CN116789366A - Composite glass powder and preparation method and application thereof - Google Patents
Composite glass powder and preparation method and application thereof Download PDFInfo
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- CN116789366A CN116789366A CN202310656728.9A CN202310656728A CN116789366A CN 116789366 A CN116789366 A CN 116789366A CN 202310656728 A CN202310656728 A CN 202310656728A CN 116789366 A CN116789366 A CN 116789366A
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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
- C03C12/00—Powdered glass; Bead compositions
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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Abstract
The application belongs to the technical field of fuel cells, and particularly relates to composite glass powder and a preparation method and application thereof. A composite glass frit comprising a core and a shell layer coating the core; the material of the core comprises glass powder A, and the material of the shell comprises glass powder B; the softening temperature of the core is higher than the softening temperature of the shell; the size of the core is 7-20 μm; the thickness of the shell layer is 2-4 mu m; in the composite glass powder, the mass percentages of the glass powder A and the glass powder B are respectively 70-95% and 5-30%. The core and the shell are respectively glass powder with high softening point and low softening point, and the glass powder B with low softening temperature of the shell is firstly softened at high temperature to form liquid phase, so that the glass powder A with high softening temperature, which is coated inside, is uniformly distributed at the part of the device to be sealed, the sealing performance is good, and the sealing requirement of the SOFC can be met.
Description
Technical Field
The application belongs to the technical field of fuel cells, and particularly relates to composite glass powder and a preparation method and application thereof.
Background
The fuel cell is widely used in production and life due to the characteristics of high power generation efficiency, high reliability and the like. Among them, the Solid Oxide Fuel Cell (SOFC) is the fuel cell with the most extensive application prospect due to the advantages of wide fuel selection range, high fuel gas utilization rate, no pollution of combustion products and the like, and has become the preferred object of the efficient and environment-friendly power generation technology in the future.
For SOFCs, gas leakage can greatly reduce the service life and reliability of the cell, and when serious, the cell can fail or even explode, so the sealing problem of the SOFCs is one of main research directions for improving the performance of the SOFCs. Particularly, the anode-electrolyte-cathode of the flat plate SOFC with the sandwich structure needs to be connected with connectors on two sides through sealing materials, so that the leakage of anode and cathode gases is prevented, the absolute insulation between components is ensured, the sealing effect is achieved, and long-time circulation is satisfied in high-temperature oxidation and reduction atmosphere without leakage. Sealing glass sintering is often used for sealing treatment in the prior art, but in the sintering process, the thickness of a sintered sealing layer is difficult to control due to interference of factors such as powder particle size, dispersibility and the like, and a thin layer area is easy to crack under the working condition of thermal cycle, so that the problems of gas leakage and the like are solved; in addition, the crystalline phase precipitated in the sealing glass layer is various, the controllability is poor, and when the SOFC with special structural design is sealed, the phenomenon of unstable temperature field easily occurs in partial areas, so that the glass powder is excessively sintered and the internal stress is increased, thereby causing the cracking of the sealing layer and the reduction of the service life of the SOFC.
Therefore, there is a need to provide a composite glass powder which has good sealing performance and strong controllability and can meet the sealing requirement of SOFC.
Disclosure of Invention
The present application is directed to solving one or more of the problems of the prior art and providing at least one of a beneficial choice or creation of conditions. The application provides composite glass powder which has good sealing performance and strong controllability and can meet the sealing requirement of SOFC.
The application is characterized in that: the application adopts spherical composite glass powder with a core-shell structure, and the composite glass powder comprises a core and a shell layer for coating the core; the material of the core comprises glass powder A, and the material of the shell comprises glass powder B; the softening temperature of the glass powder A is higher than that of the glass powder B, so that the softening temperature of the core is higher, and the softening temperature of the shell is lower; the glass powder B with low softening temperature of the shell layer plays a role in uniform dispersion, namely, the shell layer is firstly softened to form a liquid phase at high temperature, so that the glass powder A with high softening temperature, which is coated inside, can be uniformly distributed on the corresponding part of a device to be sealed, and a good sealing effect is obtained; the gaps among the glass powders A with high softening temperature firmly fix the glass powders B with low softening temperature in the glass powders A with high softening temperature due to capillary effect, so that the glass powders B with low softening temperature are prevented from being deposited at the bottom of the sealing layer in a concentrated way due to fluidity, and further, the glass phases of the sealing layer are uniformly distributed, and sintering cracks caused by layering of the glass phases are prevented; meanwhile, the specific addition amount of the glass powder A and the glass powder B can realize controllable adjustment of crystal size, avoid excessive precipitation caused by overlarge size of single powder and ensure that a stable sealing layer with good sealing performance is formed.
