass ratio of solvent are 1:1.5-2.0:0.8-1.2.
3. the preparation method of encapsulant as claimed in claim 1, it is characterised in that:The solvent is pressed for ethanol with dimethylbenzene Mass ratio 30-90:The mixed liquor of 10-70.
4. the preparation method of encapsulant as claimed in claim 1, it is characterised in that:The pulvis is Al2O3Micro mist and DT4 Glass dust is according to mass ratio 50-90:The mixture of 10-50.
5. the preparation method of encapsulant as claimed in claim 1, it is characterised in that:The pulvis is by G glass dust and six Square boron nitride shines mass ratio 50-90:The mixture of 10-50.
6. the preparation method of encapsulant as claimed in claim 1, it is characterised in that:The binding agent is polyvinyl alcohol contracting fourth Aldehyde.
7. the preparation method of encapsulant as claimed in claim 1, it is characterised in that:The plasticizer is poly- alkyl glycol With one or two mixtures in butyl benzyl.
8. the preparation method of encapsulant as claimed in claim 1, it is characterised in that:The defrother is cyclohexanone.
9. the preparation method of encapsulant as claimed in claim 1, it is characterised in that:With Z in the mechanical milling processrO2Ball is Ball-milling medium, ball is about 3 with the ratio for adding powder:1.
CN201611225683.6A 2016-12-27 2016-12-27 Method for manufacturing sealing material Pending CN106699136A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573674A (en) * 2017-09-06 2018-01-12 苏州纽东精密制造科技有限公司 A kind of preparation method of encapsulant
CN108054408A (en) * 2017-12-15 2018-05-18 武汉华科福赛新能源有限责任公司 A kind of solid-oxide fuel cell stack compression sealing material and preparation method thereof
CN108519419A (en) * 2018-03-27 2018-09-11 常州联德电子有限公司 The compression encapsulating method of oxygen sensor used in vehicle
CN112928299A (en) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 Novel high-temperature composite sealing material and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573674A (en) * 2017-09-06 2018-01-12 苏州纽东精密制造科技有限公司 A kind of preparation method of encapsulant
CN108054408A (en) * 2017-12-15 2018-05-18 武汉华科福赛新能源有限责任公司 A kind of solid-oxide fuel cell stack compression sealing material and preparation method thereof
CN108519419A (en) * 2018-03-27 2018-09-11 常州联德电子有限公司 The compression encapsulating method of oxygen sensor used in vehicle
CN112928299A (en) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 Novel high-temperature composite sealing material and application thereof
CN112928299B (en) * 2019-12-06 2022-10-18 中国科学院大连化学物理研究所 High-temperature composite sealing material and application thereof

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Application publication date: 20170524