CN110519870A - A kind of graphene/lowpriced metal alloy conductive material, resistance slurry, heater and its preparation and application - Google Patents
A kind of graphene/lowpriced metal alloy conductive material, resistance slurry, heater and its preparation and application Download PDFInfo
- Publication number
- CN110519870A CN110519870A CN201810491757.3A CN201810491757A CN110519870A CN 110519870 A CN110519870 A CN 110519870A CN 201810491757 A CN201810491757 A CN 201810491757A CN 110519870 A CN110519870 A CN 110519870A
- Authority
- CN
- China
- Prior art keywords
- layer
- graphene
- dielectric layer
- glass
- conductive material
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 111
- 239000002002 slurry Substances 0.000 title claims abstract description 41
- 239000004020 conductor Substances 0.000 title claims abstract description 28
- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 100
- 239000011521 glass Substances 0.000 claims abstract description 74
- 239000000843 powder Substances 0.000 claims abstract description 61
- 229910045601 alloy Inorganic materials 0.000 claims description 90
- 239000000956 alloy Substances 0.000 claims description 90
- 239000000758 substrate Substances 0.000 claims description 67
- 239000010935 stainless steel Substances 0.000 claims description 46
- 229910001220 stainless steel Inorganic materials 0.000 claims description 46
- 229910000831 Steel Inorganic materials 0.000 claims description 40
- 239000010959 steel Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 34
- 238000005245 sintering Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical group CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- 239000013008 thixotropic agent Substances 0.000 claims description 10
- 230000006798 recombination Effects 0.000 claims description 9
- 238000005215 recombination Methods 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 3
- 229910005569 NiB Inorganic materials 0.000 claims description 3
- 229910003322 NiCu Inorganic materials 0.000 claims description 3
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000001723 curing Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 42
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 22
- 238000007650 screen-printing Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- 238000000227 grinding Methods 0.000 description 18
- 239000012046 mixed solvent Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000011812 mixed powder Substances 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 14
- 229960000935 dehydrated alcohol Drugs 0.000 description 13
- 230000008859 change Effects 0.000 description 12
- 230000035939 shock Effects 0.000 description 12
- 206010037660 Pyrexia Diseases 0.000 description 10
- 239000010965 430 stainless steel Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000004321 preservation Methods 0.000 description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- 239000001856 Ethyl cellulose Substances 0.000 description 8
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- 238000005422 blasting Methods 0.000 description 8
- 229920001249 ethyl cellulose Polymers 0.000 description 8
- 235000019325 ethyl cellulose Nutrition 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
Landscapes
- Resistance Heating (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to conductive material fields, and in particular to a kind of graphene/lowpriced metal alloy conductive material, which is characterized in that include graphene, alloyed powder and glass powder.The present invention also provides the electrocondution slurries comprising the conductive material；Heater comprising the conductive material；The present invention also provides the preparation method and application of the heater.The advantages that conductive material of the present invention has excellent performance, and film heater as made from it has safety good, at low cost, and good conductivity, binding force is strong, and heating speed is fast, particularly suitable in permanent lod.
Description
Technical field
The present invention relates to a kind of doped graphene alloy heat generating film preparation of stainless base steel and its applications, and in particular to stainless
Application of the doped graphene alloy heat generating film heater of base steel in permanent lod.
Background technique
It is existing with the problems such as traditional heating mode reflected service life is short, heating method is not flexible, heating efficiency is low
Traditional heating mode be no longer satisfied existing needs, Electric radiant Heating Film constantly came out as the product of heating element in recent years,
And ceramic base, glass base, polymer matrix, Metal Substrate can be divided by substrate according to thick-film heating element, wherein Metal Substrate belongs to not
The steel substrate that becomes rusty be it is most widely used, stainless base steel heating element have power density it is big, it is small in size, be easily installed and anti-vibration etc. is all
More advantages.But since insulating properties of the stainless base steel heating film to substrate requires high, heating speed, anti-oxidant energy to heating film
The performance indicators such as power, binding force all have higher requirements.If Chinese patent is " based on the large power thick film circuit of stainless steel substrate with leading
Plasma-based material and its preparation process " (application number: 02139895.X) describe silver-colored palladium resistance slurry printing stainless steel substrate as big
Power circuit.Due to using noble metal as conductive phase, production cost is considerably increased, heating film inoxidizability is poor；Again
Then silver is easy migration during the sintering process, the insulating properties of the stainless steel substrate it is difficult to ensure that.As Chinese patent " is based on stainless base steel
YBCO thick-film resistor paste of plate and preparation method thereof " (it is thick 201010158934) application number: to describe stainless steel substrate YBCO
Film resistance.Due to the higher cost using synthesis in solid state YBCO, purity is lower, and there are production cost or excessively high, thermal expansion systems
The disadvantages of number matching is poor, and the electric conductivity of resistive film is poor, and electrothermal calefactive rate is affected.Therefore, current urgent to be essential
It asks and exactly finds a kind of low cost, good conductivity, the thick film heating resistance material highly-safe, heating speed is fast.
Summary of the invention
To solve the deficiencies in the prior art, an object of the present disclosure is, it is conductive to provide a kind of graphene/lowpriced metal alloy
A kind of material (present invention also abbreviation conductive material or electrically conductive composition), it is desirable to provide conduction material with excellent conductive performance
Material.
Second purpose of the invention is, provides a kind of comprising the doping of the graphene/lowpriced metal alloy conductive material
Graphene resistance alloys slurry.
For at high cost, the poorly conductive that solves existing stainless steel substrate thick film heating film, binding force is poor, heating speed slowly
Defect.Third purpose of the present invention is, it is desirable to provide one kind includes the graphene/lowpriced metal alloy conductive material, and is had
The doped graphene alloy heat generating film heater of the stainless base steel of one brand new characteristic.
4th purpose of the invention is, provides a kind of preparation of the doped graphene alloy heat generating film heater of stainless base steel
Method.
5th purpose of the invention is, provides a kind of answering for the doped graphene alloy heat generating film heater of stainless base steel
With.
A kind of graphene/lowpriced metal alloy conductive material includes graphene, alloyed powder and glass powder.
Raw material and production can be substantially reduced by the collaboration between component using conductive material of the present invention
Cost；Moreover, it can also aid in the densification for the heating film for being sintered the conductive material, reduce the heating film that sintering obtains
Defect, make heating film have higher stability.In addition, present invention doped graphene in lowpriced metal alloy is used as a part
Conductive phase can greatly increase the electric conductivity of film, simultaneously because it increases alloy conductive particle and glass with lamellar structure
Glass binder and bond strength with dielectric layer, doped graphene adjust the work of the thermal expansivity of film layer wherein also functioning to simultaneously
With these all enhance the mechanical anti-thermal shock characteristic of film layer, improve the stability of film, extend the service life of heater.
Preferably, glass powder fusing point is 600 DEG C~800 DEG C in the graphene/lowpriced metal alloy conductive material.
Further preferably, glass powder is devitrified glass.
Still more preferably, the solid-phase component of the glass powder is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3。
Preferably, the alloyed powder is at least one of NiB, NiCu, NiFe, NiAlCr.It is closed using base metal
Gold replaces noble metal, reduces the cost of raw material, while alloy and graphene cooperation, can also reduce sintering temperature, make
Film can be sintered more densification and reduce defect, reduce process costs, improve the stability of film layer.
Still more preferably, the alloyed powder is NiB.The study found that using NiB and graphene and the glass
Synergy it is more excellent, resistance variations caused by film layer sweeps away the thermal pressure of generation also in heat can be further reduced, mentioned significantly
The stability of high film layer.
Preferably, the graphene is multi-layer graphene, with a thickness of 1nm~100nm.The graphene of the preferred thickness and its
His ingredient synergy is good, can further coordinated regulation film layer electric conductivity.
Preferably, the parts by weight of alloyed powder are 45~90 parts in the graphene/lowpriced metal alloy conductive material；
The parts by weight of graphene are 1~10 part；The parts by weight of glass powder are 1~15 part.It is small in the component collaboration, in the preferred model
Effect under enclosing is more excellent.
The present invention also provides a kind of doped graphene resistance alloys slurries, include the graphene/lowpriced metal alloy
Conductive material and organic carrier.
Preferably, the organic carrier includes solvent, thickener, thixotropic agent, surfactant and binder.
The solvent is terpinol, butyl acetate, one or more in dibutyl phthalate.Into
One step is preferred, and the solvent is the mixture of terpinol, butyl acetate, dibutyl phthalate.
The thickener can be the interior conventional material with thickening effect of industry, preferably ethyl cellulose.
The thixotropic agent can be the interior conventional material with anti-thixotroping of industry, preferably rilanit special.
The surfactant can be the conventional material with raising surface-active in industry, preferably oleic acid.
The binder can mention highly viscous conventional material, preferably polyvinyl butyral to have in industry.
Preferably, in the organic carrier, the mass parts of solvent, thickener, thixotropic agent, surfactant and binder
Ratio is 85-93: 8-14: 1-4: 1-4: 1-8.
Preferably, organic carrier account for the mass percent of the doped graphene resistance alloys slurry be 10%~
30%.Surplus is the graphene/lowpriced metal alloy conductive material.
Further preferably, in the doped graphene resistance alloys slurry, as mass fraction, alloyed powder 45%~
90%, graphene 1%~10%, glass powder 1%~15%, organic carrier 10%~30%.
The present invention also provides a kind of doped graphene alloy heat generating film heaters of stainless base steel, include stainless base steel
Bottom, two opposite planes are compounded with thermal insulation layer and dielectric layer 1 respectively；1 surface recombination of dielectric layer has dielectric layer 2；It is situated between
2 surface recombination of matter layer has resistance alloys layer；Resistance alloys layer surface is compounded with insulated thermal insulating layer；
The resistance alloys layer contains the graphene/lowpriced metal alloy conductive material.
The present invention provides a kind of brand new and have innovation ingredient advantage stainless base steel doped graphene alloy
Heating film heating-body；The longitudinal section of the doped graphene alloy heat generating film heater of the stainless base steel is (perpendicular to the hair
The section in the direction of hot body plane) it is successively compound thermal insulation layer, stainless steel substrate, dielectric layer 1, dielectric layer 2, alloy electricity
Resistance layer and insulated thermal insulating layer.
Heater of the present invention, stainless steel substrate is as substrate, with excellent heating conduction, and has excellent
Mechanical performance, resistance material (slurry) of the present invention use on stainless base steel as fever film layer, can satisfy stainless base steel
The high-power use of heater can sustain powerful thermal shock, and heating efficiency is high, also high using temperature.Moreover,
The present invention also innovatively makes substrate, dielectric layer, alloy using compound dielectric layer (successively compound dielectric layer 1 and dielectric layer 2)
Resistive layer more preferably carries out the collaboration matching of thermal expansivity, enhance while increasing substrate insulating properties mutual bond strength and
Stability.
Preferably, the resistance alloys layer is obtained by the doped graphene resistance alloys slurry curing.
The present invention, the dielectric layer 1 contain glass 1, and the dielectric layer 2 contains glass 2；
The fusing point of glass 1 is 800~1000 DEG C；The fusing point of glass 2 is 600~800 DEG C.
In the present invention, by the use of the successively compound dielectric layer 1 and dielectric layer 2, can make substrate, dielectric layer,
Resistance alloys layer more preferably carries out the matching of thermal expansivity, enhance while increasing substrate insulating properties mutual bond strength and
Stability.
Preferably, the glass 1 is devitrified glass, solid-phase component SiO2-Al2O3-CaO-MgO-B2O3。
Preferably, the glass 2 is devitrified glass, solid-phase component SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3。
The material of the thermal insulation layer can be used having for row industry routine and insulate and thermally conductive material.
The material of the insulated thermal insulating layer can be the material with insulated heat effect of row industry routine.
Insulated thermal insulating layer and thermal insulation layer are applied by being arranged in the top and bottom of heater, can further be promoted and be added
The thermal conversion efficiency of heater.
Thickness between each layer can be adjusted as needed, it is preferable that dielectric layer 1 is with a thickness of 80 μm~140 μm；Medium
Layer 2 is with a thickness of 50 μm~80 μm.
The present invention also provides the preparation sides of the doped graphene alloy heat generating film heater of the stainless base steel described in one kind
Method, comprising the following steps:
Step 1: stainless steel substrate surface is pre-processed；
Step 2: solvent, thickener, thixotropic agent, surfactant, binder are mixed, organic carrier is obtained；
Step 3: glass 1, glass 2 are mixed with organic carrier respectively, respectively obtain dielectric paste 1 and dielectric paste 2；
Step 4: dielectric paste 1 is compounded in a plane of pretreated stainless steel substrate, dry, sintering, In
The dielectric layer 1 is formed on stainless steel substrate；Then the surface recombination dielectric paste 2 of dielectric layer 1, drying, sintering are being situated between again
1 surface of matter layer forms the dielectric layer 2；
Step 5: alloyed powder, Graphene powder, glass powder are mixed, the graphene/lowpriced metal alloy conduction material is obtained
Material；
Step 6: mixing organic carrier is prepared into the graphene/lowpriced metal alloy conductive material and step 2,
Obtain the doped graphene resistance alloys slurry；
Step 7: doped graphene resistance alloys slurry is compounded on the dielectric layer 2 in step 4, dry, sintering, In
The resistance alloys layer is formed on dielectric layer 2 (present invention is also referred to as heating layer)；
Step 8: the resistance alloys layer that step 7 is obtained sprays one layer of insulated heat slurry；Compound Jie of stainless steel substrate
The opposite face of matter layer 1 sprays one layer of insulating heat-conductive slurry, dry, obtains the doped graphene alloy heat generating of the stainless base steel
Film heater.
The stainless steel substrate is a kind of in 430,304,316.
In the preparation method, the organic carrier includes mixed solvent, thickener, thixotropic agent, surfactant, glues
Tie agent；Wherein, the mass parts ratio of solvent, thickener, thixotropic agent, surfactant and binder is 85-93: 8-14: 1-4:
1-4:1-8；The mixed solvent is terpinol, butyl acetate, a kind of or more in dibutyl phthalate
Kind.
The glass powder 1 is devitrified glass, solid-phase component SiO2-Al2O3-CaO-MgO-B2O3, glass powder 2 is crystallite
Glass, solid-phase component SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3。
Preferably, the glass 2 of the graphene/lowpriced metal alloy conductive material glass powder and dielectric layer 2 is
Identical material.
The sintering process of dielectric layer 1 described in step 4 are as follows: in air, arrived with 2 DEG C/min~10 DEG C/min heating rate
300 DEG C~500 DEG C, 1h~5h is kept the temperature, then with 0.5 DEG C/min~10 DEG C/min heating rate to 800 DEG C~1000 DEG C, heat preservation
1h~5h.
2 sintering process of dielectric layer are as follows: in air, with 2 DEG C/min~10 DEG C/min heating rate to 300 DEG C~500 DEG C,
1h~5h is kept the temperature, then with 0.5 DEG C/min~10 DEG C/min heating rate to 600 DEG C~800 DEG C, keeps the temperature 1h~5h.
Alloyed powder described in step 5 is one or more in NiB, NiCu, NiFe, NiAlCr.
Graphene described in step 5 is multi-layer graphene, with a thickness of 1nm~100nm.
As mass fraction, alloyed powder 45%~90%, graphene 1%~10%, glass powder 1%~15% have airborne
Body 10%~30%.
Resistance alloys layer described in step 7 be sintered sintering process are as follows: vacuum degree be 10-4~10-3In Pa vacuum, with 2 DEG C/
Min~10 DEG C/min heating rate keeps the temperature 0.5h~2h, then with 0.5 DEG C/min~10 DEG C/min liter to 300 DEG C~500 DEG C
Warm rate keeps the temperature 0.5h~3h to 600 DEG C~800 DEG C.
A kind of doped graphene alloy heat generating film heater of preferred stainless base steel of the present invention, preparation method include
Following steps:
Step 1: stainless steel substrate surface is subjected to blasting treatment.
Step 2: by mixed solvent, thickener, thixotropic agent, surfactant, binder be uniformly mixed be made have it is airborne
Body.
Step 3: glass powder 1, glass powder 2 are uniformly mixed to get with deployed organic carrier respectively dielectric paste 1,
Dielectric paste 2.
Step 4: dielectric paste 1, dielectric paste 2 are taken up in order of priority by silk-screen printing and are imprinted on pretreated stainless steel
Dry on substrate, sintering obtains the stainless steel substrate with insulating layer.
Step 5: alloyed powder, Graphene powder, glass powder 2 are uniformly mixed to get mixed powder.
Step 6: doping stone is uniformly mixed to get by organic carrier is prepared into mixed powder and step 2 that step 5 obtains
Black alkene resistance alloys slurry.
Step 7: doped graphene resistance alloys slurry is imprinted in step 4 by certain circuit pattern by silk-screen printing
Stainless steel substrate on, dry, sintering obtains stainless base steel heating layer.
Step 8: the compound coating surface of the stainless steel that step 7 is obtained sprays one layer of insulated heat slurry, back side spraying
One layer of insulating heat-conductive slurry is dried to obtain a kind of doped graphene alloy heat generating film heater of stainless base steel.
The present invention also provides the application of the heater described in one kind, the application includes being applied in permanent lod.
Beneficial effects of the present invention:
(1) of the invention since function mutually uses lowpriced metal alloy (NiB series), electric conductivity and conductive noble metal difference are not
Greatly, to replace noble metal membrane material, since alloy melting point is lower than the sintering temperature of single metal, to reduce heating film sintering
Temperature greatly reduces material and preparation cost.
(2) present invention is mixed with graphene in resistance alloys slurry, increases the electric conductivity of heating film, accelerates and adds
Thermal velocity, while the mechanical performance of film layer is also increased, enhance heating film and dielectric layer binding force, and make its heat shock resistance
Performance also greatly improves.
(3) present invention employs the devitrified glasses with different gradient fusing points as stainless steel substrate compound medium layer, increases
The insulation performance for adding substrate stainless steel, reduces that substrate, dielectric layer, matched coefficients of thermal expansion is poor between resistive layer three asks
Topic, improves the binding force between three, while improving the thermal shock resistance and heater element security performance of heating film.
The resistivity of heater of the present invention reaches as high as 2.04 × 10-6 Ω m, compared to not using the present invention
The structure and the electrically conductive composition case, lift up to 27.8 times；
The insulation resistance of heater of the present invention reaches as high as 8G Ω, compared to not using the structure of the invention
And the case of the electrically conductive composition, lift up to 167%；
The heating rate of heater of the present invention reaches as high as 50 DEG C/s, compared to not using the knot of the invention
The case of structure and the electrically conductive composition, lifts up to 116%；
The thermal shock resistance resistance varying-ratio of heater of the present invention is minimum up to 1%, compared to not using this
The structure of invention and the case of the electrically conductive composition reduce up to 15 times；
Bond strength between each layer of heater of the present invention is I grade, compared to do not use it is of the invention described in
The case of structure and the electrically conductive composition improves 2 ranks；
Detailed description of the invention
Attached drawing 1 is the preparation flow figure of stainless steel substrate compound medium layer of the present invention
Attached drawing 2 is a kind of preparation flow figure of the doped graphene alloy heat generating film heater of stainless base steel of the present invention
Attached drawing 3 is a kind of structural schematic diagram of the doped graphene alloy heat generating film heater of stainless base steel of the present invention；
In Fig. 3,1: insulated thermal insulating layer, 2: resistance alloys layer, 3: dielectric layer 2,4: dielectric layer 1,5: stainless steel substrate, 6: absolutely
Edge heat-conducting layer.
Specific embodiment
Following embodiment is implemented by aforesaid operations method:
Stainless steel substrate compound medium layer uses preparation flow shown in FIG. 1 in following embodiment.
Heating film heating-body uses preparation flow shown in Fig. 2 in following embodiment.
The graphene is multi-layer graphene, with a thickness of 1nm~100nm.
The devitrified glass 1 is devitrified glass, solid-phase component SiO2-Al2O3-CaO-MgO-B2O3；Fusing point be 800~
1000℃；
2 solid-phase component of devitrified glass is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3；Fusing point is 600 DEG C~800
℃；
Insulated heat coating is obtained using existing Conventional insulation insulating moulding coating, and the insulated heat coating is, for example, Guangzhou
Also take in the fresh material Science and Technology Ltd. offer the CN-302A trade mark material；
Insulating heat-conductive coating is obtained using existing Conventional insulation heat-conductive coating, and the insulating heat-conductive coating is, for example, Guangzhou
Also take in the fresh material Science and Technology Ltd. offer the CN-202A trade mark material.
The heater is made by structural schematic diagram described in Fig. 3 in following embodiment；As shown in Figure 1, the hair
Hot body includes stainless steel base 5, and two opposite planes are compounded with thermal insulation layer 6 and dielectric layer 1 (4) respectively；Dielectric layer 1
(4) surface recombination has dielectric layer 2 (3)；Dielectric layer 2 (3) surface recombination has resistance alloys layer 2；2 surface recombination of resistance alloys layer has
Insulated thermal insulating layer 1.
Embodiment 1:
Blasting treatment, blast time 30min are carried out to 430 stainless steel substrate surfaces.By terpinol: butyl
Mixing needed for acetate, dibutyl phthalate weight part ratio prepare this experiment for 70: 20: 10
Solvent, by mixed solvent: ethyl cellulose: polyvinyl butyral: rilanit special: it is 85 that oleic acid weight part, which is compared,
: prepare this experiment required organic carrier at 8: 1: 1: 1.It will take 40g organic carrier and 60g devitrified glass 1 that 2h is mixed, then use
Three-roll grinder grinds 5 times repeatedly and obtains dielectric paste 1.Dielectric paste 1 is printed on 430 with plane pattern by silk-screen printing
Stainless steel substrate surface, print pass are 3 times, finally the good sample of silk-screen are put into air dry oven at 80 DEG C dry
1h.After drying, takes out sample and is put into Muffle furnace by the sintering of following technique: with 2 DEG C/min heating rate to 300 DEG C, keeping the temperature 1h,
Then with 0.5 DEG C/min heating rate to 800 DEG C, 1h is kept the temperature.Take 40g organic carrier and 60g devitrified glass 2 that 2h is mixed,
It grinds 5 times repeatedly with three-roll grinder again and obtains dielectric paste 2.Dielectric paste 2 is printed with plane pattern by silk-screen printing
On above-mentioned 1 surface of dielectric layer, print pass is 3 times, and finally the good sample of silk-screen is put into air dry oven and is done at 80 DEG C
Dry 1h.After drying, takes out sample and be put into Muffle furnace by the sintering of following technique: with 2 DEG C/min heating rate to 300 DEG C, heat preservation
1h keeps the temperature 1h, obtains stainless steel based composite dielectric layer then with 0.5 DEG C/min heating rate to 600 DEG C.
45gNiB alloyed powder, 1g graphene, 1g microcrystalline glass powder 2 are taken, wherein graphene is placed in oxygen with a thickness of 1nm, mixing
Change in zirconium ball grinder, add a certain amount of dehydrated alcohol, so that powder and dehydrated alcohol is mixed into paste, a certain amount of oxidation is added
Zirconium ball milling pearl, ratio of grinding media to material 1: 1, wherein big-and-middle bead than 5: 3: 2, is subsequently placed in ball mill with 24 hours of 200r/min ball milling,
Material is filtered out from zirconia ball grinding jar, merging air dry oven is dry, and after dry, material is ground into uniform powder
Shape crosses 100 mesh standard sieve and obtains alloy mixed powder.
It takes 10g organic carrier and above-mentioned 47g alloy mixed powder that 2h is mixed, then is ground repeatedly with three-roll grinder 5 times
Doped graphene resistance alloys slurry is obtained, by silk-screen printing by doped graphene resistance alloys slurry with certain shapes pattern
Circuit be printed on above-mentioned, print pass is 5 times, finally the good sample of silk-screen is put into air dry oven at 80 DEG C dry
1h.After drying, take out sample and be put into vacuum drying oven by the sintering of following technique: vacuum degree control is 10-4Within the scope of Pa, with 2 DEG C/
Min heating rate keeps the temperature 0.5h to 300 DEG C, and then with 0.5 DEG C/min heating rate to 600 DEG C, heat preservation 0.5h obtains stainless steel
Base heating film heating-body.One layer of insulated heat coating finally is sprayed in fever film surface, sprays one layer at the stainless steel substrate back side
Insulating heat-conductive coating is put into air dry oven at 80 DEG C dry 1h.
By a kind of doped graphene alloy heat generating film heater progress resistivity survey of stainless base steel obtained in embodiment
Examination, result performance have excellent electric conductivity, and resistivity is 2.04 × 10-6Ω·m；Insulating properties is tested, insulated electro
Resistance is 8G Ω；Heating film heating rate is tested, as a result 7s reaches 300 DEG C；Experimental test is analyzed through thermal shock resistance,
As a result it shows thermal cycle 1000 times, change in resistance 1%, film has no oxidation；Measured through attachment fastness, film and dielectric layer, medium
The attachment degree of layer and substrate is I grades, and it is high to show bond strength between three.
Embodiment 2:
Blasting treatment, blast time 30min are carried out to 304 stainless steel substrate surfaces.By terpinol: butyl
Mixed solvent needed for acetate, dibutyl phthalate weight part ratio prepare this experiment for 70: 20: 10, by mixed solvent:
Ethyl cellulose: polyvinyl butyral: rilanit special: oleic acid weight part is compared prepares needed for this experiment for 93: 14: 4: 4: 8
Organic carrier.It will take 20g organic carrier and 80g devitrified glass 1 that 2h is mixed, then be ground repeatedly with three-roll grinder 5 times
Obtain dielectric paste 1.Dielectric paste 1 is printed on 304 stainless steel substrate surfaces, printing time with plane pattern by silk-screen printing
Number is 3 times, and the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into
It is sintered in Muffle furnace by following technique: with 10 DEG C/min heating rate to 500 DEG C, keeping the temperature 5h, then heated up with 10 DEG C/min fast
Rate keeps the temperature 5h to 1000 DEG C.It takes 20g organic carrier and 80g devitrified glass 2 that 2h is mixed, then is ground repeatedly with three-roll grinder
It grinds 5 times and obtains dielectric paste 2.Dielectric paste 2 is printed on above-mentioned 1 surface of dielectric layer with plane pattern by silk-screen printing, is printed
Brush number is 3 times, and the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, sample is taken out
It is put into Muffle furnace and is sintered by following technique: with 10 DEG C/min heating rate to 500 DEG C, 5h is kept the temperature, then with 10 DEG C/min liter
Warm rate keeps the temperature 5h, obtains stainless steel based composite dielectric layer to 800 DEG C.
90gNiCu alloyed powder, 10g graphene, 15g microcrystalline glass powder 2 are taken, wherein graphene mixes with a thickness of 100nm,
It is placed in zirconia ball grinding jar, adds a certain amount of dehydrated alcohol, powder and dehydrated alcohol is made to be mixed into paste, be added a certain amount of
Zirconium oxide ball milling pearl, ratio of grinding media to material 1: 1, wherein big-and-middle bead than 5: 3: 2, is subsequently placed in ball mill with 200r/min ball milling 24
Hour, material is filtered out from zirconia ball grinding jar, merging air dry oven is dry, and after dry, material is ground into uniformly
It is powdered, cross 100 mesh standard sieve obtain alloy mixed powder.
It takes 30g organic carrier and above-mentioned 115g alloy mixed powder that 2h is mixed, then is ground repeatedly with three-roll grinder 5 times
Doped graphene resistance alloys slurry is obtained, by silk-screen printing by doped graphene resistance alloys slurry with certain shapes pattern
Circuit be printed on above-mentioned, print pass is 5 times, finally the good sample of silk-screen is put into air dry oven at 80 DEG C dry
1h.After drying, take out sample and be put into vacuum drying oven by the sintering of following technique: vacuum degree control is 10-3Within the scope of Pa, with 10 DEG C/
Min heating rate keeps the temperature 2h to 500 DEG C, and then with 10 DEG C/min heating rate to 800 DEG C, heat preservation 3h obtains stainless base steel hair
Hotting mask heater.One layer of insulated heat coating finally is sprayed in fever film surface, sprays one layer of insulation at the stainless steel substrate back side
Heat conducting coating is put into air dry oven at 80 DEG C dry 1h.
By a kind of doped graphene alloy heat generating film heater progress resistivity survey of stainless base steel obtained in embodiment
Examination, result performance have excellent electric conductivity, and resistivity is 4.12 × 10-6Ω·m；Insulating properties is tested, insulated electro
Resistance is 7.5G Ω；Heating film heating rate is tested, as a result 6s reaches 300 DEG C；Experimental test is analyzed through thermal shock resistance,
Its result shows thermal cycle 1000 times, and change in resistance 1%, film has no oxidation；Measured through attachment fastness, film and dielectric layer, be situated between
The attachment degree of matter layer and substrate is I grades, and it is high to show bond strength between three.
Embodiment 3:
Blasting treatment, blast time 30min are carried out to 316 stainless steel substrate surfaces.By terpinol: butyl
Mixed solvent needed for acetate, dibutyl phthalate weight part ratio prepare this experiment for 70: 20: 10, by mixed solvent:
Ethyl cellulose: polyvinyl butyral: rilanit special: oleic acid weight part is compared prepares needed for this experiment for 90: 10: 2: 2: 4
Organic carrier.It will take 30g organic carrier and 70g devitrified glass 1 that 2h is mixed, then be ground repeatedly with three-roll grinder 5 times
Obtain dielectric paste 1.Dielectric paste 1 is printed on 316 stainless steel substrate surfaces, printing time with plane pattern by silk-screen printing
Number is 3 times, and the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into
It is sintered in Muffle furnace by following technique: with 5 DEG C/min heating rate to 400 DEG C, 3h is kept the temperature, then with 5 DEG C/min heating rate
To 900 DEG C, 3h is kept the temperature.It takes 30g organic carrier and 70g devitrified glass 2 that 2h is mixed, then grinds 5 repeatedly with three-roll grinder
It is secondary to obtain dielectric paste 2.Dielectric paste 2 is printed on above-mentioned 1 surface of dielectric layer, printing time with plane pattern by silk-screen printing
Number is 3 times, and the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into
It is sintered in Muffle furnace by following technique: with 5 DEG C/min heating rate to 400 DEG C, 3h is kept the temperature, then with 5 DEG C/min heating rate
To 700 DEG C, 3h is kept the temperature, stainless steel based composite dielectric layer is obtained.
70gNiFe alloyed powder, 5g graphene, 7g microcrystalline glass powder 2 are taken, wherein graphene is placed in a thickness of 50nm, mixing
In zirconia ball grinding jar, a certain amount of dehydrated alcohol is added, so that powder and dehydrated alcohol is mixed into paste, a certain amount of oxygen is added
Change zirconium ball milling pearl, ratio of grinding media to material 1: 1, wherein than 5: 3: 2, to be subsequently placed in ball mill small with 200r/min ball milling 24 for big-and-middle bead
When, material is filtered out from zirconia ball grinding jar, merging air dry oven is dry, and after dry, material is ground into uniformly
It is powdered, it crosses 100 mesh standard sieve and obtains alloy mixed powder.
It takes 15g organic carrier and above-mentioned 82g alloy mixed powder that 2h is mixed, then is ground repeatedly with three-roll grinder 5 times
Doped graphene resistance alloys slurry is obtained, by silk-screen printing by doped graphene resistance alloys slurry with certain shapes pattern
Circuit be printed on above-mentioned, print pass is 5 times, finally the good sample of silk-screen is put into air dry oven at 80 DEG C dry
1h.After drying, take out sample and be put into vacuum drying oven by the sintering of following technique: vacuum degree control is 10-3Within the scope of Pa, with 4 DEG C/
Min heating rate keeps the temperature 1h to 400 DEG C, and then with 5 DEG C/min heating rate to 700 DEG C, heat preservation 2h obtains stainless base steel fever
Film heater.One layer of insulated heat coating finally is sprayed in fever film surface, one layer of insulation is sprayed at the stainless steel substrate back side and leads
Hot coating is put into air dry oven at 80 DEG C dry 1h.
By a kind of doped graphene alloy heat generating film heater progress resistivity survey of stainless base steel obtained in embodiment
Examination, result performance have excellent electric conductivity, and resistivity is 3.22 × 10-6Ω·m；Insulating properties is tested, insulated electro
Resistance is 7.6G Ω；Heating film heating rate is tested, as a result 6s reaches 300 DEG C；Experimental test is analyzed through thermal shock resistance,
Its result shows thermal cycle 1000 times, and change in resistance 1%, film has no oxidation；Measured through attachment fastness, film and dielectric layer, be situated between
The attachment degree of matter layer and substrate is I grades, and it is high to show bond strength between three.
Embodiment 4:
Blasting treatment, blast time 30min are carried out to 430 stainless steel substrate surfaces.By terpinol: butyl
Mixed solvent needed for acetate, dibutyl phthalate weight part ratio prepare this experiment for 70: 20: 10, by mixed solvent:
Ethyl cellulose: polyvinyl butyral: rilanit special: oleic acid weight part is compared prepares needed for this experiment for 88: 9: 3: 2: 5
Organic carrier.It will take 35g organic carrier and 65g devitrified glass 1 that 2h is mixed, then be ground repeatedly 5 times with three-roll grinder
To dielectric paste 1.Dielectric paste 1 is printed on 430 stainless steel substrate surfaces, print pass with plane pattern by silk-screen printing
It is 3 times, the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into horse
It is not sintered in furnace by following technique: with 3 DEG C/min heating rate to 450 DEG C, keeping the temperature 4h, then arrived with 8 DEG C/min heating rate
850 DEG C, keep the temperature 2h.It takes 35g organic carrier and 65g devitrified glass 2 that 2h is mixed, then is ground repeatedly with three-roll grinder 5 times
Obtain dielectric paste 2.Dielectric paste 2 is printed on above-mentioned 1 surface of dielectric layer, print pass with plane pattern by silk-screen printing
It is 3 times, the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into horse
It is not sintered in furnace by following technique: with 6 DEG C/min heating rate to 350 DEG C, keeping the temperature 2h, then arrived with 2 DEG C/min heating rate
750 DEG C, 4h is kept the temperature, stainless steel based composite dielectric layer is obtained.
60gNiAlCr alloyed powder, 3g graphene, 5g microcrystalline glass powder 2 are taken, wherein graphene is set with a thickness of 35nm, mixing
In zirconia ball grinding jar, a certain amount of dehydrated alcohol is added, powder and dehydrated alcohol is made to be mixed into paste, is added a certain amount of
Zirconium oxide ball milling pearl, ratio of grinding media to material 1: 1, wherein than 5: 3: 2, to be subsequently placed in ball mill small with 200r/min ball milling 24 for big-and-middle bead
When, material is filtered out from zirconia ball grinding jar, merging air dry oven is dry, and after dry, material is ground into uniformly
It is powdered, it crosses 100 mesh standard sieve and obtains alloy mixed powder.
It takes 10g organic carrier and above-mentioned 68g alloy mixed powder that 2h is mixed, then is ground repeatedly with three-roll grinder 5 times
Doped graphene resistance alloys slurry is obtained, by silk-screen printing by doped graphene resistance alloys slurry with certain shapes pattern
Circuit be printed on above-mentioned, print pass is 5 times, finally the good sample of silk-screen is put into air dry oven at 80 DEG C dry
1h.After drying, take out sample and be put into vacuum drying oven by the sintering of following technique: vacuum degree control is 10-3Within the scope of Pa, with 4 DEG C/
Min heating rate keeps the temperature 1h to 400 DEG C, and then with 5 DEG C/min heating rate to 700 DEG C, heat preservation 2h obtains stainless base steel fever
Film heater.One layer of insulated heat coating finally is sprayed in fever film surface, one layer of insulation is sprayed at the stainless steel substrate back side and leads
Hot coating is put into air dry oven at 80 DEG C dry 1h.
By a kind of doped graphene alloy heat generating film heater progress resistivity survey of stainless base steel obtained in embodiment
Examination, result performance have excellent electric conductivity, and resistivity is 3.68 × 10-6Ω·m；Insulating properties is tested, insulated electro
Resistance is 7.3G Ω；Heating film heating rate is tested, as a result 8s reaches 300 DEG C；Experimental test is analyzed through thermal shock resistance,
Its result shows thermal cycle 1000 times, and change in resistance 1%, film has no oxidation；Measured through attachment fastness, film and dielectric layer, be situated between
The attachment degree of matter layer and substrate is I grades, and it is high to show bond strength between three.
Comparative example 1:
It is compared with embodiment 1, difference essentially consists in, and not in dielectric layer 1 surface recombination, one layer of dielectric layer 2, concrete operations are such as
Under:
Blasting treatment, blast time 30min are carried out to 430 stainless steel substrate surfaces.By terpinol: butyl
Mixed solvent needed for acetate, dibutyl phthalate weight part ratio prepare this experiment for 70: 20: 10, by mixed solvent:
Ethyl cellulose: polyvinyl butyral: rilanit special: oleic acid weight part is compared prepares needed for this experiment for 85: 8: 1: 1: 1
Organic carrier.It will take 40g organic carrier and 60g devitrified glass 1 that 2h is mixed, then be ground repeatedly 5 times with three-roll grinder
To dielectric paste 1.Dielectric paste 1 is printed on 430 stainless steel substrate surfaces, print pass with plane pattern by silk-screen printing
It is 3 times, the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into horse
It is not sintered in furnace by following technique: with 2 DEG C/min heating rate to 300 DEG C, 1h is kept the temperature, then with 0.5 DEG C/min heating rate
To 800 DEG C, 1h is kept the temperature, stainless base steel Single Medium layer is obtained.
45gNiB alloyed powder, 1g graphene, 1g microcrystalline glass powder 2 are taken, wherein graphene is placed in oxygen with a thickness of 1nm, mixing
Change in zirconium ball grinder, add a certain amount of dehydrated alcohol, so that powder and dehydrated alcohol is mixed into paste, a certain amount of oxidation is added
Zirconium ball milling pearl, ratio of grinding media to material 1: 1, wherein big-and-middle bead than 5: 3: 2, is subsequently placed in ball mill with 24 hours of 200r/min ball milling,
Material is filtered out from zirconia ball grinding jar, merging air dry oven is dry, and after dry, material is ground into uniform powder
Shape crosses 100 mesh standard sieve and obtains alloy mixed powder.
It takes 10g organic carrier and above-mentioned 47g alloy mixed powder that 2h is mixed, then is ground repeatedly with three-roll grinder 5 times
Doped graphene resistance alloys slurry is obtained, by silk-screen printing by doped graphene resistance alloys slurry with certain shapes pattern
Circuit be printed on above-mentioned, print pass is 5 times, finally the good sample of silk-screen is put into air dry oven at 80 DEG C dry
1h.After drying, take out sample and be put into vacuum drying oven by the sintering of following technique: vacuum degree control is 10-4Within the scope of Pa, with 2 DEG C/
Min heating rate keeps the temperature 0.5h to 300 DEG C, and then with 0.5 DEG C/min heating rate to 600 DEG C, heat preservation 0.5h obtains stainless steel
Base heating film heating-body.One layer of insulated heat coating finally is sprayed in fever film surface, sprays one layer at the stainless steel substrate back side
Insulating heat-conductive coating is put into air dry oven at 80 DEG C dry 1h.
By a kind of doped graphene alloy heat generating film heater progress resistivity survey of stainless base steel obtained in comparative example
Examination, result performance have excellent electric conductivity, and resistivity is 3.22 × 10-6Ω·m；Insulating properties is tested, insulated electro
Resistance is 3G DEG C；Heating film heating rate is tested, as a result 7s reaches 300 DEG C；Experimental test is analyzed through thermal shock resistance,
As a result it shows thermal cycle 1000 times, change in resistance 8%, film has no oxidation；Measured through attachment fastness, film and dielectric layer, medium
The attachment degree of layer and substrate is III level, and it is low to show bond strength between three.
Comparative example 2:
Compared with embodiment 1, difference essentially consists in, resistive layer do not select the present invention claims alloy, graphene and glass
Components system (using the single metal replacement alloy), concrete operations are as follows:
Blasting treatment, blast time 30min are carried out to 430 stainless steel substrate surfaces.By terpinol: butyl
Mixed solvent needed for acetate, dibutyl phthalate weight part ratio prepare this experiment for 70: 20: 10, by mixed solvent:
Ethyl cellulose: polyvinyl butyral: rilanit special: oleic acid weight part is compared prepares needed for this experiment for 85: 8: 1: 1: 1
Organic carrier.It will take 40g organic carrier and 60g devitrified glass 1 that 2h is mixed, then be ground repeatedly 5 times with three-roll grinder
To dielectric paste 1.Dielectric paste 1 is printed on 430 stainless steel substrate surfaces, print pass with plane pattern by silk-screen printing
It is 3 times, the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into horse
It is not sintered in furnace by following technique: with 2 DEG C/min heating rate to 300 DEG C, 1h is kept the temperature, then with 0.5 DEG C/min heating rate
To 800 DEG C, 1h is kept the temperature.It takes 40g organic carrier and 60g devitrified glass 2 that 2h is mixed, then grinds 5 repeatedly with three-roll grinder
It is secondary to obtain dielectric paste 2.Dielectric paste 2 is printed on above-mentioned 1 surface of dielectric layer, printing time with plane pattern by silk-screen printing
Number is 3 times, and the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into
It is sintered in Muffle furnace by following technique: with 2 DEG C/min heating rate to 300 DEG C, keeping the temperature 1h, then heated up with 0.5 DEG C/min fast
Rate keeps the temperature 1h, obtains stainless steel based composite dielectric layer to 600 DEG C.
45gNi metal powder, 1g graphene, 1g microcrystalline glass powder 2 are taken, wherein graphene is placed in oxygen with a thickness of 1nm, mixing
Change in zirconium ball grinder, add a certain amount of dehydrated alcohol, so that powder and dehydrated alcohol is mixed into paste, a certain amount of oxidation is added
Zirconium ball milling pearl, ratio of grinding media to material 1: 1, wherein big-and-middle bead than 5: 3: 2, is subsequently placed in ball mill with 24 hours of 200r/min ball milling,
Material is filtered out from zirconia ball grinding jar, merging air dry oven is dry, and after dry, material is ground into uniform powder
Shape crosses 100 mesh standard sieve and obtains metal mixed powder.
It takes 10g organic carrier and above-mentioned 47g metal mixed powder that 2h is mixed, then is ground repeatedly with three-roll grinder 5 times
Doped graphene metallic resistance slurry is obtained, by silk-screen printing by doped graphene metallic resistance slurry with certain shapes pattern
Circuit be printed on above-mentioned, print pass is 5 times, finally the good sample of silk-screen is put into air dry oven at 80 DEG C dry
1h.After drying, take out sample and be put into vacuum drying oven by the sintering of following technique: vacuum degree control is 10-4Within the scope of Pa, with 2 DEG C/
Min heating rate keeps the temperature 0.5h to 300 DEG C, and then with 0.5 DEG C/min heating rate to 600 DEG C, heat preservation 0.5h obtains stainless steel
Base heating film heating-body.One layer of insulated heat coating finally is sprayed in fever film surface, sprays one layer at the stainless steel substrate back side
Insulating heat-conductive coating is put into air dry oven at 80 DEG C dry 1h.
By a kind of doped graphene metal heating film heating-body progress resistivity survey of stainless base steel obtained in comparative example
Examination, result performance have excellent electric conductivity, and resistivity is 4.67 × 10-6Ω·m；Insulating properties is tested, insulated electro
Resistance is 8G Ω；Heating film heating rate is tested, as a result 13s reaches 300 DEG C；Experimental test is analyzed through thermal shock resistance,
Its result shows thermal cycle 1000 times, and change in resistance 15%, film aoxidizes；Measured through attachment fastness, film and dielectric layer, be situated between
The attachment degree of matter layer and substrate is I grades, and it is high to show bond strength between three.
Comparative example 3:
It is compared with embodiment 1, the main distinction is, resistive layer is not added with graphene, specific as follows:
Blasting treatment, blast time 30min are carried out to 430 stainless steel substrate surfaces.By terpinol: butyl
Mixed solvent needed for acetate, dibutyl phthalate weight part ratio prepare this experiment for 70: 20: 10, by mixed solvent:
Ethyl cellulose: polyvinyl butyral: rilanit special: oleic acid weight part is compared prepares needed for this experiment for 85: 8: 1: 1: 1
Organic carrier.It will take 40g organic carrier and 60g devitrified glass 1 that 2h is mixed, then be ground repeatedly 5 times with three-roll grinder
To dielectric paste 1.Dielectric paste 1 is printed on 430 stainless steel substrate surfaces, print pass with plane pattern by silk-screen printing
It is 3 times, the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into horse
It is not sintered in furnace by following technique: with 2 DEG C/min heating rate to 300 DEG C, 1h is kept the temperature, then with 0.5 DEG C/min heating rate
To 800 DEG C, 1h is kept the temperature.It takes 40g organic carrier and 60g devitrified glass 2 that 2h is mixed, then grinds 5 repeatedly with three-roll grinder
It is secondary to obtain dielectric paste 2.Dielectric paste 2 is printed on above-mentioned 1 surface of dielectric layer, printing time with plane pattern by silk-screen printing
Number is 3 times, and the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, takes out sample and be put into
It is sintered in Muffle furnace by following technique: with 2 DEG C/min heating rate to 300 DEG C, keeping the temperature 1h, then heated up with 0.5 DEG C/min fast
Rate keeps the temperature 1h, obtains stainless steel based composite dielectric layer to 600 DEG C.
45gNiB alloyed powder, 1g microcrystalline glass powder 2 are taken, mixes, is placed in zirconia ball grinding jar, is added a certain amount of anhydrous
Ethyl alcohol makes powder and dehydrated alcohol be mixed into paste, a certain amount of zirconium oxide ball milling pearl, ratio of grinding media to material 1: 1, wherein large, medium and small is added
Ball is subsequently placed in ball mill with 24 hours of 200r/min ball milling, material is filtered out from zirconia ball grinding jar than 5: 3: 2
Come, merging air dry oven is dry, after dry, material is ground into uniform powdered, crossing 100 mesh standard sieve, to obtain alloy mixed
Close powder.
It takes 10g organic carrier and above-mentioned 46g alloy mixed powder that 2h is mixed, then is ground repeatedly with three-roll grinder 5 times
Resistance alloys slurry is obtained, resistance alloys slurry is printed on to above-mentioned, print by silk-screen printing with the circuit of certain shapes pattern
Brush number is 5 times, and the good sample of silk-screen is finally put into air dry oven at 80 DEG C dry 1h.After drying, sample is taken out
Be put into vacuum drying oven and be sintered by following technique: vacuum degree control is 10-4Within the scope of Pa, with 2 DEG C/min heating rate to 300 DEG C,
0.5h is kept the temperature, then with 0.5 DEG C/min heating rate to 600 DEG C, heat preservation 0.5h obtains stainless base steel heating film heating-body.Finally
One layer of insulated heat coating is sprayed in fever film surface, one layer of insulating heat-conductive coating is sprayed at the stainless steel substrate back side, is put into drum
1h is dried in wind drying box at 80 DEG C.
By a kind of alloy heat generating film heater progress resistivity measurement of stainless base steel obtained in comparative example, result table
Now there is poor electric conductivity, resistivity is 6.04 × 10-5Ω·m；Insulating properties is tested, insulation resistance is 5.5G Ω；
Heating film heating rate is tested, as a result 10s reaches 300 DEG C；Experimental test, result performance are analyzed through thermal shock resistance
Thermal cycle 1000 times, change in resistance 13%, film has no oxidation；It is measured through attachment fastness, film is III with dielectric layer attachment degree
The attachment degree of grade, dielectric layer and substrate is I grades, and it is low to show bond strength between three.
It can be seen that the doped graphene alloy heat generating film conductivity of stainless base steel of the invention is good, adds from embodiment 1-4
The advantages that thermal velocity is fast, adhesive strength is high, safety is good.
If not it can be seen that using doped graphene alloy of the invention from embodiment 1 and comparative example 1-3 as function phase,
And not have the devitrified glass of different gradient fusing points as stainless steel substrate compound medium layer using the present invention, then it is formed
The shortcomings that disadvantage of heating film electric conductivity difference, heating film heating-body heating speed is slow, low efficiency, and film and dielectric layer,
Adhesive strength degradation between dielectric layer and substrate three.
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that these
It is merely illustrative of, after having read above content of the invention, those skilled in the art can make various change to the present invention
Dynamic or modification, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (10)
1. a kind of graphene/lowpriced metal alloy conductive material, which is characterized in that include graphene, alloyed powder and glass powder.
2. graphene as described in claim 1/lowpriced metal alloy conductive material, which is characterized in that glass powder is devitrified glass,
Its solid-phase component is SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3-Bi2O3；Fusing point is 600 DEG C~800 DEG C.
Preferably, the alloyed powder is at least one of NiB, NiCu, NiFe, NiAlCr；
Preferably, the graphene is multi-layer graphene, with a thickness of 1nm~100nm.
3. graphene as claimed in claim 1 or 2/lowpriced metal alloy conductive material, which is characterized in that the parts by weight of alloyed powder
It is 45~90 parts；The parts by weight of graphene are 1~10 part；The parts by weight of glass powder are 1~15 part.
4. a kind of doped graphene resistance alloys slurry, which is characterized in that include the described in any item graphite of claims 1 to 3
Alkene/lowpriced metal alloy conductive material and organic carrier；
Preferably, the organic carrier includes solvent, thickener, thixotropic agent, surfactant and binder.
5. doped graphene resistance alloys slurry as claimed in claim 4, which is characterized in that
In the organic carrier, solvent, thickener, thixotropic agent, surfactant and binder mass parts ratio be 85-93:
8-14:1-4:1-4:1-8；
The mass percent that organic carrier accounts for the doped graphene resistance alloys slurry is 10%~30%；
The solvent is terpinol, butyl acetate, one or more in dibutyl phthalate.
6. a kind of doped graphene alloy heat generating film heater of stainless base steel, which is characterized in that include stainless steel base, phase
Pair two planes be compounded with thermal insulation layer and dielectric layer 1 respectively；1 surface recombination of dielectric layer has dielectric layer 2；2 table of dielectric layer
Face is compounded with resistance alloys layer；Resistance alloys layer surface is compounded with insulated thermal insulating layer；
The resistance alloys layer contains the described in any item graphenes of claims 1 to 3/lowpriced metal alloy conductive material；It is excellent
Choosing is obtained by the described in any item doped graphene resistance alloys slurry curings of claim 4~5.
7. the doped graphene alloy heat generating film heater of stainless base steel as claimed in claim 6, which is characterized in that described
Dielectric layer 1 contains glass 1, and the dielectric layer 2 contains glass 2；
The fusing point of glass 1 is 800 DEG C~1000 DEG C；The fusing point of glass 2 is 600 DEG C~800 DEG C；
Preferably, the glass 1 is devitrified glass, solid-phase component SiO2-Al2O3-CaO-MgO-B2O3；
Preferably, the glass 2 is devitrified glass, solid-phase component SiO2-Al2O3-CaO-MgO-B2O3-Bi2O3。
8. a kind of preparation of the doped graphene alloy heat generating film heater of the described in any item stainless base steels of claim 6~7
Method, which comprises the following steps:
Step 1: stainless steel substrate surface is pre-processed；
Step 2: solvent, thickener, thixotropic agent, surfactant, binder are mixed, organic carrier is obtained；
Step 3: glass 1, glass 2 are mixed with organic carrier respectively, respectively obtain dielectric paste 1 and dielectric paste 2；
Step 4: dielectric paste 1 is compounded in a plane of pretreated stainless steel substrate, dry, sintering, stainless
The dielectric layer 1 is formed on steel substrate；Then the surface recombination dielectric paste 2 of dielectric layer 1, drying are sintered, in dielectric layer again
1 surface forms the dielectric layer 2；
Step 5: alloyed powder, Graphene powder, glass powder are mixed, the graphene/lowpriced metal alloy conductive material is obtained；
Step 6: it mixes, obtains by organic carrier is prepared into the graphene/lowpriced metal alloy conductive material and step 2
The doped graphene resistance alloys slurry；
Step 7: doped graphene resistance alloys slurry is compounded on the dielectric layer 2 in step 4, dry, sintering, in medium
The resistance alloys layer is formed on layer 2；
Step 8: the resistance alloys layer that step 7 is obtained sprays one layer of insulated heat slurry；Stainless steel substrate compound medium layer 1
Opposite face spray one layer of insulating heat-conductive slurry, it is dry, obtain the doped graphene alloy heat generating film hair of the stainless base steel
Hot body.
9. preparation method as claimed in claim 8, it is characterised in that: the stainless steel substrate is a kind of in 430,304,316；
Preferably, in step 4,1 sintering process of dielectric layer are as follows: in air, with 2 DEG C/min~10 DEG C/min heating speed
Rate keeps the temperature 1h~5h to 300 DEG C~500 DEG C, then with 0.5 DEG C/min~10 DEG C/min heating rate to 800 DEG C~1000 DEG C,
Keep the temperature 1h~5h；
Preferably, 2 sintering process of dielectric layer are as follows: in air, with 2 DEG C/min~10 DEG C/min heating rate to 300 DEG C~500
DEG C, 1h~5h is kept the temperature, then with 0.5 DEG C/min~10 DEG C/min heating rate to 600 DEG C~800 DEG C, keeps the temperature 1h~5h；
In step 7, resistance alloys layer sintering process are as follows: vacuum degree be 10-4~10-3In Pa vacuum, with 2 DEG C/min~10 DEG C/
Min heating rate keeps the temperature 0.5h~2h, then with 0.5 DEG C/min~10 DEG C/min heating rate to 600 to 300 DEG C~500 DEG C
DEG C~800 DEG C, keep the temperature 0.5h~3h.
10. any one of heater described in a kind of claim 6-7 or claim 8~9 preparation method hair obtained
The application of hot body, it is characterised in that: the application includes being applied in permanent lod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810491757.3A CN110519870B (en) | 2018-05-21 | 2018-05-21 | Graphene/base metal alloy conductive material, resistance paste, heating element, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810491757.3A CN110519870B (en) | 2018-05-21 | 2018-05-21 | Graphene/base metal alloy conductive material, resistance paste, heating element, preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110519870A true CN110519870A (en) | 2019-11-29 |
| CN110519870B CN110519870B (en) | 2020-06-26 |
Family
ID=68621656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810491757.3A Active CN110519870B (en) | 2018-05-21 | 2018-05-21 | Graphene/base metal alloy conductive material, resistance paste, heating element, preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110519870B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111447694A (en) * | 2020-04-15 | 2020-07-24 | 广东康烯科技有限公司 | Palladium quantum dot doped graphene-based electric heating plate and electric heating device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1937856A (en) * | 2006-07-28 | 2007-03-28 | 王克政 | Rare earth basic-metal resistance size for metal base board based rare earth thick film circuit and its preparing process |
| CN105472791A (en) * | 2015-12-23 | 2016-04-06 | 东莞珂洛赫慕电子材料科技有限公司 | Rare earth-doped semiconductor infrared radiation thick-film electronic paste and preparation method therefor |
| CN107396466A (en) * | 2017-07-03 | 2017-11-24 | 王克政 | Electric slurry and preparation method thereof, thick film circuit chip thermal source and preparation method thereof |
| CN107979880A (en) * | 2017-12-19 | 2018-05-01 | 广东美的厨房电器制造有限公司 | Thick film heating plate and there is its electric steam box |
-
2018
- 2018-05-21 CN CN201810491757.3A patent/CN110519870B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1937856A (en) * | 2006-07-28 | 2007-03-28 | 王克政 | Rare earth basic-metal resistance size for metal base board based rare earth thick film circuit and its preparing process |
| CN105472791A (en) * | 2015-12-23 | 2016-04-06 | 东莞珂洛赫慕电子材料科技有限公司 | Rare earth-doped semiconductor infrared radiation thick-film electronic paste and preparation method therefor |
| CN107396466A (en) * | 2017-07-03 | 2017-11-24 | 王克政 | Electric slurry and preparation method thereof, thick film circuit chip thermal source and preparation method thereof |
| CN107979880A (en) * | 2017-12-19 | 2018-05-01 | 广东美的厨房电器制造有限公司 | Thick film heating plate and there is its electric steam box |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111447694A (en) * | 2020-04-15 | 2020-07-24 | 广东康烯科技有限公司 | Palladium quantum dot doped graphene-based electric heating plate and electric heating device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110519870B (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107182139B (en) | Metal film porous ceramic heating body and application thereof | |
| CN107173849B (en) | A kind of conductivity ceramics film Multi-hole ceramic heating element and its application | |
| CN107747080B (en) | Radar and infrared compatible stealth coating capable of resisting temperature of 600 ℃ and preparation method thereof | |
| CN101321415B (en) | Rare earth thick film circuit electrical heating element based on aluminum nitride minicrystal ceramic substrates and its preparation technique | |
| CN105825913A (en) | Anti-aging back silver pulp used in crystalline silicon solar cell and preparation method for same | |
| CN100499940C (en) | Rare earth electrode slurry of rare earth thick film circuit based on metal plate and its preparation technology | |
| CN101714439B (en) | Zinc oxide resistance piece and preparation method thereof | |
| CN103476156B (en) | Glass ceramic heating substrate coated with inorganic thick film, preparing method and heating assembly | |
| CN105163539B (en) | Zirconia ceramics rear cover with wireless charging function and its manufacturing method | |
| CN104505139A (en) | Low-resistance high-efficiency lead-free back silver pulp for amorphous silicon solar battery | |
| CN107564601A (en) | A kind of backplate slurry for two-sided PERC solar cells and preparation method thereof | |
| CN103332942B (en) | Low temperature sintered Ni metal fiber composite ceramic substrate | |
| CN107396466A (en) | Electric slurry and preparation method thereof, thick film circuit chip thermal source and preparation method thereof | |
| CN111601407B (en) | Graphene heating film for electric heating picture and preparation method thereof | |
| CN114792588B (en) | Preparation method of conductive silver paste for spraying electrode silver grid aerosol of solar cell | |
| CN109215837A (en) | A kind of conductive silver slurry used for solar batteries and preparation method thereof | |
| CN106810915B (en) | A kind of novel magnetic exothermic paint | |
| CN105176103A (en) | Thick film circuit insulating dielectric slurry for aluminum substrates, and preparation method thereof | |
| CN102786294A (en) | Insulating layer slurry of chip-type oxygen sensor and insulating layer preparation method | |
| CN110519870A (en) | A kind of graphene/lowpriced metal alloy conductive material, resistance slurry, heater and its preparation and application | |
| CN103367546A (en) | Preparation technology of photovoltaic battery front-face electrode | |
| CN111063477B (en) | Stainless steel substrate thick film circuit insulating medium slurry and preparation method thereof | |
| CN103177790B (en) | The preparation method of solar cell back surface field transition slurry and preparation method thereof and solar battery sheet and solar battery sheet | |
| CN114058196A (en) | Heat-conducting insulating slurry, preparation method and heating device thereof | |
| CN108682478B (en) | Composite oxide microcrystalline glass, insulating medium slurry, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |