CN101654364B - Method for extruding tubular ceramic products by virtue of composite thermoplastic medium - Google Patents
Method for extruding tubular ceramic products by virtue of composite thermoplastic medium Download PDFInfo
- Publication number
- CN101654364B CN101654364B CN200910092907A CN200910092907A CN101654364B CN 101654364 B CN101654364 B CN 101654364B CN 200910092907 A CN200910092907 A CN 200910092907A CN 200910092907 A CN200910092907 A CN 200910092907A CN 101654364 B CN101654364 B CN 101654364B
- Authority
- CN
- China
- Prior art keywords
- pipe
- hours
- temperature
- ceramic products
- solvent
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000004902 Softening Agent Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007767 bonding agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004200 microcrystalline wax Substances 0.000 claims description 2
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims 3
- 150000002148 esters Chemical class 0.000 claims 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims 1
- -1 titanic acid ester Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 5
- 239000004014 plasticizer Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 9
- 238000005245 sintering Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- YMVZSICZWDQCMV-UHFFFAOYSA-N [O-2].[Mn+2].[Sr+2].[La+3] Chemical compound [O-2].[Mn+2].[Sr+2].[La+3] YMVZSICZWDQCMV-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a method for extruding tubular ceramic products by virtue of composite thermoplastic medium; low-temperature binders, plasticiser, lubricating agents, surface active agents and solvent are pre-mixed, and the mixture is melted down by heating, and is stirred uniformly; ceramic powder material is added in the mixture by one to four times, and the mixture is stirred uniformly until the solvent is completely volatilized, the mixture is stirred at the temperature of 70-90 DEG C for 1-10 hours, and high-temperature binders are added in after the temperature in raised to 140-170 DEG C, and then the temperature is reduced to 70-90 DEG C, and the mixture is stirred for 2-10 hours to form ceramic mud; and then the ceramic mud is decayed for 12-48 hours at the temperature of 100-130 DEG C in a vacuum drying chamber, the ceramic mud is refined and carries out tube extrusion, so as to form a tube blank; the tube blank is soaked with the solvent for 12-48 hours at the normal temperature, or is bathed by constant-temperature water for 2-12 hours at the temperature of 40-90 DEG C, the dried tube blank carries out rubber discharge and is sintered into a ceramic body. The method is suitable for preparing branch tubes with long and thin walls or blind tubes, and the production efficiency and product quality can be ensured at the same time.
Description
Technical field
The present invention relates to a kind of forming technique of tubular ceramic products, relate in particular to a kind of method by the composite thermoplastic medium extruding tubular ceramic products.
Background technology
Tubular ceramic products is used in industry very extensively, like tubular type electronic component, tubular heater, thermocouple protection cover, tubular solid oxide fuel cell, tubular type oxygen permeable film or the like, has all used slight ceramic tube.
The forming technique of slight ceramic tube of the prior art mainly contains following several kinds:
Injection forming, extrusion moulding, extrude after isostatic pressing etc. again, these three kinds of tubular type forming process of ceramics technology are the technology of comparative maturity in the prior art, all possess himself distinctive advantage.
There is following shortcoming at least in above-mentioned prior art:
Production efficiency and quality product can not be guaranteed simultaneously, are difficult to moulding blind pipe or the like.
Summary of the invention
The purpose of this invention is to provide a kind ofly fast, simply and efficiently by the method for composite thermoplastic medium extruding tubular ceramic products, this method can prepare pipe (comprising siphunculus and blind pipe) elongated and that wall is thin.
The objective of the invention is to realize through following technical scheme:
Method by the composite thermoplastic medium extruding tubular ceramic products of the present invention comprises step:
A, with low temperature bonding agent, softening agent and lubricant, tensio-active agent, solvent pre-mixing, heating makes its fusing, and stirs;
B, divide 1～4 time to add ceramic powder, and stir, volatilize fully to solvent;
C, 70～90 ℃ down stir 1～10 hour after, add high-temperature agglomerant after being warmed up to 140～170 ℃, be cooled to 70～90 ℃ again, stirring becomes pug after 2～10 hours;
D, old homogenizing: with said pug in vacuum drying oven 100～130 ℃ old 12～48 hours, back chopping is subsequent use;
E, concise pug also squeeze pipe: amount is as required selected said pug for use; Descend concise 2～5 times at 110～140 ℃; Afterwards; Carry out five sections temperature controls by 60～90 ℃, 80～110 ℃, 90～115 ℃, 100～125 ℃, 110～130 ℃, under vacuumizing, squeeze pipe afterwards, process the pipe that needs shape;
F, solvent soaking degreasing and drying: said pipe was soaked 12～48 hours with solvent at normal temperatures, or at 40～90 ℃ of following waters bath with thermostatic control 2～12 hours, after drying 6～24 hours;
G, binder removal and sinter porcelain into: with dried pipe binder removal and sinter porcelain body into.
