CN115386304B - High-heat-conductivity inorganic adhesive powder and preparation method and application method thereof - Google Patents
High-heat-conductivity inorganic adhesive powder and preparation method and application method thereof Download PDFInfo
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- CN115386304B CN115386304B CN202210702835.6A CN202210702835A CN115386304B CN 115386304 B CN115386304 B CN 115386304B CN 202210702835 A CN202210702835 A CN 202210702835A CN 115386304 B CN115386304 B CN 115386304B
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- 239000000843 powder Substances 0.000 title claims abstract description 202
- 239000000853 adhesive Substances 0.000 title claims abstract description 166
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 60
- 239000000945 filler Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000007580 dry-mixing Methods 0.000 claims abstract description 36
- 238000000227 grinding Methods 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000002694 phosphate binding agent Substances 0.000 claims abstract description 17
- 238000005303 weighing Methods 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 57
- 239000002002 slurry Substances 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical group [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 9
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 9
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 claims description 2
- 235000019785 monomagnesium phosphate Nutrition 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 20
- 239000010452 phosphate Substances 0.000 abstract description 20
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 238000001723 curing Methods 0.000 description 37
- 239000000463 material Substances 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- -1 alkali metal dihydrogen phosphate Chemical class 0.000 description 11
- 238000011049 filling Methods 0.000 description 10
- 238000004382 potting Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J1/00—Adhesives based on inorganic constituents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides high-heat-conductivity inorganic adhesive powder, a preparation method and a using method thereof, wherein the preparation method comprises the following steps: weighing raw material powder according to a preset proportion, placing the raw material powder in a ball milling tank, and placing light grinding balls matched with the raw material in mass in the ball milling tank, wherein the raw material components comprise AlN filler, phosphate binder, curing agent, stabilizer and water reducer; placing the ball milling tank in a ball mill for preliminary dry mixing; grinding the powder after preliminary dry mixing; and (3) placing the ground powder in a ball milling tank again, placing the ball milling tank in a ball mill, and performing secondary dry mixing to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder. The high-heat-conductivity inorganic adhesive prepared from the high-heat-conductivity inorganic adhesive powder can improve the heat conductivity of phosphate adhesive while ensuring the excellent performance of the phosphate adhesive, and can be applied to the field of packaging of electronic devices such as temperature sensor temperature sensing parts and the like.
Description
Technical Field
The invention relates to the technical field of high-temperature-resistant adhesive powder preparation, in particular to high-heat-conductivity inorganic adhesive powder, and a preparation method and a use method thereof.
Background
Aerospace technology is an important manifestation of national science and technology, industry and defense, and integrates many of the most advanced achievements of science and technology in the world today. Among them, the application of sensor technology is very widespread in the aerospace field. An aircraft is typically equipped with thousands or even tens of thousands of different types of sensors to ensure safe operation of the aircraft. The temperature sensor is one of the important application categories, and is mainly used for monitoring the brake temperature, the engine temperature, the cabin temperature and the like of the landing gear of the aircraft.
The most important part of the temperature sensor is its temperature sensing part. In the temperature sensing component, the space between the inside of the sleeve and the thermal resistance wire needs to be filled with an adhesive in a potting way. Temperature sensors are often subjected to severe operating environments, often subjected to large temperature gradient changes and large magnitude vibration loads in a short period of time, causing thermal failure or some vibration fatigue damage. This also becomes a safety hazard during operation of the aircraft.
Because of the special working environment of the temperature sensor, the longer service life and the higher reliability of the temperature sensor are ensured, and the higher requirements on the performance of the potting adhesive are provided: firstly, the potting adhesive has high heat conductivity, so that the temperature measurement efficiency of the sensor is ensured; secondly, the potting adhesive needs to have higher bonding strength, so that the stability of the sensor in a high-vibration environment is ensured; meanwhile, the potting adhesive also needs to have certain high temperature resistance, electrical insulation performance, better fluidity, good potting performance and the like. However, it is difficult for the current high temperature resistant adhesives to meet these performance requirements simultaneously.
Disclosure of Invention
The embodiment of the invention provides high-heat-conductivity inorganic adhesive powder, a preparation method and a use method thereof, and the high-heat-conductivity inorganic adhesive prepared from the high-heat-conductivity inorganic adhesive powder can improve the heat conductivity of phosphate adhesive while ensuring the excellent performance of the phosphate adhesive, and can be applied to the field of packaging of electronic devices such as temperature sensor temperature sensing parts and the like.
The technical scheme provided by the embodiment of the invention is as follows:
the invention provides a preparation method of high-heat-conductivity inorganic adhesive powder, which comprises the following steps:
weighing raw material powder according to a preset proportion, and placing the raw material powder in a ball milling tank, wherein light grinding balls matched with the raw material in mass are placed in the ball milling tank, and the raw material comprises the following components: alN filler, phosphate binder, curing agent, stabilizer and water reducer;
placing the ball milling tank in a ball mill for preliminary dry mixing;
grinding the powder after preliminary dry mixing;
and (3) placing the ground powder in a ball milling tank again, and placing the ball milling tank in a ball mill for secondary dry mixing to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
Illustratively, the placing the ball milling tank in a ball mill for primary dry mixing and/or the placing the ball milling tank in a ball mill for secondary dry mixing specifically comprises:
the ball milling tank is placed in a ball mill, and dry-mixed for 1-2 hours at the speed of 200-400 rpm.
Illustratively, when the powder after preliminary dry mixing is ground, the grinding time is 10 to 20 minutes.
The AlN filler is prepared from two AlN powders with different average particle sizes, wherein the two AlN powders are respectively a first AlN powder and a second AlN powder, the average particle size of the first AlN powder is larger than that of the second AlN powder, the average particle size of the first AlN powder is 10-80 mu m, the average particle size of the second AlN powder is 0.5-5 mu m, and the weight ratio of the first AlN powder to the second AlN powder is 1.5:1-3:1.
Illustratively, the phosphate binder includes one or more of aluminum dihydrogen phosphate, alkali metal dihydrogen phosphate, and alkaline earth metal dihydrogen phosphate, and the mass of the phosphate binder is 7% -20% of the mass of the AlN filler.
Illustratively, the curing agent comprises one or more of magnesium oxide, aluminum oxide, zinc oxide, chromium oxide and other metal oxides, and the mass of the curing agent is 0.01-0.5% of the mass of the AlN filler.
Illustratively, the stabilizer is nano-silica, and the mass of the stabilizer is 0.5% -2.0% of the mass of the AlN filler.
Illustratively, the water reducer comprises one or more of inorganic water reducers such as sodium hexametaphosphate, sodium tripolyphosphate, sodium polyphosphate, borax and the like, and the mass of the water reducer is 0.1-1.0% of the mass of the AlN filler.
The invention also provides high-heat-conductivity inorganic adhesive powder, which is prepared by the preparation method of the high-heat-conductivity inorganic adhesive powder.
The invention also provides a use method of the high-heat-conductivity inorganic adhesive powder, which comprises the following steps: adding 15-20% of water into the high-heat-conductivity inorganic adhesive powder, stirring and mixing to obtain uniform slurry, smearing or filling the uniform slurry in a region to be glued, and curing for 2-24 hours at the temperature of between room temperature and 120 ℃ to cure the uniform slurry.
The embodiment of the invention has the following beneficial effects:
the high-heat-conductivity inorganic adhesive powder, the preparation method and the use method thereof provided by the embodiment of the invention have the advantages of simple and quick preparation process and simple and convenient use method, and are beneficial to large-scale production. The high-heat-conductivity inorganic adhesive prepared from the adhesive powder can be used as a special potting adhesive for aviation onboard temperature sensors, which has the advantages of high heat conductivity, good fluidity, low curing temperature, high compression and shear strength, good electrical insulation, high thermal stability and the like.
Drawings
The accompanying drawings, which are incorporated herein and form a part of the specification, illustrate embodiments of the present invention and, together with the description, further serve to explain the principles of the invention and to enable a person skilled in the pertinent art to make and use the invention.
FIG. 1 is a cross-sectional SEM image after curing of the adhesive prepared in example 2 of the present invention, wherein FIG. 1 (a) is an image at 100 times magnification and FIG. 1 (b) is an image at 500 times magnification;
FIG. 2 is a schematic diagram showing the viscosity change of the adhesive slurries prepared in examples 2 to 6 of the present invention;
FIG. 3 is a graph showing the thermal conductivity change curve of the cured adhesives prepared in examples 2 to 6 of the present invention;
FIG. 4 is a graph showing the change of the bonding strength of the adhesives prepared in examples 2 to 6 according to the present invention after curing, wherein FIG. 4 (a) is a graph showing the change of the compressive strength of the adhesives after curing; FIG. 4 (a) is a graph showing the change in shear strength after curing of the adhesive;
fig. 5 is a graph showing the morphology of the adhesive prepared in example 2 of the present invention after curing and before and after heat preservation in a high temperature oven at 600 ℃ for 2 hours, wherein fig. 5 (a) is a graph showing the morphology of the adhesive before heat treatment and fig. 5 (b) is a graph showing the morphology of the adhesive after heat treatment.
Detailed Description
The invention provides high-heat-conductivity inorganic adhesive powder, and a preparation method and a use method thereof, which are described in detail below with reference to the accompanying drawings and specific examples. While the invention has been described herein in terms of the preferred and preferred embodiments, the following embodiments are intended to be more illustrative, and may be implemented in many alternative ways as will occur to those of skill in the art; and the accompanying drawings are only for the purpose of describing the embodiments more specifically and are not intended to limit the invention specifically.
Before explaining in detail a high thermal conductive inorganic adhesive powder, a preparation method thereof, and a use method thereof provided in the embodiments of the present disclosure, the following description is necessary for the related art:
the high-temperature resistant adhesive can be divided into an organic type and an inorganic type according to different raw materials. The organic adhesive can generate strong bonding effect with the matrix, but has limited heat resistance and aging resistance, and is not suitable for a service environment at high temperature for a long time. Chinese patent CN112322244A discloses an organic adhesive taking polyurethane resin and the like as raw materials, overcomes the limitation that an organic silica gel adhesive and the like can only be used at 200-250 ℃ for a short time, improves the use temperature range to 350-400 ℃, has limited lifting effect, and is not suitable for encapsulating a temperature sensor for aerospace.
In contrast, inorganic adhesives can still maintain their own excellent properties at high temperatures, and have long service lives and are not prone to aging. At present, silicate inorganic adhesives are applied in a plurality of fields, but the curing temperature is high, and metal substrates are corroded by silicate components in the adhesives at high temperature, so that the service life is seriously influenced. Chinese patent CN109749633B discloses a silicate high temperature resistant adhesive which uses water glass, alumina powder and the like as main raw materials and can be cured at normal temperature, and can resist high temperature of 1600 ℃, and shear strength at 1600 ℃ is several times that of conventional inorganic adhesive, but curing time is longer, and the adhesive needs to be kept stand at normal temperature for more than 48 hours.
The phosphate inorganic adhesive has low curing temperature, good high temperature resistance after curing, good matching with metal, ceramic, glass and other materials, and high adhesive strength, environmental friendliness and low cost, so that the phosphate inorganic adhesive is widely concerned and applied. Chinese patent CN108083665a discloses a composite high temperature adhesive of aluminum dihydrogen phosphate-silica micropowder, which uses aluminum dihydrogen phosphate as adhesive, silica micropowder, alumina powder, etc. as filler, and magnesium oxide as curing agent, and can be cured at normal temperature for 24 hours, and its young's modulus, flexural strength, compressive strength and shear strength are 19.32GPa, 9.46MPa, 15.6MPa and 2.72MPa respectively at 1500 ℃.
Although the phosphate adhesive has a plurality of advantages, the phosphate adhesive has lower heat conductivity, and is difficult to meet the fields of temperature sensors and the like with higher requirements on the heat dissipation capacity of materials.
At present, researchers in the field focus on traditional performances such as high temperature resistance, bonding strength, curing rate and the like of an adhesive, but under the condition of ensuring the performances, how to improve the heat dissipation performance of the adhesive has not been reported in the related art.
Al N is a ceramic material with excellent comprehensive performance, the theoretical thermal conductivity of the material can reach 320W/m.K, and the material has the excellent characteristics of good electrical insulation, low dielectric constant and dielectric loss, thermal expansion coefficient matched with silicon, stable chemical performance, no toxicity and the like. Therefore, al N is now the most desirable electronic device packaging material. The related art has paid great attention to the preparation of thermally conductive composites with Al N as a filler. However, in the field of high temperature resistant adhesives, development of a high thermal conductivity inorganic adhesive using a phosphate binder as a matrix and Al N as a filler is urgent.
The high-heat-conductivity inorganic adhesive powder, the preparation method thereof and the high-heat-conductivity inorganic adhesive provided by the embodiment of the invention can improve the heat conductivity of the phosphate adhesive while ensuring the excellent performance of the phosphate adhesive, and can be applied to the field of packaging of electronic devices such as temperature sensing parts of temperature sensors.
The embodiment of the invention provides a preparation method of high-heat-conductivity inorganic adhesive powder, which comprises the following steps:
firstly, weighing raw material powder according to a preset proportion, and placing the raw material powder in a ball milling tank, wherein light grinding balls matched with the raw material in mass are placed in the ball milling tank, and the components of the raw material comprise AlN filler, phosphate binder, curing agent, stabilizer and water reducer which are mixed according to a preset mass ratio;
step two, placing the ball milling tank in a ball mill for preliminary dry mixing;
grinding the powder after preliminary dry mixing;
and fourthly, placing the ground powder in a ball milling tank again, and placing the ball milling tank in a ball mill for secondary dry mixing to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
The preparation method of the high-heat-conductivity inorganic adhesive powder provided by the scheme has the advantages of simple and quick preparation process, simple and convenient use method and contribution to large-scale production; the high-heat-conductivity inorganic adhesive prepared from the adhesive powder can be used as a special potting adhesive for aviation onboard temperature sensors, which has the advantages of high heat conductivity, good fluidity, low curing temperature, high compression and shearing strength, good electrical insulation, high thermal stability and the like.
The first step of placing the ball milling tank in a ball mill for preliminary dry blending specifically includes:
the ball milling tank is placed in a ball mill, and dry-mixed for 1-2 hours at the speed of 200-400 rpm.
Illustratively, when the powder after preliminary dry mixing is ground, the grinding time is 10 to 20 minutes.
The ball milling tank is placed in a ball mill for secondary dry mixing in the fourth step, which specifically comprises the following steps:
the ball milling tank is placed in a ball mill, and dry-mixed for 1-2 hours at the speed of 200-400 rpm.
The AlN filler is prepared from two AlN powders with different average particle sizes, wherein the two AlN powders are respectively a first AlN powder and a second AlN powder, the average particle size of the first AlN powder is larger than that of the second AlN powder, the average particle size of the first AlN powder is 10-80 mu m, the average particle size of the second AlN powder is 0.5-5 mu m, and the weight ratio of the first AlN powder to the second AlN powder is 1.5:1-3:1.
In theory, alN powder having a larger average particle diameter contributes more to improvement of the thermal conductivity of the system. On one hand, the specific surface area of the powder with large particle size is small, so that the contact area between the powder and the matrix on the heat conduction channel is small, the interface thermal resistance is low, and the obtained composite material has high heat conductivity; on the other hand, the powder with large particle size has lower surface energy and better dispersibility, and is beneficial to improving the fluidity of adhesive slurry.
However, the inventors have found that if only AlN powder having a large average particle diameter is used as a filler, the filler needs to have a reasonable particle size distribution. When filling is carried out by adopting the filler with single particle size, the maximum filling fraction of the filler in the matrix is not more than the volume fraction of the filler in the closest packing, thus the space utilization rate is low, and the heat conductivity and the strength of the system are greatly improved. And the AlN powder with large particles and small particles is mixed and then used as a filler, so that the problem can be well solved. Under ideal conditions, large-particle-size AlN powder particles are closely stacked, small-particle-size AlN powder particles can be filled in gaps of the large-particle-size AlN powder, the large-particle-size AlN powder is a heat conduction main body, and the small-particle-size AlN powder serves as a heat conduction bridge. Compared with AlN powder with single particle size as stuffing, the space utilization rate is greatly raised, and the system has high heat conductivity and raised strength.
Therefore, in the scheme, the AlN filler is prepared from two AlN powder grades with different average particle sizes, so that the space utilization rate can be improved, and the system can obtain higher heat conductivity and strength.
It should be understood that the above is only a preferred embodiment, and in practical applications, the AlN filler may be composed of one kind of AlN powder, or may be prepared from two or more kinds of AlN powders having different average particle diameters.
Illustratively, the phosphate binder includes one or more of aluminum dihydrogen phosphate, alkali metal dihydrogen phosphate, and alkaline earth metal dihydrogen phosphate, and the mass of the phosphate binder is 7% -20% of the mass of the AlN filler.
By adopting the scheme, on one hand, when the ratio M/P of the content M of the phosphate metal ions to the phosphorus content P is smaller, the bonding system is more stable, but the curing property and the water resistance of the bonding agent are reduced. Conversely, when the value of M/P is large, the curability and water resistance of the adhesive are improved to some extent, but at the same time the stability of the adhesive is lowered. On the other hand, the kind of metal element can also have direct influence on the performance of the phosphate binder, for example, if the metal in the phosphate is calcium and zinc, the water resistance of the binder is stronger than that of magnesium, and if the metal is manganese, iron and copper, the water resistance is weaker; when the metal is magnesium, calcium, copper, iron and zinc, the adhesiveness of the binder is sequentially reduced.
In the invention, the phosphate binder is one or more of aluminum dihydrogen phosphate, alkali metal dihydrogen phosphate and alkaline earth metal dihydrogen phosphate, and the addition amount of the phosphate binder is 7-20% of the AlN filler, so that the excellent performance of the phosphate adhesive is ensured, and the heat conductivity of the phosphate adhesive is improved, and the phosphate adhesive can be applied to the field of packaging of electronic devices such as temperature sensor temperature sensing parts.
Further, the curing agent may include one or more of metal oxides such as magnesium oxide, aluminum oxide, zinc oxide, and chromium oxide, and the mass of the curing agent may be 0.01% to 0.5% of the mass of the AlN filler.
By adopting the scheme, in the low-temperature curing molding method, no matter what the preparation of the phosphate composite material in the reinforcing mode is, the metal oxide auxiliary agent is adopted to promote the curing condensation of the phosphate, so that the metal oxide powder is selected as the curing agent in the scheme. The curing agent of the phosphate binder usually adopts magnesium oxide, aluminum oxide, zinc oxide or chromium oxide and other powder, but zinc oxide has high reactivity and high speed, and the excessive addition amount easily causes high porosity, non-compact stacking and poor mechanical strength of the binder matrix; the reactivity of alumina and chromia is low, and when the addition amount is low, the phosphate binder matrix is incompletely and incompletely cured, so that the problems of low strength, easy moisture absorption and the like are caused. Therefore, the addition amount needs to be regulated according to the type of the metal oxide, so that a proper curing rate is obtained to ensure the stable performance of the adhesive.
Based on the above, the inventor has creatively studied, and in the embodiment of the invention, the curing agent in the raw material is one or more of metal oxides such as magnesium oxide, aluminum oxide, zinc oxide, chromium oxide and the like, and the addition amount of the curing agent is 0.01% -0.2% of the mass of the AlN filler.
Further, the stabilizer is illustratively nano-silica, the mass of the stabilizer being 0.5% to 2.0% of the mass of the AlN filler.
In the scheme, when the nanoscale silicon dioxide particles are dispersed in water or other solvents, a large number of active groups such as water, hydroxyl groups and the like are contained on the surfaces of the nanoscale silicon dioxide particles, and are crosslinked with phosphate active hydroxyl groups, so that netlike macromolecules are more easily formed, and the stability and the bonding strength of the adhesive are improved. Meanwhile, the nanoscale silicon dioxide particles can form a film at room temperature, and the formed film layer can be used as a crystallization center of phosphate curing nucleation, so that the energy required by curing the adhesive is reduced, and the curing temperature of the adhesive is reduced. In addition, the combination of low-temperature film formation of the nano-scale silicon dioxide particles and high-temperature film formation of the phosphate effectively eliminates shrinkage bubble phenomenon which is easy to occur in single film formation. The nano silicon dioxide particles coated on the surface of the curing agent can also slow down the curing speed of the curing agent, so that the prepared adhesive has a smooth surface and a compact interior after being cured, and has excellent moisture resistance.
Illustratively, the water reducer comprises one or more of inorganic water reducers such as sodium hexametaphosphate, sodium tripolyphosphate, sodium polyphosphate, borax and the like, and the mass of the water reducer is 0.1-1.0% of the mass of the AlN filler.
By adopting the scheme, the water reducer can be adsorbed on the surfaces of particles after being dissolved in water, so that the zeta potential of the surfaces of the particles is improved, the mutual repulsive force among the particles is increased, and free water wrapped in an aggregation structure consisting of microparticles is released. Therefore, the addition of a proper amount of water reducer can reduce the mixing water consumption of the adhesive slurry under the condition of keeping the fluidity of the adhesive slurry unchanged, thereby improving the strength and the heat conductivity of the adhesive. It will of course be appreciated that the choice of the water reducing agent is not limited to the above list of materials.
The invention also provides high-heat-conductivity inorganic adhesive powder, which is prepared by the preparation method of the high-heat-conductivity inorganic adhesive powder, wherein the high-heat-conductivity inorganic adhesive powder comprises the following components in percentage by mass: alN filler: phosphate binder: curing agent: stabilizing agent: water reducer = 1: (7% -20%): (0.01% -0.5%): (0.5% -2.0%): (0.1% -1.0%).
The invention also provides a use method of the high-heat-conductivity inorganic adhesive powder, which comprises the following steps: the high-heat-conductivity inorganic adhesive powder provided by the embodiment of the disclosure is added with 15-20% of water by mass, stirred and mixed into uniform slurry, the uniform slurry is smeared or filled in a region to be glued, and the uniform slurry is cured for 2-24 hours at the room temperature of 120 ℃ so as to be cured.
In the scheme, when the high-heat-conductivity inorganic adhesive powder is used, 15-20% of water by mass of the high-heat-conductivity inorganic adhesive powder is added into the high-heat-conductivity inorganic adhesive powder, and the mixture is stirred and mixed into uniform slurry; then, the high heat conduction inorganic adhesive is smeared or filled on the area to be smeared (namely the product to be smeared with the adhesive), and is solidified for 2-24 hours at the room temperature to 120 ℃.
The method of preparing the high thermal conductive inorganic adhesive powder provided by the present invention is described in more detail below in several exemplary embodiments.
Example 1
The preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
firstly, weighing 30g of AlN filler (the AlN filler is prepared from 12.0g of AlN powder with the average particle size of 2 mu m and 18.0g of AlN powder with the average particle size of 60 mu m), 2.0g of aluminum dihydrogen phosphate powder, 2.0g of magnesium dihydrogen phosphate powder, 0.10g of zinc oxide powder, 0.40g of nano silicon dioxide powder and 0.20g of sodium tripolyphosphate powder according to the mass ratio, and placing the raw materials into a ball milling tank, wherein the ball milling tank is provided with light grinding balls with the number matched with the mass of the raw materials;
step two, adopting a planetary ball mill, and rotating for 90 minutes at a speed of 400 revolutions per minute to preliminarily dry-mix the raw materials;
grinding the powder after preliminary dry mixing for 15 minutes;
and fourthly, placing the ground powder into a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
Mixing the prepared high-heat-conductivity inorganic adhesive powder with deionized water according to a ratio of 100:15 are mixed into uniform slurry according to the mass ratio, the slurry is filled in a mould, and the slurry is fully solidified after heat preservation is carried out for 5 hours at 90 ℃.
Example 2:
the preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
firstly, weighing 30g of AlN filler (the AlN filler is prepared from 10.0g of AlN powder with the average particle size of 1 mu m and 20.0g of AlN powder with the average particle size of 50 mu m), 3.0g of aluminum dihydrogen phosphate powder, 0.03g of magnesium oxide powder, 0.45g of nano silicon dioxide powder and 0.15g of sodium hexametaphosphate powder according to the mass ratio, and placing the raw materials into a ball milling tank, wherein the ball milling tank is provided with a number of light grinding balls matched with the mass of the raw materials;
step two, adopting a planetary ball mill to rotate for 120 minutes at the speed of 300 revolutions per minute so as to preliminarily dry-mix the raw materials;
grinding the powder after preliminary dry mixing for 20 minutes;
and fourthly, placing the ground powder into a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
Mixing the prepared high-heat-conductivity inorganic adhesive powder with deionized water according to a ratio of 100:16 are mixed into uniform slurry according to the mass ratio, the slurry is filled in a mould after the viscosity is measured, and the slurry is completely solidified after the temperature is kept at 80 ℃ for 6 hours. The thermal conductivity, compressive strength, and shear strength of the cured adhesive were measured in the same manner as in example 1.
Example 3:
the preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
step one: the preparation method comprises the steps of weighing 30.0g of AlN filler (the AlN filler is prepared from 10.0g of AlN powder with the average particle size of 1 mu m and 20.0g of AlN powder with the average particle size of 50 mu m), 3.0g of aluminum dihydrogen phosphate powder, 0.03g of magnesium oxide powder, 0.45g of nano silicon dioxide powder and 0.15g of sodium hexametaphosphate powder according to the mass ratio, placing the materials in a ball milling tank, and placing light grinding balls with the number matched with the mass of the materials in the ball milling tank.
Step two: the raw materials were preliminarily dry blended by rotating with a planetary ball mill at 300 rpm for 120 minutes.
And thirdly, grinding the powder after preliminary dry mixing for 20 minutes.
And fourthly, placing the ground powder into a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
Mixing the prepared adhesive powder with deionized water according to a ratio of 100:17, measuring the viscosity of the slurry, filling the slurry into a mould, and preserving the temperature at 80 ℃ for 6 hours, and then completely solidifying the slurry. The thermal conductivity, compressive strength, and shear strength of the cured adhesive were measured in the same manner as in example 1.
Example 4:
the preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
step one: the preparation method comprises the steps of weighing 30.0g of AlN filler (the AlN filler is prepared by grading 10.0g of AlN powder with the average particle size of 1 mu m and 20.0g of AlN powder with the average particle size of 50 mu m), 3.0g of aluminum dihydrogen phosphate powder, 0.03g of magnesium oxide powder, 0.45g of nano silicon dioxide powder and 0.15g of sodium hexametaphosphate powder according to the mass ratio, placing the materials in a ball milling tank, and placing light grinding balls with the number matched with the mass of the materials in the ball milling tank.
Step two: the raw materials were preliminarily dry blended by rotating with a planetary ball mill at 300 rpm for 120 minutes.
Step three: grinding the powder after preliminary dry mixing for 20 minutes;
step four: and (3) placing the ground powder in a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
The adhesive powder prepared is mixed with deionized water according to the proportion of 100:18, measuring the viscosity of the slurry, filling the slurry into a mould, and keeping the temperature at 80 ℃ for 6 hours, and then completely solidifying the slurry. The thermal conductivity, compressive strength, and shear strength of the cured adhesive were measured in the same manner as in example 1.
Example 5:
the preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
step one: the preparation method comprises the steps of weighing 30.0g of AlN filler (the AlN filler is prepared by grading 10.0g of AlN powder with the average particle size of 1 mu m and 20.0g of AlN powder with the average particle size of 50 mu m), 3.0g of aluminum dihydrogen phosphate powder, 0.03g of magnesium oxide powder, 0.45g of nano silicon dioxide powder and 0.15g of sodium hexametaphosphate powder according to the mass ratio, placing the materials in a ball milling tank, and placing light grinding balls with the number matched with the mass of the materials in the ball milling tank.
Step two: rotating the raw materials for 120 minutes at a speed of 300 revolutions per minute by using a planetary ball mill, and primarily dry-mixing the raw materials;
step three: grinding the powder after preliminary dry mixing for 20 minutes;
step four: and (3) placing the ground powder in a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
The adhesive powder prepared is mixed with deionized water according to the proportion of 100:19, measuring the viscosity of the slurry, filling the slurry into a mould, and keeping the temperature at 80 ℃ for 6 hours, and then completely solidifying the slurry. The thermal conductivity, compressive strength, and shear strength of the cured adhesive were measured in the same manner as in example 1.
Example 6:
the preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
step one: weighing 30g of AlN filler (the AlN filler is prepared by grading 10.0g of AlN powder with the average particle size of 1 mu m and 20.0g of AlN powder with the average particle size of 50 mu m), 3.0g of alkali metal dihydrogen phosphate, 0.03g of alumina powder, 0.45g of nano silicon dioxide powder and 0.15g of sodium tripolyphosphate according to the mass ratio, placing the materials in a ball milling tank, and placing light grinding balls with the number matched with the mass of the materials in the ball milling tank;
step two: rotating the raw materials for 120 minutes at a speed of 300 revolutions per minute by using a planetary ball mill, and primarily dry-mixing the raw materials;
step three: grinding the powder after preliminary dry mixing for 20 minutes;
step four: and (3) placing the ground powder in a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
The adhesive powder prepared is mixed with deionized water according to the proportion of 100:20, measuring the viscosity of the slurry, filling the slurry into a mould, and keeping the temperature at 80 ℃ for 6 hours, and then completely solidifying the slurry. The thermal conductivity, compressive strength, and shear strength of the cured adhesive were measured in the same manner as in example 1.
Example 7
The preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
step one: weighing 100g of AlN filler (AlN filler is prepared by grading AlN powder with the average particle size of 10 mu m and AlN powder with the average particle size of 0.5 mu m according to the weight ratio of 1.5:1), 20g of alkaline earth metal dihydrogen phosphate, 0.5g of zinc oxide powder, 2.0g of nano silicon dioxide and 1.0g of sodium polyphosphate, placing the materials in a ball milling tank, and placing light grinding balls with the number matched with the mass of the materials in the ball milling tank;
step two: rotating the raw materials for 60 minutes at a speed of 200 revolutions per minute by using a planetary ball mill, and primarily dry-mixing the raw materials;
step three: grinding the powder after preliminary dry mixing for 10 minutes;
step four: and (3) placing the ground powder in a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
The adhesive powder prepared is mixed with deionized water according to the proportion of 100:15, measuring the viscosity of the slurry, filling the slurry into a mould, and keeping the temperature at room temperature for 24 hours, wherein the slurry is completely solidified.
Example 8
The preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
step one: weighing 100g of AlN filler (AlN filler is prepared by grading AlN powder with the average particle size of 80 mu m and AlN powder with the average particle size of 5 mu m according to the weight ratio of 3:1), 7g of a mixture of aluminum dihydrogen phosphate and alkali metal dihydrogen phosphate, 0.01g of chromium oxide, 0.5g of nano silicon dioxide and 0.1g of borax, placing the materials in a ball milling tank, and placing light grinding balls with the number matched with the mass of the materials in the ball milling tank;
step two: rotating the raw materials for 100 minutes at a speed of 400 revolutions per minute by using a planetary ball mill, and primarily dry-mixing the raw materials;
step three: grinding the powder after preliminary dry mixing for 15 minutes;
step four: and (3) placing the ground powder in a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
The adhesive powder prepared is mixed with deionized water according to the proportion of 100:18, measuring the viscosity of the slurry, filling the slurry into a mould, and keeping the temperature at 120 ℃ for 2 hours, and then completely solidifying the slurry.
Example 9
The preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
step one: weighing 100g of AlN filler (AlN filler is prepared by mixing AlN powder with an average particle size of 60 mu m and AlN powder with an average particle size of 2 mu m according to a weight ratio of 2:1), 15g of aluminum dihydrogen phosphate, a mixture of alkali metal dihydrogen phosphate and alkaline earth metal dihydrogen phosphate, 0.1g of magnesium oxide and aluminum oxide, 1.0g of nano silicon dioxide and 0.6g of sodium hexametaphosphate, placing the materials into a ball milling tank, and placing light grinding balls with the number matched with the mass of the materials into the ball milling tank;
step two: rotating the raw materials for 80 minutes at a speed of 400 revolutions per minute by using a planetary ball mill, and primarily dry-mixing the raw materials;
step three: grinding the powder after preliminary dry mixing for 15 minutes;
step four: and (3) placing the ground powder in a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
The adhesive powder prepared is mixed with deionized water according to the proportion of 100:20, measuring the viscosity of the slurry, filling the slurry into a mould, and preserving the temperature at 80 ℃ for 5 hours, and then completely solidifying the slurry.
Example 10
The preparation method of the high-heat-conductivity inorganic adhesive powder specifically comprises the following steps:
step one: weighing 100g of AlN filler (AlN filler is prepared by grading AlN powder with the average particle size of 50 mu m and AlN powder with the average particle size of 2 mu m according to the weight ratio of 1.8:1), 10g of aluminum dihydrogen phosphate, 0.5g of magnesia powder, 2.0g of nano silicon dioxide and 0.5g of sodium hexametaphosphate, placing the materials into a ball milling tank, and placing light grinding balls with the number matched with the mass of the materials into the ball milling tank;
step two: rotating the raw materials for 60 minutes at a speed of 250 revolutions per minute by using a planetary ball mill, and primarily dry-mixing the raw materials;
step three: grinding the powder after preliminary dry mixing for 18 minutes;
step four: and (3) placing the ground powder in a ball milling tank again, and repeating the second step to obtain the uniformly mixed high-heat-conductivity inorganic adhesive powder.
The adhesive powder prepared is mixed with deionized water according to the proportion of 100:16 are mixed into uniform slurry according to the mass ratio, the slurry is filled in a mould after the viscosity is measured, and the slurry is completely solidified after the temperature is kept at room temperature for 24 hours.
The high-heat-conductivity inorganic adhesive powder and the prepared high-heat-conductivity inorganic adhesive provided by the invention are subjected to performance test as follows.
The cross section of the adhesive prepared in the example 2 after curing is characterized by adopting an SEM (electron scanning microscope), and the SEM (figure 1) shows that the cross section of the adhesive is relatively flat, and most of AlN powder particles with large particle size are wrapped by AlN powder particles with small particle size, so that the adhesive has obvious densification effect by using a filler grading method.
Taking examples 2-6 as examples, performance tests were performed on high thermal conductivity inorganic adhesives as follows:
the high thermal conductivity inorganic adhesive slurries provided in examples 2-6 were subjected to viscosity testing according to GB/T2794-1995 adhesive viscosity determination, the results of which are shown in FIG. 2. From the test results obtained in fig. 2, it can be seen that the adhesive powder was mixed with deionized water at 100:20, and when the water adding amount is fixed, the viscosity of the slurry is reduced along with the increase of the shearing rate; at the same shear rate, the viscosity of the slurry decreases with increasing water addition.
The cured adhesives provided in examples 2-6 were subjected to thermal conductivity testing, and the test results are shown in fig. 3. As can be seen from FIG. 3, the cured adhesive has higher thermal conductivity which can reach 3.18W/m.K at most, and is suitable for the fields with higher requirements on the heat dissipation performance of the adhesive. Furthermore, it can be seen from fig. 3 that the thermal conductivity of the adhesive tends to decrease with increasing amount of water added.
The cured adhesives provided in examples 2-6 were tested for mechanical properties and the test results are shown in FIG. 4. As can be seen from FIG. 4, the compressive strength is up to 20MPa, and the shearing strength is up to more than 1MPa, which indicates that the adhesive has good mechanical properties and is suitable for the environment with higher requirement on shock resistance. In addition, as can be seen from the graph of fig. 4, both the compressive strength and the shear strength tend to decrease with increasing water addition.
Fig. 5 is a graph showing the morphology of the adhesive prepared in example 2 of the present invention after curing and before and after heat preservation in a high temperature oven at 600 ℃ for 2 hours, wherein fig. 5 (a) is a graph showing the morphology of the adhesive before heat treatment and fig. 5 (b) is a graph showing the morphology of the adhesive after heat treatment. As can be seen from FIG. 5, after the heat treatment, the surface of the adhesive has no cracking and chipping phenomena, and has no obvious change compared with the surface before the heat treatment, which shows that the adhesive has good high temperature resistance.
By combining the above results of the performance tests of examples 2 to 6, the fluidity, heat conducting property and mechanical property of the adhesive slurry can be regulated and controlled by adjusting the mass ratio of the adhesive powder to deionized water so as to achieve the required comprehensive performance.
Compared with the existing adhesive, the preparation method of the high-heat-conductivity inorganic adhesive powder and the high-heat-conductivity inorganic adhesive powder, provided by the invention, have the advantages of simple and quick preparation process, convenience in use, good fluidity, low curing temperature, high heat conductivity, high thermal stability, high compression resistance and shearing strength, high resistivity and other comprehensive performances, and can be used for bonding or encapsulating occasions with high heat conduction requirements, such as airborne temperature sensors, temperature sensing parts and the like.
The invention is intended to cover any alternatives, modifications, equivalents, and variations that fall within the spirit and scope of the invention. In the following description of preferred embodiments of the invention, specific details are set forth in order to provide a thorough understanding of the invention, and the invention will be fully understood to those skilled in the art without such details. In other instances, well-known methods, procedures, flows, components, circuits, and the like have not been described in detail so as not to unnecessarily obscure aspects of the present invention.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The preparation method of the high-heat-conductivity inorganic adhesive powder is characterized by comprising the following steps of:
weighing raw material powder according to a preset proportion, and placing the raw material powder in a ball milling tank, wherein light grinding balls matched with the raw material in mass are placed in the ball milling tank, and the raw material comprises AlN filler, phosphate binder, curing agent, stabilizer and water reducer;
placing the ball milling tank in a ball mill for preliminary dry mixing;
grinding the powder after preliminary dry mixing;
placing the ground powder in a ball milling tank again, placing the ball milling tank in a ball mill, and performing secondary dry mixing to obtain uniformly mixed high-heat-conductivity inorganic adhesive powder;
the phosphate binder is aluminum dihydrogen phosphate and magnesium dihydrogen phosphate, and the mass of the phosphate binder is 7% -20% of the mass of the AlN filler;
the AlN filler is prepared from two AlN powders with different average particle sizes, wherein the two AlN powders are respectively a first AlN powder and a second AlN powder, the average particle size of the first AlN powder is larger than that of the second AlN powder, the average particle size of the first AlN powder is 10-80 mu m, the average particle size of the second AlN powder is 0.5-5 mu m, and the weight ratio of the first AlN powder to the second AlN powder is 1.5:1-3:1;
the curing agent comprises metal oxide, wherein the metal oxide is one or more of magnesium oxide, aluminum oxide, zinc oxide and chromium oxide, and the mass of the curing agent is 0.01-0.5% of the mass of the AlN filler;
the stabilizer is nano silicon dioxide, and the mass of the stabilizer is 0.5% -2.0% of the mass of the AlN filler;
the water reducer comprises an inorganic water reducer, wherein the inorganic water reducer comprises one or more of sodium hexametaphosphate, sodium tripolyphosphate, sodium polyphosphate and borax, and the mass of the water reducer is 0.1-1.0% of the mass of the AlN filler.
2. The method for preparing the high thermal conductivity inorganic adhesive powder according to claim 1, wherein the ball milling pot is placed in a ball mill for primary dry mixing and/or the ball milling pot is placed in a ball mill for secondary dry mixing, specifically comprising:
the ball milling tank is placed in a ball mill, and dry-mixed for 1-2 hours at the speed of 200-400 rpm.
3. The method for preparing a high thermal conductivity inorganic adhesive powder according to claim 1, wherein the grinding time is 10 to 20 minutes when the powder after preliminary dry mixing is ground.
4. A high thermal conductive inorganic adhesive powder prepared by the method of preparing a high thermal conductive inorganic adhesive powder according to any one of claims 1 to 3.
5. A method of using a highly thermally conductive inorganic adhesive powder, the method comprising: the high heat conduction inorganic adhesive powder as claimed in claim 4 is added with 15 to 20 percent of water by mass, stirred and mixed into uniform slurry, the uniform slurry is smeared or filled in a region to be smeared, and the uniform slurry is solidified for 2 to 24 hours at the room temperature of between 120 ℃.
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