CN110330345B - Silicon nitride ceramic material, preparation method thereof and ceramic mold - Google Patents
Silicon nitride ceramic material, preparation method thereof and ceramic mold Download PDFInfo
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- CN110330345B CN110330345B CN201910593679.2A CN201910593679A CN110330345B CN 110330345 B CN110330345 B CN 110330345B CN 201910593679 A CN201910593679 A CN 201910593679A CN 110330345 B CN110330345 B CN 110330345B
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 116
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000919 ceramic Substances 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 45
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 26
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims description 35
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 14
- 238000000462 isostatic pressing Methods 0.000 claims description 12
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
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- 238000007517 polishing process Methods 0.000 description 2
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- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
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- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- QEZGRWSAUJTDEZ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(piperidine-1-carbonyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)C(=O)N1CCCCC1 QEZGRWSAUJTDEZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
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- 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
- C04B35/584—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 silicon nitride
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/806—
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
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- C04B2235/3826—Silicon carbides
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Abstract
The invention relates to a silicon nitride ceramic material, a preparation method thereof and a ceramic die, wherein the silicon nitride ceramic material comprises the following components in percentage by weight: 80-98% of silicon nitride powder, 1-10% of silicon nitride crystal whisker and silicon carbide crystal whisker and 1-10% of rare earth oxide. The silicon nitride ceramic material adopts the specific components and the proportion, and not only can the thermal shock resistance of the material be enhanced, but also the bending strength and the fracture toughness of the silicon nitride ceramic material can be improved through the combined action of the silicon nitride whiskers, the silicon carbide whiskers and the rare earth oxide on the silicon nitride powder.
Description
Technical Field
The invention relates to the technical field of ceramic material preparation, in particular to a silicon nitride ceramic material, a preparation method thereof and a ceramic die.
Background
The moulds used in the current molten metal casting industry are generally sand grinding and hard alloy moulds which have poor thermal shock resistance, are easy to corrode, are easy to bring impurities into molten aluminum and molten copper, influence the product quality and have poor demoulding effect. Generally, the use of several or several tens of molds requires the replacement of the mold, so that the production cost is high.
Silicon nitride of the formula Si3N4Is an important structural ceramic material and is an atomic crystal. The super-hard material is a super-hard material, has lubricity, wear resistance, good oxidation resistance at high temperature and strong cold and hot impact resistance, cannot be broken when heated in air at the temperature of more than 1000 ℃ and rapidly heated after being rapidly cooled, is corrosion-resistant, and is acid and alkali resistant (except hydrofluoric acid). The silicon nitride material has such excellent characteristics, and is very suitable for being used as a mold for producing aluminum casting lift tubes, radiant tubes, thermocouple protection tubes and other related accessories in molten metal processing equipment. However, the existing silicon nitride ceramic material has the characteristic of ceramic brittleness, which is limited by the bending strength and fracture toughness, and the existing silicon nitride ceramic materialThe material cannot be applied to the field of dies with higher requirements on mechanical impact.
Disclosure of Invention
Based on this, there is a need for a silicon nitride ceramic material capable of improving bending strength and fracture toughness, a method for preparing the same, and a ceramic mold.
A silicon nitride ceramic material comprises the following components in percentage by weight: 80-98% of silicon nitride powder, 1-10% of silicon nitride crystal whisker and silicon carbide crystal whisker and 1-10% of rare earth oxide.
The silicon nitride ceramic material adopts the specific components and the proportion, and not only can enhance the thermal shock resistance of the material, but also can improve the bending strength and the fracture toughness of the silicon nitride ceramic material through the combined action of the silicon nitride whiskers, the silicon carbide whiskers and the rare earth oxide on the silicon nitride powder, so that the silicon nitride ceramic material can be applied to the field of dies with higher requirements on mechanical shock, such as dies produced by related accessories in molten metal processing equipment.
In one embodiment, the aspect ratio of the silicon nitride whisker to the silicon carbide whisker is 1 (15-30).
In one embodiment, the rare earth oxide is selected from at least one of yttrium oxide, lanthanum oxide, praseodymium oxide, and scandium oxide.
