CN117534445A - Al (aluminum) alloy 2 O 3 AlN in-situ composite ceramic, method for preparing AlN in-situ composite ceramic by additive manufacturing and application of AlN in-situ composite ceramic - Google Patents
Al (aluminum) alloy 2 O 3 AlN in-situ composite ceramic, method for preparing AlN in-situ composite ceramic by additive manufacturing and application of AlN in-situ composite ceramic Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000000654 additive Substances 0.000 title claims abstract description 39
- 230000000996 additive effect Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 229910052782 aluminium Inorganic materials 0.000 title claims description 4
- 239000000956 alloy Substances 0.000 title claims description 3
- 229910045601 alloy Inorganic materials 0.000 title claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000005238 degreasing Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229920001568 phenolic resin Polymers 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 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 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000008157 edible vegetable oil Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 238000004100 electronic packaging Methods 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000017525 heat dissipation Effects 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
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- 229920001903 high density polyethylene Polymers 0.000 description 6
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- 238000012545 processing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 241000486661 Ceramica Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Ceramic Products (AREA)
Abstract
The invention provides an Al 2 O 3 -AlN in-situ composite ceramic and methods and applications for preparing the same, the methods comprising: mixing aluminum oxide powder, a stabilizer and a solvent, and ball-milling to obtain a first mixture; heating and stirring the first mixture, mixing with a binder, and then pressurizing and stirring to obtain a second mixture; the second mixture is cooled and crushed in sequence, and the obtained granular material is manufactured by additive material to obtain a formed workpiece; degreasing the molded workpiece, and sintering the degreased workpiece under the condition of nitrogen element to obtain Al 2 O 3 -AlN in situ composite ceramic. The invention combines Al 2 O 3 Low cost of ceramic and high thermal conductivity of AlN ceramic, integrated with additive manufacturingThe method has the advantages of complicated structure, low cost, simple operation, contribution to the improvement of the surface heat dissipation capacity of the chip packaging substrate, and solving the failure problem caused by the difference of the thermal expansion coefficients of the ceramic surface and the chip.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to an Al 2 O 3 AlN in-situ composite ceramic and additive manufacturingMethods and uses for making the same.
Background
Currently, aluminum oxide (Al 2 O 3 ) The ceramic has low cost, simple process and good comprehensive mechanical property, and is widely applied to chip packaging substrates of thick film integrated circuits in the electronic manufacturing industry. However, al 2 O 3 Ceramics have low thermal conductivity and are not easy to use in high power devices. The AlN ceramic substrate has a high thermal conductivity, and is greatly favored in high-power devices requiring high thermal conductivity. And along with the high-speed development of industrial technology, the trend of application requirements of high-power devices is steadily rising, and the application prospect of the AlN ceramic substrate is quite broad.
However, al 2 O 3 The substrate has the characteristic of low heat conductivity (25W/mK), and is easy to cause mismatch with the thermal expansion coefficient of the chip, thereby affecting the application of the substrate in ultra-high power. AlN ceramic substrate has high heat conductivity (210W/mK), and gradually replaces Al in high-power devices requiring high heat conduction 2 O 3 A substrate. However, relative to Al 2 O 3 Other problems exist with substrates, alN ceramic substrates, such as high material and processing costs, difficult processing, and susceptibility to damage to the structural integrity of the substrate during use due to poor toughness.
Alumina (Al) 2 O 3 ) And AlN ceramic substrates are usually processed by adopting the traditional casting method, dry pressing method, material reduction machining and other processes. There are great limitations in the processing of ceramic substrates formed by casting, mainly because it is difficult to realize the manufacture of complex structures by casting; the dry pressing method adopts a complex structure of a die for forming the ceramic substrate in one step, but the die opening cost is high, and the die design of the complex structure is difficult; the material reduction processing is used as a complementary technology of a casting method and a dry pressing method, can greatly solve the structural molding problem, but the problems of cutter breakage, material fracture to be processed and the like are easy to occur when materials with higher hardness such as AlN ceramics are manufactured, and the processing time and the material cost are higher.
Therefore, development of a new preparation of Al is required 2 O 3 AlN in-situ composite ceramicA method for producing porcelain.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides an Al 2 O 3 AlN in-situ composite ceramic, and method for preparing the AlN in-situ composite ceramic by additive manufacturing and application thereof, and by adopting the method for additive manufacturing, the cost is reduced, the operation is simple, and the Al can be solved 2 O 3 Failure caused by inconsistent thermal expansion coefficients of ceramic surface and chip, and is beneficial to improving Al 2 O 3 And AlN, and reduces the probability of damaging the substrate in the use process.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an additive manufacturing process for preparing Al 2 O 3 -a method of AlN in-situ composite ceramic, the method comprising the steps of:
(1) Mixing aluminum oxide powder, a surface modifier, a stabilizer and a solvent, and sequentially performing ball milling and drying to obtain a first mixture; heating and stirring the first mixture, mixing with a binder, and then pressurizing and stirring to obtain a second mixture;
(2) The second mixture is cooled and crushed in sequence to obtain particles; the granules are manufactured by additive manufacturing to obtain a molded workpiece;
(3) Degreasing the molded workpiece, and sintering the degreased workpiece under the condition of nitrogen element to obtain Al 2 O 3 -AlN in situ composite ceramic.
