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CN116751034B - Preparation method of high-strength alumina ceramic substrate - Google Patents

Preparation method of high-strength alumina ceramic substrate Download PDF

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Publication number
CN116751034B
CN116751034B CN202310590574.8A CN202310590574A CN116751034B CN 116751034 B CN116751034 B CN 116751034B CN 202310590574 A CN202310590574 A CN 202310590574A CN 116751034 B CN116751034 B CN 116751034B
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ceramic substrate
mixing
roller
sintering
stirring
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CN116751034A (en
Inventor
许杨生
沈一舟
王维敏
胡玉龙
陈云
张跃
钱语尧
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Zhejiang Dongci Technology Co ltd
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Zhejiang Dongci Technology Co ltd
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10Shaped 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F29/00Mixers with rotating receptacles
    • B01F29/60Mixers with rotating receptacles rotating about a horizontal or inclined axis, e.g. drum mixers
    • B01F29/61Mixers with rotating receptacles rotating about a horizontal or inclined axis, e.g. drum mixers comprising liquid spraying devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F29/00Mixers with rotating receptacles
    • B01F29/60Mixers with rotating receptacles rotating about a horizontal or inclined axis, e.g. drum mixers
    • B01F29/62Mixers with rotating receptacles rotating about a horizontal or inclined axis, e.g. drum mixers without bars, i.e. without mixing elements; characterised by the shape or cross section of the receptacle, e.g. of Y-, Z-, S- or X- shape; with cylindrical receptacles rotating about an axis at an angle to their longitudinal axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80Mixing plants; Combinations of mixers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80Mixing plants; Combinations of mixers
    • B01F33/836Mixing plants; Combinations of mixers combining mixing with other treatments
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/71Feed mechanisms
    • B01F35/717Feed mechanisms characterised by the means for feeding the components to the mixer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/71Feed mechanisms
    • B01F35/717Feed mechanisms characterised by the means for feeding the components to the mixer
    • B01F35/7179Feed mechanisms characterised by the means for feeding the components to the mixer using sprayers, nozzles or jets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00Producing shaped prefabricated articles from the material
    • B28B1/29Producing shaped prefabricated articles from the material by profiling or strickling the material in open moulds or on moulding surfaces
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
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Abstract

The invention relates to a preparation method of a high-strength alumina ceramic substrate, which comprises the following preparation steps of firstly, mixing and stirring at one time, namely, adding alumina, a sintering aid, a colorant, a dispersing agent and a plasticizer into a stirring barrel according to a proportion, and fully stirring to obtain a mixture; step two, a secondary mixing and stirring process, wherein a certain amount of binder and the mixture in the step one are added into a mixing device to be mixed and stirred to obtain pasty slurry; step three, a casting forming process, namely adding the paste slurry obtained in the step two into a thick film casting machine for casting forming to obtain a multilayer ceramic substrate; and step four, a high-temperature sintering process, namely placing the formed ceramic substrate into a high-temperature sintering furnace, and introducing hydrogen and nitrogen into the sintering furnace in proportion, wherein the sintering temperature is 1600-1700 ℃, so that the ceramic substrate is formed, and the problems of poor product quality stability and insufficient strength are solved.

Description

Preparation method of high-strength alumina ceramic substrate
Technical Field
The invention relates to the technical field of ceramic substrate manufacturing, in particular to a preparation method of a high-strength alumina ceramic substrate.
Background
Ceramic substrates refer to special process plates in which copper foil is bonded directly to the surface (single or double sided) of an alumina (Al 2O 3) or aluminum nitride (AlN) ceramic substrate at high temperature. The ultrathin composite substrate has excellent electrical insulation performance, high heat conduction property, excellent soldering property and high adhesion strength, can etch various patterns like a PCB, and has great current carrying capacity. Therefore, ceramic substrates have become a base material for high-power electronic circuit structure technology and interconnection technology.