In one embodiment, the rare earth oxide has a median particle size of 0.8 to 1.0 micron.
In one embodiment, the mass content of α -phase silicon nitride in the silicon nitride powder is more than 91%, and the median particle size is 0.6-0.8 microns.
A preparation method of a silicon nitride ceramic material comprises the following steps:
mixing silicon nitride powder, silicon nitride whiskers, silicon carbide whiskers and rare earth oxide in an organic solvent for pulping, and then drying and granulating to obtain granulated powder; in the silicon nitride powder, the silicon nitride whisker and the silicon carbide whisker, according to the weight percentage, the silicon nitride powder is 80-98 percent, the silicon nitride whisker and the silicon carbide whisker are 1-10 percent in total, and the rare earth oxide is 1-10 percent;
preparing the granulation powder into a green body; and
and sintering and forming the green body.
In one embodiment, the step of preparing the granulated powder into a green body specifically includes the steps of:
performing bidirectional compression molding on the granulated powder until the density of the green body reaches (1.6-1.8) g/cm3Then isostatic pressing is carried out to obtain a green body;
wherein the pressure of the two-way compression molding is 120MPa to 180MPa, and the pressure of the isostatic pressing is 180MPa to 240 MPa.
In one embodiment, the step of sintering and shaping the green body specifically includes the following steps:
filling protective gas into the green body, pressurizing to 1-5 MPa, and presintering at 1300-1380 ℃; then sintering for 2-8 hours at 1700-1850 ℃ under the pressure of 7-10 MPa.
In one embodiment, the temperature control step in the sintering is as follows:
heating to 800 ℃ at the temperature of 3-5 ℃ per minute, and pressurizing to 1-2 MPa;
heating to 800-1600 deg.c at 2-3 deg.c/min, pressurizing to 3-5 MPa at 1200 deg.c and 5-7 MPa at 1400 deg.c;
heating from 1600 ℃ to 1700 ℃ -1850 ℃ at the temperature of 1 ℃ -3 ℃ per minute, pressurizing to 7 MPa-10 MPa, and preserving heat and pressure for 2-8 hours.
A ceramic die is made of the silicon nitride ceramic material or the silicon nitride ceramic material prepared by the preparation method.
Drawings
FIG. 1 is a photograph of a green body after pre-sintering and before sintering of example 1;
fig. 2 is a photograph of the green body after sintering and before polishing process of example 1.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An embodiment of the present invention provides a silicon nitride ceramic material, which comprises the following components by weight: 80-98% of silicon nitride powder, 1-10% of silicon nitride crystal whisker and silicon carbide crystal whisker and 1-10% of rare earth oxide.
The silicon nitride ceramic material adopts the specific components and the proportion, and not only can enhance the thermal shock resistance of the material, but also can improve the bending strength and the fracture toughness of the silicon nitride ceramic material through the combined action of the silicon nitride whiskers, the silicon carbide whiskers and the rare earth oxide on the silicon nitride powder, so that the silicon nitride ceramic material can be applied to the field of dies with higher requirements on mechanical shock, such as dies produced by related accessories in molten metal processing equipment.
Compared with the traditional silicon nitride ceramic material, the silicon nitride ceramic material prepared by the invention has the advantages of high temperature resistance, good thermal shock resistance, difficult corrosion, good demoulding condition, no influence on the product quality, capability of continuously using hundreds of moulds to thousands of moulds, remarkably prolonged service life and reduced production cost of castings.
Furthermore, in the silicon nitride ceramic material, by weight percentage, the silicon nitride powder is 88 to 95 percent, the silicon nitride whisker and the silicon carbide whisker are 3 to 7 percent in total, and the rare earth oxide is 2 to 5 percent.
Furthermore, in the silicon nitride ceramic material, by weight percentage, the silicon nitride powder is 91% -94%, the silicon nitride whisker and the silicon carbide whisker are 4% -6% in total, and the rare earth oxide is 2% -4%.
Furthermore, in the silicon nitride ceramic material, by weight percentage, the silicon nitride powder is 92%, the silicon nitride whisker and the silicon carbide whisker are 5% in total, and the rare earth oxide is 3%.
In one embodiment, the length-diameter ratio of the silicon nitride whisker to the silicon carbide whisker is 1 (15-30). The silicon nitride whisker and the silicon carbide whisker with the length-diameter ratio in the range are selected, so that the bending strength and the fracture toughness of the silicon nitride ceramic material can be further improved.
Further, the silicon nitride whiskers and the silicon carbide whiskers can be prepared by reducing silicon oxide under the conditions of carbon and nitrogen.
Furthermore, the mass ratio of the silicon nitride whisker to the silicon carbide whisker is (2-3): 1, so that the complementary reinforcing effect of the silicon nitride whisker and the silicon carbide whisker can be fully exerted.
In one embodiment, the rare earth oxide is selected from at least one of yttria, lanthana, praseodymia, and scandia.
Further, the mass ratio of the rare earth oxide selected from yttrium oxide and lanthanum oxide is (3-5) to (3-5).
Further, the median particle diameter of the rare earth oxide is 0.8 to 1.0 micron.
In one embodiment, the α -phase silicon nitride powder has a mass content of greater than 91% and a median particle size of 0.6-0.8 microns, and further the purity of the silicon nitride powder is greater than 99.5%.
The invention also provides a preparation method of the silicon nitride ceramic material, which comprises the following steps of S1-S3:
step S1: mixing silicon nitride powder, silicon nitride whiskers, silicon carbide whiskers and rare earth oxide in an organic solvent for pulping, and then drying and granulating to obtain granulated powder; the silicon nitride powder, the silicon nitride crystal whisker and the silicon carbide crystal whisker are 80 to 98 percent, 1 to 10 percent and 1 to 10 percent of rare earth oxide in percentage by weight.
In one embodiment, the slurry preparation step of step S1 adopts a ball milling process, and uses silicon nitride balls as a ball milling medium, and the ball milling time is 3 hours to 16 hours. Specifically, the diameter of the ball milling media is 3.0 mm to 5.0 mm. The organic solvent in step S1 may be acetone or absolute ethanol.
In some embodiments, in the drying and granulating step, the temperature of the air outlet is set to be 85-95 ℃, and the granularity D50 of the granulated powder is 60-80 microns.
Step S2: and preparing the granulated powder into a green body.
In one embodiment, the step of preparing the granulated powder into a green body specifically comprises the steps of: performing bidirectional compression molding on the granulated powder until the density of the green body reaches (1.6-1.8) g/cm3And then isostatic pressing is carried out to obtain a green body. Wherein the pressure of the two-way compression molding is 120MPa to 180MPa, and the pressure of the isostatic pressing is 180MPa to 240 MPa. The purpose of uniform compression molding can be achieved by adopting bidirectional compression molding and combining specific process parameters, and meanwhile, the uniformity and compactness of the green body are better by adopting isostatic pressing and combining the specific process parameters.
Further, the pressure of the two-way compression molding is 150MPa to 180MPa, and the pressure of the isostatic pressing is 200MPa to 240 MPa.
Further, the molding die adopted by the bidirectional compression molding is a hard alloy dry pressing die, and specifically, the material of the hard alloy dry pressing die contains 2 wt% -5 wt%. Furthermore, the mould pressing die adopted by the bidirectional mould pressing forming comprises an upper die, a middle die and a lower die which are matched with each other, so that the upper die, the middle die and the lower die can respectively perform bidirectional precise movement in the pressing process, and the purpose of uniform pressing forming is achieved.
In some embodiments, the step of isostatic pressing comprises: the two-way compression molding blank is vacuum-packed by a special vacuum packing bag, wherein the special vacuum packing bag is made of polyethylene PE, 10-30 wt% of linear low-density polyethylene is added during preparation, and the toughness of the packing bag is enhanced so as to be suitable for high-pressure molding.
Step S3: and sintering and forming the green body.
And S3, sintering and forming to obtain the blank, namely the silicon nitride ceramic material.
In one embodiment, the step of sintering and shaping the green body specifically comprises the following steps: filling protective gas into the green body to protect and pressurize the green body to 1MPa to 5MPa, and presintering the green body at 1300 ℃ to 1380 ℃; then sintering for 2-8 hours at 1700-1850 ℃ under the pressure of 7-10 MPa.
Specifically, the shielding gas may be nitrogen.
In this way, the uniformity and compactness of the green body are improved through the green body manufacturing step S2 and the pre-sintering step S3, so that the size shrinkage of each part of the product can be accurately controlled during sintering, and the problem that the size of the product is difficult to control is solved.
Further, a step of precision machining may be further included between the step of pre-sintering and the step of sintering. In order to realize the preparation of products with complex shapes, precision machining before sintering is required to reduce the precision machining amount of the products after sintering, but the precision machining in machining equipment cannot be realized due to low green body strength, so that the green body strength is improved by adopting a pre-sintering mode to meet the precision machining requirement of the machining equipment. It is understood that the sintering step may be followed by, or may not be followed by, a second precision machining step.
In one embodiment, the temperature control step of sintering after the step of pre-sintering is as follows: heating to 800 ℃ at the temperature of 3-5 ℃ per minute, and pressurizing to 1-2 MPa; heating to 800-1600 deg.c at 2-3 deg.c/min, pressurizing to 3-5 MPa at 1200 deg.c and 5-7 MPa at 1400 deg.c; heating from 1600 ℃ to 1700 ℃ -1850 ℃ at the temperature of 1 ℃ -3 ℃ per minute, pressurizing to 7 MPa-10 MPa, and preserving heat and pressure for 2-8 hours; cooling to 800 ℃ at the temperature of 2 ℃ per minute, and then cooling along with the furnace.
Wherein, the vacuum pumping is carried out in the process of heating to 800 ℃ at the temperature of 3-5 ℃ per minute, and the subsequent pressurization is carried out by filling protective gas such as nitrogen and the like.
Further, the presintering pressure may be 1MPa or 5MPa, and the presintering temperature may be 1300 ℃, 1320 ℃, or 1380 ℃. The sintering pressure can be 7MPa, 8MPa, 9MPa or 10MPa, the sintering temperature can be 1700 ℃, 1750 ℃, 1800 ℃ and 1850 ℃, and the sintering time can be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours or 8 hours.
In some embodiments, step S4 may also be included after step S3: and polishing the sintered and molded blank.
Further, the polishing process specifically comprises the following steps: and ultrasonically cleaning the sintered and molded blank, putting the blank into vibration grinding and polishing equipment, adding an abrasive and an emulsion with a proper volume and weight, performing vibration grinding and polishing treatment, ultrasonically cleaning the blank after the polishing treatment is finished, and completely drying the blank. Wherein the abrasive can be a silicon nitride grinding ball with the diameter of 0.8 mm-1.2 mm and 1 wt% -5 wt% of 120-mesh and 300-mesh diamond abrasive.
On one hand, the preparation method adopts the specific components and the proportion, and not only can enhance the thermal shock resistance of the material, but also can improve the bending strength and the fracture toughness of the silicon nitride ceramic material through the combined action of the silicon nitride whiskers, the silicon carbide whiskers and the rare earth oxide on the silicon nitride powder.
On the other hand, the processes of the steps S2 and S3 are optimized, so that the silicon nitride ceramic material with qualified dimensional precision, good use effect and long service life can be prepared.
The invention also provides a ceramic die which is made of the silicon nitride ceramic material or the silicon nitride ceramic material prepared by the preparation method.
The ceramic die has the advantages of excellent thermal shock resistance, bending strength and fracture toughness, qualified dimensional precision, good use effect and long service life.
The following are specific examples.
Example 1
Preparing a silicon nitride mould for the copper casting mould core:
s1, preparing and granulating raw materials, wherein the raw materials comprise 5 wt% of silicon nitride whiskers and silicon carbide whiskers (the length-diameter ratio is 1: 15-30, the mass ratio is 3:1), 3 wt% of yttrium oxide and lanthanum oxide (the mass ratio of yttrium oxide to lanthanum oxide is 5:3, and the particle size D50 is 0.8 micrometer), 92 wt% of silicon nitride raw material powder (the purity is 99.5%, the phase α is 91%, and the particle size D50 is 0.6 micrometer), mixing the raw materials, taking absolute ethyl alcohol as a mixing medium, taking silicon nitride spheres (the diameter is 5.0 millimeter) as a ball milling medium, carrying out ball milling for 16 hours, drying and granulating after slurry discharge, setting the air outlet temperature to be 90 ℃, and setting the particle size D50 of the granulated powder to be 65 micrometers.
S2, green body forming: calculating the sizes of the blanks and the weight of required powder according to the product, designing the size of a mould, adjusting the pressure, and performing dry pressing; the mould pressing mould adopted by the bidirectional mould pressing forming comprises an upper mould, a middle mould and a lower mould which are matched with each other. In this example, the weight of the powder was 2.8 kg, the cavity powder charge height was 71.4mm, the upper die was pushed down to the middle die 10mm, the upper and lower dies were moved down simultaneously, the lower die was moved relatively and pressed up by the press setting, the die pressing pressure was 180MPa, and a thickness of 35mm and a green body density of 1.6g/cm were obtained3The mold core blank of (1). Vacuum packaging the blank with a special vacuum packaging bag, and performing isostatic pressing under the pressure of 240MPa to obtain a blank with better uniformity and compactness, wherein the density of the blank reaches 1.8g/cm3。
S3, pre-burning: and (3) placing the middle die into a lower die in a charging furnace, vacuumizing, heating to 800 ℃, filling nitrogen gas for protection, pressurizing to 3MPa, and then heating to 1360 ℃ of presintering temperature for presintering. And after the pre-sintering is finished, machining the blank to an accurate size by utilizing machining equipment. The resulting green body is shown in FIG. 1.
And (3) sintering: and (4) charging and placing the middle die into the lower die. Specifically, vacuumizing and heating are started, the temperature is increased to 800 ℃ at 5 ℃ per minute, and the pressure is increased to 2MPa under the protection of nitrogen gas; heating to 800-1600 deg.C at 3 deg.C per minute, wherein the pressure is increased to 5MPa at 1200 deg.C and to 7MPa at 1400 deg.C; heating to 1850 deg.C at 2 deg.C/min, pressurizing to 10MPa, maintaining at sintering temperature for 6 hr, cooling to 800 deg.C at 2 deg.C/min, and cooling with furnace. The resulting green body is shown in fig. 2. Comparing fig. 1 and fig. 2, it can be seen that the color and size of the green material after pre-sintering and sintering are different. The pre-sintered green body is lighter in color and larger in size (as shown in fig. 1); the green body shrinks more and becomes darker after sintering (as shown in fig. 2).
S4, polishing: and (2) cleaning the sintered product by ultrasonic waves, putting the sintered product into a special vibration grinding and polishing device, adding an abrasive (a silicon nitride grinding ball with the diameter of 1.0mm and 3 wt% of 180-mesh diamond abrasive) and an emulsion, carrying out vibration grinding and polishing treatment, cleaning the sintered product by ultrasonic waves after the polishing treatment is finished, and completely drying the product. The obtained silicon nitride mold has smooth surface and qualified size precision.
Example 2
The difference between the embodiment 2 and the embodiment 1 is that the raw materials comprise 7 wt% of silicon nitride whiskers and silicon carbide whiskers (the length-diameter ratio is 1: 15-30, and the mass ratio is 3:1), 2 wt% of yttrium oxide and lanthanum oxide (the mass ratio of yttrium oxide to lanthanum oxide is 5:3, and the particle size D50 is 0.8 micron), and 91 wt% of silicon nitride raw material powder (the purity is more than 99.5%, the α phase is more than 91%, and the particle size D50 is 0.6 micron).