Accordingly, in a first aspect the present application provides a composite glass frit.
Specifically, the composite glass powder comprises a core and a shell layer coating the core; the material of the core comprises glass powder A, and the material of the shell layer comprises glass powder B;
the softening temperature of the core is higher than the softening temperature of the shell layer;
the size of the core is 7-20 μm; the thickness of the shell layer is 2-4 mu m;
in the composite glass powder, the mass percentages of the glass powder A and the glass powder B are respectively 70-95% and 5-30%.
Specifically, when the mass percentage of the glass powder A (i.e. core) is too large, the mass percentage of the corresponding glass powder B (i.e. shell) is too small, a uniform wrapping structure is difficult to form, the thermal expansion coefficient of the composite glass powder is smaller when the high-melting-point content is large, and when the composite glass powder is used in a melting way, the sealing performance is reduced because the content of the glass powder B with low softening temperature is too small to fill gaps among close-packed; when the mass percentage of the glass powder A (i.e. core) is too small, the corresponding glass powder B (i.e. shell) with low softening temperature is too large, and the glass powder B with low softening point is deposited at the lower interface, so that the composite glass powder is layered, the sealing performance of a sealing layer is seriously affected, in addition, the too low content of the glass powder A can cause the thermal expansion coefficient to be too large, sintering cracks are generated at the contact interface with a sealing device, and the strength of the sealing layer is further reduced.
Preferably, the softening temperature of the core is 750-880 ℃; the softening temperature of the shell layer is 600-700 ℃.
Preferably, the crystallization temperature of the core is 780-940 ℃; the crystallization temperature of the shell layer is 720-780 ℃.
Preferably, in the composite glass powder, the mass percentages of the glass powder A and the glass powder B are 85-92% and 8-15%, respectively.
Preferably, the core has a size of 11-16 μm.
Preferably, the particle size of the composite glass frit is 9-24 μm.
Further preferably, the particle size of the composite glass frit is 13-20 μm.
Specifically, when the particle size of the glass powder A or the particle size of the composite glass powder is too large, the maximum close packing is difficult to realize, the gap between the powder bodies is too large, air holes are formed in the sealing layer due to non-compact filling in the sintering process, and even the device is communicated with the air holes after long-term operation to cause serious sintering cracks and other phenomena, so that the sealing layer is invalid; when the particle size of the glass powder A or the particle size of the composite glass powder is too small, the composite glass powder has small softening degree and low deformation when being sintered, and the sealing performance does not reach the standard.
Preferably, the glass powder A has a spherical structure; the composite glass powder is of a spherical structure.
Specifically, the glass powder A has a spherical structure, so as to ensure that uniform spherical composite glass powder is formed after the glass powder B with low softening temperature is coated. From microscopic analysis, the spherical composite glass powder can obtain maximum density accumulation in the accumulation process, so that air holes generated due to insufficient accumulation density are reduced, the air holes are further filled by softening the glass phase with a shell layer and a low softening temperature at a high temperature, and the porosity formed by sintering a sealing layer is greatly reduced; if the composite glass frit is not spherical particles, enrichment or lack of a low softening point glass phase is easily caused at the time of sintering, and thus pores or cracks are easily generated.
Preferably, the glass powder A comprises SiO in percentage by mass 2 25-40％、B 2 O 3 10-25％、Al 2 O 3 0-15％、ZrO 2 0-10% of oxide M 1 20-60% and 0-10% of additive; the oxide M 1 At least two selected from MgO, caO, srO, baO; the additive is selected from TiO 2 、Bi 2 O 3 、La 2 O 3 、Gd 2 O 3 、Y 2 O 3 At least one of them.
Preferably, the glass powder B comprises SiO in percentage by mass 2 30-55％、B 2 O 3 5-20％、TiO 2 0-10% of oxide M 2 20-35% and 0-20% of additive; the oxide M 2 At least two selected from CaO, srO, baO; the additive is selected from CeO 2 、HfO 2 、Gd 2 O 3 And Y 2 O 3 At least one of them.
In a second aspect, the application provides a method for preparing the composite glass powder according to the first aspect of the application.
Specifically, the preparation method of the composite glass powder comprises the following steps:
mixing, reacting and drying the glass powder A, the glass powder B and the solvent to obtain the composite glass powder;
the glass powder A is subjected to the following treatment process before being added: mixing glass powder A, surface modifier and water, heating and drying.