Technical scheme by the invention described above provides can be found out; Method by the composite thermoplastic medium extruding tubular ceramic products of the present invention; Because at first with low temperature bonding agent, softening agent and lubricant, tensio-active agent, solvent pre-mixing, heating makes its fusing, and stirs; Divide then to add ceramic powder for 1～4 time, and stir, volatilize fully to solvent, and 70～90 ℃ stir 1～10 hour down after, add high-temperature agglomerant after being warmed up to 140～170 ℃, be cooled to 70～90 ℃ again, stirring becomes pug after 2～10 hours; Afterwards with pug in vacuum drying oven 100～130 ℃ old 12～48 hours, carry out concise pug again and squeeze pipe, process pipe; Pipe was soaked 12～48 hours with solvent at normal temperatures, or 40～90 ℃ of following waters bath with thermostatic control 2～12 hours, dried pipe binder removal also sintered porcelain body into.Be applicable to the siphunculus or the blind pipe of the elongated thin-walled of preparation, production efficiency and quality product can be guaranteed simultaneously.
Embodiment
Method by the composite thermoplastic medium extruding tubular ceramic products of the present invention, its preferable embodiment comprises step:
1, with low temperature bonding agent, softening agent, lubricant, the pre-mixing of tensio-active agent agent solvent, heating makes its fusing, stirs.
Wherein the low temperature bonding agent can be paraffin, and its consumption can be 10～30% of solid powder (ceramic powder) weight;
Wherein softening agent and lubricant can be following one or several, and its consumption is 0.3～5% of a solid powder weight: Witcizer 300, diethyl phthalate, DOP, Triple Pressed Stearic Acid, class of department class, oleic acid, sad, microcrystalline wax, metatitanic acid fat, silane, vegetables oil;
Wherein solvent can be following one or several, and its consumption is 0～50% of a solid powder weight: distilled gasoline, diesel oil, normal heptane;
2, divide 1～4 time and add ceramic powder, stir, volatilize fully to solvent.
3, can use two roller stirrers 70～90 ℃ stir 1～10 hour after, add high-temperature agglomerant after being warmed up to 140～170 ℃, be cooled to 70～90 ℃ again, stirred 2～10 hours, certain solvent and sticker can volatilize in this process.
Wherein high-temperature agglomerant can be following one or several, and its consumption is 5～20% of a solid powder weight: Vilaterm, Vestolen PP 7052, Atactic Polypropelene, PS, Rohm tech inc, ethylene vinyl acetate copolymer, ethylene acrylic second resin copolymer;
4, old homogenizing, with the pug after stirring in vacuum drying oven 100～130 ℃ old 12～48 hours, the back chopping is subsequent use.
5, concise pug can descend concise 2～5 times at 110～140 ℃ in screw-type extruder earlier, makes it more even before squeezing pipe.
6, squeeze pipe, can divide five sections temperature controls, be respectively 60～90 ℃, 80～110 ℃, 90～115 ℃, 100～125 ℃, 110～130 ℃.Add a suitable type head, control screw-type extruder rotating speed squeezes vitrified pipe on the stainless steel tubular axis vacuumizing down.
7, behind the cool to room temperature, pipe is taken off, can use special end socket mould, under the situation of heating, pipe one end is sealed, process blind pipe.
8, solvent soaking degreasing and drying: can use one or more solvents such as distilled gasoline, diesel oil, heptane to soak at normal temperatures 12～48 hours, or water bath with thermostatic control (40～90 ℃) 2～12 hours, remove most of paraffin, softening agent and lubricant.After drying 6～24 hours.
9, binder removal and sinter porcelain into burns till porcelain body with dried pipe according to certain binder removal and sintering schedule.
10, be machined to the product necessary requirement.
The present invention is a kind of method of extruding tubular ceramic products of ability widespread usage; Be applicable to the siphunculus or the blind pipe of the elongated thin-walled of preparation; Also be applicable to fine and close pipe of preparation or perforated tube; Be particularly useful for making the tubular module of SOFC (SOFC), the tubular module of composite conductor oxygen-permeating film etc.Prepared tube outer diameter can be φ 10～30mm, and thickness of pipe is 1～5mm, and length is 100～2000mm etc.Wherein:
SOFC (SOFC) is the electrochemical generating unit that a kind of chemical energy with fuel is converted into electric energy, mainly contains tubular structure and plate armature at present.The advantage of tubular structure: intensity is high, and without elevated-temperature seal, enlarge easily and produce, the high-temperature machinery good stability, anti-thermal shock resistance properties is good.Siemens-Westinghouse Electric adopts extruding-out process to prepare strontium lanthanum manganese oxide (LSM) cathode branch stay tube, uses electrochemical vapour deposition (EVD) (EVD) technology preparation compact YSZ dielectric substrate behind the sintering again, and its monocell length can reach 1.5～2m.
Composite conductor oxygen-permeating film is one type of ceramic membrane that at high temperature has electronics and oxygen conduction simultaneously.Its oxygen flow process is not with the transmission of molecular oxygen form but conducts oxygen with the form of ion-oxygen through oxygen vacancies that the diffusion selectivity to oxygen is 100% in theory.The same with SOFC, oxygen permeable film is tube-separating type structure and plate armature also, and the tubular type oxygen permeable film is because of its distinctive advantage, dynamically provides on the projects such as oxygen at methane portion oxidation reformation hydrogen production and oxidative coupling reaction to be widely used.It is the oxygen permeable film pipe of 1.52m that U.S. Praxair company adopts extruding-out process to prepare length, and is assembled into reactor drum.
The present invention can prepare the vitrified pipe of the ability that has specific characteristics in said product well.
Specific embodiment one:
Preparation YSZ dense electrolyte blind pipe, step is following:
With YSZ powder and paraffin, Triple Pressed Stearic Acid, department class 40 is blended in the distilled gasoline fully stirring and dissolving, volatilizees fully to gasoline.Wherein the add-on of paraffin, Triple Pressed Stearic Acid, class of department 40, distilled gasoline is respectively 18%, 2%, 0.5%, 33% of solid powder weight.
With two roller stirrers 80 ℃ stir 2 hours after, add Vilaterm after being warmed up to 160 ℃, be cooled to 80 ℃ again, stir and obtained pug in 6 hours.Can certain solvent and the sticker of volatilization in this process.Wherein poly add-on is 10% of a solid powder weight.
Pug was left standstill under 120 ℃ in vacuum drying oven old 24 hours, after to be cut into fragment subsequent use.
In screw-type extruder under 130 ℃ with concise 2 times of pug, make it more even.
Add a suitable type head, the control rotating speed vacuumizes down vitrified pipe is squeezed on the stainless steel tubular axis, and five sections temperature controls are respectively 80 ℃, and 90 ℃, 100 ℃, 110 ℃, 115 ℃, the green compact external diameter is φ 20mm, and length is 300mm, and wall thickness is 2mm.
Behind the cool to room temperature, pipe is taken off,, under the situation of heating, pipe one end is sealed, process blind pipe with special end socket mould.
Pipe is placed distilled gasoline, soaked at normal temperatures 48 hours, outwell gasoline, dry 12 hours.
According to certain binder removal system and the sintering schedule of YSZ pipe is burnt till porcelain.Sintering temperature is 1300 ℃.
Processing is polished to the product necessary requirement.
Adopt the YSZ ionogen blind pipe of this method preparation, straight degree and circularity are good, and wall thickness is even, and intensity is high, and density is high, and specific density reaches 97%, and shrinking percentage is about 20%, and the pipe that obtains at last is of a size of: external diameter φ 16mm, length 250mm, wall thickness 1.5mm.Satisfy the requirement of dense electrolyte pipe.
Specific embodiment two:
Preparation YSZ/NiO porous anode supports blind pipe, comprising:
Adopt carbon dust as pore-forming material, raw material weight is than being YSZ: NiO: C=1: 1: 0.3.
All the other process methodes before the sintering are identical with specific embodiment one with step.
According to certain binder removal and the pre-burning of row's carbon system, at 950 ℃ of following pre-burning pipes, obtain porous anode and support blind pipe, pipe is of a size of: external diameter φ 20mm, length 400mm, wall thickness 2mm; Porosity is 30%.Its directly spend and circularity good, wall thickness is even, and certain self-supporting strength is arranged, pipe does not have to shrink basically, satisfies the requirement of anode support tube.
Specific embodiment three:
Preparation YSZ/LSM porous cathode supports blind pipe, and pipe is of a size of: external diameter φ 20mm, and length 600mm, wall thickness 2mm, porosity is 30%, comprising:
Adopt carbon dust as pore-forming material, raw material weight is than being YSZ: LSM: C=1: 1: 0.3.
Calcined temperature is 900 ℃, and all the other process methodes are identical with specific embodiment two with step.
The cathode support blind pipe that obtains, pipe is of a size of: external diameter φ 20mm, length 600mm, wall thickness 2mm; Porosity is 30%.Its directly spend and circularity good, wall thickness is even, and certain self-supporting strength is arranged, pipe does not have to shrink basically, satisfies the requirement of anode support tube.
Specific embodiment four:
Preparation Ba
1.0Co
0.7Fe
0.2Nb
0.1O
3-δ(BCFN) the fine and close blind pipe of oxygen permeable film, pipe is of a size of: external diameter 16mm, length 700mm, wall thickness 1.5mm comprises:
Under 1140 ℃, sinter vitrified pipe into, except that sintering, process for making is identical with specific embodiment one with step.
The vitrified pipe density that makes is high, and specific density is 95%, and Guan Zhidu and circularity are good, and wall thickness is even, and intensity is high.Shrinking percentage is about 30%.Can know the surface compact atresia from the SEM photo, can see tangible crystal boundary, grain-size is at 1～5 μ m, and section has a small amount of closed pores and a small amount of defective, is mostly along brilliant fracture.Adopt its specific conductivity performance of direct current four end electrode methods test, 900 ℃ reach 10S/cm.
Compare with existing vitrified pipe technology of preparing, the present invention has following advantage:
Be fit to serialization, robotization, mechanize production, production efficiency is high, production cost is relatively low; Be fit to extrude ceramic of compact pipe (do not add pore-forming material, density is 90%～99%) or porous ceramic pipe (add pore-forming material, porosity is 10%～60%), applied widely; Be fit to extrude elongated thin-wall ceramic pipe, external diameter is φ 10～30mm, and length is 100～2000mm, and thickness is 1～5mm, and wall thickness is even, and pipe circularity is good, and intensity is higher, and end socket is processed blind pipe easily; Thermoplastic polymer then has the characteristic of anti-repeated heating, and they are softening when heating, and hardening when cooling can qualitative change not take place with thermal cycling.Therefore pug ability recirculation utilization cuts the waste; Easily densified sintering product (not adding pore-forming material) with burn till porous (adding pore-forming material) vitrified pipe, sintering is not yielding, the yield rate height burns till the blank strength height.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.
Claims (8)
1. the method by the composite thermoplastic medium extruding tubular ceramic products is characterized in that, comprises step:
A, with low temperature bonding agent, softening agent and lubricant, tensio-active agent, solvent pre-mixing, heating makes its fusing, and stirs;
B, divide 1～4 time to add ceramic powder, and stir, volatilize fully to solvent;
C, 70～90 ℃ down stir 1～10 hour after, add high-temperature agglomerant after being warmed up to 140～170 ℃, be cooled to 70～90 ℃ again, stirring becomes pug after 2～10 hours;
D, old homogenizing: with said pug in vacuum drying oven 100～130 ℃ old 12～48 hours, back chopping is subsequent use;
E, refining pug also squeeze pipe: amount is as required selected said pug for use; 110～140 ℃ of following refinings 2～5 times; Afterwards; Carry out five sections temperature controls by 60～90 ℃, 80～110 ℃, 90～115 ℃, 100～125 ℃, 110～130 ℃, under vacuumizing, squeeze pipe afterwards, process the pipe that needs shape;
F, solvent soaking degreasing and drying: said pipe was soaked 12～48 hours with solvent at normal temperatures, or at 40～90 ℃ of following waters bath with thermostatic control 2～12 hours, after drying 6～24 hours;
G, binder removal and sinter porcelain into: with dried pipe binder removal and sinter porcelain body into;
In the said steps A:
Said low temperature bonding agent comprises paraffin, and its consumption is 10～30% of a ceramic powder weight;
Said softening agent and lubricant comprise following one or more, its consumption is 0.3～5% of a ceramic powder weight: Witcizer 300, diethyl phthalate, DOP, hard ester acid, oleic acid, sad, microcrystalline wax, titanic acid ester, silane, vegetables oil;
Said solvent comprise following one or more, its consumption be ceramic powder weight more than 0% to 50%, do not comprise 0% of ceramic powder weight: distilled gasoline, diesel oil, normal heptane;
Among the said step C:
Stir with two roller stirrers; Said high-temperature agglomerant comprise following one or more, its consumption is 5～20% of a ceramic powder weight: Vilaterm, Vestolen PP 7052, PS, Rohm tech inc, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer.
