CN104860682A - Cofired ceramic heating member preparation technology - Google Patents
Cofired ceramic heating member preparation technology Download PDFInfo
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- CN104860682A CN104860682A CN201410066362.0A CN201410066362A CN104860682A CN 104860682 A CN104860682 A CN 104860682A CN 201410066362 A CN201410066362 A CN 201410066362A CN 104860682 A CN104860682 A CN 104860682A
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Abstract
The invention relates to the technical field of heating member preparation and especially relates to a cofired ceramic heating member preparation technology. The cofired ceramic heating member preparation technology orderly comprises material blending, ball milling, drainage, molding and drying, printing, lamination, sintering and electrode connection. The cofired ceramic heating member preparation technology has simple processes. A blank is sintered under normal pressure in a tunnel kiln-combined reduction sintering atmosphere so that continuous production is realized, production efficiency is high, a liquid sintering method is used, a sintering temperature is low, a production cost is low and large scale production is realized.
Description
Technical field
The present invention relates to the fabricating technology field of heating member, particularly relate to a kind of preparation technology of ceramic heating body of cofired materials.
Background technology
Silicon nitride heating plate is a kind of device in conjunction with high-performance silicon nitride ceramics matrix and long lifetime powerful hot metal heating wire, it is little that it has volume, large and the thermo-efficiency high of power, is also proved to be a kind of safe and reliable heating system by silicon nitride heating plate heat production simultaneously.
Silicon nitride is as a kind of covalent linkage compound, and spread coefficient is little, does not have fusing point, decomposes ammonification and silicon about 2173K, is difficult to sintering.At present, traditional silicon nitride ceramics heating piece is embedded in alpha-silicon nitride powders by tungsten filament to be molded into plates hot pressed sintering and to form, the well heater of this explained hereafter is owing to being subject to process technology limit, and tungsten filament is difficult to location, causes position to offset in moulding process, overall heater is caused to conduct heat uneven, simultaneously because tungsten filament and beta-silicon nitride powder have obvious interface, be difficult to into after sintering and be integrated, tungsten filament and ceramic contact surface form space, form selective oxidation in heat-processed, reduce the work-ing life of fever tablet.The sintering of current silicon nitride ceramics heating piece also has employing reaction sintering and hot pressed sintering, but reaction sintering density is poor, poor mechanical property, although hot pressed sintering density is high, mechanical property is good, and cost is higher, is difficult to scale operation.Therefore, the above problems demand solves.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of and be beneficial to the preparation technology of ceramic heating body that continuous seepage, production efficiency are high, be beneficial to large-scale production, cofired materials that production cost is low.
The present invention is achieved through the following technical solutions.
A preparation technology for the ceramic heating body of cofired materials, comprises following processing step:
A, batch mixing: the Si taking 65-98% by mass percentage
3n
4, 0.1-10% the Y of MgO, 0.1-5%
2o
3, 0.1-5% Al
2o
3, 0.1-5% SiO
2, 0.1-5% La
2o
3, the BN of 0.1-5% mixing and stirring, make ceramic substrate powder;
B, ball milling: the ceramic substrate powder that step a is obtained is added mill ball, solvent and tackiness agent and puts into ball grinder and carries out wet ball grinding, the time of wet ball grinding is 8-24h; Wet ball grinding can improve mill efficiency, and diameter of particle is reduced, and specific surface area increases, increased activity.
C, deaeration: the compound after wet ball grinding in step b is carried out deaeration under vacuum;
D, shaping with drying: the compound casting machine curtain coating in step c to be made ceramic substrate or use and roll film device and be rolled into ceramic substrate, and ceramic substrate is carried out drying;
E, printing: by silk-screen printing technique by resistance slurry printing dried ceramic substrate surface in steps d, resistance slurry forms the heating circuit of reciprocal inflection structure on the surface of ceramic substrate;
F, to laminate: the ceramic substrate that the ceramic substrate obtain a slice steps d and a slice step e are printed with the circuit that generates heat laminates makes base substrate;
G, sintering: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbed insulating powder, then sintered at ambient pressure by the base substrate be embedded in insulating powder with box-type furnace or tunnel furnace, sintering atmosphere is nitrogen and hydrogen gas mixture, and blank sintering obtains ceramic heating body work in-process; Adopt tunnel furnace in conjunction with reductive sintered atmosphere at normal pressure-sintered base substrate, can realize continuous seepage, output becomes every day 48 batches from original every day 1 batch, production efficiency improves 48 times, and continuous prodution is beneficial to energy-conservation, greatly reduces production cost, is beneficial to enterprise and accomplishes scale production; Simultaneously because hydrogen atom radius is very little, be easy to diffusion and the hole elimination that is conducive to holding one's breath, the oxonium ion in aluminum oxide lattice can also be made in a hydrogen atmosphere to lose relatively easily, form room, acceleration oxonium ion spreads, therefore in a hydrogen atmosphere can acceleration of sintering effectively, make ceramic obtain good density.