Specifically, the surface modifier can be used as an organic matter to volatilize completely in a drying process or a glue discharging sintering process of a subsequent sealing application, and the sealing effect of the device is not affected.
Specifically, the surface of the glass powder A is activated by adding the surface modifier in the treatment before adding the glass powder A, so that the glass powder B can be better and uniformly attached on the surface of the glass A, and the controllable adjustment of the thickness of the shell layer can be realized by controlling the dosage and the reaction time of the surface modifier.
Preferably, the solvent is at least one selected from ethanol, acetone and diethyl ether.
Preferably, the addition amount of the solvent is 1.4 to 2.2 times the sum of the addition amounts of the glass frit a and the glass frit B.
Further preferably, the addition amount of the solvent is 1.5 to 2 times the sum of the addition amounts of the glass frit a and the glass frit B.
Preferably, the temperature of the reaction is 200-400 ℃, and the time of the reaction is 3-8h.
Specifically, if the reaction time is too short, the thickness of the shell layer is insufficient, and at the moment, the glass powder A with a high softening point occupies relatively high, so that the softening point temperature of the composite glass powder is higher, the density of the sealing layer is reduced during sealing, and defects such as cracks and the like are easy to occur in the sintering process; if the reaction time is too long, the thickness of the shell layer is too large, the composite glass powder is easy to be excessively large in volume and loose in surface, compact accumulation is difficult to form in the later sintering process, defects such as air holes or cracks are generated, and the device is easy to leak.
Preferably, in the treatment process before adding the glass powder A, the heating adopts a water bath heating mode.
Further preferably, the heating is performed in a sealed state by water bath heating.
Preferably, the heating temperature is 60-100 ℃, and the heating time is 6-12h.
Further preferably, the heating temperature is 75-95 ℃, and the heating time is 8-10h.
Preferably, the temperature of the glass powder A is 75-110 ℃ in the treatment process before adding; further preferably, the drying temperature is 80-100 ℃.
Preferably, the water is deionized water.
Preferably, the surface modifier is at least one selected from cetyltrimethylammonium bromide, glycerol and polyvinyl alcohol.
Preferably, in the treatment process before adding the glass powder A, the mass ratio of the glass powder A to the surface modifier is 8-15:1.
preferably, the glass powder A, the surface modifier and the water are added in the amounts of 20-50%, 1-10% and 40-70% by mass percent respectively.
Specifically, when the content of the surface modifier is too small, the surface activation degree of the glass powder A is insufficient (the number of chain groups of the surface access modifier or the surface roughness is insufficient), so that the formed network structure or spiral structure is insufficient to adsorb and fix enough amount of the glass powder B, the coating cannot reach the required thickness, the coating effect of the outer layer is too small, the coating is uneven or the surface is loose, and the subsequent performance is affected; when the content of the surface modifier is too large, the adsorption capacity of the surface of the glass powder A enables the shell layer formed by wrapping to be too thick, the heat preservation time is required to be prolonged to ensure that the inner core leaks out during sintering and melting, the whole size of the composite glass powder is too large, defects such as sintering cracks and the like are easy to generate, and the sealing performance is poor during sealing.
Preferably, the preparation method of the glass powder A comprises the following steps:
and mixing, melting, cold quenching, ball milling and granulating the components of the glass powder A to obtain the glass powder A.
Preferably, the melting temperature is 1300-1700 ℃, and the melting heat preservation time is 1-5h.
Further preferably, the melting temperature is 1450-1650 ℃, and the melting incubation time is 2-4h.
Specifically, the cold quenching, ball milling and granulating all adopt conventional preparation processes, and the application has no special requirements.
Preferably, the preparation method of the glass powder B comprises the following steps:
and mixing, melting, cold quenching and ball milling the components of the glass powder B to obtain the glass powder B.
Preferably, the melting temperature is 1100-1500 ℃, and the melting heat preservation time is 1-5h.
Further preferably, the melting temperature is 1250-1450 ℃, and the melting heat preservation time is 2-4h.
Preferably, the particle size of the glass powder B is 0.5-3 mu m; further preferably, the particle size of the glass frit B is 0.5 to 1.5. Mu.m.
A third aspect of the application provides a fuel cell.
Specifically, the fuel cell comprises the composite glass frit according to the first aspect of the present application.