The additive manufacturing method provided by the invention prepares Al 2 O 3 Method for preparing AlN in-situ composite ceramic by adopting additive manufacturing mode to prepare Al 2 O 3 Forming a workpiece, and avoiding the problems of material waste and overhigh cost caused by material reduction manufacturing; meanwhile, al is realized by adopting an in-situ composite AlN forming mode 2 O 3 -AlN-complexing to give the material Al 2 O 3 Low cost of ceramic and high thermal conductivity of AlN ceramic, and in-situ compounding of Al 2 O 3 And AlN, the bonding strength of the AlN and the AlN is high, and the performance is excellent.
Preferably, the mass ratio of the alumina powder, the surface modifier and the stabilizer in the step (1) is 15-35:1:1-3, for example, 15:1:2, 16:1:1, 17:1:3, 18:1:1.5, 19:1:2.2, 20:1:2.5, 21:1:1.8, 22:1:2, 23:1:2, 24:1:2 or 25:1:2, etc., but not limited to the recited values, other non-recited values in the range are equally applicable.
According to the invention, the aluminum oxide powder without the stabilizer is subjected to sintering nitridation, so that the AlN phase content is obviously reduced, and the specific gravity of Al, O and N phases is increased, so that the surface heat dissipation capacity is reduced; in addition, when the mass ratio of the stabilizer to be added is too high, new phases of nitridation of the stabilizer may occur, which may affect the formation of AlN.
Preferably, the stabilizer comprises zirconia.
Preferably, the surface modifying agent comprises stearic acid and/or calcium lignosulfonate.
Preferably, the solvent comprises ethanol and/or water.
Preferably, the total volume of the alumina powder, the surface modifier and the stabilizer and the volume ratio of the solvent are 0.5 to 1.2:1, for example, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1 or 1.2:1, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the rotation speed of the ball mill is 100-500 r/min, for example, 100r/min, 120r/min, 150r/min, 180r/min, 200r/min, 220r/min, 250r/min, 280r/min, 300r/min, 350r/min, 400r/min, 450r/min or 500r/min, etc., but the ball mill is not limited to the listed values, and other non-listed values in the range are equally applicable.
Preferably, the ball milling time is 1-20 h, for example, 1h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h or 20h, etc.
The temperature of the drying is preferably 50 to 100 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, or 100 ℃, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
The temperature of the heating and stirring in the step (1) is preferably 60 to 260 ℃, and may be, for example, 60 ℃, 76 ℃, 92 ℃, 105 ℃, 125 ℃, 135 ℃, 155 ℃, 165 ℃, 185 ℃, 200 ℃, 210 ℃, 250 ℃, 260 ℃, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the heating and stirring time is 30 to 240min, for example, 30min, 55min, 75min, 100min, 125min, 145min, 170min, 195min, 215min or 240min, etc., but not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the mass ratio of the binder to the first mixture is 1:3 to 4.5, for example, may be 1:3, 1:3.1, 1:3.2, 1:3.5, 1:3.8, 1:4.0, 1:4.2 or 1:4.5, etc., but are not limited to the recited values, other non-recited values within this range are equally applicable.
Preferably, the binder comprises any one or a combination of at least two of stearic acid, polyethylene glycol, phenolic resin, epoxy resin, ethylcellulose, polystyrene, polypropylene, polyethylene, polyvinyl alcohol, polyvinyl butyral, or paraffin wax, wherein typical but non-limiting combinations are polyethylene glycol and phenolic resin combinations, epoxy resin and phenolic resin combinations, polyethylene glycol and epoxy resin combinations, ethylcellulose and phenolic resin combinations, polyethylene glycol and ethylcellulose combinations.
The pressure of the pressure stirring is preferably 10 to 120MPa, and may be, for example, 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 80MPa, 100MPa, 110MPa, 120MPa, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The time of the pressure stirring is preferably 1 to 10 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, etc., but not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the cooling in step (2) is cooling to room temperature.
The particle size of the crushed granules is preferably 1 to 10mm, and may be, for example, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the nozzle size of the additive manufacturing is 0.05 to 3mm, for example, 0.05mm, 0.38mm, 0.71mm, 1.04mm, 1.37mm, 1.69mm, 2.02mm, 2.35mm, 2.68mm or 3mm, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
The additive manufacturing layer preferably has a thickness of 0.05 to 0.35mm, for example, 0.05mm, 0.09mm, 0.12mm, 0.15mm, 0.19mm, 0.22mm, 0.25mm, 0.29mm, 0.32mm, or 0.35mm, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the printing speed of the additive manufacturing is 5-100 mm/s, for example, 5mm/s, 16mm/s, 27mm/s, 37mm/s, 48mm/s, 58mm/s, 69mm/s, 79mm/s, 90mm/s or 100mm/s, etc., but not limited to the recited values, other non-recited values within this range are equally applicable.
Preferably, the feed flow rate of the additive manufacturing is 70-100%, for example, 70%, 74%, 77%, 80%, 84%, 87%, 90%, 94%, 97% or 100%, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, step (2) further comprises: and polishing the surface of the molded workpiece.
The surface roughness Ra after polishing is preferably 0.1 to 1.6, and may be, for example, 0.1, 0.2, 0.3, 0.5, 0.8, 1.0, 1.1, 1.5, or 1.6, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the degreasing method in step (3) comprises solvent degreasing and/or thermal degreasing.
Preferably, the solvent employed for degreasing the solvent comprises any one or a combination of at least two of water, ethanol, n-heptane, kerosene, diesel oil or edible oil, wherein typical but non-limiting combinations are combinations of water and ethanol, combinations of n-heptane and ethanol, combinations of water and n-heptane, combinations of kerosene and ethanol, combinations of edible oil and ethanol.
Preferably, the thermal degreasing includes heating to a first temperature at a first heating rate for a first time, heating to a second temperature at a second heating rate for a second time, heating to a third temperature at a third heating rate for a third time, and heating to a fourth temperature at a fourth heating rate for a fourth time.
Preferably, the first temperature rising rate is 0.2 to 5 ℃/min, for example, 0.2 ℃/min, 0.74 ℃/min, 1.27 ℃/min, 1.8 ℃/min, 2.34 ℃/min, 2.87 ℃/min, 3.4 ℃/min, 3.94 ℃/min, 4.47 ℃/min or 5 ℃/min, etc., but the first temperature rising rate is not limited to the recited values, and other non-recited values within the range are equally applicable.
The first temperature is preferably 60 to 100 ℃, and may be 60 ℃, 65 ℃, 69 ℃, 74 ℃, 78 ℃, 83 ℃, 87 ℃, 92 ℃, 96 ℃, or 100 ℃, for example, but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the first time is 30min to 10h, for example, 30min, 40min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the second temperature rising rate is 0.2 to 5 ℃/min, for example, 0.2 ℃/min, 0.74 ℃/min, 1.27 ℃/min, 1.8 ℃/min, 2.34 ℃/min, 2.87 ℃/min, 3.4 ℃/min, 3.94 ℃/min, 4.47 ℃/min or 5 ℃/min, etc., but the second temperature rising rate is not limited to the recited values, and other non-recited values within the range are equally applicable.
The second temperature is preferably 180 to 220 ℃, and may be 180 ℃, 185 ℃, 189 ℃, 194 ℃, 198 ℃, 203 ℃, 207 ℃, 212 ℃, 216 ℃, 220 ℃, or the like, for example, but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the second time is 30min to 12h, for example, 30min, 40min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 12h, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the third temperature rising rate is 0.2 to 5 ℃ per minute, for example, 0.2 ℃ per minute, 0.74 ℃ per minute, 1.27 ℃ per minute, 1.8 ℃ per minute, 2.34 ℃ per minute, 2.87 ℃ per minute, 3.4 ℃ per minute, 3.94 ℃ per minute, 4.47 ℃ per minute, 5 ℃ per minute, or the like, but not limited to the recited values, and other non-recited values within the range are equally applicable.
The third temperature is preferably 380 to 420 ℃, and may be 380 ℃, 385 ℃, 389 ℃, 394 ℃, 398 ℃, 403 ℃, 407 ℃, 412 ℃, 416 ℃, 420 ℃, or the like, for example, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the third time is 30min to 12h, for example, 30min, 40min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 12h, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the fourth temperature rising rate is 0.2 to 5 ℃ per minute, for example, 0.2 ℃ per minute, 0.74 ℃ per minute, 1.27 ℃ per minute, 1.8 ℃ per minute, 2.34 ℃ per minute, 2.87 ℃ per minute, 3.4 ℃ per minute, 3.94 ℃ per minute, 4.47 ℃ per minute, 5 ℃ per minute, or the like, but not limited to the recited values, and other non-recited values within the range are equally applicable.
The fourth temperature is preferably 550 to 600 ℃, and may be 550 ℃, 556 ℃, 562 ℃, 567 ℃, 573 ℃, 578 ℃, 584 ℃, 589 ℃, 595 ℃, 600 ℃, or the like, for example, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the fourth time is 30min to 8h, for example, 30min, 40min, 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the conditions of the nitrogen-containing element in step (3) include: the surface is coated with any one or a combination of at least two of nitrogen element, introduced nitrogen gas, or a compound containing nitrogen element.
The temperature rise rate of the sintering treatment is preferably 0.5 to 10 ℃ per minute, and may be, for example, 0.5 ℃ per minute, 1.6 ℃ per minute, 2.7 ℃ per minute, 3.7 ℃ per minute, 4.8 ℃ per minute, 5.8 ℃ per minute, 6.9 ℃ per minute, 7.9 ℃ per minute, 9 ℃ per minute, or 10 ℃ per minute, etc., but is not limited to the recited values, and other values not recited in the range are equally applicable.
The final temperature of the sintering treatment is preferably 1200 to 2100 ℃, and may be, for example, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃, 1800 ℃, 1900 ℃, 2000 ℃, 2100 ℃, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
In the invention, the problem of deformation of the ceramic substrate is caused by the higher sintering temperature, and the problem of difficult AlN generation is caused by the lower sintering temperature.
The sintering treatment is preferably carried out at a final temperature for 1 to 8 hours, and may be, for example, 1 hour, 1.8 hours, 2.6 hours, 3.4 hours, 4.2 hours, 4.9 hours, 5.7 hours, 6.5 hours, 7.3 hours, or 8 hours, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Mixing aluminum oxide powder, a surface modifier, a stabilizer and a solvent, and performing ball milling for 1-20 hours at a rotating speed of 100-500 r/min, wherein the mass ratio of the aluminum oxide powder to the surface modifier to the stabilizer is 15-35:1:1-3, the total volume ratio of the aluminum oxide powder to the surface modifier to the stabilizer to the solvent is 0.5-1.2:1, and the time is 1-20 hours; obtaining a first mixture;
heating and stirring the first mixture at 60-200 ℃ for 30-240 min, mixing with a binder, and then stirring for 1-10 h under the pressure of 10-120 MPa to obtain a second mixture;
the mass ratio of the binder to the first mixture is 1:3 to 4.5;
(2) The second mixture is cooled to room temperature and crushed in sequence to obtain particles with the particle diameter of 1-10 mm; the alumina particles are manufactured by additive, the size of a nozzle is 0.05-3 mm, the thickness of a layer is 0.05-0.35 mm, the printing speed is 5-100 mm/s, and the feeding flow is 70-100%, so that a formed workpiece is obtained; polishing the surface of the molded workpiece to ensure that the surface roughness Ra of the polished workpiece is 0.1-1.6;
(3) Degreasing the formed workpiece, heating the degreased workpiece to 1200-2100 ℃ at a heating rate of 0.5-10 ℃/min under the condition of nitrogen element, and preserving heat for 1-8 h at the final temperature to perform sintering treatment to obtain Al 2 O 3 -AlN in situ composite ceramic.
In a second aspect, the present invention provides an Al 2 O 3 -AlN in-situ composite ceramic, said Al 2 O 3 Preparation of Al by AlN in situ composite ceramic using additive manufacturing according to the first aspect 2 O 3 -AlN in-situ composite ceramic.
Preferably, the Al 2 O 3 The AlN content in the AlN in-situ composite ceramic is 40 to 100%, for example 40%, 47%, 54%, 60%, 67%, 74%, 80%, 87%, 94% or 100% etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the Al 2 O 3 Al in AlN in-situ composite ceramic 2 O 3 The content is 0.1 to 20%, for example, 0.1%, 2.4%, 4.6%, 6.8%, 9%, 11.2%, 13.4%, 15.6%, 17.8% or 20%, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the Al 2 O 3 The AlN in-situ composite ceramic has a thickness of 500nm to 5mm, for example 500nm, 1000nm, 1500nm, 2000nm, 3000nm, 5000nm, 1mm, 1.5mm, 2.0mm, 2.5mm, 3.0mm, 3.5mm, 4.0mm, 4.5mm or 5.0mm, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
In a third aspect, the invention is an Al as described in the second aspect 2 O 3 -application of AlN in-situ composite ceramic in ceramic substrates for electronic packaging.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The additive manufacturing method provided by the invention prepares Al 2 O 3 The method for preparing the AlN in-situ composite ceramic is simple to operate and low in cost;
(2) The additive manufacturing method provided by the invention prepares Al 2 O 3 Al prepared by AlN in-situ composite ceramic method 2 O 3 The problem of inconsistent thermal expansion coefficients of the AlN in-situ composite ceramic and the chip is improved;
(3) Al provided by the invention 2 O 3 Al in AlN in-situ composite ceramic 2 O 3 The interface bonding strength with AlN is high, which is beneficial to reducing the probability of damaging the substrate in the use process.
Drawings
FIG. 1 shows Al obtained in example 1 of the present invention 2 O 3 SEM image of AlN in-situ composite ceramic.
FIG. 2 shows Al obtained in example 1 of the present invention 2 O 3 -integral structure diagram of AlN in-situ composite ceramic.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The embodiment provides an additive manufacturing method for preparing Al 2 O 3 -a method of AlN in-situ composite ceramic, the method comprising the steps of:
(1) Mixing 100g of alumina powder, 2.5g of stearic acid, 5g of zirconia and ethanol, wherein the volume ratio of the total volume of the alumina powder, the stearic acid and the zirconia to the volume ratio of the ethanol agent is 1:1, placing the mixture into a ball milling tank, sealing, performing ball milling at the rotating speed of 256r/min for 2h, and placing the ball milled powder into a drying box at 60 ℃ for drying for 2h to obtain a first mixture;
heating the roller of the stirring device to 160 ℃, adding 107.5g of the first mixture onto the roller, stirring for 30min, mixing the mixture into a binder (10.75 g of paraffin, 5g of High Density Polyethylene (HDPE), 3.75g of thermoplastic Phenolic Resin (Phenolic Resin), 2g of polyethylene glycol (n=600)), and then stirring for 6h under a pressure of 30MPa (keeping the temperature of the original roller) to obtain a second mixture;
(2) The second mixture is cooled to room temperature in sequence and cut into 2-3mm granules; the aluminum oxide particles are manufactured by additive, a machine heating module heats and extrudes aluminum oxide feed to manufacture a workpiece according to a solid slicing model, the size of a nozzle is 0.5mm, the thickness of a layer is 0.2mm, the printing speed is 20mm/s, and the feeding flow is 100%, so that a formed workpiece is obtained; polishing the surface of the molded workpiece to enable the surface roughness Ra after polishing to be 0.2;
(3) The molded workpiece is placed into a heat treatment furnace, heated to 80 ℃ at 0.5 ℃/min for heat preservation for 5 hours, heated to 180 ℃ at 0.5 ℃/min for heat preservation for 10 hours, heated to 260 ℃ at 0.5 ℃/min for heat preservation for 8 hours, and heated to 380 ℃ at 0.5 ℃/min for heat preservation for 8 hours. Cooling at a speed of 1 ℃/min to 70 ℃, degreasing with a furnace cooling to room temperature, wrapping the degreased workpiece with graphite paper, placing the degreased workpiece into a carbon atmosphere furnace, vacuumizing, introducing nitrogen, heating to 1800 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours at a final temperature to perform sintering treatment to obtain Al 2 O 3 -AlN in situ composite ceramic.
Al prepared in this example 2 O 3 The overall structure of the AlN in-situ composite ceramic is shown in FIG. 2, and the SEM image is shown in FIG. 1, from which Al can be seen 2 O 3 The surface microstructure of the AlN in-situ composite ceramic is uniformly distributed, no obvious pores are found on the surface, and the whole structure is compact.
Example 2
The embodiment provides an additive manufacturing method for preparing Al 2 O 3 -a method of AlN in-situ composite ceramic, the method comprising the steps of:
(1) Mixing 125g of alumina powder, 2.5g of stearic acid, 5g of zirconia and ethanol, wherein the volume ratio of the total volume of the alumina powder, the stearic acid and the zirconia to the volume ratio of the ethanol agent is 1.2:1, placing the mixture into a ball milling tank, sealing, performing ball milling at the rotating speed of 128r/min for 20h, and placing the ball milled powder into a drying box at 65 ℃ for drying for 3h to obtain a first mixture;
heating the roller of the stirring device to 200 ℃, adding 132.5g of the first mixture onto the roller, stirring for 15min, mixing the mixture into a binder (13 g of paraffin, 7g of High Density Polyethylene (HDPE), 6g of thermoplastic Phenolic Resin (Phenolic Resin), 4g of polyethylene glycol (n=600)), and then stirring under pressure of 50MPa for 3h (keeping the temperature of the original roller) to obtain a second mixture;
(2) The second mixture is cooled to room temperature in turn and cut into particles with the diameter of 3-5 mm; the aluminum oxide particles are manufactured by additive, a machine heating module heats and extrudes aluminum oxide feed to manufacture a workpiece according to a solid slicing model, the size of a nozzle is 3mm, the thickness of a layer is 0.35mm, the printing speed is 50mm/s, and the feeding flow is 70%, so that a formed workpiece is obtained; polishing the surface of the molded workpiece to ensure that the surface roughness Ra of the polished workpiece is 1.0;
(3) The molded workpiece is placed into a heat treatment furnace, is heated to 100 ℃ at 5 ℃/min for heat preservation for 3 hours, is heated to 190 ℃ for heat preservation for 8 hours at 0.2 ℃/min, is heated to 420 ℃ for heat preservation for 12 hours at 0.5 ℃/min, and is heated to 600 ℃ for heat preservation for 1 hour at 5 ℃/min. Cooling at 2 deg.C/min to 78 deg.C, degreasing with furnace cooling to room temperature, placing urea around the degreased workpiece, placing into furnace, heating to 2100 deg.C at heating rate of 10 deg.C/min, and holding at final temperature for 1 hr for sintering treatment to obtain Al 2 O 3 -AlN in situ composite ceramic.
Example 3
The embodiment provides an additive manufacturing method for preparing Al 2 O 3 -a method of AlN in-situ composite ceramic, the method comprising the steps of:
(1) Mixing 75g of aluminum oxide powder, 2g of stearic acid, 4g of zirconium oxide and ethanol, wherein the volume ratio of the total volume of the aluminum oxide powder, the stearic acid and the zirconium oxide to the volume ratio of the ethanol agent is 0.5:1, placing the mixture into a ball milling tank, sealing the mixture, performing ball milling at the rotating speed of 384r/min for 1h, and placing the ball milled powder into a drying box at 65 ℃ for drying for 4h to obtain a first mixture;
heating the roller of the stirring device to 100 ℃, adding 81g of the first mixture to the roller, stirring for 60min, mixing the mixture with a binder (6 g of polyethylene glycol (n=600), 5g of polyethylene glycol (n=2000), 5g of Low Density Polyethylene (LDPE), 4g of High Density Polyethylene (HDPE)) and then stirring for 10h under a pressure of 20MPa (keeping the temperature of the original roller) to obtain a second mixture;
(2) The second mixture is cooled to room temperature in sequence and cut into particles with the diameter of 1-2 mm; the aluminum oxide particles are manufactured by additive, a machine heating module heats and extrudes aluminum oxide feed to manufacture a workpiece according to a solid slicing model, the size of a nozzle is 0.05mm, the thickness of a layer is 0.05mm, the printing speed is 20mm/s, and the feeding flow is 80%, so that a formed workpiece is obtained; polishing the surface of the molded workpiece to ensure that the surface roughness Ra of the polished workpiece is 0.5;
(3) Degreasing the formed workpiece by an ethanol solvent (placing a sample into a beaker filled with the ethanol solvent, heating to 52 ℃ in a water bath or an oil bath pot for 5 hours), wrapping the degreased workpiece by graphite paper, placing the wrapped workpiece into a carbon atmosphere furnace, vacuumizing, introducing nitrogen, heating to 1400 ℃ at a heating rate of 0.5 ℃/min, and preserving the temperature for 5 hours at a final temperature for sintering treatment to obtain Al 2 O 3 -AlN in situ composite ceramic.
Example 4
The embodiment provides an additive manufacturing method for preparing Al 2 O 3 The method of AlN in-situ composite ceramic is the same as example 1 except that the mass ratio of alumina powder to zirconia is 50:1, and is not repeated here.
In the in-situ composite ceramic obtained later in this example, the AlN content was extremely low, only within 10%, and the thermal conductivity was only 35W/(m.k).
Example 5
The embodiment provides an additive manufacturing method for preparing Al 2 O 3 The method of AlN in-situ composite ceramic is the same as example 1 except that the mass ratio of alumina powder to zirconia is 10:1, and is not repeated here.
The in-situ composite ceramic obtained later in this example contains ZrN and ZrNO and other impurity phases, resulting in a thermal conductivity of only 127 of 35W/(m·k).
It can be seen from the combination of examples 1 and examples 4 to 5 that the invention is more beneficial to ensuring the composition in the in-situ composite ceramic and the thermal conductivity of the final composite ceramic by controlling the mass ratio of the alumina powder to the zirconia within a specific range.
Example 6
The embodiment provides an additive manufacturing method for preparing Al 2 O 3 The method of AlN in-situ composite ceramic is the same as that of example 1 except that the final temperature in step (3) is 2200 ℃, and will not be described here.
In the embodiment, the surface of the workpiece is obviously bent and deformed due to the excessively high final temperature, so that the integral structure is influenced.
Example 7
The embodiment provides an additive manufacturing method for preparing Al 2 O 3 The method of AlN in-situ composite ceramic is the same as that of example 1 except that the final temperature in step (3) is 1000 ℃, and will not be described here.
In the embodiment, the surface of the workpiece is loose, the strength is low, alN is difficult to form, and the thermal conductivity is only 25W/(m.k).
As can be seen from the combination of example 1 and examples 6 to 7, the additive manufacturing method provided by the invention prepares Al 2 O 3 The AlN in-situ composite ceramic method is more beneficial to improving the strength and the heat conductivity of the product only by controlling the final temperature within a specific range.
Comparative example 1
This comparative example provides a method for preparing Al 2 O 3 The method of AlN in-situ composite ceramic is the same as that of example 1 except that the sintering treatment of step (3) is not performed, and will not be described here.
In the comparative example, the surface of the workpiece has obvious powder dropping phenomenon, is loose and extremely low in strength, cannot form AlN, and has the thermal conductivity of only 22W/(m.k).
Comparative example 2
This comparative example provides a method for preparing Al 2 O 3 AlN sourceThe method of the bit composite ceramic is the same as that of example 1 except that nitrogen is not introduced in the sintering treatment of step (3), and will not be described here.
The ceramic phase composition of this comparative example is shown as Al 2 O 3 No AlN was generated, and the thermal conductivity was only 25W/(m·k).
As can be seen from a combination of example 1 and comparative examples 1 to 2, the present invention is capable of promoting the formation of AlN phase in a nitrogen-containing gas source or a nitrogen-containing compound, and is superior to Al 2 O 3 Al synthesized by the method 2 O 3 The thermal conductivity of the AlN in-situ composite ceramic is obviously increased, and the AlN in-situ composite ceramic has the capability of increasing the heat dissipation of the chip packaging substrate. From the interfacial analysis of the microstructure, al 2 O 3 The AlN in-situ composite ceramic interface has no obvious pores and cracks, which proves that Al 2 O 3 AlN composite ceramic and Al 2 O 3 Has good interface bonding.
Comparative example 3
This comparative example provides a method for preparing Al 2 O 3 The method of AlN in-situ composite ceramic is the same as that of example 1 except that the pressurized stirring in step (1) and the cooling and crushing in step (2) are not performed, and the particles with the average particle diameter of 2-3mm are obtained by ball milling after directly mixing the binder, and the details are not repeated.
The testing method comprises the following steps: observing and measuring Al by using a scanning electron microscope 2 O 3 Cross-sectional thickness of AlN in-situ composite ceramic, semi-quantitatively analyzing Al by XRD 2 O 3 Al in AlN in-situ composite ceramic 2 O 3 Content and AlN content, al was measured by the flat plate method 2 O 3 Thermal conductivity of AlN in-situ composite ceramic, and observing Al by adopting a scanning electron microscope 2 O 3 AlN in-situ composite ceramic Al 2 O 3 The AlN interface bonding has obvious defects such as cracks and pores.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) As can be seen from the comprehensive examples 1-3, the additive manufacturing method provided by the invention prepares Al 2 O 3 Al with excellent performance can be prepared by the AlN in-situ composite ceramic method 2 O 3 An AlN in-situ composite ceramic having a high bonding strength and a thermal conductivity of 160W/(m.k) or more;
(2) As can be seen from the comprehensive example 1 and the comparative example 3, the method selects the combination of the steps of ball milling, drying, heating and stirring, pressurizing and stirring, cooling and crushing, and the steps sequentially act on each other according to a specific sequence, so that the ceramic product with higher bonding strength and higher compactness can be obtained.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (10)
1. Additive manufacturing preparation Al 2 O 3 -a method of AlN in-situ composite ceramic, characterized in that the method comprises the steps of:
(1) Mixing aluminum oxide powder, a surface modifier, a stabilizer and a solvent, and sequentially performing ball milling and drying to obtain a first mixture; heating and stirring the first mixture, mixing with a binder, and then pressurizing and stirring to obtain a second mixture;
(2) The second mixture is cooled and crushed in sequence to obtain particles; the granules are manufactured by additive manufacturing to obtain a molded workpiece;
(3) Degreasing the molded workpiece, and sintering the degreased workpiece under the condition of nitrogen element to obtain Al 2 O 3 -AlN in situ composite ceramic.
2. The method according to claim 1, wherein the mass ratio of the alumina powder, the surface modifier and the stabilizer in step (1) is 15-35:1:1-3;
preferably, the stabilizer comprises zirconia;
preferably, the surface modifying agent comprises stearic acid and/or calcium lignosulfonate;
preferably, the solvent comprises ethanol and/or water;
preferably, the volume ratio of the total volume of the alumina powder, the surface modifier and the stabilizer to the volume of the solvent is 0.5-1.2:1;
preferably, the rotation speed of the ball milling is 100-500 r/min;
preferably, the ball milling time is 1-20 h;
preferably, the temperature of the drying is 50-100 ℃.
3. The method according to claim 1 or 2, wherein the temperature of the heating and stirring in step (1) is 60 to 260 ℃;
preferably, the heating and stirring time is 30-240 min;
preferably, the mass ratio of the binder to the first mixture is 1:3 to 4.5;
preferably, the binder comprises any one or a combination of at least two of stearic acid, polyethylene glycol, phenolic resin, epoxy resin, ethylcellulose, polystyrene, polypropylene, polyethylene, polyvinyl alcohol, polyvinyl butyral or paraffin;
preferably, the pressure of the pressurized stirring is 10-120 MPa;
preferably, the time of the pressurized stirring is 1 to 10 hours.
4. A method according to any one of claims 1 to 3, wherein the cooling in step (2) is to room temperature;
preferably, the particle size of the crushed granular material is 1-10 mm;
preferably, the size of the nozzle for additive manufacturing is 0.05-3 mm;
preferably, the additive manufactured layer has a thickness of 0.05-0.35 mm;
preferably, the printing speed of the additive manufacturing is 5-100 mm/s;
preferably, the feed flow rate of the additive manufacturing is 70-100%.
5. The method according to any one of claims 1 to 4, wherein step (2) further comprises: polishing the surface of the molded workpiece;
preferably, the polished surface roughness Ra is 0.1 to 1.6.
6. The method according to any one of claims 1 to 5, wherein the degreasing method in step (3) comprises solvent degreasing and/or thermal degreasing;
preferably, the solvent used for degreasing comprises any one or a combination of at least two of water, ethanol, n-heptane, kerosene, diesel oil and edible oil;
preferably, the thermal degreasing includes heating to a first temperature at a first heating rate for a first time, heating to a second temperature at a second heating rate for a second time, heating to a third temperature at a third heating rate for a third time, and heating to a fourth temperature at a fourth heating rate for a fourth time;
preferably, the first heating rate is 0.2-5 ℃/min;
preferably, the first temperature is 60-100 ℃;
preferably, the first time is 30 min-10 h;
preferably, the second heating rate is 0.2-5 ℃/min;
preferably, the second temperature is 180-220 ℃;
preferably, the second time is 30 min-12 h;
preferably, the third heating rate is 0.2-5 ℃/min;
preferably, the third temperature is 380-420 ℃;
preferably, the third time is 30 min-12 h;
preferably, the fourth heating rate is 0.2-5 ℃/min;
preferably, the fourth temperature is 550-600 ℃;
preferably, the fourth time is 30 min-8 h.
7. The method according to any one of claims 1 to 6, wherein the conditions of the nitrogen-containing element in step (3) include: coating the surface with any one or a combination of at least two of nitrogen element, introduced nitrogen or compound containing nitrogen element;
preferably, the temperature rising rate of the sintering treatment is 0.5-10 ℃/min;
preferably, the final temperature of the sintering treatment is 1200-2100 ℃;
preferably, the sintering treatment is maintained at the final temperature for 1 to 8 hours.
8. The method according to any one of claims 1 to 7, characterized in that it comprises the steps of:
(1) Mixing aluminum oxide powder, a surface modifier, a stabilizer and a solvent, and performing ball milling for 1-20 hours at a rotating speed of 100-500 r/min, wherein the mass ratio of the aluminum oxide powder to the surface modifier to the stabilizer is 15-35:1:1-3, the total volume ratio of the aluminum oxide powder to the surface modifier to the stabilizer to the solvent is 0.5-1.2:1, and the time is 1-20 hours; obtaining a first mixture;
heating and stirring the first mixture at 60-200 ℃ for 30-240 min, mixing with a binder, and then stirring for 1-10 h under the pressure of 10-120 MPa to obtain a second mixture;
the mass ratio of the binder to the first mixture is 1:3 to 4.5;
(2) The second mixture is cooled to room temperature and crushed in sequence to obtain particles with the particle diameter of 1-10 mm; the alumina particles are manufactured by additive, the size of a nozzle is 0.05-3 mm, the thickness of a layer is 0.05-0.35 mm, the printing speed is 5-100 mm/s, and the feeding flow is 70-100%, so that a formed workpiece is obtained; polishing the surface of the molded workpiece to ensure that the surface roughness Ra of the polished workpiece is 0.1-1.6;
(3) Degreasing the formed workpiece, heating the degreased workpiece to 1200-2100 ℃ at a heating rate of 0.5-10 ℃/min under the condition of nitrogen element, and preserving heat for 1-8 h at the final temperature to perform sintering treatment to obtain Al 2 O 3 -AlN in situ composite ceramic.
9. Al (aluminum) alloy 2 O 3 -AlN in-situ composite ceramic, characterized in that the Al 2 O 3 -AlN in situ composite ceramic for preparing Al using additive manufacturing according to any of claims 1-8 2 O 3 -AlN in situ composite ceramic;
preferably, the Al 2 O 3 The AlN content in the AlN in-situ composite ceramic is 40-100%;
preferably, the Al 2 O 3 Al in AlN in-situ composite ceramic 2 O 3 The content is 0.1-20%;
preferably, the Al 2 O 3 The AlN in-situ composite ceramic has a thickness of 500nm to 5mm.
10. An Al of claim 9 2 O 3 -application of AlN in-situ composite ceramic in ceramic substrates for electronic packaging.
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| CN202311627400.0A CN117534445A (en) | 2023-11-30 | 2023-11-30 | Al (aluminum) alloy 2 O 3 AlN in-situ composite ceramic, method for preparing AlN in-situ composite ceramic by additive manufacturing and application of AlN in-situ composite ceramic |
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