The application publication No. CN112174648A discloses a preparation method of a high-purity alumina ceramic substrate, which comprises the following steps: s1, placing 99-99.5 parts by weight of high-purity aluminum oxide powder and 0.5-1 part by weight of sintering aid into a ball mill; s2, loading the slurry into a slurry barrel after vacuum defoaming, adding a catalyst and an initiator, uniformly stirring, injecting the slurry into a mold after gas source connection, curing and demolding to obtain a blank; s3, softening after drying the blank, cutting the blank into pieces and drying; s4, sintering the blank piece, and flattening to obtain the substrate. The substrate disclosed by the invention is low in sintering temperature, wide in sintering range and controllable in sintering shrinkage. The invention uses the air source to apply pressure to the slurry, so that the slurry is injected into the mould from bottom to top, and the problems of large blank density difference and large forming defects caused by deposition of materials with high specific gravity in the slurry to the bottom of the mould are avoided.
The invention optimizes the formula and process of alumina ceramic, and the ceramic substrate is obtained by stirring the mixture formed by the adhesive, alumina, sintering aid, colorant, dispersing agent and plasticizer.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and provides a preparation method of a high-strength alumina ceramic substrate, which solves the problems of poor product quality stability and insufficient strength of a product due to the steps of a first mixing and stirring process, a second mixing and stirring process, a third casting and forming process, a fourth high-temperature sintering process.
Aiming at the technical problems, the invention adopts the following technical scheme: a preparation method of a high-strength alumina ceramic substrate is characterized by comprising the following steps: comprises the following preparation steps of the preparation method,
Step one, a primary mixing and stirring procedure, namely adding alumina, a sintering aid, a colorant, a dispersing agent and a plasticizer into a stirring barrel according to a proportion, and fully stirring to obtain a mixture;
Step two, a secondary mixing and stirring process, wherein a certain amount of binder and the mixture in the step one are added into a mixing device 1 to be mixed and stirred to obtain pasty slurry;
Step three, a casting forming process, namely adding the paste slurry obtained in the step two into a thick film casting machine for casting forming to obtain a multilayer ceramic substrate;
and step four, a high-temperature sintering process, namely placing the formed ceramic substrate into a high-temperature sintering furnace, and introducing hydrogen and nitrogen into the sintering furnace in proportion, wherein the sintering temperature is 1600-1700 ℃, so as to form the ceramic substrate.
As a preference, the alumina is 60-65 parts by weight, the sintering aid is 10-15 parts by weight, the colorant is 3-6 parts by weight, the plasticizer is 8-12 parts by weight, and the binder is 15-22 parts by weight.
As an optimization, in the second step, the mixing device comprises a supporting frame, a material scattering component, a material spraying mechanism and a mixing barrel rotating in the supporting frame, one end of the mixing barrel is provided with a sealing door in a rotating mode, the other end face of the mixing barrel is provided with a toothed ring, a driving component meshed with the toothed ring and driving the mixing barrel to rotate is arranged below the toothed ring, the material scattering component is used for uniformly smearing adhesive on the inner surface of the mixing barrel when the mixing barrel rotates, and the material spraying mechanism is used for extending into the mixing barrel to spray the mixture on the surface of the adhesive to form paste slurry when the mixing barrel rotates.
As one preferable, the material scattering component comprises a material scattering roller and a blocking rod which is arranged inside the material scattering roller in a sliding manner, wherein a plurality of material scattering holes are uniformly formed in the material scattering roller and the blocking rod, and the material scattering holes of the material scattering roller and the blocking rod are staggered.
As one preferable, the material spraying mechanism comprises a material spraying roller and a material receiving hopper arranged on the material spraying roller, a plurality of material spraying holes are uniformly formed in the surface of the material spraying roller, the tail end of the material spraying roller is connected with an air pipe, and the other end of the material spraying roller is connected to an air pump.
Preferably, the driving assembly comprises a motor and a gear driven by the motor, wherein the gear is arranged to be meshed with the toothed ring in height.
As a preference, in the casting molding process in the third step, the transmission speed of the casting belt in the casting machine is 380-420mm/min.
Preferably, in the casting molding process in the third step, the heating extrusion section of the casting machine is divided into a section T1 and a section T2, the temperature of the section T1 is 42-45 ℃, and the temperature of the section T2 is 68-72 ℃.
Preferably, in the fourth step, the flexural strength of the sintered ceramic substrate is 400-500Mpa.
As still another preferable mode, in the fourth step, the ratio of hydrogen to nitrogen in the sintering furnace is 1:3.
The invention has the beneficial effects that:
1. Through placing in the mixing drum and evenly scribble the spill material subassembly of spreading at the mixing drum inner wall with the binder when the mixing drum rotates, place in the mixing drum and spray the material mechanism on binder surface with the mixture when the mixing drum rotates, can make mixture and binder intensive mixing in the mixing drum, make the ceramic substrate stability of making better.
2. In the casting forming process, the drying temperature of the casting machine must be below the boiling point of the slurry solvent, so that the film blank is prevented from generating bubbles or cracks due to too large humidity gradient.
In conclusion, the product produced by the equipment has the advantages of good product quality stability, high strength and the like, and is particularly suitable for the technical field of ceramic substrate manufacturing.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, it being obvious that the drawings described below are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for preparing a high strength alumina ceramic substrate;
FIG. 2 is an operational diagram of a method for preparing a high strength alumina ceramic substrate;
FIG. 3 is a schematic structural view of a mixing device;
FIG. 4 is a cross-sectional view of a mixing device;
FIG. 5 is a right side view of the mixing device;
FIG. 6 is an enlarged view of a portion of the mixing device at A;
FIG. 7 is a partial enlarged view at B of the mixing device;
fig. 8 is a partial enlarged view at C of the mixing device.
Labeling the attached drawings; 1. a mixing device; 2. a support frame; 3. a spreading component; 4. a spraying mechanism; 5. a drive assembly;
6. Mixing drum 10. Sealing door; 11. a toothed ring; 41. a spreading roller; 42. a blocking lever; 43. a spreading hole; 51. a spraying roller; 52. a spraying hole; 53. an air pipe; 54. an air pump; 55. a receiving hopper; 61. a motor; 62. a gear;
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings.
Detailed Description
Example 1
As shown in fig. 1 to 8, a method for preparing a high strength alumina ceramic substrate comprises: comprises the following preparation steps of the preparation method,
Step one, a primary mixing and stirring procedure, namely adding alumina, a sintering aid, a colorant, a dispersing agent and a plasticizer into a stirring barrel according to a proportion, and fully stirring to obtain a mixture;
Step two, a secondary mixing and stirring process, wherein a certain amount of binder and the mixture in the step one are added into a mixing device 1 to be mixed and stirred to obtain pasty slurry;
Step three, a casting forming process, namely adding the paste slurry obtained in the step two into a thick film casting machine for casting forming to obtain a multilayer ceramic substrate;
and step four, a high-temperature sintering process, namely placing the formed ceramic substrate into a high-temperature sintering furnace, and introducing hydrogen and nitrogen into the sintering furnace in proportion, wherein the sintering temperature is 1600-1700 ℃, so as to form the ceramic substrate.
It is worth mentioning here that adding the paste slurry after mixing and stirring into a thick film casting machine for molding, then sintering in a high-temperature sintering furnace to form a ceramic substrate, so that the molded ceramic substrate has better stability and higher strength, and the BYK111 material is adopted as the dispersing agent.
The aluminum oxide-based composite material comprises, by weight, 100 parts of aluminum oxide 60-65 parts, a sintering aid 10-15 parts, a colorant 3-6 parts, a plasticizer 8-12 parts and a binder 15-22 parts.
It is worth mentioning here that the alumina has a particle size of D50, D10, D90, and DOP (dioctylphthalate) is used as plasticizer.
As shown in fig. 3, in the second step, the mixing device 1 includes a supporting frame 2, a spreading component 3, a spraying mechanism 4, and a mixing drum 6 rotatably disposed in the supporting frame 2, a sealing door 10 rotatably disposed at one end of the mixing drum 6, a toothed ring 11 disposed at the other end of the mixing drum, and a driving component 5 meshed with the toothed ring 11 and driving the mixing drum 6 to rotate and disposed below the toothed ring 11, wherein the spreading component 3 is used for uniformly spreading the adhesive on the inner surface of the mixing drum 6 when the mixing drum 6 rotates, and the spraying mechanism 4 is used for extending into the mixing drum 6 to spray the mixture on the surface of the adhesive to form paste slurry when the mixing drum 6 rotates.
It should be mentioned that, through placing the material scattering component 3 that evenly smears the binder on the inner wall of the mixing drum 6 when the mixing drum 6 rotates in the mixing drum 6, placing the material spraying mechanism 4 that sprays the mixture on the surface of the binder when the mixing drum 6 rotates in the mixing drum 6, the mixture and the binder can be fully mixed in the mixing drum 6, so that the stability of the manufactured ceramic substrate is better.
As shown in fig. 7, the spreading assembly 3 includes a spreading roller 41 and a blocking rod 42 slidably disposed inside the spreading roller 41, where the spreading roller 41 and the blocking rod 42 are uniformly provided with a plurality of spreading holes 43, and the spreading holes 43 of the spreading roller 41 and the blocking rod 42 are staggered.
It should be noted that, by providing the blocking plate 42 in the spreading roller 41, when the material needs to be spread, the blocking rod 42 is pulled to make the spreading holes 43 on the blocking rod 42 and the spreading roller 41 coincide, and the material is spread out, so that the waste of the raw material can be prevented.
As shown in fig. 5 and 6, the spraying mechanism 4 includes a spraying roller 51 and a receiving hopper 52 disposed on the spraying roller 51, a plurality of spraying holes 52 are uniformly formed on the surface of the spraying roller 51, the end of the spraying roller 51 is connected with an air pipe 53, and the other end of the spraying roller is connected to an air pump 54.
As shown in fig. 5, the driving assembly 5 includes a motor 61 and a gear 62 driven by the motor 61, and the gear 62 is disposed at a height to be engaged with the toothed ring 11.
It should be noted that, the gear 62 is meshed with the toothed ring 11 to drive the mixing drum 6 to rotate, so that the mixing drum 6 can rotate more stably.
In the casting molding process in the third step, the transmission speed of the casting belt in the casting machine is 380-420mm/min.
In the casting molding process in the third step, the heating extrusion section of the casting machine is divided into a T1 section and a T2 section, the temperature of the T1 section is 42-45 ℃, and the temperature of the T2 section is 68-72 ℃.
And step four, sintering to obtain the ceramic substrate with flexural strength of 400-500Mpa.
In the fourth step, the ratio of hydrogen to nitrogen in the sintering furnace is 1:3.
The working process is as follows:
The worker adds alumina, sintering aid, colorant, dispersant and plasticizer into the mixing drum according to proportion, stir fully to get the mixture;
The worker opens the sealing door 10 in the mixing device 1, starts the driving component 5 to drive the mixing barrel 6 to rotate through the toothed ring 11, stretches the material scattering component 3 into the mixing barrel 6, pulls the blocking rod 42 to enable the material scattering holes 43 on the blocking rod 42 and the material scattering roller 41 to coincide, and uniformly scatters the adhesive in the material scattering roller 41 on the inner surface of the mixing barrel 6;
After the binder is scattered, a worker closes the sealing door 10, stretches the spraying roller 51 into the mixing barrel 6, pours the stirred mixture into the receiving hopper 55, starts the air pump 54, sprays the mixture in the spraying roller 51 through the spraying holes 52 through the air pipe 53, uniformly sprays the mixture on the inner surface of the mixing barrel 6, and opens the sealing door 10 after the mixing is completed, and takes out the pasty slurry;
The worker adds the paste slurry into a thick film casting machine to carry out casting molding to obtain a multilayer ceramic substrate;
The workers put the formed ceramic substrate into a high-temperature sintering furnace, hydrogen and nitrogen are introduced into the sintering furnace in proportion, and the sintering temperature is 1600-1700 ℃ to form the ceramic substrate.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "front and rear", "left and right", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of description and simplification of the description, and do not indicate or imply that the apparatus or component in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the invention.
Of course in this technical solution, those skilled in the art should understand that the term "a" or "an" should be understood as "at least one" or "one or more", i.e., in one embodiment, the number of one element may be one, while in another embodiment, the number of the element may be plural, the term "a" should not be construed as limiting the number
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art under the technical teaching of the present invention should be covered. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (7)

1. A preparation method of a high-strength alumina ceramic substrate is characterized by comprising the following steps: comprises the following preparation steps of the preparation method,
Step one, a primary mixing and stirring procedure, namely adding alumina, a sintering aid, a colorant, a dispersing agent and a plasticizer into a stirring barrel according to a proportion, and fully stirring to obtain a mixture;
step two, a secondary mixing and stirring process, wherein a certain amount of binder and the mixture in the step one are added into a mixing device (1) to be mixed and stirred to obtain pasty slurry;
Step three, a casting forming process, namely adding the paste slurry obtained in the step two into a thick film casting machine for casting forming to obtain a multilayer ceramic substrate;
Step four, a high-temperature sintering process, namely placing the formed ceramic substrate into a high-temperature sintering furnace, and introducing hydrogen and nitrogen into the sintering furnace in proportion, wherein the sintering temperature is 1600-1700 ℃, so as to form the ceramic substrate;
In the second step, the mixing device (1) comprises a supporting frame (2), a spreading component (3), a spraying mechanism (4) and a mixing barrel (6) which is rotationally arranged in the supporting frame (2), a sealing door (10) is rotationally arranged at one end of the mixing barrel (6), a toothed ring (11) is arranged at the other end face of the mixing barrel, a driving component (5) which is meshed with the toothed ring (11) and drives the mixing barrel (6) to rotate is arranged below the toothed ring (11), the spreading component (3) is used for uniformly smearing adhesive on the inner surface of the mixing barrel (6) when the mixing barrel (6) rotates, and the spraying mechanism (4) is used for extending into the mixing barrel (6) to spray the mixture on the surface of the adhesive to form pasty slurry when the mixing barrel (6) rotates;
The material scattering assembly (3) comprises a material scattering roller (41) and a blocking rod (42) which is arranged in the material scattering roller (41) in a sliding manner, wherein a plurality of material scattering holes (43) are uniformly formed in the material scattering roller (41) and the blocking rod (42), and the material scattering holes (43) of the material scattering roller (41) and the blocking rod (42) are staggered;
The material spraying mechanism (4) comprises a material spraying roller (51) and a material receiving hopper (55) arranged on the material spraying roller (51), a plurality of material spraying holes (52) are uniformly formed in the surface of the material spraying roller (51), the tail end of the material spraying roller (51) is connected with an air pipe (53), and the other end of the air pipe is connected to an air pump (54).
2. The method for preparing a high strength alumina ceramic substrate according to claim 1, wherein the alumina is 60-65 parts by weight, the sintering aid is 10-15 parts by weight, the colorant is 3-6 parts by weight, the plasticizer is 8-12 parts by weight, and the binder is 15-22 parts by weight.
3. The method for preparing a high-strength alumina ceramic substrate according to claim 1, wherein the driving assembly (5) comprises a motor (61) and a gear (62) driven by the motor (61), and the gear (62) is arranged to be meshed with the toothed ring (11).
4. The method for producing a high-strength alumina ceramic substrate according to claim 1, wherein the tape transfer speed in the casting machine is 380-420mm/min in the casting molding process in the step three.
5. The method for preparing a high-strength alumina ceramic substrate according to claim 1, wherein in the casting process in the third step, the heating extrusion section of the casting machine is divided into a T1 section and a T2 section, the temperature of the T1 section is 42-45 ℃, and the temperature of the T2 section is 68-72 ℃.
6. The method for producing a high strength alumina ceramic substrate according to claim 1, wherein in the fourth step, the flexural strength of the sintered ceramic substrate is 400 to 500Mpa.
7. The method for producing a high-strength alumina ceramic substrate according to claim 1, wherein in the fourth step, the ratio of hydrogen to nitrogen in the sintering furnace is 1:3.
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