2. the method by the composite thermoplastic medium extruding tubular ceramic products according to claim 1 is characterized in that, in the said step e:
Earlier in screw-type extruder, carry out refining, make it more even before squeezing pipe; Selecting for use afterwards needs the type of shape head, through said screw-type extruder pipe is squeezed on the stainless steel tubular axis; Behind cool to room temperature, pipe is taken off.
3. the method by the composite thermoplastic medium extruding tubular ceramic products according to claim 2 is characterized in that, the said pipe in the step e is sealed an end under the situation of heating, processes blind pipe.
4. the method by the composite thermoplastic medium extruding tubular ceramic products according to claim 1; It is characterized in that; Solvent in the said step F comprise following one or more: distilled gasoline, diesel oil, heptane are used to remove most of paraffin, softening agent and lubricant.
5. the method by the composite thermoplastic medium extruding tubular ceramic products according to claim 1 and 2 is characterized in that, prepared tubular ceramic products comprises the siphunculus and/or the blind pipe of elongated thin-walled.
6. according to each described method of claim 1 to 4, it is characterized in that prepared tubular ceramic products comprises fine and close pipe and/or perforated tube by the composite thermoplastic medium extruding tubular ceramic products.
7. the method by the composite thermoplastic medium extruding tubular ceramic products according to claim 6 is characterized in that, prepared tubular ceramic products comprises the tubular module and/or the oxygen permeable film tubular module of SOFC.
8. according to each described method by the composite thermoplastic medium extruding tubular ceramic products of claim 1 to 4, it is characterized in that the external diameter of prepared tubular ceramic products is φ 10～30mm, thickness of pipe is 1～5mm, and length is 100～2000mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910092907A CN101654364B (en) | 2009-09-10 | 2009-09-10 | Method for extruding tubular ceramic products by virtue of composite thermoplastic medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910092907A CN101654364B (en) | 2009-09-10 | 2009-09-10 | Method for extruding tubular ceramic products by virtue of composite thermoplastic medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101654364A CN101654364A (en) | 2010-02-24 |
| CN101654364B true CN101654364B (en) | 2012-10-24 |
Family
ID=41708854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910092907A Expired - Fee Related CN101654364B (en) | 2009-09-10 | 2009-09-10 | Method for extruding tubular ceramic products by virtue of composite thermoplastic medium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101654364B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2637252C1 (en) * | 2016-09-13 | 2017-12-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Пензенский государственный университет" (ФГБОУ ВО "Пензенский государственный университет") | Complex binder for forming roducts from non-plastic ceramic powders |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102642240B (en) * | 2012-04-25 | 2013-12-25 | 深圳顺络电子股份有限公司 | Manufacture method of ferrite core blank and ferrite core |
| CN105605333A (en) * | 2016-03-04 | 2016-05-25 | 孙欣 | Pipeline for conveying pulverized coal |
| CN105570563A (en) * | 2016-03-04 | 2016-05-11 | 孙欣 | Dust removal pipeline |
| CN105587944A (en) * | 2016-03-04 | 2016-05-18 | 孙欣 | Denitration pipeline |
| CN106887617B (en) * | 2017-02-11 | 2019-08-06 | 佛山索弗克氢能源有限公司 | Fuel cell |
| CN107845822B (en) * | 2017-11-03 | 2020-08-28 | 广东康荣高科新材料股份有限公司 | Fuel cell anode support extrusion pug and preparation method thereof |
| CN108726995A (en) * | 2018-04-16 | 2018-11-02 | 司马云 | A kind of board-like ceramic filtration membrane of hollow structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460661A (en) * | 2003-06-03 | 2003-12-10 | 浙江大学 | Method for preparing functional gradient material by adopting doctor-blade casting process |
| CN101293776A (en) * | 2007-04-27 | 2008-10-29 | 四川君立投资集团有限责任公司 | Industrial standard blackbody molding method |
