CN1328218C - Thin ceramic film preparation method - Google Patents
Thin ceramic film preparation method Download PDFInfo
- Publication number
- CN1328218C CN1328218C CNB2005100103051A CN200510010305A CN1328218C CN 1328218 C CN1328218 C CN 1328218C CN B2005100103051 A CNB2005100103051 A CN B2005100103051A CN 200510010305 A CN200510010305 A CN 200510010305A CN 1328218 C CN1328218 C CN 1328218C
- Authority
- CN
- China
- Prior art keywords
- powder
- ceramic
- buffer layer
- particle diameter
- mould
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The utility model relates to a thin ceramic film sheet preparing method, particularly to the preparing method of a ceramic sheet. In order to solve the problems that in the existing thin ceramic film sheet preparing method, when a ceramic film sheet, the thickness of which is about 50 mum is prepared, cost is high, and technology is complicated, and the prepared thin ceramic film sheet can not reach the requirement of high mechanical strength, steps of the method of the present invention comprise that 1. assembling mould; 2. forming buffer layer; 3. adding ceramic powder; 4. dry rolling and forming; 5. demoulding; 6. sintering at high temperature. By using the compact ceramic film sheet which is prepared by the present invention and is 20 mum to 250 mum in thickness, the present invention is suitable for the technical field of all the ceramic film sheets using the thickness. Particularly, the ceramic film sheet can be used for manufacturing an electrolyte film sheet of a solid oxide fuel battery of an electrolyte automatic supporting structure. The ceramic film sheet prepared by the present invention has the same body density and higher mechanical strength as traditional dry pressing and has the advantages of simple technology and easy operation.
Description
Technical field:
The present invention relates to a kind of preparation method of ceramic plate.
Background technology:
At present, method preparations such as thin ceramic film mainly adopts dry pressing, casting method, rolls embrane method, electrophoretic deposition, but, when preparation thickness is lower than the diaphragm of 50 μ m, usually need go up at the supporter (substrate) of certain thickness (500～2000 μ m) and make, have enough physical strengths to guarantee base substrate and the device that burns till.For traditional dry-pressing, half-dried pressure in addition etc. the static pressure ceramic process, though can obtain to have enough high-intensity base substrate, the restriction that used by mould can not be used for directly preparing the diaphragm of very little thickness (below the 100 μ m) usually; Yet the curtain coating of employing, when rolling methods such as film, though can under a stable condition, obtain the diaphragm of 50 μ m left and right thicknesses, but owing in moulding process, must use organism such as more binding agent, solvent, so blank density is lower, must discharge organism by careful control heating schedule in the sintering process, therefore higher, the complex process of cost also is difficult to obtain higher diaphragm intensity.
Summary of the invention:
The objective of the invention is for the preparation method that solves existing thin ceramic film in preparation thickness cost height, complex process when being ceramic diaphragm about 50 μ m, and prepared thin ceramic film can't reach the problem of the requirement of high mechanical strength, thereby a kind of preparation method of thin ceramic film is provided.
The step of the inventive method comprises: one, assembly jig: put into briquetting 2 in mould 1; Two, buffer layer moulding: sprinkle the buffering material of nano level particle diameter on briquetting 2, insert formpiston 3 then in mould 1, pressurization gently flattens described buffering material, forms buffer layer 4; Three, add ceramics powder: the ceramics powder of micron order particle diameter evenly is sprinkled upon the top of buffer layer 4, forms diaphragm bisque 5, wherein the quality of the ceramics powder of the described micron order particle diameter on every square centimeter is 10mg～100mg on the cross section of mould 1; Four, dry-pressing formed: using tabletting machine is 10～800MPa at pressure, to diaphragm bisque 5 pressurizations 0.1～10min, forms ceramic membrane base 6; Five, the demoulding: ceramic membrane base 6 when mould 1 takes out, is utilized the difference of ceramic membrane base 6 and buffer layer 4 swell increment in knockout course to realize separating automatically of ceramic membrane base 6 and buffer layer 4, thereby obtains independently ceramic membrane base 6; Six, high temperature sintering: the ceramic membrane base 6 after the demoulding is placed in the high-temperature electric resistance furnace, be warming up to 1000～1600 ℃ of sintering temperatures rapidly, with ceramic membrane base 6 densified sintering products, ceramic membrane base 6 furnace cooling are taken out to room temperature, can obtain required ceramic diaphragm, the material of buffering described in the moulding of step 2 buffer layer mainly is made up of the ceramics powder and the activated carbon powder of the nano level particle diameter that is used to prepare ceramic diaphragm, the particle diameter of the ceramics powder of described nano level particle diameter is 5～500nm, and the quality of described activated carbon powder accounts for 1～20% of described buffering material total mass.
