CN1405798A - Chip-type negative temperature coefficient thermistor and its manufacturing method by pure wet method - Google Patents
Chip-type negative temperature coefficient thermistor and its manufacturing method by pure wet method Download PDFInfo
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- CN1405798A CN1405798A CN 02135087 CN02135087A CN1405798A CN 1405798 A CN1405798 A CN 1405798A CN 02135087 CN02135087 CN 02135087 CN 02135087 A CN02135087 A CN 02135087A CN 1405798 A CN1405798 A CN 1405798A
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- 238000000465 moulding Methods 0.000 claims description 16
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- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
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- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
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- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
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- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 3
- 230000007306 turnover Effects 0.000 claims description 3
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Abstract
THe ingredient and weight content in percentage of the thermistor is as following MnO2 45%-60%, Co3O4 35%-50%, Al2O3 0.5%-10%, CaO 0.5%-2.5%, CuO 0.5%-2.5%, Fe3O4 0.5%-2.5%, NiO2 0.5-2.5%, SiO2 0.1-1.0%. The resistivity rho of the thermister is 100-5000 ohm.cm. The variance value B is 3500-4200. The thermistor is made through the processes of preparing powdered ingredient, manufacturing paste, wet process casting and surface coating etc. The immersion method, spraying method or printing method are utilized in the surface coating procedure. The invention possesses the features of high acceptability, stable value of resistance, simple device, easy of operation and steady quality. The qualified rate is raised to 60%-890%, also the solderability is raised.
Description
Technical field the present invention relates to a kind of chip-type negative temperature coefficient thermistor and manufacturing method by pure wet method thereof.
Background technology in the prior art, chip-type negative temperature coefficient thermistor device (hereinafter to be referred as the chip NTC themistor) is the novel chip temperature-sensitive element that utilizes the high technology content that powder forms through chip technology manufacturings such as pure wet method curtain coating, lamination, cutting, sintering, end-blocking, burning end, three layers of plating, is widely used in a plurality of fields such as various mobile communication equipments, business automation equipment, household electrical appliance, medicine equipment, automobile.It is divided into monolithic type, multi-layered type, three kinds of primary structure forms of thick-film type.Domestic and international nearly all manufacturer all adopts and utilizes slurry to become dry film, lamination, all press " dry technology for production " of aftershaping to be made at present.Because the system film, all domestic production of equipment such as pressures can only import, costing an arm and a leg, it is huge to invest.In addition, during surface applied is handled since the characteristic of chip NTC element directly and the physical dimension of element particularly the stability of the size between the two ends conductive electrode and material property direct association is arranged, present its product percent of pass of domestic main manufacturer has only 30-50%, formula R=ρ L/S by resistance analyzes, its chief reason is except the L size can not guarantee just can not to guarantee resistance stable, and the plating bath of plating can cause material property ρ to change to the erosion of material.
The method that summary of the invention the objective of the invention is to utilize fluidics quantitatively to flow out and obtains homogeneous film thickness is made the chip NTC themistor, and after sinter molding, increase by one surface applied treatment process, the glass glaze of coating one deck insulation between chip surface two electrodes, to address the above problem, improve product percent of pass and solderability.
In order to achieve the above object, the present invention has adopted following technical scheme: develop a kind of negative tempperature coefficient thermistor, the composition of this thermistor and weight percentage are: MnO
245%-60%, Co
3O
435%-50%, Al
2O
30.5%-10%, CaO0.5%-2.5%, CuO 0.5%-2.5%, Fe
3O
40.5%-2.5%, NiO
20.5%-2.5%, SiO
20.1%-1.0%, the electricalresistivity of described thermistor are 100-5000 Ω .cm, and the B value is 3500-4200.
The manufacture method of thermistor of the present invention, adopt pure wet production slice heat sensitive resistor, its detailed process is: the preparation of (1) ceramic powder: each composition is ground also evenly mix 15-30 hour to particle diameter 1.0-1.5 μ m in proportion, 150 ℃ of oven dry, 40 orders sieve, and place interior 900-1000 ℃ of crucible/insulation 3h to sinter the burning piece into, add flux again by the even ball milling 24h of ceramic ball milling (water mill) technology, dried the 40-100 mesh sieve for 150 ℃, the powder preparation is finished.(2) dispose slurry then: by following composition and weight ratio each composition fully is mixed into the slurry that viscosity is 15000-50000cps: adhesive B-7320: 200-400 order bismuth oxide: solvent: above-mentioned powder is 122: 17: 280: 280, described solvent is the mixture that propyl acetate and isobutanol are prepared by weight 70-90: 10-30, (3) flow casting molding then: the slurry that configures is placed in the funneling circulating tank, on the metal support plate, carry out the moulding of casting film-forming superimposition printing, getting thickness is the film of 10-40 μ m, annular transmits and dries each layer through baking oven with 50-80 ℃, circulation is made to the number of plies and the thickness of design, oven dry is after cutting, separate, binder removal, sintering gets single idiosome chip, (4) surface applied is handled then: with the glass glaze of coating one deck insulation between the single idiosome chip surface two end electrodes, concrete grammar is: A, infusion process: adopt end-blocking a kind of rhyme scheme in Chinese operas serving as the prelude to a complete score for voices mode, between chip gripper and two blocks of rubber slabs, time processing 3000-5000 grain, whole then plate soak with deployed glass paste in, form uniform watch crystal glaze slurry coat, oven dry again, take off plate, 800-1000 ℃ of 0.5-1.5 hour sintering of dress and the interior insulation of saggar, form evenly, fine and close glass glaze layer, perhaps B, spraying process: chip adopts braid shake dish mode, with on the chip in a V-type rail groove vibrations headtotail atomizer of approach of going ahead, watch crystal glaze slurry sprays from top to bottom, once spray the two sides, oven dry, turn over turnback by shake dish chip, spray again, oven dry again, 800-1000 ℃ of 0.5-1.5 hour sintering of dress and the interior insulation of saggar, form evenly, fine and close glass glaze layer, or C, print process: with 2000-3000PCS chip proper alignment in a rubber disc, four limit rubber chuck folders tighten up whole board chip are clamped, adopt silk-screen printing technique with printing of glass glaze slurry and chip surface, oven dry, another side is printed in upset again, oven dry, loose again chuck turns over all chips and turn 90 degrees, republish remaining two faces, keep 800-1000 ℃ of 0.5-1.5 hour sintering of temperature, form evenly, fine and close glass glaze layer, last (5) will be through the chip after the surface treatment through upper end electrode, silver ink firing, electroplate.
In implementing process of the present invention, during flow casting molding, the slurry that configures is placed in the circulating tank of the funneling casting apparatus of wet method, on the metal support plate, carry out the moulding of casting film-forming superimposition printing, dynamic balancing is stable as long as control slurry liquid level keeps, connecting gear at the uniform velocity, steadily, then the thickness on the support plate will be even, regulates the unlatching size of the funnel edge of a knife and the speed of connecting gear, just can obtain 10-40 μ m thickness; Beyond all doubt, surface applied processing of the present invention depends on special installation and carries out, use its simple equipment, this technology increases the surface applied treatment process one after sinter molding, the glass glaze of coating one deck insulation between chip surface two electrodes, can solve foregoing problems, make product percent of pass bring up to 60%-80%, solderability also improves greatly.Used adhesive B-7320 is polyvinyl butyral (PVA) the class adhesive that Shanghai reagent head factory is produced.
The present invention's technical scheme preferably can be: the composition and the weight percent of the dielectric glass layer glaze that surface applied is handled consist of: SiO
250%-70%, AL
2O
315%-30%, ZnO2%-6%, CaO 5%-15%, MgO 2%-6%, Pb
3O
42%-6%, with above each composition through grinding even mixing 24 hours, oven dry places in the crucible to keep 1000-1150 ℃ of sintering 3 hours, pours into when being cooled to 900 ℃ and makes fritted glaze in the deionized water, being ground to grain diameter D50 is below the 2.5 μ m, oven dry is sieved, and gets the glass glaze powder, press the glass glaze powder again: A-21 portions of resin terpinol: the parts by weight of absolute ethyl alcohol=100: 20-25: 30-40: 50-800 batching fully mixes to the slurry of 15000-50000cps and gets final product.The absolute ethyl alcohol that the present invention uses has bigger amount ranges can be regulated, so that the viscosity adjustment of mixture is to the degree of handled easily; Used A-21 resin is Hong Kong PVA resinoid that company produces when being good.
The present invention's technical scheme preferably also can be: use special equipment to finish the overall process of manufacturing process, the equipment that described flow casting molding adopts has funneling circulating tank (1), annular connecting gear (3), funneling circulating tank (1) is positioned at the top of metal support plate (2), and baking oven (5) is housed on the annular connecting gear (3); The equipment of the infusion process that surface applied is handled has last offset plate (6) and following offset plate (7), and several chips (8) are uniformly distributed between two offset plates; The equipment of the spraying process that surface applied is handled has atomising device (9), V-way (10) and shake dish (11), atomising device (9) is positioned at the top of V-way (10), and baking oven (12) is positioned on the V-way (10), and chip (13) is positioned at the groove of V-way (10); The equipment of the print process that surface applied is handled has offset plate (14), has the groove that adapts with chip (15) in the offset plate (14).Above device structure is simple, can satisfy the requirement of the pure wet manufacturing process of negative tempperature coefficient thermistor, produces the product of good quality.
Compared with prior art, the present invention has following tangible advantage: 1, technology is simple, and operation of equipment is convenient, is easy to control; 2, adopt the process of pure wet method slice heat sensitive resistor, avoid adopting and utilize slurry to become dry film, lamination, all press " dry technology for production " of aftershaping, overcome because of the cost an arm and a leg disadvantage of investment huge apparatus and dependence on import of use; 3, this technology increases the surface applied treatment process one after sinter molding, and the glass glaze of coating one deck insulation can make product percent of pass bring up to 60-80% between chip surface two electrodes, and solderability also improves greatly, and its reliable in quality is stable.
Be drawing explanation of the present invention below the description of drawings:
Fig. 1 is the vertical structure schematic diagram of flow casting molding equipment;
Fig. 2 is the planar structure schematic diagram of flow casting molding equipment;
Fig. 3 is the equipment schematic side view of surface applied processing-infusion process;
Fig. 4 is the equipment floor map of surface applied processing-infusion process;
Fig. 5 is the device structure schematic diagram of surface applied processing-spraying process;
Fig. 6 is that the A of Fig. 5 is to view;
Fig. 7 is the equipment floor map of surface applied processing-print process;
Fig. 8 is the equipment schematic side view of surface applied processing-print process.
With reference to Fig. 1-Fig. 2, among the figure, the 1st, funnel, the 2nd, support plate, the 3rd, connecting gear, the 4th, slurry liquid level, the 5th, baking oven, during use, the slurry that configures is placed in the funneling circulating tank (1), on metal support plate (2), carry out the moulding of casting film-forming superimposition printing, getting thickness is the film of 10-40 μ m, through connecting gear (3) annular transmit and through baking oven (5) with 50-80 ℃ of each layer of oven dry, circulation is made to the number of plies and the thickness of design, dries after cutting, separation, binder removal, sintering get single idiosome chip.
With reference to Fig. 3-Fig. 4, among the figure, the 6th, last offset plate, the 7th, following offset plate, the 8th, chip adopts end-blocking a kind of rhyme scheme in Chinese operas serving as the prelude to a complete score for voices mode, between chip gripper and two blocks of rubber slabs, time processing 3000-5000 grain, whole then plate soak with deployed glass paste in, form uniform watch crystal glaze slurry coat.
With reference to Fig. 5-Fig. 6, among the figure, the 9th, atomising device, the 10th, guide rail, the 11st, shake dish, the 12nd, baking oven, the 13rd, chip, during use, chip adopts braid shake dish mode, with on the chip in a V-type rail groove vibrations headtotail atomizer of approach of going ahead, watch crystal glaze slurry sprays from top to bottom, once spray the two sides, oven dry is turned over turnback by shake dish chip and is sprayed.
With reference to Fig. 7-Fig. 8, among the figure, the 14th, offset plate, the 15th, chip, during use with 2000-3000PCS chip proper alignment in a rubber disc, four limit rubber chucks folder tightens up whole board chip clamping, adopt silk-screen printing technique with printing of glass glaze slurry and chip surface, oven dry, upset printing another side again.
By specific embodiment the present invention is carried out more detailed description below the embodiment:
The manufacturing of embodiment 1:0603 type 10K Ω chip NTC thermistor
(1) prepares powder earlier: take by weighing each composition: MnO by following weight percentage earlier
245%, Co
3O
448%, Al
2O
32%, CaO 0.5%, and CuO 1%, Fe
3O
40.5%, NiO
22.5%, SiO
20.5%, with each composition carry out ball milling (water mill) evenly ball milling 20 hours to particle diameter 1.2 μ m, 150 ℃ of oven dry, 40 orders sieve, place interior 900-1000 ℃ of crucible/insulation 3h to sinter the burning piece into, add flux again by the even ball milling 24h of ceramic ball milling (water mill) technology, dried the 40-100 mesh sieve for 150 ℃, the powder preparation is finished.(2) configuration slurry: by following composition and weight ratio each composition fully is mixed into slurry: adhesive B-7320: 200-400 order bismuth oxide: solvent: above-mentioned powder is 122: 17: 280: 280, wherein solvent is the mixture that propyl acetate and isobutanol were prepared by weight 80: 20, the viscosity of slurry is the slurry of 16000cps, (3) flow casting molding then: the slurry that configures is placed in the funneling circulating tank, on the metal support plate, carry out the moulding of casting film-forming superimposition printing, getting thickness is the film of 20 μ m, annular transmits and dries each layers through baking oven with 80 ℃, circulation is made to 55 layers, thickness 1100 μ m, the oven dry back cuts into 0603 by the generous .75mm of long 2.0mm and gives birth to embryo, separate, binder removal, sintering, chamfering gets single chip, (4) infusion process surface applied is handled then: with the glass glaze of coating one deck insulation between single idiosome chip surface two electrodes, use Fig. 3, equipment shown in 4, adopt end-blocking a kind of rhyme scheme in Chinese operas serving as the prelude to a complete score for voices mode, between chip gripper and two blocks of rubber slabs, 3000 of time processing, whole then plate soak with deployed glass paste in, form uniform watch crystal glaze slurry coat, oven dry again, take off plate, keep 900 ℃ of 1 hour sintering of temperature, form evenly, fine and close glass glaze layer, last (5) will be through the chip after the surface treatment through upper end electrode, silver ink firing, electroplate.
The composition and the weight percent of the dielectric glass layer glaze that surface applied is handled consist of: SiO
269%, AL
2O
315%, ZnO 6%, and CaO 5%, and MgO 2%, Pb
3O
43%, through grinding even mixing 24 hours, oven dry places in the crucible to keep 1050 ℃ of sintering 3 hours with above each composition, pour into when being cooled to 900 ℃ and make fritted glaze in the deionized water, be ground to below the grain diameter 2.5 μ m, oven dry is sieved, get the glass glaze powder, press the glass glaze powder again: A-21 portions of resin terpinol: absolute ethyl alcohol=100: 20: 40: 300 parts by weight batching, fully mix to the slurry of 15000cps and get final product 450 Ω .cm, changing value B is 3800.
The manufacturing of embodiment 2 0603 type 47K Ω chip NTC thermistors
Method and step: different is to adopt the spraying process surface applied to handle, and uses Fig. 5, the equipment shown in 6, and all the other are all with embodiment 1.
Powder preparation: MnO
258%, Co
3O
435%, Al
2O
31%, CaO 2.5%, and CuO 1%, Fe
3O
42%, NiO
20.5%, SiO
21.0%, each composition is carried out ball milling (water mill) evenly mix 20 hours to particle diameter 1.2 μ m, 150 ℃ of oven dry, 40 orders sieve, prepare casting slurry again, through curtain coating, cutting, binder removal, sintering, chamfering, adopt spraying process again: chip adopts braid shake dish mode, with on the chip in a V-type rail groove vibrations headtotail atomizer of approach of going ahead, watch crystal glaze slurry sprays from top to bottom, once sprays the two sides, oven dry, turn over turnback by shake dish chip, spray again, oven dry again, 950 ℃/0.5-1.5 of dress and the interior insulation of saggar hour sintering forms evenly, fine and close glass glaze layer.The composition and the weight percent of dielectric glass layer glaze consist of: SiO
250%, Al
2O
325%, ZnO 2%, and CaO 13%, and MgO 6%, Pb
3O
44%.The electricalresistivity of gained thermistor is 2000 Ω .cm, and changing value B is 4000.
The manufacturing of embodiment 3 0805 type 10K Ω chip NTC thermistors
Method and step: different is to adopt the print process surface applied to handle, and uses Fig. 7, the equipment shown in 8, and all the other are all with embodiment 1.
Batching: MnO
250%, Co
3O
440%, Al
2O
37%, CaO 0.5%, CuO0.6%, NiO
20.9%, SiO
21.0%, each composition is carried out ball milling (water mill) evenly mix 20 hours to particle diameter 1.2 μ m, 50 ℃ of oven dry, 300 orders sieve, 2000-3000PCS chip proper alignment is handled in a rubber disc, thereafter keep 1000 ℃/0.5 hour sintering of temperature, the composition and the weight percent of dielectric glass layer glaze consist of: SiO
260%, Al
2O
320%, ZnO3%, CaO 10%, and MgO 2%, Pb
3O
45%.The electricalresistivity of gained chip NTC thermistor is 500 Ω .cm, and changing value B is 3980.
Claims (7)
1, a kind of chip-type negative temperature coefficient thermistor is made by the mixture of metal oxide and flux, it is characterized in that: the composition of thermistor and weight percentage are:
MnO
2 45％-60％
Co
3O
4 35％-50％
Al
2O
3 0.5％-10％
CaO 0.5％-2.5％
CuO 0.5％-2.5％
Fe
3O
4 0.5％-2.5％
NiO
2 0.5％-2.5％
SiO
2 0.1％-1.0％
The electricalresistivity of described thermistor is 100-5000 Ω .cm, and the B value is 3500-4200.
2, the manufacture method of the described thermistor of claim 1 is characterized in that: adopt pure wet production slice heat sensitive resistor, its detailed process is:
(1) ceramic powder preparation: each composition is ground also evenly mix 15-30 hour in proportion to particle diameter 1.0-1.2 μ m, 150 ℃ of oven dry, 40 orders sieve, place interior 900-1000 ℃ of crucible/insulation 3h to sinter the burning piece into, add flux again by the even ball milling 24h of ceramic ball milling (water mill) technology, dried the 40-100 mesh sieve for 150 ℃, then
(2) configuration slurry: the abundant ball milling of each composition is mixed into the slurry that viscosity is 15000-50000cps by following composition and weight ratio:
Adhesive B-7320: bismuth oxide: solvent: above-mentioned powder is 122: 17: 280: 280, and described solvent is the mixture that propyl acetate and isobutanol are prepared by weight 70-90: 10-30, then
(3) flow casting molding: the slurry that configures is placed in the funneling circulating tank, on the metal support plate, carry out the moulding of casting film-forming superimposition printing, getting thickness is the film of 10-40 μ m, annular transmits and dries each layer through baking oven with 50-80 ℃, circulation is made to the number of plies and the thickness of design, oven dry is after cutting, separation, binder removal, sintering, chamfering get single chip, then
(4) surface applied is handled: with the glass glaze of coating one deck insulation between single chip surface two electrodes, concrete grammar is:
A, infusion process: adopt end-blocking a kind of rhyme scheme in Chinese operas serving as the prelude to a complete score for voices mode, between chip gripper and two blocks of rubber slabs, time processing 3000-5000 grain, whole then plate soak with deployed glass paste in, form uniform watch crystal glaze slurry coat, again oven dry, take off plate, keep 800-1000 ℃ of 0.5-1.5 hour sintering of temperature, form the glass glaze layer of even compact, perhaps
B, spraying process: chip adopts braid shake dish mode, with on the chip in a V-type rail groove vibrations headtotail atomizer of approach of going ahead, watch crystal glaze slurry sprays from top to bottom, once sprays the two sides, oven dry, turn over turnback by shake dish chip, spray again, oven dry again keeps 800-1000 ℃ of 0.5-1.5 hour sintering of temperature, form the glass glaze layer of even compact, or
C, print process: with 2000-3000PCS chip proper alignment in a rubber disc, four limit rubber chuck folders tighten up whole board chip are clamped, adopt silk-screen printing technique with printing of glass glaze slurry and chip surface, oven dry, upset printing another side again, oven dry, loose again chuck turns over all chips and turn 90 degrees, and republishes remaining two faces, keeps 800-1000 ℃ of 0.5-1.5 hour sintering of temperature, form the glass glaze layer of even compact, last
(5) will be through the chip after the surface treatment through upper end electrode, silver ink firing, plating.
3, method according to claim 2 is characterized in that: the composition and the weight percent of the dielectric glass layer glaze that surface applied is handled consist of:
SiO
2 50％-70％
AL
2O
3 15％-30％
ZnO 2％-6％
CaO 5％-15％
MgO 2％-6％
Pb
3O
4 2％-6％
With above each composition through grinding even mixing 24 hours, oven dry, place in the crucible and kept 1000-1150 ℃ of sintering 3 hours, pouring into when being cooled to 900 ℃ and make fritted glaze in the deionized water, is below the 2.5 μ m by ball milling to grain diameter D50, oven dry, sieve, the glass glaze powder, press the glass glaze powder again: A-21 portions of resin terpinol: the parts by weight of absolute ethyl alcohol=100: 20-25: 30-40: 50-800 are prepared burden, and fully mix to the slurry of 15000-50000cps to get final product.
4, method according to claim 2, it is characterized in that: the equipment that flow casting molding adopts has funneling circulating tank (1), annular connecting gear (3), funneling circulating tank (1) is positioned at the top of metal support plate (2), and baking oven (5) is housed on the annular connecting gear (3).
5, method according to claim 2 is characterized in that: the equipment of the infusion process that surface applied is handled has last offset plate (6) and following offset plate (7), and several chips (8) are uniformly distributed between two offset plates.
6, method according to claim 2, it is characterized in that: the equipment of the spraying process that surface applied is handled has atomising device (9), V-way (10) and shake dish (11), atomising device (9) is positioned at the top of V-way (10), baking oven (12) is positioned on the V-way (10), and chip (13) is positioned at the groove of V-way (10).
7, method according to claim 2 is characterized in that: the equipment of the print process that surface applied is handled has offset plate (14), has the groove that adapts with chip (15) in the offset plate (14).
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