Example 3
The difference between the embodiment 3 and the embodiment 1 is that the raw materials comprise 10 wt% of silicon nitride whiskers and silicon carbide whiskers (the length-diameter ratio is 1: 15-30, and the mass ratio is 3:1), 1 wt% of yttrium oxide and lanthanum oxide (the mass ratio of yttrium oxide to lanthanum oxide is 5:3, and the particle size D50 is 0.8 micron), and 89 wt% of silicon nitride raw material powder (the purity is more than 99.5%, the α phase is more than 91%, and the particle size D50 is 0.6 micron).
Example 4
The difference between the embodiment 4 and the embodiment 1 is that the raw materials comprise 1 wt% of silicon nitride whiskers and silicon carbide whiskers (the length-diameter ratio is 1: 15-30, and the mass ratio is 3:1), 10 wt% of yttrium oxide and lanthanum oxide (the mass ratio of yttrium oxide to lanthanum oxide is 1:1, and the particle size D50 is 1.0 micron), and 89 wt% of silicon nitride raw material powder (the purity is more than 99.5%, the α phase is more than 91%, and the particle size D50 is 0.8 micron).
Example 5
Example 5 differs from example 1 in that: all of yttrium oxide and lanthanum oxide were replaced with yttrium oxide.
Example 6
Example 6 differs from example 1 in that: and replacing all the yttrium oxide and the lanthanum oxide with the mass ratio of 5:3 by the praseodymium oxide and the scandium oxide with the same total weight and the mass ratio of 5: 3.
Example 7
Example 7 differs from example 1 in that: the molding pressure in step S2 was 150MPa, and the isostatic pressing pressure was 200 MPa.
Example 8
Example 8 differs from example 1 in that: the molding pressure in step S2 was 120MPa, and the isostatic pressing pressure was 180 MPa.
Example 9
Example 9 differs from example 1 in that: the pre-firing temperature was 1100 ℃.
Example 10
Example 10 differs from example 1 in that: specifically, vacuumizing and heating are started, the temperature is increased to 800 ℃ at 5 ℃ per minute, and the pressure is increased to 2MPa under the protection of nitrogen gas; raising the temperature of 800-1600 ℃ at 5 ℃ per minute, wherein the pressure is increased to 5MPa at 1200 ℃ and to 7MPa at 1400 ℃; heating to 1600-1850 deg.C at 5 deg.C per minute, pressurizing to 10MPa, maintaining at sintering temperature for 6 hr, cooling to 800 deg.C at 2 deg.C per minute, and cooling with furnace.
Comparative example 1
Comparative example 1 differs from example 1 in that: the silicon nitride whisker and the silicon carbide whisker in the raw material are all replaced by the silicon carbide whisker.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that the raw materials comprise 12 wt% of silicon nitride whiskers and silicon carbide whiskers (the length-diameter ratio is 1: 15-30), 1 wt% of yttrium oxide and lanthanum oxide (the mass ratio of yttrium oxide to lanthanum oxide is 1:1, and the particle size D50 is 0.8 micron), and 87 wt% of silicon nitride raw material powder (the purity is more than 99.5%, the α phase is more than 91%, and the particle size D50 is 0.6 micron).
The silicon nitride molds prepared in examples 1 to 10 and comparative examples 1 to 2 were subjected to thermal shock resistance, bending strength and fracture toughness tests, and the thermal shock resistance test method was: the samples were heated to 1200 ℃ for 10 minutes and then rapidly (less than 2 seconds) immersed in water at 20 ℃ for the number of cycles. The test standards of the bending strength and the fracture toughness are GB/T6569-2006/ISO 14704: 2000 and GB/T23806-2009, the results obtained from the tests are shown in the following table.
| Group of | Number of thermal shock resistance | Bending strength (MPa) | Fracture toughness (MPa. m)1/2) | Service life (mould) |
| Example 1 | 20 | 950 | 7.2 | 800 |
| Example 2 | 15 | 920 | 7.1 | 650 |
| Example 3 | 15 | 850 | 6.9 | 640 |
| Example 4 | 16 | 880 | 6.8 | 665 |
| Example 5 | 15 | 880 | 6.9 | 645 |
| Example 6 | 19 | 930 | 7.3 | 720 |
| Example 7 | 15 | 920 | 7.0 | 660 |
| Example 8 | 17 | 860 | 7.0 | 690 |
| Example 9 | 18 | 920 | 7.1 | 715 |
| Example 10 | 16 | 890 | 7.0 | 684 |
| Comparative example 1 | 9 | 620 | 5.3 | 86 |
| Comparative example 2 | 8 | 580 | 5.1 | 78 |
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The silicon nitride ceramic material is characterized by comprising the following components in percentage by weight: 80-98% of silicon nitride powder, 1-10% of silicon nitride whisker and silicon carbide whisker and 1-10% of rare earth oxide; the mass ratio of the silicon nitride whiskers to the silicon carbide whiskers is (2-3): 1, and the length-diameter ratio of the silicon nitride whiskers to the silicon carbide whiskers is 1: (15-30).
2. The silicon nitride ceramic material of claim 1, wherein the raw materials comprise, in weight percent: the silicon nitride powder accounts for 88 to 95 percent, the silicon nitride crystal whisker and the silicon carbide crystal whisker account for 3 to 7 percent, and the rare earth oxide accounts for 2 to 5 percent.
3. The silicon nitride ceramic material of claim 1, wherein the rare earth oxide is selected from at least one of yttria, lanthana, praseodymia, and scandia.
4. The silicon nitride ceramic material of claim 3, wherein the rare earth oxide has a median particle size of 0.8 microns to 1.0 microns.
5. The silicon nitride ceramic material of any one of claims 1 to 4, wherein the mass content of α phase silicon nitride in the silicon nitride powder is more than 91%, and the median particle diameter is 0.6 to 0.8 μm.
6. The preparation method of the silicon nitride ceramic material is characterized by comprising the following steps of:
mixing silicon nitride powder, silicon nitride whiskers, silicon carbide whiskers and rare earth oxide in an organic solvent for pulping, and then drying and granulating to obtain granulated powder; the silicon nitride powder, the rare earth oxide, the silicon nitride whisker and the silicon carbide whisker are respectively 80-98 percent, 1-10 percent and 1-10 percent of rare earth oxide; the mass ratio of the silicon nitride whiskers to the silicon carbide whiskers is (2-3) to 1, and the length-diameter ratio of the silicon nitride whiskers to the silicon carbide whiskers is 1 (15-30);
preparing the granulation powder into a green body; and
and sintering and forming the green body.
7. The method of claim 6, wherein the step of forming the granulated powder into a green body comprises the steps of:
performing bidirectional compression molding on the granulated powder until the density of the green body reaches (1.6-1.8) g/cm3Then isostatic pressing is carried out to obtain a green body;
wherein the pressure of the two-way compression molding is 120MPa to 180MPa, and the pressure of the isostatic pressing is 180MPa to 240 MPa.
8. The method according to claim 6, wherein the step of sintering and shaping the green body comprises the following steps:
filling protective gas into the green body, pressurizing to 1-5 MPa, and presintering at 1300-1380 ℃; then sintering for 2-8 hours at 1700-1850 ℃ under the pressure of 7-10 MPa.
9. The method of claim 8, wherein the temperature control step during the sintering is as follows:
heating to 800 ℃ at the temperature of 3-5 ℃ per minute, and pressurizing to 1-2 MPa;
heating from 800 ℃ to 1600 ℃ at the temperature of 2-3 ℃ per minute, wherein the pressure is increased to 3-5 MPa when the temperature is increased to 1200 ℃, and the pressure is increased to 5-7 MPa when the temperature is increased to 1400 ℃;
heating from 1600 ℃ to 1700 ℃ -1850 ℃ at the temperature of 1 ℃ -3 ℃ per minute, pressurizing to 7 MPa-10 MPa, and preserving heat and pressure for 2-8 hours.
10. A ceramic mold, which is characterized by being made of the silicon nitride ceramic material according to any one of claims 1 to 5 or the silicon nitride ceramic material prepared by the preparation method according to any one of claims 6 to 9.
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