H, receiving electrode: plating nickel on surface process is carried out at half-finished for ceramic heating body two ends or sidepiece, then soldering extraction electrode is carried out at the position after Nickel Plating Treatment, obtained ceramic heating body finished product.
Wherein, step g sintering is specially: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbed insulating powder, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 5-29%, and the volume percent of nitrogen in mixed gas is 71%-95%, and blank sintering obtains ceramic heating body work in-process.The volume percent of hydrogen is greater than 1%, restitutive protection's effect of mixed gas can be ensured, simultaneously because hydrogen belongs to flammable explosive gas, therefore the volume percent of hydrogen is made to be less than 40%, reduce potential safety hazard, therefore the volume percent of hydrogen 1-40% makes mixed gas can play reductibility protection and explosion-proof effect simultaneously; Hydrogen in the present invention is made for being decomposed by ammonia, higher relative to the nitrogen cost of outsourcing, in mixed gas, therefore makes the volume percent of nitrogen be 60%-99%, higher than the volume percent of the 1-40% of hydrogen, can save production cost further.
Wherein, step g sintering is specially: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbeds insulating powder, and the insulating powder burying burning is Si
3n
4with the mixture of BN, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 10-25%, the volume percent of nitrogen in mixed gas is 75%-90%, control the dew-point temperature of water vapor in mixed gas lower than 50 DEG C, blank sintering obtains ceramic heating body work in-process.
Wherein, step g sinter tunnel furnace used be divided into connect successively binder removal district, sintering zone and cooling zone, the temperature of binder removal district, sintering zone and cooling zone is respectively 300-1300 DEG C, 1600-1850 DEG C, 1850-25 DEG C, base substrate respectively in binder removal district, the sintering time of sintering zone and cooling zone is 3-8h, 1-3h, 8-12h.Replace traditional box-type furnace, because tunnel furnace is divided into binder removal district, sintering zone and cooling zone, make base substrate can realize binder removal successively, the operation of high temperature sintering and cooling, when the blank sintering of last batch is complete, tunnel furnace is without the need to again experiencing long intensification, the base substrate that can drop into again next batch immediately sinters, eliminate box-type furnace need repeatedly heat up when the base substrate that stoking is multiple batches of, the operation of cooling, adopt tunnel furnace can realize continuous circulationization to produce, output becomes every day 48 batches from original every day 1 batch, production efficiency improves 48 times, production efficiency improves greatly, and be more conducive to energy-conservation, greatly reduce production cost, the sintering temperature of 1600-1850 DEG C ensures that firing of ceramic heating body is effective, avoids the hydrogen explosion that high temperature causes simultaneously.
Resistance slurry in step e is made up of the raw material of following mass percent:
Solid formation 70-90%
Carrier 10-30%;
Wherein, solid formation is made up of the raw material of following mass percent:
Conductive phase 60-99%
Glassy phase 1-40%;
Conductive phase is the mixture of one or more in tungsten, manganese, molybdenum;
Glassy phase is made up of the raw material of following mass percent:
Si
3N
465-98%
MgO 0.1-10%
Y
2O
30.1-5%
Al
2O
30.1-5%
SiO
2 0.1-5%
La
2O
30.1-5%
BN 0.1-5%；
Wherein, carrier is made up of the raw material of following mass percent:
Terpineol 350 50-80%
Tributyl citrate 8-30%
Diethylene glycol monobutyl ether amyl acetate 8-30%
Viscotrol C 0.1-2%
Ethyl cellulose 3-10%
Yelkin TTS 0.3-1.5%
Department class 85 0.5-3%.
In resistance slurry, conductive phase plays conduction; Glassy phase grills thoroughly anti-reflection layer and cohesive action for rising during sintering; Carrier mainly provides the effect of conductive phase and glassy phase dispersion, in the constitutive material of carrier, Terpineol 350 and diethylene glycol monobutyl ether amyl acetate are all as solvent, tributyl citrate is as fluidizer, Viscotrol C is as thixotropic agent, and ethyl cellulose is thickening material, and Yelkin TTS and Si Ban 85 are all as tensio-active agent, carrier makes resistance slurry have to be applicable to the rheological property of the viscosity, thixotropy etc. of silk screen printing by materialization effect, the printing precision making silk screen printing can obtain needing and effect.
Terpineol 350 colourless liquid or low melting point clear crystals body, have cloves taste, and its molecular formula is C
10h
18o, molecular weight is 154.2516, and relative density is 0.9337 (20/4 DEG C), and solidification point is 2 DEG C.Specific rotation is [α]-0 ° of 10' ~+0 ° 10 ', and boiling range is 214 ~ 224 DEG C, is refracted as nD (20 DEG C) 1.4825 ~ 1.4850.1 part of Terpineol 350 can be dissolved in the ethanolic soln of 2 parts of (volumes) 70%, is slightly soluble in water and glycerine, can be used as senior solvent.
The chemical name of citric acid is 3-hydroxyl-3-carboxyl pentanedioic acid tri-n-butyl, and be a kind of ester compound, be colourless or weak yellow liquid, its molecular formula is C
18h
32o
7, molar mass is 36044 g/mol, can be mixed with acetone, CCl4, mineral oil, acetic acid, Viscotrol C, alcohol and solvent phase thereof; Water insoluble, nonpoisonous and tasteless, volatility is little, heat-resisting fast light water-fast, good with consistencies such as Vinylite, cellulose acetate, acetoxybutanoic acid Mierocrystalline cellulose, ethyl cellulose, benzyl celluloses, is the good softening agent of plasticising usefulness; Antibacterium of also having does not grow bacterium, nonirritant again, flame retardant resistance and degradability.
Diethylene glycol monobutyl ether amyl acetate is also known as butyl acetic ester, and its molecular formula is C
10h
20o
4, molecular weight is 204.26, and boiling point is 246.4 DEG C (0.101mpa), and flash-point is 116 DEG C, is slightly soluble in water, energy and most of immiscible organic solvent.Diethylene glycol monobutyl ether amyl acetate, owing to having higher boiling point, is beneficial to high temperature sintering.
Viscotrol C is colourless or micro-yellowy clarification thick liquid, and smell is light then micro-pungent, and Viscotrol C is easily molten in ethanol, can mix arbitrarily with dehydrated alcohol, chloroform, ether or Glacial acetic acid; Relative density (d20 DEG C 4 DEG C): 0.9550-0.9700, refractive index (n20 DEG C of D): 1.4765-1.4819, viscosity (E020 DEG C) is greater than 14, zero pour (DEG C) :-10, burning-point (DEG C): 322, iodine number (g iodine/100g oil): 82-86, saponification value (mgKOH/g oil): 176-187, thiocyanogen value: 81-82, total fatty acid content (%) about 96, lipid acid molecular-weight average is 290-300.Viscotrol C has good intermiscibility to nitrocellulose, ethyl cellulose, cellulose acetate butyrate, polymeric amide, fourth trimeric cyanamide (or urea) formaldehyde resin, rosin, shellac etc., the viscosity of resistance slurry can be increased as thixotropic agent, and make it have thixotropy.
Ethyl cellulose is also known as cellulosic ether, and its softening temperature is 135 ~ 155 DEG C, and fusing point is 165 ~ 185 DEG C, bulk specific weight 0.3 ~ 0.4 gram/cc, relative density 1.07 ~ 1.18 grams/cc, it dissolves in more organic solvent, in resistance slurry, play thickening material.
Yelkin TTS belongs to a kind of mixture, it is the one group of filemot oil material be present among animal vegetable tissue and yolk, its constituent comprises phosphoric acid, choline, lipid acid, glycerine, glycolipid, tri-glyceride and phosphatide (as phosphatidylcholine, phosphatidylethanolamine and phosphatidylinositols), and the solubleness of Yelkin TTS in water is lower.In aqueous, according to different hydration (hydration, aquation) and temperature condition, its phosphatide can form liposome, lipid bilayer, micelle (micelles) or plate laminate structure, and therefore Yelkin TTS is the tensio-active agent that one has both sexes (amphoteric) feature.
The molecular formula of class 85 of department is C
60h
108o
8, its molecular weight is 957.51, and its amber oily liquids, has fat note, is dissolved in dimethylbenzene, mineral oil, oleum gossypii seminis and acetone, and relative density is 0.92 ~ 0.98, and fusing point is 10 DEG C, and hydrophilic and oleophilic value (HLB) is 1.8, and viscosity is about 200mPas(25 DEG C).Class 85 of department has fixing hydrophilic and oleophilic group, aligns, can form unimolecular layer at fluid surface in the surface energy of solution, and reduces interfacial tension between two kinds of liquid significantly, and surface tension can be made significantly to decline.
Preferably, the resistance slurry in step e is made up of the raw material of following mass percent:
Solid formation 75-85%
Carrier 15-25%;
Wherein, solid formation is made up of the raw material of following mass percent:
Conductive phase 70-90%
Glassy phase 10-30%;
Conductive phase is the mixture of one or more in tungsten, manganese, molybdenum;
Glassy phase is made up of the raw material of following mass percent:
Si
3N
475-90%
MgO 4-8%
Y
2O
32-4%
Al
2O
32-4%
SiO
2 2-4%
La
2O
32-4%
BN 2-4%；
Wherein, carrier is made up of the raw material of following mass percent:
Terpineol 350 60-70%
Tributyl citrate 12-25%
Diethylene glycol monobutyl ether amyl acetate 12-25%
Viscotrol C 0.5-1.5%
Ethyl cellulose 4-8%
Yelkin TTS 0.5-1.2%
Department class 85 1-2.5%.
More preferred, the resistance slurry in step e is made up of the raw material of following mass percent:
Solid formation 80%
Carrier 20%;
Wherein, solid formation is made up of the raw material of following mass percent:
Conductive phase 80%
Glassy phase 20%;
Conductive phase is the mixture of one or more in tungsten, manganese, molybdenum;
Glassy phase is made up of the raw material of following mass percent:
Si
3N
480%
MgO 7%
Y
2O
33%
Al
2O
32%
SiO
23%
La
2O
32%
BN 3%；
Wherein, carrier is made up of the raw material of following mass percent:
Terpineol 350 65%
Tributyl citrate 14%
Diethylene glycol monobutyl ether amyl acetate 12%
Viscotrol C 1%
Ethyl cellulose 5%
Yelkin TTS 1%
Class 85 2% of department.
Wherein, obtained ceramic heating body is the one in tabular, pole shape, circular tube shaped, and pole shape or circular tube shaped ceramic heating body are rolled by tabular ceramic heating body and form.
Beneficial effect of the present invention is: the preparation technology of the ceramic heating body of cofired materials of the present invention sequentially by batch mixing, ball milling, be filtered dry, shaping and dry, print, laminate, sinter and receiving electrode operation, whole manufacturing process is simple, adopt tunnel furnace in conjunction with reductive sintered atmosphere at normal pressure-sintered base substrate, be beneficial to continuous seepage, production efficiency is high, and be sintered to liquid phase sintering, sintering temperature is low, and production cost is low, is beneficial to and accomplishes scale production; And the heating layer of ceramic heating body of the present invention is by the heating circuit of resistance slurry printing, in the base substrate that ceramic substrate is overrided to form, the position of heating layer is placed in the middle, and evenly, inner combination is fine and close, long service life in heat radiation.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
embodiment 1.
The preparation technology of the ceramic heating body of a kind of cofired materials of the present embodiment, it comprises following processing step:
A, batch mixing: take the Si of 65% by mass percentage
3n
4, the MgO of 10%, the Y of 5%
2o
3, 5% Al
2o
3, 5% SiO
2, 5% La
2o
3, 5% BN and mixing and stirring, make ceramic substrate powder;
B, ball milling: the ceramic substrate powder that step a is obtained is added mill ball, solvent and tackiness agent and puts into ball grinder and carries out wet ball grinding, the time of wet ball grinding is 8h;
C, deaeration: the compound after wet ball grinding in step b is carried out deaeration under vacuum;
D, shaping with drying: the compound casting machine curtain coating in step c to be made ceramic substrate or use and roll film device and be rolled into ceramic substrate, and ceramic substrate is carried out drying;
E, printing: by silk-screen printing technique by resistance slurry printing dried ceramic substrate surface in steps d, resistance slurry forms the heating circuit of reciprocal inflection structure on the surface of ceramic substrate; Resistance slurry is that the solid formation of 70% and the carrier of 30% form by mass percent; Solid formation is that the tungsten of 60% and the glassy phase of 40% form by mass percent; Glassy phase by 65% Si
3n
4, the MgO of 10%, the Y of 5%
2o
3, 5% Al
2o
3, 5% SiO
2, 5% La
2o
3, 5% BN mixing and stirring form; Terpineol 350, the tributyl citrate of 30%, diethylene glycol monobutyl ether amyl acetate, the Viscotrol C of 2%, ethyl cellulose, the Yelkin TTS of 1.5%, the class of department 85 of 3% of 10% of 30% that carrier is 50% by mass percent form;
F, to laminate: the ceramic substrate that the ceramic substrate obtain a slice steps d and a slice step e are printed with the circuit that generates heat laminates makes base substrate;
G, sintering: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbeds insulating powder, and the insulating powder burying burning is Si
3n
4with the mixture of BN, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, tunnel furnace is divided into the binder removal district connected successively, sintering zone and cooling zone, binder removal district, the temperature of sintering zone and cooling zone is respectively 300 DEG C, 1600 DEG C, 25 DEG C, base substrate is respectively in binder removal district, the sintering time of sintering zone and cooling zone is 3h, 1h, 8h, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 1%, the volume percent of nitrogen in mixed gas is 99%, control the dew-point temperature of water vapor in mixed gas lower than 50 DEG C, blank sintering obtains ceramic heating body work in-process,
H, receiving electrode: plating nickel on surface process is carried out at half-finished for ceramic heating body two ends or sidepiece, then soldering extraction electrode is carried out at the position after Nickel Plating Treatment, obtained ceramic heating body finished product.
embodiment 2.
The preparation technology of the ceramic heating body of a kind of cofired materials of the present embodiment, it comprises following processing step:
A, batch mixing: take the Si of 98% by mass percentage
3n
4, the MgO of 0.5%, the Y of 0.5%
2o
3, 0.2% Al
2o
3, 0.3% SiO
2, 0.2% La
2o
3, 0.3% BN and mixing and stirring, make ceramic substrate powder;
B, ball milling: the ceramic substrate powder that step a is obtained is added mill ball, solvent and tackiness agent and puts into ball grinder and carries out wet ball grinding, the time of wet ball grinding is 11h;
C, deaeration: the compound after wet ball grinding in step b is carried out deaeration under vacuum;
D, shaping with drying: the compound casting machine curtain coating in step c to be made ceramic substrate or use and roll film device and be rolled into ceramic substrate, and ceramic substrate is carried out drying;
E, printing: by silk-screen printing technique by resistance slurry printing dried ceramic substrate surface in steps d, resistance slurry forms the heating circuit of reciprocal inflection structure on the surface of ceramic substrate; Resistance slurry is that the solid formation of 90% and the carrier of 10% form by mass percent; Solid formation is that the manganese of 99% and the glassy phase of 1% form by mass percent; Glassy phase by 98% Si
3n
4, the MgO of 0.5%, the Y of 0.5%
2o
3, 0.2% Al
2o
3, 0.3% SiO
2, 0.2% La
2o
3, 0.3% BN mixing and stirring form; Terpineol 350, the tributyl citrate of 8%, diethylene glycol monobutyl ether amyl acetate, the Viscotrol C of 0. 2%, ethyl cellulose, the Yelkin TTS of 0.3%, the class of department 85 of 0.5% of 3% of 8% that carrier is 80% by mass percent form;
F, to laminate: the ceramic substrate that the ceramic substrate obtain a slice steps d and a slice step e are printed with the circuit that generates heat laminates makes base substrate;
G, sintering: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbeds insulating powder, and the insulating powder burying burning is Si
3n
4with the mixture of BN, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, tunnel furnace is divided into the binder removal district connected successively, sintering zone and cooling zone, binder removal district, the temperature of sintering zone and cooling zone is respectively 500 DEG C, 1650 DEG C, 100 DEG C, base substrate is respectively in binder removal district, the sintering time of sintering zone and cooling zone is 3h, 2h, 9h, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 40%, the volume percent of nitrogen in mixed gas is 60%, control the dew-point temperature of water vapor in mixed gas lower than 45 DEG C, blank sintering obtains ceramic heating body work in-process,
H, receiving electrode: plating nickel on surface process is carried out at half-finished for ceramic heating body two ends or sidepiece, then soldering extraction electrode is carried out at the position after Nickel Plating Treatment, obtained ceramic heating body finished product.
embodiment 3.
The preparation technology of the ceramic heating body of a kind of cofired materials of the present embodiment, it comprises following processing step:
A, batch mixing: take the Si of 75% by mass percentage
3n
4, the MgO of 8%, the Y of 4%
2o
3, 4% Al
2o
3, 3% SiO
2, 3% La
2o
3, 3% BN and mixing and stirring, make ceramic substrate powder;
B, ball milling: the ceramic substrate powder that step a is obtained is added mill ball, solvent and tackiness agent and puts into ball grinder and carries out wet ball grinding, the time of wet ball grinding is 14h;
C, deaeration: the compound after wet ball grinding in step b is carried out deaeration under vacuum;
D, shaping with drying: the compound casting machine curtain coating in step c to be made ceramic substrate or use and roll film device and be rolled into ceramic substrate, and ceramic substrate is carried out drying;
E, printing: by silk-screen printing technique by resistance slurry printing dried ceramic substrate surface in steps d, resistance slurry forms the heating circuit of reciprocal inflection structure on the surface of ceramic substrate; Resistance slurry is that the solid formation of 75% and the carrier of 25% form by mass percent; Solid formation is that the molybdenum of 70% and the glassy phase of 30% form by mass percent; Glassy phase by 75% Si
3n
4, the MgO of 8%, the Y of 4%
2o
3, 4% Al
2o
3, 3% SiO
2, 3% La
2o
3, 3% BN mixing and stirring form; Terpineol 350, the tributyl citrate of 25%, diethylene glycol monobutyl ether amyl acetate, the Viscotrol C of 1.5%, ethyl cellulose, the Yelkin TTS of 1.2%, the class of department 85 of 2.5% of 8% of 25% that carrier is 60% by mass percent form;
F, to laminate: the ceramic substrate that the ceramic substrate obtain a slice steps d and a slice step e are printed with the circuit that generates heat laminates makes base substrate;
G, sintering: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbeds insulating powder, and the insulating powder burying burning is Si
3n
4with the mixture of BN, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, tunnel furnace is divided into the binder removal district connected successively, sintering zone and cooling zone, binder removal district, the temperature of sintering zone and cooling zone is respectively 700 DEG C, 1700 DEG C, 200 DEG C, base substrate is respectively in binder removal district, the sintering time of sintering zone and cooling zone is 5h, 3h, 10h, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 15%, the volume percent of nitrogen in mixed gas is 85%, control the dew-point temperature of water vapor in mixed gas lower than 40 DEG C, blank sintering obtains ceramic heating body work in-process,
H, receiving electrode: plating nickel on surface process is carried out at half-finished for ceramic heating body two ends or sidepiece, then soldering extraction electrode is carried out at the position after Nickel Plating Treatment, obtained ceramic heating body finished product.
embodiment 4.
The preparation technology of the ceramic heating body of a kind of cofired materials of the present embodiment, it comprises following processing step:
A, batch mixing: take the Si of 90% by mass percentage
3n
4, the MgO of 4%, the Y of 2%
2o
3, 1% Al
2o
3, 1% SiO
2, 1% La
2o
3, 1% BN and mixing and stirring, make ceramic substrate powder;
B, ball milling: the ceramic substrate powder that step a is obtained is added mill ball, solvent and tackiness agent and puts into ball grinder and carries out wet ball grinding, the time of wet ball grinding is 18h;
C, deaeration: the compound after wet ball grinding in step b is carried out deaeration under vacuum;
D, shaping with drying: the compound casting machine curtain coating in step c to be made ceramic substrate or use and roll film device and be rolled into ceramic substrate, and ceramic substrate is carried out drying;
E, printing: by silk-screen printing technique by resistance slurry printing dried ceramic substrate surface in steps d, resistance slurry forms the heating circuit of reciprocal inflection structure on the surface of ceramic substrate; Resistance slurry is that the solid formation of 85% and the carrier of 15% form by mass percent; Solid formation by mass percent be the tungsten of 30%, the molybdenum of 60% and 10% glassy phase form; Glassy phase by 90% Si
3n
4, the MgO of 4%, the Y of 2%
2o
3, 1% Al
2o
3, 1% SiO
2, 1% La
2o
3, 1% BN mixing and stirring form; Terpineol 350, the tributyl citrate of 12%, diethylene glycol monobutyl ether amyl acetate, the Viscotrol C of 0.5%, ethyl cellulose, the Yelkin TTS of 0.5%, the class of department 85 of 1% of 4% of 12% that carrier is 70% by mass percent form;
F, to laminate: the ceramic substrate that the ceramic substrate obtain a slice steps d and a slice step e are printed with the circuit that generates heat laminates makes base substrate;
G, sintering: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbeds insulating powder, and the insulating powder burying burning is Si
3n
4with the mixture of BN, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, tunnel furnace is divided into the binder removal district connected successively, sintering zone and cooling zone, binder removal district, the temperature of sintering zone and cooling zone is respectively 900 DEG C, 1750 DEG C, 300 DEG C, base substrate is respectively in binder removal district, the sintering time of sintering zone and cooling zone is 6h, 3h, 11h, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 20%, the volume percent of nitrogen in mixed gas is 80%, control the dew-point temperature of water vapor in mixed gas lower than 35 DEG C, blank sintering obtains ceramic heating body work in-process,
H, receiving electrode: plating nickel on surface process is carried out at half-finished for ceramic heating body two ends or sidepiece, then soldering extraction electrode is carried out at the position after Nickel Plating Treatment, obtained ceramic heating body finished product.
embodiment 5.
The preparation technology of the ceramic heating body of a kind of cofired materials of the present embodiment, it comprises following processing step:
A, batch mixing: take the Si of 80% by mass percentage
3n
4, the MgO of 7%, the Y of 3%
2o
3, 2% Al
2o
3, 3% SiO
2, 2% La
2o
3, 3% BN and mixing and stirring, make ceramic substrate powder;
B, ball milling: the ceramic substrate powder that step a is obtained is added mill ball, solvent and tackiness agent and puts into ball grinder and carries out wet ball grinding, the time of wet ball grinding is 20h;
C, deaeration: the compound after wet ball grinding in step b is carried out deaeration under vacuum;
D, shaping with drying: the compound casting machine curtain coating in step c to be made ceramic substrate or use and roll film device and be rolled into ceramic substrate, and ceramic substrate is carried out drying;
E, printing: by silk-screen printing technique by resistance slurry printing dried ceramic substrate surface in steps d, resistance slurry forms the heating circuit of reciprocal inflection structure on the surface of ceramic substrate; Resistance slurry is that the solid formation of 80% and the carrier of 20% form by mass percent; Solid formation by mass percent be the tungsten of 40%, the manganese of 40% and 20% glassy phase form; Glassy phase by 80% Si
3n
4, the MgO of 7%, the Y of 3%
2o
3, 2% Al
2o
3, 3% SiO
2, 2% La
2o
3, 3% BN mixing and stirring form; Terpineol 350, the tributyl citrate of 14%, diethylene glycol monobutyl ether amyl acetate, the Viscotrol C of 1%, ethyl cellulose, the Yelkin TTS of 1%, the class of department 85 of 2% of 5% of 12% that carrier is 65% by mass percent form;
F, to laminate: the ceramic substrate that the ceramic substrate obtain a slice steps d and a slice step e are printed with the circuit that generates heat laminates makes base substrate;
G, sintering: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbeds insulating powder, and the insulating powder burying burning is Si
3n
4with the mixture of BN, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, tunnel furnace is divided into the binder removal district connected successively, sintering zone and cooling zone, binder removal district, the temperature of sintering zone and cooling zone is respectively 1100 DEG C, 1800 DEG C, 400 DEG C, base substrate is respectively in binder removal district, the sintering time of sintering zone and cooling zone is 7h, 3h, 12h, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 5%, the volume percent of nitrogen in mixed gas is 95%, control the dew-point temperature of water vapor in mixed gas lower than 30 DEG C, blank sintering obtains ceramic heating body work in-process,
H, receiving electrode: plating nickel on surface process is carried out at half-finished for ceramic heating body two ends or sidepiece, then soldering extraction electrode is carried out at the position after Nickel Plating Treatment, obtained ceramic heating body finished product.
embodiment 6.
The preparation technology of the ceramic heating body of a kind of cofired materials of the present embodiment, it comprises following processing step:
A, batch mixing: take the Si of 70% by mass percentage
3n
4, the MgO of 9%, the Y of 5%
2o
3, 4% Al
2o
3, 4% SiO
2, 4% La
2o
3, 4% BN and mixing and stirring, make ceramic substrate powder;
B, ball milling: the ceramic substrate powder that step a is obtained is added mill ball, solvent and tackiness agent and puts into ball grinder and carries out wet ball grinding, the time of wet ball grinding is 24h;
C, deaeration: the compound after wet ball grinding in step b is carried out deaeration under vacuum;
D, shaping with drying: the compound casting machine curtain coating in step c to be made ceramic substrate or use and roll film device and be rolled into ceramic substrate, and ceramic substrate is carried out drying;
E, printing: by silk-screen printing technique by resistance slurry printing dried ceramic substrate surface in steps d, resistance slurry forms the heating circuit of reciprocal inflection structure on the surface of ceramic substrate; Resistance slurry is that the solid formation of 80% and the carrier of 20% form by mass percent; Solid formation by mass percent be the manganese of 20%, the molybdenum of 40% and 40% glassy phase form; Glassy phase by 70% Si
3n
4, the MgO of 9%, the Y of 5%
2o
3, 4% Al
2o
3, 4% SiO
2, 4% La
2o
3, 4% BN mixing and stirring form; Terpineol 350, the tributyl citrate of 20%, diethylene glycol monobutyl ether amyl acetate, the Viscotrol C of 1%, ethyl cellulose, the Yelkin TTS of 1%, the class of department 85 of 1% of 2% of 20% that carrier is 55% by mass percent form;
F, to laminate: the ceramic substrate that the ceramic substrate obtain a slice steps d and a slice step e are printed with the circuit that generates heat laminates makes base substrate;
G, sintering: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbeds insulating powder, and the insulating powder burying burning is Si
3n
4with the mixture of BN, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, tunnel furnace is divided into the binder removal district connected successively, sintering zone and cooling zone, binder removal district, the temperature of sintering zone and cooling zone is respectively 1300 DEG C, 1850 DEG C, 500 DEG C, base substrate is respectively in binder removal district, the sintering time of sintering zone and cooling zone is 8h, 2h, 12h, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 10%, the volume percent of nitrogen in mixed gas is 90%, control the dew-point temperature of water vapor in mixed gas lower than 25 DEG C, blank sintering obtains ceramic heating body work in-process,
H, receiving electrode: plating nickel on surface process is carried out at half-finished for ceramic heating body two ends or sidepiece, then soldering extraction electrode is carried out at the position after Nickel Plating Treatment, obtained ceramic heating body finished product.
The performance testing index of the ceramic heating body that embodiment 1 ~ embodiment 6 is made is in table 1.
Table 1
。
As can be seen from Table 1, the High anti bending strength of the ceramic heating body that embodiment 1 ~ embodiment 6 is made, long service life, power stability, heating efficiency are high.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (8)
1. a preparation technology for the ceramic heating body of cofired materials, is characterized in that: comprise following processing step:
A, batch mixing: the Si taking 65-98% by mass percentage
3n
4, 0.1-10% the Y of MgO, 0.1-5%
2o
3, 0.1-5% Al
2o
3, 0.1-5% SiO
2, 0.1-5% La
2o
3, the BN of 0.1-5% mixing and stirring, make ceramic substrate powder;
B, ball milling: the ceramic substrate powder that step a is obtained is added mill ball, solvent and tackiness agent and puts into ball grinder and carries out wet ball grinding, the time of wet ball grinding is 8-24h;
C, deaeration: the compound after wet ball grinding in step b is carried out deaeration under vacuum;
D, shaping with drying: the compound casting machine curtain coating in step c to be made ceramic substrate or use and roll film device and be rolled into ceramic substrate, and ceramic substrate is carried out drying;
E, printing: by silk-screen printing technique by resistance slurry printing dried ceramic substrate surface in steps d, resistance slurry forms the heating circuit of reciprocal inflection structure on the surface of ceramic substrate;
F, to laminate: the ceramic substrate that the ceramic substrate obtain a slice steps d and a slice step e are printed with the circuit that generates heat laminates makes base substrate;
G, sintering: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbed insulating powder, then sintered at ambient pressure by the base substrate be embedded in insulating powder with box-type furnace or tunnel furnace, sintering atmosphere is nitrogen and hydrogen gas mixture, and blank sintering obtains ceramic heating body work in-process;
H, receiving electrode: plating nickel on surface process is carried out at half-finished for ceramic heating body two ends or sidepiece, then soldering extraction electrode is carried out at the position after Nickel Plating Treatment, obtained ceramic heating body finished product.
2. the preparation technology of the ceramic heating body of a kind of cofired materials according to claim 1, it is characterized in that: step g sintering is specially: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbed insulating powder, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 1-40%, the volume percent of nitrogen in mixed gas is 60%-99%, and blank sintering obtains ceramic heating body work in-process.
3. the preparation technology of the ceramic heating body of a kind of cofired materials according to claim 1, is characterized in that: step g sintering is specially: the base substrate that step f is obtained is placed in plumbago crucible or molybdenum crucible, and imbeds insulating powder, and the insulating powder burying burning is Si
3n
4with the mixture of BN, then with box-type furnace or tunnel furnace, the base substrate be embedded in insulating powder is sintered at ambient pressure, sintering atmosphere is nitrogen and hydrogen gas mixture, the volume percent of hydrogen in mixed gas is 5-29%, the volume percent of nitrogen in mixed gas is 71%-95%, control the dew-point temperature of water vapor in mixed gas lower than 50 DEG C, blank sintering obtains ceramic heating body work in-process.
4. the preparation technology of the ceramic heating body of a kind of cofired materials according to claim 1, it is characterized in that: step g sinter tunnel furnace used be divided into connect successively binder removal district, sintering zone and cooling zone, the temperature of binder removal district, sintering zone and cooling zone is respectively 300-1300 DEG C, 1600-1850 DEG C, 1850-25 DEG C, base substrate respectively in binder removal district, the sintering time of sintering zone and cooling zone is 3-8h, 1-3h, 8-12h.
5. the preparation technology of the ceramic heating body of a kind of cofired materials according to claim 1, is characterized in that: the resistance slurry in step e is made up of the raw material of following mass percent:
Solid formation 70-90%
Carrier 10-30%;
Wherein, solid formation is made up of the raw material of following mass percent:
Conductive phase 60-99%
Glassy phase 1-40%;
Conductive phase is the mixture of one or more in tungsten, manganese, molybdenum;
Glassy phase is made up of the raw material of following mass percent:
Si
3N
465-98%
MgO 0.1-10%
Y
2O
30.1-5%
Al
2O
30.1-5%
SiO
2 0.1-5%
La
2O
30.1-5%
BN 0.1-5%；
Wherein, carrier is made up of the raw material of following mass percent:
Terpineol 350 50-80%
Tributyl citrate 8-30%
Diethylene glycol monobutyl ether amyl acetate 8-30%
Viscotrol C 0.1-2%
Ethyl cellulose 3-10%
Yelkin TTS 0.3-1.5%
Department class 85 0.5-3%.
6. the preparation technology of the ceramic heating body of a kind of cofired materials according to claim 1, is characterized in that: the resistance slurry in step e is made up of the raw material of following mass percent:
Solid formation 75-85%
Carrier 15-25%;
Wherein, solid formation is made up of the raw material of following mass percent:
Conductive phase 70-90%
Glassy phase 10-30%;
Conductive phase is the mixture of one or more in tungsten, manganese, molybdenum;
Glassy phase is made up of the raw material of following mass percent:
Si
3N
475-90%
MgO 4-8%
Y
2O
32-4%
Al
2O
32-4%
SiO
2 2-4%
La
2O
32-4%
BN 2-4%；
Wherein, carrier is made up of the raw material of following mass percent:
Terpineol 350 60-70%
Tributyl citrate 12-25%
Diethylene glycol monobutyl ether amyl acetate 12-25%
Viscotrol C 0.5-1.5%
Ethyl cellulose 4-8%
Yelkin TTS 0.5-1.2%
Department class 85 1-2.5%.
7. the preparation technology of the ceramic heating body of a kind of cofired materials according to claim 1, is characterized in that: the resistance slurry in step e is made up of the raw material of following mass percent:
Solid formation 80%
Carrier 20%;
Wherein, solid formation is made up of the raw material of following mass percent:
Conductive phase 80%
Glassy phase 20%;
Conductive phase is the mixture of one or more in tungsten, manganese, molybdenum;
Glassy phase is made up of the raw material of following mass percent:
Si
3N
480%
MgO 7%
Y
2O
33%
Al
2O
32%
SiO
23%
La
2O
32%
BN 3%；
Wherein, carrier is made up of the raw material of following mass percent:
Terpineol 350 65%
Tributyl citrate 14%
Diethylene glycol monobutyl ether amyl acetate 12%
Viscotrol C 1%
Ethyl cellulose 5%
Yelkin TTS 1%
Class 85 2% of department.
8. the preparation technology of the ceramic heating body of a kind of cofired materials according to claim 1, it is characterized in that: obtained ceramic heating body is the one in tabular, pole shape, circular tube shaped, and pole shape or circular tube shaped ceramic heating body are rolled by tabular ceramic heating body and form.
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Effective date of registration: 20211229 Address after: 517000 plant of Guangdong hemi Technology Co., Ltd. in the west of Binjiang Road and in the south of Gaoxin fifth road, high tech Zone, Heyuan City, Guangdong Province Patentee after: GUANGDONG GUOYAN NEW MATERIAL Co.,Ltd. Address before: 523000 Sima Village Industrial Zone, Changping Town, Dongguan City, Guangdong Province Patentee before: Key Material Co.,Ltd. |