| CN101381241A (en) * | 2008-10-16 | 2009-03-11 | 武汉科技大学 | Porous breathable refractory materials for upper nozzle and production method thereof |
-
2009
- 2009-09-10 CN CN200910092907A patent/CN101654364B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460661A (en) * | 2003-06-03 | 2003-12-10 | 浙江大学 | Method for preparing functional gradient material by adopting doctor-blade casting process |
| CN101293776A (en) * | 2007-04-27 | 2008-10-29 | 四川君立投资集团有限责任公司 | Industrial standard blackbody molding method |
| CN101381241A (en) * | 2008-10-16 | 2009-03-11 | 武汉科技大学 | Porous breathable refractory materials for upper nozzle and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2007-290951A 2007.11.08 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2637252C1 (en) * | 2016-09-13 | 2017-12-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Пензенский государственный университет" (ФГБОУ ВО "Пензенский государственный университет") | Complex binder for forming roducts from non-plastic ceramic powders |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101654364A (en) | 2010-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101654364B (en) | Method for extruding tubular ceramic products by virtue of composite thermoplastic medium | |
| Hedayat et al. | Review on fabrication techniques for porous electrodes of solid oxide fuel cells by sacrificial template methods | |
| CN107112545B (en) | Anode for solid oxide fuel cell, method for producing same, and method for producing electrolyte layer-electrode assembly for fuel cell | |
| CN1212788A (en) | Low cost stable air electrode material for high temp. solid oxide electrolyte electrochemical cells | |
| CN1961443A (en) | Nickel foam and felt-based anode for solid oxide fuel cells | |
| JP2016031933A (en) | Proton-conducting laminate structure | |
| KR101179130B1 (en) | Segment-in-series type sofc sub-module, preparation method thereof and segment-in-series type sofc module using the same | |
| JP2009037874A (en) | Manufacturing method of air electrode support type single cell for intermediate temperature actuating solid oxide fuel cell | |
| KR101341969B1 (en) | Segment-in-series type sofc sub-module, manufacturing method thereof and segment-in-series type sofc module using the same | |
| Sotomayor et al. | Characterization of 430L porous supports obtained by powder extrusion moulding for their application in solid oxide fuel cells | |
| CN107180978A (en) | A kind of tubular solid oxide fuel cell anode support and preparation method thereof | |
| JP6830696B2 (en) | Electrochemical reaction electrode with SiC ceramic film and its manufacturing method | |
| CN104518231A (en) | Solid oxide fuel cell stack | |
| Suzuki et al. | Development of cube-type SOFC stacks using anode-supported tubular cells | |
| Jardiel et al. | Fabrication of 8-YSZ thin-wall tubes by powder extrusion moulding for SOFC electrolytes | |
| JP4305898B2 (en) | Electrochemical equipment | |
| Hanifi et al. | Development of redox resistant fully infiltrated tubular SOFCs | |
| JP2000106192A (en) | Substrate tube for fuel cell and its material | |
| CN104347886B (en) | Fuel cell ceramic proton exchange membrane material and use thereof | |
| CN103613066B (en) | Technique for preparing synthetic gas from wet carbon dioxide by electrocatalysis | |
| KR20130019170A (en) | Preparation method of anode support for tubular solid oxide fuel cell, anode support prepared therewith and tubular solid oxide fuel cell comprising the same | |
| JP2012209152A (en) | Method for manufacturing anode support type solid oxide fuel cell | |
| Ruiz‐Morales et al. | Cost‐Effective Microstructural Engineering of Solid Oxide Fuel Cell Components for Planar and Tubular Designs | |
| Amiri et al. | Effect of pore formers characteristics and melt infiltration parameters on microstructure and electrical properties of BaCe0. 7Zr0. 1Y0. 2O3− δ-carbonate composite electrolyte | |
| Suzuki et al. | Development of fabrication/integration technology for micro tubular SOFCs |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121024 Termination date: 20160910 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |