CN117362045A - High-thermal-conductivity aluminum nitride ceramic and preparation method thereof - Google Patents
High-thermal-conductivity aluminum nitride ceramic and preparation method thereof Download PDFInfo
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 89
- 239000000919 ceramic Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 97
- 238000010438 heat treatment Methods 0.000 claims abstract description 81
- 238000001816 cooling Methods 0.000 claims abstract description 52
- 239000011812 mixed powder Substances 0.000 claims abstract description 39
- 229920003023 plastic Polymers 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 34
- 238000009694 cold isostatic pressing Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000462 isostatic pressing Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 238000005266 casting Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000010583 slow cooling Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000000357 thermal conductivity detection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a high thermal conductivity aluminum nitride ceramic and a preparation method thereof, wherein a first sintering aid, a second sintering aid, a third sintering aid and aluminum nitride powder are uniformly mixed to obtain mixed powder, then an adhesive aqueous solution is added, and after uniform ball milling, isostatic pressing is carried out to obtain an aluminum nitride ceramic green body; heating the aluminum nitride ceramic green body to 400 ℃ at the heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 4 hours-24 hours, heating to 600 ℃ to 800 ℃ at the heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 8 hours-36 hours, and naturally cooling along with a furnace to perform plastic removal; and (3) placing the green body subjected to plastic removal into a sintering furnace, heating to 1600-2200 ℃ at a heating rate of 0.5-1 ℃/min under inert atmosphere, preserving heat for 8-48 hours, cooling to 900 ℃ at a cooling rate of 0.1-0.5 ℃/min after sintering, and naturally cooling with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to high-thermal-conductivity aluminum nitride ceramic and a preparation method thereof.
Background
The aluminum nitride ceramic has the advantages of high heat conductivity, low dielectric constant, high resistivity, no toxicity, corrosion resistance, matching with the silicon thermal expansion coefficient and excellent chemical stability, so that the aluminum nitride ceramic becomes an ideal heat dissipation and packaging material for a new generation of large-scale integrated circuits, semiconductor module circuits and high-power devices, has wide application prospect in the fields of electronic information, energy chemical industry, transportation and the like, and is widely focused by a plurality of researchers in China.
Aluminum nitride belongs to covalent compounds, has small self-diffusion coefficient, is difficult to directly sinter and densify, and covers an aluminum oxide film on the surface of aluminum nitride due to the characteristic of easy oxidization, so in the actual production of aluminum nitride ceramics, a sintering aid is generally introduced to react with aluminum oxide at high temperature to generate a second phase so as to reduce the content of solid solution oxygen in crystal lattice, and sintering is promoted at the same time, so that the preparation of the aluminum nitride ceramics with high thermal conductivity is realized. A large amount of experimental study data show that the aluminum nitride ceramic can obtain higher heat conductivity by using the sintering aid than by not using the sintering aid, and in the sintering study in recent years, the effect of improving the heat conductivity by using a plurality of sintering aids is more obvious than that by using a single sintering aid.
In addition, more forming methods for preparing aluminum nitride ceramics at present are casting forming, namely, uniformly stirring aluminum nitride powder and sintering aids, and adding a binder to prepare uniform slurry; then making the slurry into ceramic green tapes through a tape casting forming machine, drying the ceramic green tapes into solid green tapes, and cutting the green tapes into green sheets; feeding the blank into a sintering furnace for sintering; and cooling the sintered substrate to obtain the ceramic wafer.
The casting molding production efficiency is highest, the continuous production and the automation of the production are easy to realize, the product quality can be improved, and the mass production is realized, but the casting method for preparing the ceramic material has very strict requirements on the process and complex steps, and the green body prepared by the casting molding method has low density, the sintered aluminum nitride ceramic has low density and the heat conducting property is difficult to improve. In addition, the existing preparation method has the problems that the temperature rising and reducing speed is too high in the preparation process, and the prepared aluminum nitride ceramic is easy to warp and deform.
Disclosure of Invention
The invention aims to provide a high-heat-conductivity aluminum nitride ceramic material and a preparation method thereof, wherein three sintering aids and a preparation method of cold isostatic pressing are adopted, and a slow temperature rising and slow temperature lowering mode is adopted in the processes of plastic removal and sintering, so that the prepared aluminum nitride ceramic has high heat conductivity and high compactness, and the problem of buckling deformation of the aluminum nitride ceramic caused by too high temperature rising and temperature lowering rate is avoided.
In a first aspect, the present invention provides a method for preparing high thermal conductivity aluminum nitride ceramics, the method comprising:
uniformly mixing the first sintering aid, the second sintering aid, the third sintering aid and aluminum nitride powder to obtain mixed powder, adding an aqueous solution of an adhesive, uniformly ball-milling, and performing cold isostatic pressing to obtain an aluminum nitride ceramic green body;
heating the aluminum nitride ceramic green body to 400 ℃ at the heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 4 hours-24 hours, heating to 600 ℃ to 800 ℃ at the heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 8 hours-36 hours, and naturally cooling along with a furnace to perform plastic removal;
and (3) placing the green body subjected to plastic removal into a sintering furnace, heating to 1600-2200 ℃ at a heating rate of 0.5-1 ℃/min under inert atmosphere, preserving heat for 8-48 hours, cooling to 900 ℃ at a cooling rate of 0.1-0.5 ℃/min after sintering, and naturally cooling with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
Preferably, the first sintering aid, the second sintering aid, and the third sintering aid include any three of rare earth metal oxides, alkaline earth metal oxides, and metal fluorides.
Preferably, the mass of the first sintering aid accounts for 0.1% -5% of the mass of the mixed powder;
the mass of the second sintering aid accounts for 0.1% -5% of the mass of the mixed powder;
the mass of the third sintering aid accounts for 0.1% -5% of the mass of the mixed powder;
the total mass of the first sintering aid, the second sintering aid and the third sintering aid is not more than 8% of the mass of the mixed powder.
Preferably, the solute in the aqueous binder solution comprises one or more of polyvinyl alcohol and polyvinyl butyral.
Preferably, the mass fraction of the adhesive aqueous solution is 8% -15%.
Preferably, the mass of the adhesive aqueous solution is 10% -18% of the mass of the mixed powder.
Preferably, the aluminum nitride powder has a particle size of 0.5 μm to 2. Mu.m.
Preferably, the inert gas forming the inert atmosphere is nitrogen with a purity of more than 99.999%.
Preferably, the pressure of the cold isostatic pressing is 150-400 MPa.
In a second aspect, the present invention provides a high thermal conductivity aluminum nitride ceramic prepared by the preparation method described in the first aspect.
The invention adopts three sintering aids and a preparation mode of cold isostatic pressing, and adopts a slow heating and slow cooling mode in the processes of removing plastic and sintering, so that the prepared aluminum nitride ceramic has high thermal conductivity and high density, and the problem of aluminum nitride ceramic warp deformation caused by too fast heating and cooling rate is avoided.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
Fig. 1 is a flowchart of a preparation method of high-thermal-conductivity aluminum nitride ceramics according to an embodiment of the invention.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The invention provides a preparation method of high-heat-conductivity aluminum nitride ceramics, which is shown in figure 1, and comprises the following steps:
and 110, uniformly mixing the first sintering aid, the second sintering aid, the third sintering aid and aluminum nitride powder to obtain mixed powder, adding an aqueous solution of an adhesive, uniformly ball-milling, and performing isostatic pressing to obtain the aluminum nitride ceramic green body.
Because of the easy oxidation property of aluminum nitride, a thin alumina film is arranged on the surface of aluminum nitride, the sintering aid can react with alumina existing on the surface of aluminum nitride at a lower sintering temperature to generate liquid-phase aluminate, the aluminum nitride particles can be rearranged due to the action of the surface tension of the liquid phase, and the mass transfer process is accelerated by the liquid phase to enable the ceramic to be more compact.