Buffering dry pressing proposed by the invention can be used for preparing the thin ceramic film of thickness in tens of μ m magnitudes.In the present invention, adding thickness in mould 1 successively is the ceramic powder of millimetre-sized buffering material and tens of μ m thickness, under common dry-pressing condition, be pressed then, after the demoulding, ceramic membrane base 6 separates because of physical properties is different voluntarily with buffer layer 4, obtain thin ceramic membrane base 6, this ceramic membrane base 6 has blank density identical with the conventional dry platen press and higher physical strength, and can adopt and the identical sintering process of the molded device of conventional dry, and need not very strictly limit the heating schedule condition, can save sintering time greatly, and manufacture craft is simple.Compare with common double-deck dry-pressing method, owing to removed support body layer, in sintering process, can avoid because of support body layer and rete sintering shrinkage temperature, the different stress that produce of shrinking percentage and the distortion that causes.The thickness of dense ceramic membrane that adopts the present invention's preparation is applicable to the field that all adopt the ceramic diaphragm of this thickness at 20～250 μ m, particularly can be used to make the electrolyte membrane of the Solid Oxide Fuel Cell of ionogen self supporting structure.
Description of drawings:
Fig. 1 is the process flow sheet that step 2 buffer layer of the present invention is formed into the step 5 demoulding, Fig. 2 is the graph of relation that adopts the ceramics powder quality of the thickness of ceramic diaphragm of embodiment seven preparations and employing, Fig. 3 is Solid Oxide Fuel Cell (SOFC) assembling when carrying out Solid Oxide Fuel Cell (SOFC) monocell performance test experiment of ceramic diaphragm that the present invention prepares and the connection diagram of metering circuit, Fig. 4 be yttria-stabilized zirconia (YSZ) electrolyte membrane of the 65 μ m thickness that prepare of the present invention when being used for Solid Oxide Fuel Cell (SOFC) experiment SOFC at the output characteristics figure of differing temps.
Embodiment:
Embodiment one: in conjunction with Fig. 1 this embodiment is described, the step of this embodiment comprises: one, assembly jig: put into briquetting 2 in mould 1; Two, buffer layer moulding: sprinkle the buffering material of nano level particle diameter on briquetting 2, insert formpiston 3 then in mould 1, pressurization gently flattens described buffering material, forms buffer layer 4; Three, add ceramics powder: the ceramics powder of micron order particle diameter evenly is sprinkled upon the top of buffer layer 4, forms diaphragm bisque 5, wherein the quality of the ceramics powder of the described micron order particle diameter on every square centimeter is 10mg～100mg on the cross section of mould 1; Four, dry-pressing formed: using tabletting machine is 10～800MPa at pressure, to diaphragm bisque 5 pressurizations 0.1～10min, forms ceramic membrane base 6; Five, the demoulding: ceramic membrane base 6 when mould 1 takes out, is utilized the difference of ceramic membrane base 6 and buffer layer 4 swell increment in knockout course to realize separating automatically of ceramic membrane base 6 and buffer layer 4, thereby obtains independently ceramic membrane base 6; Six, high temperature sintering: the ceramic membrane base 6 after the demoulding is placed in the high-temperature electric resistance furnace, is warming up to 1000～1600 ℃ of sintering temperatures rapidly,, ceramic membrane base 6 furnace cooling are taken out to room temperature, can obtain required ceramic diaphragm with ceramic membrane base 6 densified sintering products.
Embodiment two: in embodiment one, the ceramics powder that step 3 is added the described micron order particle diameter in the ceramics powder is a kind of in the micron powder of yttria-stabilized zirconia and the aluminium sesquioxide micron order ceramics powder.When adopting the thick dense ceramic membrane of ceramic powder preparation 20～250 μ m of unlike material, all can adopt method of the present invention.Adopt the diaphragm of aluminium sesquioxide micron order ceramics powder preparation to be applicable in the preparation of transmitter,, do not influence technical process of the present invention because the difference of Application Areas changes the material of ceramics powder.Thickness at the bisque of diaphragm described in the step 35 is 100～1000 μ m, and this is by the decision of the quality of employed micron order ceramics powder, also is according to the thickness of the ceramic diaphragm of required preparation and fixed.
Embodiment three: in embodiment one, the material of buffering described in the moulding of step 2 buffer layer mainly is made up of the ceramics powder and the activated carbon powder of the nano level particle diameter that is used to prepare ceramic diaphragm, the particle diameter of the ceramics powder of described nano level particle diameter is 5～500nm, and the quality of described activated carbon powder accounts for 1～20% of described buffering material total mass.The existence of buffer layer material can make whole pressurized thing have enough thickness (more than the 0.5mm) on the one hand, prevents that the core rod 3 of mould and briquetting 2 direct roof pressures are damaged together; On the other hand, buffer layer can also make the pressure of membrane layer and blank density distribute more even.
Embodiment four: this embodiment with the difference of embodiment three is: the material of buffering described in the moulding of step 2 buffer layer also comprises nickel oxide powder, the mean diameter of described nickel oxide powder is at 5～20nm, and the quality of described nickel oxide powder accounts for 40～50% of described buffering material total mass.Other compositions are identical with embodiment three.Can reduce the consumption of the ceramics powder of nano level particle diameter in the buffering material when adopting this embodiment.
Embodiment five: in embodiment one, the preparation method of the material of buffering described in the moulding of step 2 buffer layer is: the powder mixes that will form described buffering material is ground 10～30min; The thickness of buffer layer described in the step 24 is 0.5～3mm.The buffering material is block in this embodiment after finishing the buffer layer moulding process, recycles behind crushing grinding 20～30min again, saves material, helps environmental protection.
Embodiment six: this embodiment with the difference of embodiment one is: the method for taking out ceramic membrane base 6 in the step 5 demoulding is: with mould 1 reversing, add compressing tablet cover 8 in the upper end of mould 1, utilize tabletting machine that compressing tablet cover 8 is pressurizeed again, make formpiston 3 relative movement take place ceramic membrane base 6 related buffer layers 4 are ejected mould 1 with mould 1.Other steps are identical with embodiment one.When adopting this embodiment to obtain independently ceramic membrane base 6, method is simple to operation.
Embodiment seven: the difference of this embodiment and embodiment one is: step 3 adds to have prepared in the ceramics powder needs the process that vacuumizes again behind the diaphragm bisque 5, the described process that vacuumizes is: the bleeding point 7 of mould 1 is connected with vacuum pump, energising vacuumizes 1～10min, removes the gas in the diaphragm bisque 5.Other steps are identical with embodiment one.The effect that vacuumizes is to remove the air between the granule materials, can increase the density of film base so on the one hand, can reduce the amount of pressurized gas in the film base on the other hand to greatest extent, prevents the breakage of the film base that gas expansion causes after release.
Embodiment eight: in embodiment one, the thickness of ceramic membrane base 6 was 30～300 μ m during step 4 was dry-pressing formed.The thickness of the ceramic membrane base 6 after the dry-pressing is greater than the thickness of the ceramic diaphragm behind the high temperature sintering.
Embodiment nine: in embodiment one, heat up rapidly in the step 6 high temperature sintering and be meant that temperature rise rate is 3～20k/min; The high temperature sintering time is 3.5～4.5h.The present invention does not need strict heating schedule, and the high temperature sintering time about 4 hours, get final product, can save sintering time greatly.
Embodiment ten: this embodiment with the difference of embodiment one is: the diameter of the mould 1 that step 1 is used is 13mm; Be the nickel oxide powder of 5～20nm, the nanoscale powder of 8% yttria-stabilized zirconia and the mixed that activated carbon powder by mass ratio 5: 5: 1 with median size in the step 2, and adopting agate mortar to grind the buffering material that 20min makes the nano level particle diameter, the thickness of the buffer layer 4 that described buffering material forms is 1～3mm; The ceramics powder of the described micron order particle diameter in the step 3 is the micron powder of 8% yttria-stabilized zirconia of 0.04g, and the described time that vacuumizes is 2min; The pressure that described tabletting machine in the step 4 produces is 200MPa, and be 1min clamping time; In the step 6, described ceramic membrane base 6 is placed on and places 1400 ℃ high-temperature electric resistance furnace on the alumina ceramic chip, and is warmed up to 1600 ℃ with the speed of 3～10K/min, keeps four hours.Other steps are identical with embodiment one.With the ceramic diaphragm section that scanning electronic microscope observation adopts this embodiment to prepare, the thickness that records ceramic diaphragm is 63 ± 2 μ m.
In this embodiment, mould 1 is that the model that device high and new technology company of Tianjin section produces is the mould of MJY-Φ 13mm.The nanoscale powder of 8% yttria-stabilized zirconia that uses in the step 2 of this embodiment is that Japanese Tosoh company produces, and its powder granularity is at 100～200mm; The micron powder of 8% yttria-stabilized zirconia that uses in the step 3 is that China Building Materials Academy produces, and its powder granularity is 2 μ m, wherein 8% is meant that the massfraction of used yttrium oxide is 8% in 8% yttria-stabilized zirconia.The above-mentioned yttria-stabilized zirconia that adopts different manufacturer production is to realize well separating automatically with buffer layer 4 for ceramic membrane base 6.Can separate automatically with buffer layer 4 for ceramic membrane base 6 among the present invention, as long as it is just passable in micron-sized condition to satisfy the particle diameter of the described ceramics powder of particle diameter in nano level and step 3 that cushions material, wherein, the median size of the described ceramics powder in the step 3 is 1～10 micron.
Embodiment 11: the difference of this embodiment and embodiment ten is: the mixed that in the step 2 nanoscale powder and the activated carbon powder of 8% yttria-stabilized zirconia by mass ratio is 10: 1, and adopting agate mortar to grind the buffering material that 30min makes the nano level particle diameter, the thickness of the buffer layer 4 that described buffering material forms is 3mm; The ceramics powder of the described micron order particle diameter in the step 3 is the micron powder of 8% yttria-stabilized zirconia of 0.03g.Other steps are identical with embodiment ten.The nanoscale powder of 8% yttria-stabilized zirconia that uses in the step 2 of this embodiment is that Japanese Tosoh company produces, and the micron powder of 8% yttria-stabilized zirconia that uses in the step 3 is that China Building Materials Academy produces.With the ceramic diaphragm section that scanning electronic microscope observation adopts this embodiment to prepare, the thickness that records ceramic diaphragm is 40 μ m.
Embodiment 12: this embodiment with the difference of embodiment 11 is: the ceramics powder of the described micron order particle diameter in the step 3 is the micron powder of 8% yttria-stabilized zirconia of 0.014g.Other steps are identical with embodiment 11.With the ceramic diaphragm section that scanning electronic microscope observation adopts this embodiment to prepare, the thickness that records ceramic diaphragm is 25 μ m.
Embodiment 13: this embodiment with the difference of embodiment 11 is: the ceramics powder of the described micron order particle diameter in the step 3 is the micron powder of 8% yttria-stabilized zirconia of 0.132g.Other steps are identical with embodiment 11.With the ceramic diaphragm section that scanning electronic microscope observation adopts this embodiment to prepare, the thickness that records ceramic diaphragm is 0.237mm.
According to the preparation process of embodiment 11, adopt the ceramics powder of different mass to experimentize, the ceramic diaphragm of the different thickness that obtains, the relation of the thickness of ceramic diaphragm and the quality of used ceramics powder is as shown in Figure 2.Straight line in Fig. 2 "-mouthful-" is illustrated in the relation curve of the thickness that carries out the ceramic membrane base 6 before the high temperature sintering and the ceramics powder quality of employing, and straight line "-zero-" represents to carry out the relation curve of the ceramics powder quality of the thickness of the ceramic diaphragm behind the high temperature sintering and employing.The thickness (h) of the ceramic diaphragm behind the sintering and quality (m) data of ceramics powder are carried out fitting of a straight line, and the thickness h (mm of unit) that obtains the ceramic diaphragm behind compacting of Φ 13mm mould and the sintering with the pass of the quality m (g of unit) of ceramics powder is:
h＝1.8×m(mm)?(1)；
Consider the sectional area difference of different moulds, m is converted into mass area ratio M (g/cm
2), be about to
Bring in the following formula (1), promptly get when adopting different moulds 1, the mass area ratio M (g/cm of the ceramics powder of the above micron order particle diameter of cross section of thickness h of the ceramic diaphragm of preparation (mm of unit) and mould 1
2) the pass be:
h≈2.4×M(mm)?(2)，
When can prediction and calculation adopting the technical process of this embodiment with above-mentioned two formula, the thickness of the ceramic diaphragm of the quality correspondence of different ceramics powders.
Embodiment 14: this embodiment with the difference of embodiment one is: the pressure that tabletting machine described in the step 5 produces is 800MPa, and be 0.1min clamping time.Other steps are identical with embodiment one.When the hypertonia of tabletting machine, will be unfavorable for separating of rete and buffer layer.
Embodiment 15: this embodiment with the difference of embodiment one is: the pressure that tabletting machine described in the step 5 produces is 10MPa, and be 10min clamping time.Other steps are identical with embodiment one.When the hypotony of tabletting machine, then can't obtain the diaphragm of sufficient intensity.
Embodiment 16: the difference of this embodiment and embodiment one is: the mixed that in the step 2 nanoscale powder and the activated carbon powder of 8% yttria-stabilized zirconia by mass ratio is 99: 1, and adopting agate mortar to grind the buffering material that 10min makes the nano level particle diameter, the thickness of the buffer layer 4 that described buffering material forms is 2mm.Other steps are identical with embodiment one.
Embodiment 17: the difference of this embodiment and embodiment one is: the mixed that in the step 2 nanoscale powder and the activated carbon powder of 8% yttria-stabilized zirconia by mass ratio is 4: 1, and adopting agate mortar to grind the buffering material that 30min makes the nano level particle diameter, the thickness of the buffer layer 4 that described buffering material forms is 0.5mm.Other steps are identical with embodiment one.
Embodiment 18: the difference of this embodiment and embodiment one is: the base of ceramic membrane described in the step 66 is placed on and places 1000 ℃ high-temperature electric resistance furnace on the alumina ceramic chip, is warmed up to 1600 ℃ with the speed of 10～20K/min.In any one section temperature in 1000～1600 ℃, intensification can be finished step 6 high temperature sintering of the present invention rapidly.Other steps are identical with embodiment one.
As shown in Figure 3, with the part ceramic diaphragm of the method for the present invention preparation ionogen as Solid Oxide Fuel Cell (SOFC), carry out the fuel battery performance test experiments, its step is as follows:
One, apply nickel oxide-yttria-stabilized zirconia (NiO-YSZ) as anode 11 in the one side of ceramic diaphragm 12, wherein the mass ratio of nickel oxide and yttria-stabilized zirconia is 1: 1, then with described anode 11 at 1300 ℃ of following sintering 4h; The correspondence position of the another side of ceramic diaphragm 12 applies the lanthanum manganate (La of doping 30mol% strontium
0.7Sr
0.3MnO
3) as negative electrode 14, then with described negative electrode 14 at 1100 ℃ of following sintering 4h; Two, subsequently on two electrodes the separate application silver conductive adhesive and on silver-colored collector 10, paste the lead-in wire of two filamentary silvers 15 respectively as silver-colored collector 10 as electric current and voltage measurement; Three, the electrolyte membrane that this is had anode 11, negative electrode 14 and a lead-in wire is encapsulated in an end of ceramic siphunculus 9, and wherein anode 11 is in a side in the pipe, and negative electrode 14 is exposed in the air, forms a Solid Oxide Fuel Cell (SOFC) monocell; Four, (this instrument is the electro-chemical test instrument that has comprised all conventional electrochemical polarization test functions to Solartron SI 1287 electrochemical interfaces, what adopt in the present invention is the scanning electric potential method, automatically change and the outward current and the output voltage of record battery) and SI 1260 electric impedance analyzers composition battery performance testing system 16, the lead-in wire of described Solid Oxide Fuel Cell (SOFC) monocell is connected on respectively on four terminals (WE, CE, RE1, RE2) of Solartron SI 1287 electrochemical interfaces; Five, battery is placed high-temperature electric resistance furnace 13, slowly heat up, simultaneously in ceramic siphunculus 9, feed nitrogen, insulation when temperature reaches 700 ℃, and feeding hydrogen, close the valve that feeds nitrogen simultaneously, make the nickel oxide (NiO) in the anode 11 be reduced into nickel (Ni) fully, begin the performance with electrochemical interface instrument test Solid Oxide Fuel Cell (SOFC) then, the output characteristic curve of gained battery as shown in Figure 4; Six, the system 16 that forms with electric impedance analyzer and electrochemical interface instrument tests the internal resistance of Solid Oxide Fuel Cell (SOFC) monocells, and (area is than resistance, unit: Ω .cm to draw resistance on ceramic diaphragm 12 unit surfaces
2).
As shown in Figure 4, Solid Oxide Fuel Cell (SOFC) more than 1V, shows that the YSZ diaphragm is fine and close air-locked at the open circuit voltage of 650～900 ℃ of warm areas; Peak power output 800 ℃ and 900 ℃ is not 344.6 mWcm
-2And 501.6mWcm
-2, demonstrate good working performance, at 900 ℃, the area of electrolyte membrane part is 0.20 Ω .cm than resistance
2
Adopt the ceramics powder of other material to utilize method of the present invention to prepare ceramic diaphragm, also in protection scope of the present invention.
Claims (9)
1, a kind of preparation method of thin ceramic film, its step comprises: step 1, assembly jig: put into briquetting (2) in mould (1); It is characterized in that step 2, buffer layer moulding: sprinkle the buffering material of nano level particle diameter on briquetting (2), insert formpiston (3) then in mould (1), pressurization gently flattens described buffering material, forms buffer layer (4); Three, add ceramics powder: the ceramics powder of micron order particle diameter evenly is sprinkled upon the top of buffer layer (4), forms diaphragm bisque (5), wherein the quality of the ceramics powder of the described micron order particle diameter on every square centimeter is 10mg～100mg on the cross section of mould (1); Four, dry-pressing formed: using tabletting machine is 10～800MPa at pressure, to diaphragm bisque (5) pressurization 0.1～10min, forms ceramic membrane base (6); Five, the demoulding: with ceramic membrane base (6) when mould (1) takes out, utilize ceramic membrane base (6) to realize automatic separation of ceramic membrane base (6) and buffer layer (4), thereby obtain independently ceramic membrane base (6) with the difference of buffer layer (4) swell increment in knockout course; Six, high temperature sintering: the ceramic membrane base (6) after the demoulding is placed in the high-temperature electric resistance furnace, be warming up to 1000～1600 ℃ of sintering temperatures rapidly, with ceramic membrane base (6) densified sintering product, ceramic membrane base (6) furnace cooling is taken out to room temperature, can obtain required ceramic diaphragm, the material of buffering described in the moulding of step 2 buffer layer mainly is made up of the ceramics powder and the activated carbon powder of the nano level particle diameter that is used to prepare ceramic diaphragm, the particle diameter of the ceramics powder of described nano level particle diameter is 5～500nm, and the quality of described activated carbon powder accounts for 1～20% of described buffering material total mass.
2, the preparation method of a kind of thin ceramic film according to claim 1 is characterized in that step 3 adds a kind of in micron powder that the ceramics powder of the described micron order particle diameter in the ceramics powder is a yttria-stabilized zirconia and the aluminium sesquioxide micron order ceramics powder.
3, the preparation method of a kind of thin ceramic film according to claim 1, it is characterized in that the method for taking out ceramic membrane base (6) in the step 5 demoulding is: mould (1) is reversed, add compressing tablet cover (8) in the upper end of mould (1), utilize tabletting machine that compressing tablet cover (8) is pressurizeed again, make formpiston (3) relative movement take place the related buffer layer of ceramic membrane base (6) (4) is ejected mould (1) with mould (1).
4, the preparation method of a kind of thin ceramic film according to claim 1, it is characterized in that step 3 adds to have prepared in the ceramics powder needs the process that vacuumizes again behind the diaphragm bisque (5), the described process that vacuumizes is: the bleeding point (7) of mould (1) is connected with vacuum pump, energising vacuumizes 1～10min, removes the gas in the diaphragm bisque (5).
5, the preparation method of a kind of thin ceramic film according to claim 1, it is characterized in that heating up rapidly in the step 6 high temperature sintering is meant that temperature rise rate is 3～20k/min; The high temperature sintering time is 3.5～4.5h.
6, the preparation method of a kind of thin ceramic film according to claim 1, it is characterized in that the material of buffering described in the moulding of step 2 buffer layer also comprises nickel oxide powder, the mean diameter of described nickel oxide powder is at 5～20nm, and the quality of described nickel oxide powder accounts for 40～50% of described buffering material total mass.
7, the preparation method of a kind of thin ceramic film according to claim 1, it is characterized in that the preparation method of the material of buffering described in the moulding of step 2 buffer layer is: the powder mixes that will form described buffering material is ground 10～30min; The thickness of buffer layer described in the step 2 (4) is 0.5～3mm.
8,, it is characterized in that the diameter of the mould (1) that step 1 is used is 13mm according to the preparation method of claim 1,2,5,6 or 7 described a kind of thin ceramic films; Be the nickel oxide powder of 5～20nm, the nanoscale powder of 8% yttria-stabilized zirconia and the mixed that activated carbon powder by mass ratio 5: 5: 1 with median size in the step 2, and adopting agate mortar to grind the buffering material that 20min makes the nano level particle diameter, the thickness of the buffer layer (4) that described buffering material forms is 1～3mm; The ceramics powder of the described micron order particle diameter in the step 3 is the micron powder of 8% yttria-stabilized zirconia of 0.04g, and the described time that vacuumizes is 2min; The pressure that described tabletting machine in the step 4 produces is 200MPa, and be 1min clamping time; In the step 6, described ceramic membrane base (6) is placed on and places 1400 ℃ high-temperature electric resistance furnace on the alumina ceramic chip, and is warmed up to 1600 ℃ with the speed of 3～10K/min, keeps four hours.
9, according to the preparation method of claim 1,2 or 7 described a kind of thin ceramic films, it is characterized in that in the step 2 mixed that nanoscale powder and activated carbon powder with 8% yttria-stabilized zirconia by mass ratio are 10: 1, and adopting agate mortar to grind the buffering material that 30min makes the nano level particle diameter, the thickness of the buffer layer (4) that described buffering material forms is 3mm; The ceramics powder of the described micron order particle diameter in the step 3 is the micron powder of 8% yttria-stabilized zirconia of 0.03g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100103051A CN1328218C (en) | 2005-09-06 | 2005-09-06 | Thin ceramic film preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100103051A CN1328218C (en) | 2005-09-06 | 2005-09-06 | Thin ceramic film preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1765831A CN1765831A (en) | 2006-05-03 |
| CN1328218C true CN1328218C (en) | 2007-07-25 |
Family
ID=36741977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100103051A Expired - Fee Related CN1328218C (en) | 2005-09-06 | 2005-09-06 | Thin ceramic film preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1328218C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372807C (en) * | 2006-09-01 | 2008-03-05 | 哈尔滨医科大学 | Shaping method of nanometer bioceramic artificial joint |
| CN102371616B (en) * | 2011-08-16 | 2013-10-30 | 武汉凡谷电子技术股份有限公司 | Ceramic body dry-pressing and forming process |