Compared with the prior art, the technical scheme provided by the application has the following beneficial effects:
(1) The composite glass powder is of a core-shell structure, the core and the shell of the composite glass powder are respectively glass powder with high softening temperature and low softening temperature, and the glass powder B with low softening temperature of the shell plays a role in uniform dispersion, namely, the glass powder B with low softening temperature of the shell is firstly softened at high temperature to form a liquid phase, so that the glass powder A with high softening temperature, which is coated inside, is uniformly distributed at the corresponding part of a device to be sealed, and a good sealing effect is obtained; in addition, the gaps among the glass powders A with high softening temperature firmly fix the glass powders B with low softening temperature in the glass powders A with high softening temperature due to capillary effect, so that the glass powders B with low softening temperature are prevented from being intensively deposited at the bottom of the sealing layer due to fluidity, and further, the glass phases of the sealing layer are uniformly distributed, and sintering cracks caused by layering of the glass phases are prevented.
(2) According to the application, the controllable adjustment of the crystal size can be realized by adopting the specific addition amount of the glass powder A and the glass powder B, excessive precipitation caused by overlarge size of single powder is avoided, and the stable sealing layer with good sealing property is ensured to be formed.
(3) When the composite glass powder is prepared, the glass powder A needs to be treated before being added, the surface of the glass powder A is activated by adding the surface modifier, so that the glass powder B can be better and uniformly attached on the surface of the glass powder A, and the controllable adjustment of the thickness of the shell layer is realized by controlling the dosage and the reaction time of the surface modifier.
(4) The preparation process is simple and is convenient for industrial production.
Detailed Description
In order to make the technical solutions of the present application more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the application.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1
A composite glass frit comprising a core and a shell layer coating the core; the core is made of glass powder A, and the shell is made of glass powder B; the size of the core is 14 μm, and the thickness of the shell layer is 3 μm; in the composite glass powder, the mass percentages of the glass powder A and the glass powder B are respectively 80% and 20%; the glass powder A is 30% of SiO by mass percent 2 、25％ B 2 O 3 、15％Al 2 O 3 、5％ ZrO 2 20% MgO and 5% Bi 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Glass powder B is 40% SiO 2 、20％ B 2 O 3 、10％ TiO 2 20% CaO and 10% CeO 2 。
The preparation method of the composite glass powder comprises the following steps:
(1) Adding the components of the glass powder A into a mixer according to mass percent, heating and melting by using a high-temperature lifting furnace after uniformly mixing, wherein the heating and melting temperature is 1500 ℃, the heating and melting time is 3 hours, taking out after heating, performing cold quenching treatment, crushing by using a ball mill, ball milling and granulating to obtain spherical glass powder A with the particle size of 14 mu m;
(2) Adding the components of the glass powder B into a mixer according to the mass percentage, heating and melting by using a high-temperature lifting furnace after uniformly mixing, wherein the heating and melting temperature is 1300 ℃, the heating and melting time is 3 hours, taking out after heating, carrying out cold quenching treatment, and carrying out crushing and ball milling by using a ball mill to obtain the glass powder B with the particle size of 0.8 mu m;
(3) Adding 80% of glass powder A, 20% of glass powder B and 150% of ethanol into a reaction kettle, and carrying out coating reaction at 300 ℃ for 5 hours to obtain composite glass powder with a core particle size of 14 mu m and a shell thickness of 3 mu m; wherein, before adding, the glass powder A needs to be subjected to the following surface treatment process: mixing 40% of glass powder A, 4% of cetyltrimethylammonium bromide and 56% of deionized water according to the mass percentage, heating in a water bath at 85 ℃ for 9 hours, taking out, and drying at 100 ℃.
Example 2
Example 2 is different from example 1 in that in example 2, the percentages by mass of glass frit a and glass frit B are 70% and 30%, respectively, and the other is the same as example 1.
Example 3
Example 3 is different from example 1 in that in example 3, the glass frit a and glass frit B are 85% and 15% by mass, respectively, and the other is the same as example 1.
Example 4
Example 4 is different from example 1 in that in example 4, the percentages by mass of glass frit a and glass frit B are 88% and 12%, respectively, and the other is the same as example 1.
Example 5
Example 5 is different from example 1 in that in example 5, the percentages by mass of glass frit a and glass frit B are 92% and 8%, respectively, and the other is the same as example 1.
Example 6
Example 6 is different from example 1 in that in example 6, the glass frit a and glass frit B are 95% and 5% by mass, respectively, and the other is the same as example 1.
Example 7
Example 7 is different from example 4 in that in step (1), ball milling and granulating are carried out to obtain spherical glass powder A having a particle size of 7 μm, i.e., a core size of 7 μm, and the shell thickness is 3. Mu.m, in the same manner as in example 4.
Example 8
Example 8 is different from example 4 in that in step (1), ball milling and granulating are carried out to obtain spherical glass powder A having a particle size of 11 μm, i.e., a core size of 11 μm, and the shell thickness is 3. Mu.m, in the same manner as in example 4.
Example 9
Example 9 is different from example 4 in that in step (1), ball milling and granulating are carried out to obtain spherical glass powder A with a particle size of 16 μm, namely, a core size of 16 μm, and the shell thickness is still 3 μm in the same manner as in example 4.
Example 10
Example 10 is different from example 4 in that in step (1), ball milling and granulating are carried out to obtain spherical glass powder A with a particle size of 20 μm, namely, a core size of 20 μm, and the shell thickness is still 3 μm in the same manner as in example 4.
The following examples 11-24 are examples of surface treatment, coating reactions, and are set according to the process parameter values of example 4, wherein in example 4, the mass ratio of cetyltrimethylammonium bromide to glass frit a is 1:10; in the coating reaction, the reaction temperature is 300 ℃, the reaction time is 5 hours, and the glass powder B is 12wt%.
Example 11
Example 11 is different from example 4 in that in example 11, the mass ratio of cetyltrimethylammonium bromide to glass frit a is 1:8, otherwise the same as in example 4.
Example 12
Example 12 is different from example 4 in that in example 12, the mass ratio of cetyltrimethylammonium bromide to glass frit a is 1:15, otherwise the same as in example 4.
Example 13
Example 13 differs from example 4 in that in example 13, the temperature of the reaction was 200℃and the other was the same as in example 4.
Example 14
Example 14 differs from example 4 in that in example 14, the temperature of the reaction is 250℃and otherwise the same as in example 4.
Example 15
Example 15 differs from example 4 in that in example 15, the temperature of the reaction was 350℃and the other steps were the same as in example 4.
Example 16
Example 16 differs from example 4 in that in example 16, the temperature of the reaction was 400℃and the other was the same as in example 4.
Example 17
Example 17 is different from example 4 in that in example 17, the reaction time is 3h, and the other is the same as example 4.
Example 18
Example 18 differs from example 4 in that in example 18, the reaction time was 4h, and the other steps were the same as in example 4.
Example 19
Example 19 is different from example 4 in that in example 19, the reaction time is 6h, and the other is the same as example 4.
Example 20
Example 20 differs from example 4 in that in example 20, the reaction time was 8h, and the other steps were the same as in example 4.
Example 21
Example 21 is different from example 4 in that the amount of glass frit B used in example 21 is 5wt% and the other is the same as example 4.
Example 22
Example 22 differs from example 4 in that in example 22, the amount of glass frit B used was 8wt% and the other was the same as in example 4.
Example 23
Example 23 is different from example 4 in that the amount of glass frit B used in example 23 is 15wt% and the other is the same as example 4.
Example 24
Example 24 differs from example 4 in that in example 24, the amount of glass frit B used was 30wt% and the other was the same as in example 4.
Comparative example 1
Comparative example 1 differs from example 1 in that in comparative example 1, the percentages by mass of glass frit a and glass frit B are 69% and 31%, respectively, and otherwise correspond to example 1.
Comparative example 2
Comparative example 2 is different from example 1 in that in comparative example 2, the percentages by mass of glass frit a and glass frit B are 96% and 4%, respectively, and the other is the same as in example 1.
Comparative example 3
Comparative example 3 is different from example 1 in that in comparative example 3, glass frit A and glass frit B were 100% and 0% by mass, respectively, and glass frit A having particle diameters of 14 μm and 0.8 μm, respectively, was prepared in the same manner as in example 1 by coating treatment using glass frit A as a shell component, the core size was still 14. Mu.m, the shell size was still 3. Mu.m, and the other was the same as in example 1.
The preparation method of the composite glass powder of the comparative example 3 comprises the following steps:
(1) Adding the components of the glass powder A into a mixer according to mass percent, heating and melting by using a high-temperature lifting furnace after uniformly mixing, wherein the heating and melting temperature is 1500 ℃, the heating and melting time is 3 hours, taking out after heating, performing cold quenching treatment, crushing by using a ball mill, ball milling and granulating to obtain spherical glass powder A with the particle size of 14 mu m;
(2) Adding the components of the glass powder A into a mixer according to mass percent, heating and melting by using a high-temperature lifting furnace after uniformly mixing, wherein the heating and melting temperature is 1500 ℃, the heating and melting time is 3 hours, taking out after heating, performing cold quenching treatment, and then crushing and ball milling by using a ball mill to obtain spherical glass powder A with the particle size of 0.8 mu m;
(3) Adding spherical glass powder A88% with the particle size of 14 mu m, spherical glass powder A12% with the particle size of 0.8 mu m and ethanol 150% into a reaction kettle, and carrying out coating reaction at 300 ℃ for 5 hours to obtain composite glass powder with the core size of 14 mu m and the shell thickness of 3 mu m; the procedure before adding spherical glass frit A having a particle size of 14 μm was the same as in example 1.
Comparative example 4
Comparative example 4 is different from example 1 in that in comparative example 4, glass frit A and glass frit B were 0% and 100% by mass, respectively, glass frit B having particle diameters of 14 μm and 0.8 μm was prepared as in the method of step (2) similarly using glass frit B as the core, the core size was still 14 μm, the thickness of the shell layer was still 3. Mu.m, and the same as in example 1.
The preparation method of the composite glass powder of the comparative example 4 comprises the following steps:
(1) Adding the components of the glass powder B into a mixer according to the mass percentage, heating and melting by using a high-temperature lifting furnace after uniformly mixing, wherein the heating and melting temperature is 1300 ℃, the heating and melting time is 3 hours, taking out after heating, carrying out cold quenching treatment, crushing and ball milling by using a ball mill, and granulating to obtain the glass powder B with the particle size of 14 mu m;
(2) Adding the components of the glass powder B into a mixer according to the mass percentage, heating and melting by using a high-temperature lifting furnace after uniformly mixing, wherein the heating and melting temperature is 1300 ℃, the heating and melting time is 3 hours, taking out after heating, carrying out cold quenching treatment, and carrying out crushing and ball milling by using a ball mill to obtain the glass powder B with the particle size of 0.8 mu m;
(3) Adding 88% of glass powder B with the particle size of 14 mu m, 12% of glass powder B with the particle size of 0.8 mu m and 150% of ethanol into a reaction kettle, and carrying out coating reaction at the temperature of 300 ℃ for 5 hours to obtain composite glass powder with the particle size of 14 mu m and the thickness of a shell layer of 3 mu m; wherein, before adding, the glass powder B with the grain diameter of 14 mu m is subjected to the following treatment process: mixing 40% of glass powder B with the particle size of 14 μm, 4% of cetyltrimethylammonium bromide and 56% of deionized water, heating in a water bath at 85 ℃ for 9 hours, taking out, and drying at 100 ℃.
Comparative example 5
Comparative example 5 is different from example 4 in that in step (1) of comparative example 5, ball milling and granulating are carried out to obtain spherical glass powder A having a particle size of 6. Mu.m, i.e., a core size of 6. Mu.m, and the thickness of a shell layer is 3. Mu.m, in the same manner as in example 4.
Comparative example 6
Comparative example 6 is different from example 4 in that in step (1) of comparative example 6, ball milling and granulating are carried out to obtain spherical glass powder A having a particle size of 21. Mu.m, i.e., a core size of 21. Mu.m, and the thickness of a shell layer is 3. Mu.m, in the same manner as in example 4.
Comparative example 7
Comparative example 7 is different from example 4 in that in comparative example 7, the percentages by mass of glass frit a and glass frit B are 100% and 0%, respectively, i.e., the composite glass frit of comparative example 7 is a pure spherical glass frit a having no core-shell structure and the particle size of the spherical glass frit a is 14 μm, and steps (2) and (3) are not required, otherwise, as in example 4.
Comparative example 8
Comparative example 8 is different from example 4 in that in comparative example 8, the glass frit a and glass frit B are 0% and 100% by mass, respectively, the composite glass frit of comparative example 8 is a pure spherical glass frit B having no core-shell structure and the spherical glass frit B has a particle size of 14 μm, steps (1) and (3) do not need to be performed, and step (2) needs to be granulated after ball milling to obtain a spherical glass frit B having a particle size of 14 μm, otherwise, the same as example 4.
The following comparative examples 9 to 16 are comparative examples concerning surface treatment and coating reaction, and are set according to the process parameter values of example 4, wherein in example 4, the mass ratio of cetyltrimethylammonium bromide to glass frit a during the surface treatment before addition is 1:10; in the coating reaction, the reaction temperature is 300 ℃, the reaction time is 5 hours, and the glass powder B is 12wt%.
Comparative example 9
Comparative example 9 differs from example 4 in that in example 9, the mass ratio of cetyltrimethylammonium bromide to glass frit a is 1:7, otherwise the same as in example 4.
Comparative example 10
Comparative example 10 is different from example 4 in that in example 10, the mass ratio of cetyltrimethylammonium bromide to glass frit a is 1:16, otherwise the same as in example 4.
Comparative example 11
Comparative example 11 is different from example 4 in that the temperature of the reaction in comparative example 11 is 190℃and the other is the same as in example 4.
Comparative example 12
Comparative example 12 is different from example 4 in that the temperature of the reaction in comparative example 12 is 410℃and the other is the same as in example 4.
Comparative example 13
Comparative example 13 is different from example 4 in that in comparative example 13, the reaction time was 2.5 hours, and the other was the same as in example 4.
Comparative example 14
Comparative example 14 is different from example 4 in that the reaction time in comparative example 14 is 8.5 hours, and the other is the same as example 4.
Comparative example 15
Comparative example 15 is different from example 4 in that in comparative example 15, the amount of glass frit B used was 4wt% and the other was the same as in example 4.
Comparative example 16
Comparative example 16 is different from example 4 in that the amount of glass frit B used in comparative example 16 was 31wt% and the other was the same as in example 4.
The parameters of examples 1-10 and comparative examples 1-8 were selected as shown in Table 1.
Table 1: examples 1-10, comparative examples 1-8 parameter selections
The parameters of examples 4, examples 11-24, and comparative examples 9-16 were selected as shown in Table 2.
Table 2: examples 4, examples 11-24, comparative examples 9-16 parameter selections
Performance test:
the composite glass frits prepared in examples 1 to 24 and comparative examples 1 to 16 were subjected to performance tests, and the main test items and methods are shown in table 3.
Table 3: test item, test method and requirements
The composite glass frits of examples 1 to 10, comparative examples 1 to 8 were tested for softening temperature, thermal expansion coefficient, and sealability, and the test results are shown in table 4.
Table 4: test results of composite glass frits of examples 1 to 10, comparative examples 1 to 8
As can be seen from Table 4, the composite glass powders of examples 1 to 10 of the present application have suitable softening temperature, thermal expansion coefficient and good sealing performance, and can meet the sealing requirements of SOFC.
The content of the glass component A or the glass component B of comparative examples 1-2 was not within the scope of the present application, so that neither the softening temperature nor the thermal expansion property of comparative examples 1-2 was acceptable. Since the content of the glass frit a of comparative example 1 is lower than the lower limit value of the range value of the present application, the content of the glass frit a of comparative example 2 is higher than the upper limit value of the range value of the present application, when the content of the glass frit a is too high, the content of the corresponding glass frit B is too low, it is difficult to form a uniform coating structure and the thermal expansion coefficient is low, and the softening temperature of the glass frit a is high; when the content of the glass powder A is too low, the content of the corresponding glass powder B is too high, and the glass powder B with low softening temperature is deposited at the lower interface, so that the composite glass powder is layered, but is not of a uniform structure, and the softening temperature and the thermal expansion coefficient of the composite glass powder are affected.
The comparative example 3 only contains glass powder A to form a core-shell structure of A cladding A, and the comparative example 4 only contains glass powder B to form a core-shell structure of B cladding B, so that the softening temperature, the thermal expansion coefficient and the sealing property of the composite glass powder of the comparative examples 3-4 do not meet the requirements. The comparative example 3 and the comparative example 4 cannot form a core-shell structure with low shell softening temperature and high core softening temperature, so that the shell layer (glass powder B) with low softening temperature cannot be softened to form a liquid phase at first at high temperature, and the core (glass powder A) with high softening point, which is coated inside, cannot be uniformly distributed at the corresponding part of a device to be sealed, so that the sealing effect is poor; and the whole structure is not a core-shell structure of the cladding A, so that the softening temperature and the thermal expansion coefficient of the product are greatly influenced, and the product is not in the standard range.
The size of the glass frit a of comparative examples 5 to 6, i.e., the size of the core, is not within the scope of the present application, so that the sealing property of the product is poor, and the softening temperature is not acceptable when the size of the glass frit a is excessively large. When the size of the core of comparative example 6 is too large, the size of the composite powder is too large, the maximum close packing is difficult to realize, the gaps among the powder are too large, the powder is easy to generate phenomena such as sintering pores and cracks after being compounded, the sealing performance is poor, the sealing layer is invalid, and the softening temperature of the product can be influenced; when the size of the core of comparative example 5 is too small, the size of the composite powder is too small, the degree of softening and the deformation amount are low when the composite glass powder is sintered, and the sealing performance does not reach the standard.
Comparative examples 7 to 8 were non-core-shell structures, respectively, spherical glass frit a and spherical glass frit B, and at this time, both softening temperature and sealing property were poor. The method is characterized in that in the non-core-shell structure, the characteristics of high core softening temperature and low shell softening temperature in the core-shell structure cannot be fully utilized by the pure spherical glass powder A and the spherical glass powder B, so that the shell layer (glass powder B) with low softening temperature at high temperature cannot be softened to form a liquid phase, the core (glass powder A) with high softening point, which is coated inside, cannot be uniformly distributed at the corresponding part of a device to be sealed, the sealing effect is poor, and the softening temperature of a product has a larger influence, so that the softening temperature of the product is not in a standard range.
In summary, the content of the glass powder a, the content of the glass powder B, the particle size of the glass powder a (i.e. the size of the core), and the core-shell structure formed by coating the glass powder a with the glass powder B have important effects on the softening temperature, the thermal expansion coefficient and the sealing performance of the product, so that the parameters need to be reasonably controlled, so that the product has a proper softening temperature and thermal expansion coefficient, and can obtain good sealing performance when being applied to SOFC sealing.
The composite glass powders of examples 4 and examples 11 to 24 and comparative examples 9 to 16 were tested for spherical percent of pass, shell thickness and sealability, and the test results are shown in Table 5.
Table 5: test results of composite glass frits of examples 4, examples 11 to 24, and comparative examples 9 to 16
As shown in Table 5, the composite powder of the present application has high spherical yield, a shell thickness of 2 to 4. Mu.m, a proper thickness and good sealing performance.
The ratio of the glass powder A to the modifier in comparative examples 9-10 is not in the range of the application, so that the thickness of the shell layer is not qualified and the sealing property is poor. The addition amount of the modifier in comparative example 9 is insufficient, so that the coating layer is too thin, the shell layer is insufficient in thickness, at the moment, the glass powder A with high softening temperature occupies relatively high, the softening point temperature of the composite glass powder is higher, the density of the sealing layer is reduced during sealing, defects such as cracks and the like are easy to occur in the sintering process, and the sealing performance is poor. The excessive content of the modifier in comparative example 10 causes the excessive thickness of the coating layer and the excessive thickness of the shell layer, which is easy to cause the excessive volume of the composite glass powder and the loose surface, and the defects of air holes or cracks and the like are difficult to form and compact accumulation in the later sintering process, so that the leakage and the like of the device are caused.
The reaction temperatures of comparative examples 11 to 12 and the reaction times of comparative examples 13 to 14 were outside the range of the present application, so that the spherical yield, the shell thickness and the sealing properties of the products of comparative examples 11 to 14 were poor. When the reaction temperature is too low, the reaction time is too short, the reaction is insufficient, the coating is uneven, the formation of a spherical structure is influenced, the thickness of a shell layer is insufficient, at the moment, the glass powder A with a high softening point occupies a relatively high proportion, so that the softening point temperature of the composite glass powder is higher, the density of a sealing layer is reduced during sealing, defects such as cracks are easy to occur in the sintering process, and the sealing performance is poor; when the reaction temperature is too high and the reaction time is too long, the thickness of the shell layer is too large, the spherical structure is easily influenced, the composite glass powder is easily caused to be too large in volume and loose in surface, compact accumulation is difficult to form in the later sintering process, defects such as air holes or cracks are generated, leakage of a device is caused, and the sealing performance is poor.
The amount of glass frit B used in the coating reaction of comparative examples 15 to 16 was outside the range of the present application, so that the sealability of the products of comparative examples 15 to 16 was poor. When the amount of the glass frit B used is too small, the thickness of the formed shell layer is insufficient, and when the amount of the glass frit B used is too large, the insufficient thickness of the shell layer and the excessive thickness of the shell layer both make the sealing property of the composite glass frit poor, for the same reason as in the analysis of comparative examples 11 to 13.
In summary, the ratio of the glass powder a to the modifier, the temperature and time during the coating reaction, and the amount of the glass powder B during the coating reaction need to be strictly controlled within a certain range, so that the prepared product has a qualified spherical yield, a shell thickness and good sealing performance, and further has good sealing performance when applied to SOFC sealing.
The above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application.
Claims (10)
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| CN112897884A (en) * | 2021-02-22 | 2021-06-04 | 合肥邦诺科技有限公司 | Preformed low-temperature glass soldering lug and screen printing manufacturing method thereof |
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