The grain size of the aluminum nitride powder selected by the invention is 0.5-2 mu m, and the invention adopts three sintering aids, wherein the first sintering aid, the second sintering aid and the third sintering aid comprise any three of rare earth metal oxide, alkaline earth metal oxide and metal fluoride. For example, the first sintering aid, the second sintering aid, and the third sintering aid may be selected from YF 3 、CeO 2 、SmF 3 、Dy 2 O 3 、Yb 2 O 3 、Sm 2 O 3 、Y 2 O 2 、B 2 O 3 、CaO、CaF 2 Any three of these.
The proper amount of sintering aid is helpful for densification of ceramics so as to improve heat conductivity, the liquid phase formed by too little sintering aid at high temperature cannot enable far aluminum nitride particles to be close to each other, and good sintering effect cannot be achieved, but because the sintering aid and aluminate formed by the sintering aid are low in heat conductivity and obstruct phonon heat transfer, the excessive sintering aid can reduce the heat conductivity of aluminum nitride, and in the application, the consumption of the sintering aid meets the following conditions:
the mass of the first sintering aid accounts for 0.1% -5% of the mass of the mixed powder, the mass of the second sintering aid accounts for 0.1% -5% of the mass of the mixed powder, the mass of the third sintering aid accounts for 0.1% -5% of the mass of the mixed powder, and the total mass of the first sintering aid, the second sintering aid and the third sintering aid is not more than 8% of the mass of the mixed powder.
The solute in the aqueous adhesive solution comprises one or more of polyvinyl alcohol (PVA) and polyvinyl butyral (PVB), the mass fraction of the aqueous adhesive solution is 8-15%, and the mass of the aqueous adhesive solution is 10-18% of the mass of the mixed powder.
In the green forming stage, isostatic pressing is utilized, wherein liquid is utilized as a pressure conducting medium in a closed die, powder is densified by applying pressure to the powder, and the method specifically comprises the steps of cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 150-400 MPa, and the time of the cold isostatic pressing is 40-100 seconds.
Step 120, heating the aluminum nitride ceramic green body to 400 ℃ at a heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 4 hours-24 hours, heating to 600 ℃ to 800 ℃ at a heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 8 hours-36 hours, and naturally cooling along with a furnace to perform plastic removal.
The prepared aluminum nitride ceramic green body contains an aqueous solution of a binder, which is equivalent to that a part of the mass of the aluminum nitride ceramic green body is from water and a binder, the binder in the green body can be decomposed at high temperature, and the green body can be deformed and broken because the binder is rapidly decomposed and discharged in the plastic removing process. On one hand, a large number of holes are generated in the blank body due to decomposition and volatilization of the adhesive, so that the mechanical properties of the plastic-removed blank body are affected; on the other hand, the difference in the burning rate of organic matters on the surface and in the interior of the green body can cause the difference in the residual carbon content of the green body, and the green body is easy to break after plastic removal, so that the warping of the later-stage ceramic is caused.
In order to prevent the problems, the method comprises the steps of heating and cooling in two steps, slowing down the heating rate and the cooling rate, prolonging the heat preservation time, and further reducing the damage of a blank, specifically, the method comprises the steps of firstly heating to 400 ℃ at the heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 4-24 hours, and slowly heating in the stage, so that on one hand, the generation of holes is reduced when the binder is cracked, decomposed and discharged, and the blank is densified; on the other hand, the method is beneficial to the small difference of the speed of the surface and the internal binder of the green body when being discharged after being decomposed, reduces the difference of the residual carbon content of the green body, and avoids the breakage after plastic removal and the warpage of the later-stage ceramic; then heating to 600-800 ℃ at the heating rate of 0.1-0.5 ℃/min, and preserving heat for 8-36 hours, wherein the process aims to drain carbon remained by decomposing the binder as much as possible, so that the prepared green body has certain strength.
130, placing the green body after the plastic removal into a sintering furnace, heating to 1600-2200 ℃ at a heating rate of 0.5-1 ℃/min under an inert atmosphere, preserving heat for 8-48 hours, cooling to 900 ℃ at a cooling rate of 0.1-0.5 ℃/min after the sintering is finished, and naturally cooling along with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
Holes may exist in the green body after the plastic removal, so that the slow heating rate and cooling rate are beneficial to further densification of the ceramic in the sintering process, and meanwhile, the warp deformation of the ceramic is reduced.
Step 130 is performed under inert atmosphere protection, because aluminum nitride powder is oxidized in air at a temperature below 1000 ℃, even sintered compact aluminum nitride ceramics are oxidized at a temperature around 1100 ℃, and the inert atmosphere protection can prevent the phenomenon, and the inert gas forming the inert atmosphere is selected to be high-purity nitrogen with the purity higher than 99.999%.
The invention adopts three sintering aids and isostatic compaction preparation modes, and adopts a slow heating and slow cooling mode in the processes of plastic removal and sintering, so that the prepared aluminum nitride ceramic has high thermal conductivity and high density, and the problem of aluminum nitride ceramic warp deformation caused by too high heating and cooling rate is avoided.
Example 1
Step 1, weighing aluminum nitride powder in a mass ratio: YF (Yf) 3 ：Yb 2 O 3 ：Sm 2 O 3 ＝93.0：4.3：1.7:1, uniformly mixing aluminum oxide powder which is particles with the particle size of 1 mu m with a plastic bag to obtain mixed powder, adding PVA solution with the mass fraction of 12% which is prepared, fully grinding the mixed powder, maintaining the pressure at 200MPa for 90 seconds, and performing cold isostatic pressing to obtain an aluminum nitride ceramic green body.
And 2, heating the prepared green body to 400 ℃ at a heating rate of 0.2 ℃/min, preserving heat for 8 hours, heating to 650 ℃ at a heating rate of 0.2 ℃/min, preserving heat for 20 hours, and naturally cooling along with a furnace to perform plastic removal.
And 3, placing the green body after the plastic removal in a vacuum tungsten wire sintering furnace, heating to 1800 ℃ at a heating rate of 0.5 ℃/min in a high-purity nitrogen atmosphere with purity of more than 99.999%, sintering at the temperature for 24 hours, cooling to 900 ℃ at a cooling rate of 0.4 ℃/min, and cooling along with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
Example 2
Step 1, weighing aluminum nitride powder in a mass ratio: caF (CaF) 2 ：Yb 2 O 3 ：Sm 2 O 3 =92.0: 4.8:2.5:0.7, uniformly mixing aluminum nitride powder with particles with the particle size of 0.5 mu m by using a plastic bag to obtain mixed powder, adding PVB solution with the mass fraction of 8% into the mixed powder, fully grinding the mixed powder, maintaining the pressure at 150MPa for 100 seconds, and performing cold isostatic pressing to obtain the aluminum nitride ceramic green body.
And 2, heating the prepared green body to 400 ℃ at a heating rate of 0.1 ℃/min, preserving heat for 4 hours, heating to 600 ℃ at a heating rate of 0.5 ℃/min, preserving heat for 36 hours, and naturally cooling along with a furnace to perform plastic removal.
And 3, placing the green body after the plastic removal in a vacuum tungsten wire sintering furnace, heating to 2000 ℃ at a heating rate of 1 ℃/min in a high-purity nitrogen atmosphere with purity of more than 99.999%, sintering at the temperature for 8 hours, cooling to 900 ℃ at a cooling rate of 0.1 ℃/min, and cooling along with the furnace to obtain the high-thermal-conductivity aluminum nitride ceramic.
Example 3
Step 1, weighing aluminum nitride powder in mass ratio：YF 3 ：Yb 2 O 3 ：Dy 2 O 3 =97.0: 0.1:2.4:0.5, uniformly mixing alumina powder which is particles with the particle size of 2 mu m with a plastic bag to obtain mixed powder, then adding PVA solution with the mass fraction of 15% which is prepared, wherein the addition amount is 10% of the mass of the mixed powder, fully grinding, maintaining the pressure at 400MPa for 40 seconds, and performing cold isostatic pressing to obtain the aluminum nitride ceramic green body.
And 2, heating the prepared green body to 400 ℃ at a heating rate of 0.5 ℃/min, preserving heat for 24 hours, heating to 800 ℃ at a heating rate of 0.2 ℃/min, preserving heat for 20 hours, and naturally cooling along with a furnace to perform plastic removal.
And 3, placing the green body after the plastic removal in a vacuum tungsten wire sintering furnace, heating to 1600 ℃ at a heating rate of 0.5 ℃/min in a high-purity nitrogen atmosphere with purity of more than 99.999%, sintering at the temperature for 48 hours, cooling to 900 ℃ at a cooling rate of 0.5 ℃/min, and cooling along with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
Example 4
Step 1, weighing aluminum nitride powder in a mass ratio: YF (Yf) 3 ：CaO：Sm 2 O 3 =99.3: 0.5:0.1:0.1, uniformly mixing alumina powder with particles with the particle size of 0.5 mu m by using a plastic bag to obtain mixed powder, adding PVA solution with the mass fraction of 10wt% into the mixed powder, fully grinding the mixed powder with the addition amount of 18% of the mass of the mixed powder, maintaining the pressure at 300MPa for 80 seconds, and performing cold isostatic pressing to obtain the aluminum nitride ceramic green body.
And 2, heating the prepared green body to 400 ℃ at a heating rate of 0.3 ℃/min, preserving heat for 15 hours, heating to 700 ℃ at a heating rate of 0.5 ℃/min, preserving heat for 20 hours, and naturally cooling along with a furnace to perform plastic removal.
And 3, placing the green body after the plastic removal in a vacuum tungsten wire sintering furnace, heating to 2200 ℃ at a heating rate of 0.2 ℃/min in a high-purity nitrogen atmosphere with purity of more than 99.999%, sintering at the temperature for 8 hours, cooling to 900 ℃ at a cooling rate of 0.2 ℃/min, and cooling along with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
Example 5
Step 1, weighing aluminum nitride powder in a mass ratio: YF (Yf) 3 ：Y 2 O 2 ：CeO 2 =96.0: 0.1:0.5:3.4, uniformly mixing alumina powder which is particles with the particle size of 1 mu m with a plastic bag to obtain mixed powder, adding PVA solution with the mass fraction of 10wt% into the mixed powder, fully grinding the mixed powder with the mass fraction of 12%, maintaining the pressure at 250MPa for 90 seconds, and performing cold isostatic pressing to obtain the aluminum nitride ceramic green body.
And 2, heating the prepared green body to 400 ℃ at a heating rate of 0.2 ℃/min, preserving heat for 8 hours, heating to 650 ℃ at a heating rate of 0.2 ℃/min, preserving heat for 20 hours, and naturally cooling along with a furnace to perform plastic removal.
And 3, placing the green body after the plastic removal in a vacuum tungsten wire sintering furnace, heating to 1700 ℃ at a heating rate of 0.3 ℃/min in a high-purity nitrogen atmosphere with purity of more than 99.999%, sintering at the temperature for 18 hours, cooling to 900 ℃ at a cooling rate of 0.5 ℃/min, and cooling along with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
Comparative example 1
Comparative example 1 as a comparative example of example 1, the difference from example 1 is that the rate of temperature rise and the rate of temperature decrease during the course of the molding and sintering are different for comparative example 1 and example 1.
Step 1, weighing aluminum nitride powder in a mass ratio: YF (Yf) 3 ：Yb 2 O 3 ：Sm 2 O 3 =93.0: 4.3:1.7:1, uniformly mixing aluminum oxide powder which is particles with the particle size of 1 mu m with a plastic bag to obtain mixed powder, adding PVA solution with the mass fraction of 12% into the mixed powder, fully grinding the mixed powder with the mass fraction of 15%, maintaining the pressure at 200MPa for 90 seconds, and performing cold isostatic pressing to obtain an aluminum nitride ceramic green body.
And 2, heating the prepared green body to 650 ℃ at a heating rate of 5 ℃/min, preserving heat for 28 hours, then cooling to room temperature at a cooling rate of 5 ℃/min, and then removing plastic.
And step 3, placing the green body after the plastic removal in a vacuum tungsten wire sintering furnace, heating to 1800 ℃ at a heating rate of 5 ℃/min in a high-purity nitrogen atmosphere with purity of more than 99.999%, sintering for 24 hours at a secondary temperature, and cooling to room temperature at a cooling rate of 5 ℃/min to obtain the high-heat-conductivity aluminum nitride ceramic.
Example 2
Comparative example 2 as a comparative example of example 1, the difference from example 1 is that comparative example 2 was cast molding.
Step 1, weighing aluminum nitride powder in a mass ratio: YF (Yf) 3 ：Yb 2 O 3 ：Sm 2 O 3 =93.0: 4.3:1.7:1, uniformly mixing aluminum oxide powder with particles with the particle size of 1 mu m by using a plastic bag to obtain mixed powder, adding PVA solution with the mass fraction of 12% into the mixed powder, fully grinding the mixed powder to obtain aluminum nitride casting slurry, carrying out casting treatment on the aluminum nitride casting slurry, controlling the height of a casting cutter head to be 1.2mm, and the casting speed to be 1.5m/min, wherein the temperature of a drying channel is 30 ℃, 45 ℃, 65 ℃, 80 ℃, 90 ℃, 75 ℃ and 60 ℃, and carrying out drying channel treatment to obtain an aluminum nitride green body film with the thickness of 200 mu m, thus obtaining the aluminum nitride ceramic green body.
And 2, heating the prepared green body to 400 ℃ at a heating rate of 0.2 ℃/min, preserving heat for 8 hours, heating to 650 ℃ at a heating rate of 0.2 ℃/min, preserving heat for 20 hours, and naturally cooling along with a furnace to perform plastic removal.
And 3, placing the green body after the plastic removal in a vacuum tungsten wire sintering furnace, heating to 1800 ℃ at a heating rate of 0.5 ℃/min in a high-purity nitrogen atmosphere with purity of more than 99.999%, sintering at the temperature for 24 hours, cooling to 900 ℃ at a cooling rate of 0.4 ℃/min, and cooling along with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
The high thermal conductivity aluminum nitride ceramics prepared in example 1 and comparative examples 1-2 were tested for density, densification, thermal conductivity and flexural strength as follows:
(1) Density testing
The measurement is carried out according to the standard GB/T2413-1980 method for measuring the volume density of piezoelectric ceramic materials.
(2) Compactness test
The determination is carried out according to the standard GB/T3850-2015 dense sintered metal material and hard alloy density determination method.
(3) Thermal conductivity testing
The measurement is carried out according to the standard GB 2019 high thermal conductivity ceramic thermal conductivity detection.
The thermal conductivity of aluminum nitride ceramics was tested using a laser thermal conductivity tester manufactured by Linseis corporation, germany.
(4) Flexural Strength test
The measurement was carried out according to the standard GB/T4741-1999 method for testing the flexural strength of ceramic materials.
(5) Warp degree
And (5) measuring by adopting an automatic optical detection method.
The results of the tests for density, thermal conductivity, flexural strength and warpage are shown in Table 1.
TABLE 1
Comparing the data of example 1 and comparative example 1 in table 1, it can be seen that the warpage of example 1 is significantly lower than that of comparative example 1, and the density, compactibility, thermal conductivity and flexural strength are also significantly better than those of comparative example 1, because, first, a slow temperature rise and slow temperature drop mode is adopted in example 1 during the de-molding process, (1) it is advantageous to reduce the occurrence of voids during the cracking, decomposition and discharge of the binder, so that the green body densifies itself; (2) The method is beneficial to the small difference of discharge rates of the decomposed surface and internal binders of the green body, reduces the difference of residual carbon content of the green body, and avoids breaking after plastic removal and warping of later-stage ceramics; (3) The method is beneficial to exhausting the residual carbon of the binder decomposition as much as possible, so that the prepared green body has certain strength. Secondly, in the sintering process, the embodiment 1 also adopts a slow heating and slow cooling mode, which is favorable for eliminating holes possibly still existing in the green body, further densification of the ceramic in the sintering process and reducing warp deformation of the ceramic. Namely, in the process of plastic removal and sintering, the embodiment 1 adopts a slow heating and slow cooling mode, so that not only is the densification of the ceramic itself improved, but also the heat conductivity of the ceramic is improved, the bending strength is also improved, and meanwhile, the buckling deformation of the lithium nitride ceramic caused by the too fast heating rate or cooling rate is avoided.
Comparing the data in example 1 and comparative example 2 in table 1, it can be seen that the density, density and flexural strength in example 1 are significantly better than those in comparative example 2, which means that the density, thermal conductivity and flexural strength of the aluminum nitride ceramics prepared by cold isostatic pressing are significantly better than those of aluminum nitride ceramics prepared by casting, because the cold isostatic pressing can uniformly compress the powder in all directions, and the incompressibility and uniformity of the liquid are utilized to transfer the pressure characteristics, so that the stress in each direction of the powder is uniform and uniform, and the uniform stress makes the internal structure of the prepared green body uniform, i.e. the internal uniformity of the green body prepared by cold isostatic pressing is uniform, and the performance of the finally sintered aluminum nitride ceramics is improved.
The invention adopts three sintering aids and cold isostatic pressing forming preparation modes, and adopts slow heating and slow cooling modes in the processes of plastic removal and sintering, so that the prepared aluminum nitride ceramic has high thermal conductivity and high density, and the problem of aluminum nitride ceramic warp deformation caused by too high heating and cooling rate is avoided.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the high-heat-conductivity aluminum nitride ceramic is characterized by comprising the following steps of:
uniformly mixing the first sintering aid, the second sintering aid, the third sintering aid and aluminum nitride powder to obtain mixed powder, adding an aqueous solution of an adhesive, uniformly ball-milling, and performing cold isostatic pressing to obtain an aluminum nitride ceramic green body;
heating the aluminum nitride ceramic green body to 400 ℃ at the heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 4 hours-24 hours, heating to 600 ℃ to 800 ℃ at the heating rate of 0.1 ℃/min-0.5 ℃/min, preserving heat for 8 hours-36 hours, and naturally cooling along with a furnace to perform plastic removal;
and (3) placing the green body subjected to plastic removal into a sintering furnace, heating to 1600-2200 ℃ at a heating rate of 0.5-1 ℃/min under inert atmosphere, preserving heat for 8-48 hours, cooling to 900 ℃ at a cooling rate of 0.1-0.5 ℃/min after sintering, and naturally cooling with the furnace to obtain the high-heat-conductivity aluminum nitride ceramic.
2. The method of manufacturing according to claim 1, wherein the first sintering aid, the second sintering aid, and the third sintering aid comprise any three of rare earth metal oxides, alkaline earth metal oxides, and metal fluorides.
3. The method according to claim 1, wherein the mass of the first sintering aid is 0.1% -5% of the mass of the mixed powder;
the mass of the second sintering aid accounts for 0.1% -5% of the mass of the mixed powder;
the mass of the third sintering aid accounts for 0.1% -5% of the mass of the mixed powder;
the total mass of the first sintering aid, the second sintering aid and the third sintering aid is not more than 8% of the mass of the mixed powder.
4. The method of claim 1, wherein the solute in the aqueous binder solution comprises one or more of polyvinyl alcohol and polyvinyl butyral.
5. The preparation method according to claim 1, wherein the mass fraction of the aqueous binder solution is 8% -15%.
6. The method according to claim 1, wherein the mass of the aqueous binder solution is 10% -18% of the mass of the mixed powder.
7. The method according to claim 1, wherein the aluminum nitride powder has a particle size of 0.5 μm to 2 μm.
8. The method of claim 1, wherein the inert gas forming the inert atmosphere is nitrogen having a purity of greater than 99.999%.
9. The method according to claim 1, wherein the cold isostatic pressure is 150MPa-400MPa.
10. A high thermal conductivity aluminum nitride ceramic prepared by the method of any one of claims 1-9.
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