| CN103072189A (en) * | 2011-11-18 | 2013-05-01 | 常熟市创新陶瓷有限公司 | Ceramic dry pressing mold |
| CN105047974B (en) * | 2015-07-22 | 2019-02-12 | 成都先进金属材料产业技术研究院有限公司 | The compression molding method of the sticky powder of nanometer |
| CN105547775B (en) * | 2015-12-11 | 2019-01-22 | 平高集团有限公司 | Micro-crack defect standard test block manufacturing method and compacting tool set |
| CN107139313B (en) * | 2017-06-09 | 2019-03-22 | 长安大学 | A kind of intelligence tablet press machine |
| CN112638842A (en) * | 2018-06-08 | 2021-04-09 | 国立研究开发法人产业技术综合研究所 | Brittle material structure |
-
2005
- 2005-09-06 CN CNB2005100103051A patent/CN1328218C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Low-temperature SOFCs based onGd0.1Ce0.9O1.95fabricated by dry pressing Changrong Xia Meilin Liu,Solid State Ionics,Vol.第144卷 No.3.4 2001 * |
| Low-temperature SOFCs based onGd0.1Ce0.9O1.95fabricated by dry pressing Changrong Xia Meilin Liu,Solid State Ionics,Vol.第144卷 No.3.4 2001;SOFC电解质薄膜YSZ制备技术 韩敏芳 李伯涛 彭苏萍 刘丽俭，电池，第32卷第3期 2002;用于燃料电池的氧化锆薄膜制备方法进展 贾莉 吕喆 黄喜强 李国卿 苏文辉，电源技术，第28卷第7期 2004 * |
| SOFC电解质薄膜YSZ制备技术 韩敏芳 李伯涛 彭苏萍 刘丽俭，电池，第32卷第3期 2002 * |
| 用于燃料电池的氧化锆薄膜制备方法进展 贾莉 吕喆 黄喜强 李国卿 苏文辉，电源技术，第28卷第7期 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1765831A (en) | 2006-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1328218C (en) | Thin ceramic film preparation method | |
| JP2719049B2 (en) | Method for producing lanthanum chromite membrane and method for producing interconnector for solid oxide fuel cell | |
| US9962918B2 (en) | Production method for a support type coating membrane using tape casting | |
| CN103236548B (en) | Preparation method of multihole anode support of solid oxide fuel cell | |
| CN101306954B (en) | Method for preparing porous ceramic support | |
| CN102593478B (en) | Method for manufacturing multilayer thin-film solid oxide fuel cell | |
| TWI620376B (en) | Portable flame electric generation device, metal-supported solid oxide fuel cell and manufacturing methods thereof | |
| CN1913208B (en) | Middle-temperature solid oxide fuel cell system material and its cell and preparation method | |
| CN103390739A (en) | Solid oxide fuel cell cerium-oxide-based electrolyte barrier layer and preparation method thereof | |
| CN112542591B (en) | Solid fuel cell and method for manufacturing the same | |
| CN1409427A (en) | PEN multilayer film of middle temperature solid oxide fuel cell and its producing method | |
| CN103151548A (en) | Solid oxide fuel cell with Al2O3-YSZ electrolyte membrane and preparation method thereof | |
| CN112952112A (en) | Sintering method of solid oxide fuel cell | |
| JP2002175814A (en) | Manufacturing method of fuel electrode for solid electrolyte type fuel cell, the solid electrolyte type fuel cell and its manufacturing method | |
| JP2001283877A (en) | Unit cell for solid electrolytic fuel battery and its manufacturing method | |
| Hongyan et al. | Preparation and characterization of La0. 8Sr0. 04Ca0. 16Co0. 6Fe0. 4O3-δ-La0. 9Sr0. 1 Ga0. 8Mg0. 2O3 composite cathode thin film for SOFC by slurry spin coating | |
| CN109585914A (en) | The preparation method of oxide solid electrolyte sheet and the solid state battery prepared using this method | |
| CN1320677C (en) | Method of preparing yttrium oxide stable zirconium oxide electrolyte film | |
| CN104577142A (en) | Preparation method of solid oxide fuel cell gradient structure cathode film | |
| CN111416138A (en) | Proton ceramic membrane fuel cell and preparation method thereof | |
| JP3643006B2 (en) | Solid oxide fuel cell cell | |
| JP4367843B2 (en) | Fuel electrode, electrochemical cell, and method of manufacturing fuel electrode | |
| CN111370713B (en) | Method for forming solid oxide fuel cell substrate | |
| CN109346752B (en) | Preparation method of electrolyte-supported zirconium-based electrolyte film of solid oxide fuel cell | |
| KR102247782B1 (en) | A manufacturing method of solid oxide fuel cell via calendering process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |