CN117902903A - Bulk compact amorphous SiBCN ceramic block and preparation method thereof - Google Patents
Bulk compact amorphous SiBCN ceramic block and preparation method thereof Download PDFInfo
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Abstract
一种大块致密非晶SiBCN陶瓷块体及其制备方法，它涉及非晶SiBCN陶瓷块体及其制备方法。本发明要解决现有技术难以实现大块致密非晶SiBCN块体陶瓷的制备。方法：一、有机‑无机混合块体素坯/粉体的制备；二、大块致密非晶SiBCN陶瓷块体的制备。本发明用于大块致密非晶SiBCN陶瓷块体及其制备。
A bulk dense amorphous SiBCN ceramic block and a preparation method thereof, which relates to an amorphous SiBCN ceramic block and a preparation method thereof. The present invention aims to solve the problem that the prior art is difficult to achieve in the preparation of bulk dense amorphous SiBCN bulk ceramics. Method: 1. Preparation of organic-inorganic mixed block blank/powder; 2. Preparation of bulk dense amorphous SiBCN ceramic block. The present invention is used for bulk dense amorphous SiBCN ceramic blocks and their preparation.
Description
Technical Field
The invention relates to an amorphous SiBCN ceramic block and a preparation method thereof.
Background
The amorphous SiBCN ceramic material is widely applied to structural materials and functional materials because of high specific strength, high-temperature oxidation resistance, high thermal stability, low dielectric constant and low dielectric loss. However, because the amorphous SiBCN ceramic prepared by cracking the organic precursor has large shrinkage and low yield, and the compact SiBCN block cannot be produced by cracking the pure organic precursor, the preparation of the massive compact amorphous SiBCN block ceramic is difficult to realize, and the application field of the SiBCN ceramic material is limited to a certain extent. Therefore, research on bulk dense amorphous SiBCN bulk ceramic materials is an urgent problem to be solved.
Disclosure of Invention
The invention aims to solve the problem that the preparation of a large-block compact amorphous SiBCN ceramic block is difficult to realize in the prior art, and further provides a large-block compact amorphous SiBCN ceramic block and a preparation method thereof.
A large compact amorphous SiBCN ceramic block consists of a precursor derived ceramic phase and an amorphous ceramic phase, wherein the amorphous ceramic phase is uniformly filled in gaps of the precursor derived ceramic phase;
the precursor derivative ceramic phase is obtained by cracking a precursor at a high temperature; the amorphous ceramic phase is obtained by sintering mechanically alloyed inorganic amorphous SiBCN powder.
The preparation method of the large compact amorphous SiBCN ceramic block comprises the following steps:
1. Preparation of organic-inorganic mixed block biscuit/powder:
Dispersing mechanically alloyed inorganic amorphous SiBCN powder in precursor liquid, stirring to obtain pasty organic-inorganic mixed solution, vacuum curing the pasty organic-inorganic mixed solution, sequentially carrying out crushing and ball milling after curing, or sequentially carrying out crushing, ball milling and pre-pressing after curing to obtain organic-inorganic mixed block biscuit/powder; the mass ratio of the precursor liquid to the mechanically alloyed inorganic amorphous SiBCN powder is 1 (0.05-0.4);
Or solidifying the precursor liquid in an inert atmosphere, crushing after solidification to obtain precursor powder, and ball-milling and mixing the precursor powder and the mechanically alloyed inorganic amorphous SiBCN powder, or ball-milling and mixing and pre-pressing to obtain an organic-inorganic mixed block biscuit/powder; the mass ratio of the precursor powder to the mechanically alloyed inorganic amorphous SiBCN powder is 1 (0.05-0.4);
2. Preparation of a large compact amorphous SiBCN ceramic block:
and (3) sintering the organic-inorganic mixed block biscuit/powder under the conditions of inert atmosphere and sintering temperature of 1000-1600 ℃ to obtain the compact amorphous SiBCN block ceramic material.
The beneficial effects of the invention are as follows:
1. The inorganic amorphous ceramic network structures are generated after the precursor is cracked, drive is provided for rearrangement of original inorganic ceramic powder particles in the sintering process, migration of the inorganic ceramic powder particles is accelerated, holes generated after the precursor is cracked are filled with the inorganic powder, and then the compact block ceramic material is obtained. The invention realizes the low-temperature sintering densification of the bulk compact amorphous SiBCN block, solves the problem that the compact SiBCN block cannot be produced by cracking of the pure organic precursor, and is difficult to prepare the bulk compact amorphous SiBCN block ceramic.
2. Compared with the prior art, various single-element or multi-element oxide ceramics are mainly adopted as sintering aids, the precursor ceramics are adopted as main raw materials, a small amount of inorganic amorphous ceramic powder is added, an organic precursor is cracked to form an amorphous network structure, the sintering activity is high, the sintering of the mechanically alloyed SiBCN powder is promoted, the sintering temperature is reduced, and the density and the purity of a product are improved. And the low-temperature sintering is favorable for keeping an amorphous structure (no grain boundary, dislocation and the like exist, and the grain boundary and dislocation exist after crystallization), and the prepared compact block ceramic material has high strength, good oxidation resistance and excellent wave-transmitting performance.
Drawings
FIG. 1 is a flow chart of the present invention for preparing bulk dense amorphous SiBCN bulk ceramic;
FIG. 2 is an SEM image of a fracture of a compact amorphous SiBCN ceramic block prepared according to example I;
FIG. 3 is a TEM image of a dense amorphous SiBCN ceramic block prepared in example two;
FIG. 4 is a TG-DSC graph of a dense amorphous SiBCN ceramic block prepared in example three under a synthetic air atmosphere;
FIG. 5 shows the dielectric properties of a compact amorphous SiBCN ceramic block prepared in example four, where 1 is the dielectric constant and 2 is the dielectric loss;
FIG. 6 is a physical diagram of a compact amorphous SiBCN ceramic block prepared in example two;
Fig. 7 is an XRD pattern of a dense amorphous SiBCN ceramic block prepared in example one.
Detailed Description
The first embodiment is as follows: the embodiment is a large compact amorphous SiBCN ceramic block, which consists of a precursor derived ceramic phase and an amorphous ceramic phase, wherein the amorphous ceramic phase is uniformly filled in gaps of the precursor derived ceramic phase;
the precursor derivative ceramic phase is obtained by cracking a precursor at a high temperature; the amorphous ceramic phase is obtained by sintering mechanically alloyed inorganic amorphous SiBCN powder.
The beneficial effects of this embodiment are:
1. The inorganic amorphous ceramic network structures are generated after the precursor is cracked, drive is provided for rearrangement of original inorganic ceramic powder particles in the sintering process, migration of the inorganic ceramic powder particles is accelerated, holes generated after the precursor is cracked are filled with the inorganic powder, and then the compact block ceramic material is obtained. The embodiment realizes the low-temperature sintering densification of the bulk compact amorphous SiBCN block, solves the problem that the compact SiBCN block cannot be produced by cracking of the pure organic precursor, and is difficult to realize the preparation of the bulk compact amorphous SiBCN block ceramic.
2. Compared with the prior art, various single-element or multi-element oxide ceramics are mainly used as sintering aids, the precursor ceramics are used as main raw materials, a small amount of inorganic amorphous ceramic powder is added, an organic precursor is cracked to form an amorphous network structure, the sintering activity is high, the sintering of the mechanically alloyed SiBCN powder is promoted, the sintering temperature is reduced, and the density and purity of the product are improved. And the low-temperature sintering is favorable for keeping an amorphous structure (no grain boundary, dislocation and the like exist, and the grain boundary and dislocation exist after crystallization), and the compact block ceramic material prepared by the embodiment has high strength, good oxidation resistance and excellent wave-transmitting performance.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the precursor is powder or liquid, and the precursor is one or a mixture of polysilane, polysilazane, polycarbosilane, polyborosilazane and polyborosilazane. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the mechanical alloying inorganic amorphous SiBCN powder is prepared from mixed powder containing four elements of Si, B, C and N through high-energy ball milling, wherein the Si, B, C and N in the mixed powder are obtained by any combination of Si, carbon materials, BN, si 3N4, siC and B 4 C. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the carbon material is one or a mixture of more of graphite, carbon black, graphene, carbon nano tube, fullerene and diamond; the BN is one or a mixture of two of c-BN and h-BN. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: referring to fig. 1, the preparation method of the bulk compact amorphous SiBCN ceramic block according to the present embodiment is performed according to the following steps:
1. Preparation of organic-inorganic mixed block biscuit/powder:
Dispersing mechanically alloyed inorganic amorphous SiBCN powder in precursor liquid, stirring to obtain pasty organic-inorganic mixed solution, vacuum curing the pasty organic-inorganic mixed solution, sequentially carrying out crushing and ball milling after curing, or sequentially carrying out crushing, ball milling and pre-pressing after curing to obtain organic-inorganic mixed block biscuit/powder; the mass ratio of the precursor liquid to the mechanically alloyed inorganic amorphous SiBCN powder is 1 (0.05-0.4);
Or solidifying the precursor liquid in an inert atmosphere, crushing after solidification to obtain precursor powder, and ball-milling and mixing the precursor powder and the mechanically alloyed inorganic amorphous SiBCN powder, or ball-milling and mixing and pre-pressing to obtain an organic-inorganic mixed block biscuit/powder; the mass ratio of the precursor powder to the mechanically alloyed inorganic amorphous SiBCN powder is 1 (0.05-0.4);
2. Preparation of a large compact amorphous SiBCN ceramic block:
and (3) sintering the organic-inorganic mixed block biscuit/powder under the conditions of inert atmosphere and sintering temperature of 1000-1600 ℃ to obtain the compact amorphous SiBCN block ceramic material.
Specific embodiment six: the fifth difference between this embodiment and the third embodiment is that: the mechanical alloying inorganic amorphous SiBCN powder in the first step is specifically prepared by the following steps:
Placing mixed powder containing four elements of Si, B, C and N into a high-energy ball milling tank, ball milling for 25-40 h under the conditions of inert atmosphere and rotation speed of 400-800 r/min, and finally sieving with a 80-200 mesh sieve to obtain mechanically alloyed inorganic amorphous SiBCN powder; si, B, C and N in the mixed powder are obtained by any combination of Si, carbon material, BN, si 3N4, siC and B 4 C; the carbon material is one or a mixture of more of graphite, carbon black, graphene, carbon nano tube, fullerene and diamond; the BN is one or a mixture of two of c-BN and h-BN. The other is the same as in the fifth embodiment.
Seventh embodiment: this embodiment differs from one of the fifth or sixth embodiments in that: the precursor liquid in the first step is one or a mixture of more than one of polysilane, polysilazane, polycarbosilane, polyborosilazane and polyborosilazane; the inert atmosphere in the first step and the second step is one or a mixture of argon, nitrogen, ammonia and hydrogen. The other is the same as in the fifth or sixth embodiment.
Eighth embodiment: this embodiment differs from one of the fifth to seventh embodiments in that: the curing in the first step is specifically carried out for 2-4 hours under the condition that the temperature is 120-350 ℃. The others are the same as in embodiments five to seven.
Detailed description nine: this embodiment differs from one of the fifth to eighth embodiments in that: the pre-pressing in the first step is one or a combination of two of cold pressing and cold isostatic pressing; in the second step, when the organic-inorganic mixed powder is sintered, the sintering is discharge plasma sintering, hot-press sintering, air-pressure sintering, hot isostatic pressing sintering or high-pressure sintering; and in the second step, when the organic-inorganic mixed biscuit is sintered, the sintering is pressureless sintering. The others are the same as in embodiments five to eight.
Detailed description ten: this embodiment differs from one of the fifth to ninth embodiments in that: when the sintering is discharge plasma sintering, the method specifically comprises the following steps: heating to 1000-1500 ℃ at a heating rate of 30-100 ℃/min, and preserving heat for 2-10 min under the conditions of 30-100 MPa and 1000-1500 ℃;
When the sintering is hot press sintering, the method specifically comprises the following steps: heating to 1000-1600 ℃ at a heating rate of 3-20 ℃/min, and preserving heat for 30-120 min under the conditions of 40-80 MPa and 1000-1600 ℃;
when the sintering is pressureless sintering, the method specifically comprises the following steps: heating to 1000-1600 deg.c at the heating rate of 0.5-2 deg.c/min and maintaining the temperature at 1000-1600 deg.c for 30-240 min. The others are the same as in embodiments five to nine.
The following examples are used to verify the benefits of the present invention:
Embodiment one:
the preparation method of the large compact amorphous SiBCN ceramic block comprises the following steps:
1. Preparation of organic-inorganic mixed block biscuit/powder:
Dispersing 2g of mechanically alloyed inorganic amorphous SiBCN powder in 18g of polyborosilazane liquid, stirring for 5min by using a vacuum stirring deaerator at the rotating speed of 2500r/min to obtain pasty organic-inorganic mixed solution, placing the pasty organic-inorganic mixed solution in a vacuum drying box, vacuum curing for 4h at the temperature of 170 ℃, crushing after curing, placing in a ball milling tank, ball milling for 30min at the rotating speed of 400r/min, and finally sieving with a 200-mesh screen to obtain organic-inorganic mixed powder;
2. Preparation of a large compact amorphous SiBCN ceramic block:
Placing the organic-inorganic mixed powder into a graphite mold with the inner diameter of 30mm, heating to 1500 ℃ at a heating rate of 5 ℃/min under the condition of nitrogen atmosphere, and hot-pressing and sintering for 1h under the conditions of an axial pressure of 60MPa and a temperature of 1500 ℃ to obtain a compact amorphous SiBCN ceramic block;
the mechanical alloying inorganic amorphous SiBCN powder in the first step is specifically prepared by the following steps:
Placing mixed powder containing four elements of Si, B, C and N into a high-energy ball milling tank, ball milling for 40 hours under the conditions of inert atmosphere and rotating speed of 800r/min, and finally sieving with a 100-mesh sieve to obtain mechanically alloyed inorganic amorphous SiBCN powder; and the stoichiometric ratio of Si, B, C and N in the mixed powder is 2:1:3:1, and the mixed powder is obtained by combining Si, graphite and h-BN.
At high temperature, the organic polyborosilazane is cracked to generate amorphous SiBCN, the amorphous SiBCN network structure is recombined to provide driving force for rearrangement of amorphous SiBCN particles prepared by mechanical alloying, powder produced by the mechanical alloying realizes low-temperature sintering densification, and meanwhile, inorganic powder fills holes generated after precursor cracking, so that a corresponding compact amorphous SiBCN block is obtained. FIG. 2 is an SEM image of a fracture of a compact amorphous SiBCN ceramic block prepared according to example I; as can be seen from the figure, the sintered block has very dense fracture, the spherical-like particles are SiBCN powder produced by mechanical alloying, no obvious pores and defects are observed around the spherical particles (namely, the substances after cracking the organic precursor), and the pores after cracking the organic precursor are filled (namely, the filled substances are SiBCN phases of mechanical alloying).
FIG. 7 is an XRD pattern of a dense amorphous SiBCN ceramic block prepared in example one; as can be seen from the figure, the SiBCN ceramic block has an amorphous structure.
The compact amorphous SiBCN ceramic block prepared in the embodiment I has the volume density of 2.05g/cm 3 and the open porosity of 1.6%.
The compact amorphous SiBCN ceramic block prepared in the first example was subjected to a 3-point bending test, the sample size was 26mm×4mm×3mm (span 20 mm), the loading speed was 0.5mm/min, and the bending strength was 230.5MPa.
The oxidation resistance is determined according to the mass change of the sample by testing the highest temperature of 1500 ℃ under the synthetic air atmosphere at the heating speed of 10 ℃/min. The prepared compact amorphous SiBCN ceramic block has good oxidation resistance, and the mass change is lower than 1wt% after being oxidized for 5 hours at 1500 ℃.
The wave-transmitting performance is tested by adopting a high Q cavity method, the thickness of a test sample is 1mm, the diameter of the test sample is 18mm, the test temperature is room temperature, and the frequency is 18 GHz-40 GHz. The measured compact amorphous SiBCN ceramic block has lower dielectric loss (dielectric loss tangent is lower than 0.01) and dielectric constant (dielectric constant is about 5.5), and the prepared block SiBCN ceramic has excellent wave-transmitting performance.
Embodiment two:
The preparation method of the large compact amorphous SiBCN ceramic block comprises the following steps:
1. Preparation of organic-inorganic mixed block biscuit/powder:
placing polyborosilazane liquid in an alumina ark, curing the polyborosilazane liquid for 4 hours under the condition of nitrogen atmosphere and the temperature of 170 ℃, crushing after curing to obtain polyborosilazane powder, ball-milling 14g polyborosilazane powder and 4g mechanically alloyed inorganic amorphous SiBCN powder for 30 minutes under the condition of the rotating speed of 400r/min, finally sieving the mixture by a 200-mesh sieve to obtain organic-inorganic mixed powder, placing the organic-inorganic mixed powder in a steel mould with the inner diameter of 60mm, and maintaining the pressure for 5 minutes under the condition of the axial pressurization of 200MPa to obtain an organic-inorganic mixed block biscuit;
2. Preparation of a large compact amorphous SiBCN ceramic block:
Placing the organic-inorganic mixed block biscuit in an alumina ark, heating to 1200 ℃ at a heating rate of 1 ℃/min under the condition of nitrogen atmosphere by using a tube furnace, and pressureless sintering for 2 hours at the temperature of 1200 ℃ to obtain a compact amorphous SiBCN ceramic block;
the product is shown in fig. 6, and fig. 6 is a physical diagram of a compact amorphous SiBCN ceramic block prepared in example two.
At high temperature, the organic polyborosilazane is cracked to generate amorphous SiBCN, the amorphous SiBCN network structures are recombined to provide driving force for the movement of amorphous SiBCN particles prepared by mechanical alloying, so that the powder produced by the mechanical alloying realizes low-temperature sintering densification, and meanwhile, the inorganic amorphous SiBCN powder fills holes generated after precursor powder is cracked, so that a corresponding compact amorphous SiBCN block is obtained. FIG. 3 is a TEM image of a dense amorphous SiBCN ceramic block prepared in example two; as can be seen, the bulk remained amorphous after sintering, and no significant lattice fringes were observed.
The compact amorphous SiBCN ceramic block prepared in the second example has a volume density of 1.85g/cm 3 and an open porosity of 0.5%.
The dense amorphous SiBCN ceramic block prepared in example two was subjected to a 3-point bending test, the sample size was 26mm×4mm×3mm (span 20 mm), the loading speed was 0.5mm/min, and the bending strength was 286.5MPa.
The oxidation resistance is determined according to the mass change of the sample by testing the highest temperature of 1500 ℃ under the synthetic air atmosphere at the heating speed of 10 ℃/min. The SiBCN ceramic prepared by measurement has good oxidation resistance, and the quality change is lower than 2wt% after being oxidized for 5 hours at 1500 ℃.
The wave-transmitting performance is tested by adopting a high Q cavity method, the thickness of a test sample is 1mm, the diameter of the test sample is 18mm, the test temperature is room temperature, and the frequency is 18 GHz-40 GHz. The SiBCN block after sintering has lower dielectric loss (dielectric loss tangent is lower than 0.01) and dielectric constant (dielectric constant is about 4.3), and the prepared block SiBCN ceramic has excellent wave-transmitting performance.
Embodiment III:
The preparation method of the large compact amorphous SiBCN ceramic block comprises the following steps:
1. Preparation of organic-inorganic mixed block biscuit/powder:
Placing polysilazane liquid in an alumina ark, curing the polysilazane liquid for 4 hours under the condition of nitrogen atmosphere and 150 ℃, crushing after curing to obtain polysilazane powder, ball-milling 8g of polysilazane powder and 2g of mechanically alloyed inorganic amorphous SiBCN powder for 30 minutes under the condition of 400r/min of rotating speed, and finally sieving the mixture with a 200-mesh screen to obtain organic-inorganic mixed powder;
2. Preparation of a large compact amorphous SiBCN ceramic block:
Placing 3.5g of organic-inorganic mixed powder into a quartz glass sleeve with the inner diameter of 15mm, heating to 1500 ℃ at a heating rate of 5 ℃/min under the condition of nitrogen atmosphere, and hot isostatic pressing for 1h under the conditions of 150MPa and 1500 ℃ to obtain a large compact amorphous SiBCN ceramic block;
At high temperature, the organic polysilazane is cracked to generate amorphous SiCN, and the amorphous SiCN network structure is recombined to provide driving force for the movement of amorphous SiBCN particles prepared by mechanical alloying, so that the powder produced by the mechanical alloying realizes low-temperature sintering densification to obtain corresponding compact blocks.
The compact amorphous SiBCN ceramic block prepared in the third embodiment has the volume density of 2.42g/cm 3 and the open porosity of 0.4%.
The dense amorphous SiBCN ceramic block prepared in example three was subjected to a 3-point bending test, the sample size was 12mm×3mm×2mm (span 10 mm), the loading speed was 0.5mm/min, and the bending strength was 335.2MPa.
The oxidation resistance is determined according to the mass change of the sample by testing the highest temperature of 1500 ℃ under the synthetic air atmosphere at the heating speed of 10 ℃/min. FIG. 4 is a TG-DSC graph of a dense amorphous SiBCN ceramic block prepared in example three under a synthetic air atmosphere; as shown in the figure, the prepared SiBCN ceramic has good oxidation resistance, and the mass change rate is less than 2wt% after being oxidized for 5 hours at 1500 ℃.
Embodiment four:
The preparation method of the large compact amorphous SiBCN ceramic block comprises the following steps:
1. Preparation of organic-inorganic mixed block biscuit/powder:
Placing polysilazane liquid in an alumina ark, curing the polysilazane liquid for 4 hours under the condition of nitrogen atmosphere and the temperature of 150 ℃, crushing after curing to obtain polysilazane powder, ball-milling 8g of polysilazane powder and 2g of mechanically alloyed inorganic amorphous SiBCN powder for 30 minutes under the condition of the rotating speed of 400r/min, finally sieving the mixture by a 200-mesh sieve to obtain organic-inorganic mixed powder, placing 4g of organic-inorganic mixed powder in a steel mould with the inner diameter of 30mm, maintaining the pressure for 5 minutes under the condition of axial pressurization of 200MPa to obtain a biscuit, vacuum-molding the biscuit, placing the biscuit in a cold isostatic press, and maintaining the pressure for 2 minutes under the condition of the pressure of 200MPa to obtain an organic-inorganic mixed block biscuit;
2. Preparation of a large compact amorphous SiBCN ceramic block:
Placing the organic-inorganic mixed block biscuit in an alumina ark, heating to 1000 ℃ at a heating rate of 1 ℃/min under the condition of nitrogen atmosphere by using a tube furnace, and pressureless sintering for 2 hours at the temperature of 1000 ℃ to obtain a large compact amorphous SiBCN ceramic block;
At high temperature, organic polysilazane is cracked to generate amorphous SiCN, and the amorphous SiCN network structure is recombined to provide driving force for the movement of amorphous SiBCN particles prepared by mechanical alloying, so that powder produced by the mechanical alloying realizes low-temperature sintering densification, and meanwhile, inorganic amorphous SiBCN powder fills holes generated after precursor powder is cracked, so that a corresponding compact amorphous SiBCN block is obtained.
The compact amorphous SiBCN ceramic block prepared in the fourth embodiment has the volume density of 1.72g/cm 3 and the open porosity of 1.3%.
The compact amorphous SiBCN ceramic block prepared in example four was subjected to a 3-point bending test, the sample size was 26mm×4mm×3mm (span 20 mm), the loading speed was 0.5mm/min, and the bending strength was 208.4MPa.
The oxidation resistance is determined according to the mass change of the sample by testing the highest temperature of 1500 ℃ under the synthetic air atmosphere at the heating speed of 10 ℃/min. The SiBCN ceramic prepared by measurement has good oxidation resistance, and the mass change rate is lower than 2wt% after being oxidized for 5 hours at 1500 ℃.
The wave-transmitting performance is tested by adopting a high Q cavity method, the thickness of a test sample is 1mm, the diameter of the test sample is 18mm, the test temperature is room temperature, and the frequency is 18 GHz-40 GHz. FIG. 5 shows the dielectric properties of a compact amorphous SiBCN ceramic block prepared in example four, where 1 is the dielectric constant and 2 is the dielectric loss; as can be seen from the graph, the SiBCN block after sintering has lower dielectric loss ((dielectric loss tangent is lower than 0.01) and dielectric constant (dielectric constant is about 3.5), and the prepared block SiBCN ceramic has excellent wave-transmitting performance.
The mechanically alloyed inorganic amorphous SiBCN powder preparation method described in the second to fourth step one is the same as in the first embodiment.
Claims (10)
1. The bulk compact amorphous SiBCN ceramic block is characterized by comprising a precursor derived ceramic phase and an amorphous ceramic phase, wherein the amorphous ceramic phase is uniformly filled in gaps of the precursor derived ceramic phase;
the precursor derivative ceramic phase is obtained by cracking a precursor at a high temperature; the amorphous ceramic phase is obtained by sintering mechanically alloyed inorganic amorphous SiBCN powder.
2. The bulk dense amorphous SiBCN ceramic block of claim 1, wherein the precursor is a powder or a liquid and the precursor is one or a mixture of polysilane, polysilazane, polycarbosilane, polyborosilazane and polyborosilazane.
3. The bulk compact amorphous SiBCN ceramic block according to claim 1, wherein the mechanically alloyed inorganic amorphous SiBCN powder is prepared by high-energy ball milling of mixed powder containing four elements of Si, B, C and N, and Si, B, C and N in the mixed powder are obtained by any combination of Si, carbon materials, BN, si 3N4, siC and B 4 C.
4. A bulk dense amorphous SiBCN ceramic block according to claim 3, wherein said carbon material is one or a mixture of several of graphite, carbon black, graphene, carbon nanotubes, fullerenes and diamond; the BN is one or a mixture of two of c-BN and h-BN.
5. The method for preparing a bulk compact amorphous SiBCN ceramic block according to claim 1, characterized in that it comprises the following steps:
1. Preparation of organic-inorganic mixed block biscuit/powder:
Dispersing mechanically alloyed inorganic amorphous SiBCN powder in precursor liquid, stirring to obtain pasty organic-inorganic mixed solution, vacuum curing the pasty organic-inorganic mixed solution, sequentially carrying out crushing and ball milling after curing, or sequentially carrying out crushing, ball milling and pre-pressing after curing to obtain organic-inorganic mixed block biscuit/powder; the mass ratio of the precursor liquid to the mechanically alloyed inorganic amorphous SiBCN powder is 1 (0.05-0.4);
Or solidifying the precursor liquid in an inert atmosphere, crushing after solidification to obtain precursor powder, and ball-milling and mixing the precursor powder and the mechanically alloyed inorganic amorphous SiBCN powder, or ball-milling and mixing and pre-pressing to obtain an organic-inorganic mixed block biscuit/powder; the mass ratio of the precursor powder to the mechanically alloyed inorganic amorphous SiBCN powder is 1 (0.05-0.4);
2. Preparation of a large compact amorphous SiBCN ceramic block:
and (3) sintering the organic-inorganic mixed block biscuit/powder under the conditions of inert atmosphere and sintering temperature of 1000-1600 ℃ to obtain the compact amorphous SiBCN block ceramic material.
6. The method for preparing a bulk compact amorphous SiBCN ceramic block according to claim 5, wherein the mechanically alloyed inorganic amorphous SiBCN powder in the first step is prepared by the following steps:
Placing mixed powder containing four elements of Si, B, C and N into a high-energy ball milling tank, ball milling for 25-40 h under the conditions of inert atmosphere and rotation speed of 400-800 r/min, and finally sieving with a 80-200 mesh sieve to obtain mechanically alloyed inorganic amorphous SiBCN powder; si, B, C and N in the mixed powder are obtained by any combination of Si, carbon material, BN, si 3N4, siC and B 4 C; the carbon material is one or a mixture of more of graphite, carbon black, graphene, carbon nano tube, fullerene and diamond; the BN is one or a mixture of two of c-BN and h-BN.
7. The method for preparing a bulk dense amorphous SiBCN ceramic block according to claim 5, wherein the precursor liquid in the step one is one or a mixture of polysilane, polysilazane, polycarbosilane, polyborosilazane and polyborosilazane; the inert atmosphere in the first step and the second step is one or a mixture of argon, nitrogen, ammonia and hydrogen.
8. The method for preparing a bulk dense amorphous SiBCN ceramic block according to claim 5, wherein the curing in the first step is specifically performed at a temperature of 120-350 ℃ for 2-4 hours.
9. The method of claim 5, wherein the pre-pressing in step one is one or a combination of cold pressing and cold isostatic pressing; in the second step, when the organic-inorganic mixed powder is sintered, the sintering is discharge plasma sintering, hot-press sintering, air-pressure sintering, hot isostatic pressing sintering or high-pressure sintering; and in the second step, when the organic-inorganic mixed biscuit is sintered, the sintering is pressureless sintering.
10. The method for preparing a bulk dense amorphous SiBCN ceramic block according to claim 9, wherein when the sintering is spark plasma sintering, the method comprises the following steps: heating to 1000-1500 ℃ at a heating rate of 30-100 ℃/min, and preserving heat for 2-10 min under the conditions of 30-100 MPa and 1000-1500 ℃;
When the sintering is hot press sintering, the method specifically comprises the following steps: heating to 1000-1600 ℃ at a heating rate of 3-20 ℃/min, and preserving heat for 30-120 min under the conditions of 40-80 MPa and 1000-1600 ℃;
When the sintering is pressureless sintering, the method specifically comprises the following steps: heating to 1000-1600 deg.c at the heating rate of 0.5-2 deg.c/min and maintaining the temperature at 1000-1600 deg.c for 30-240 min.
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| CN119569464A (en) * | 2024-12-05 | 2025-03-07 | 哈尔滨工业大学 | Amorphous SiBCN ceramic block with high density and excellent oxidation resistance and preparation method thereof |
| CN120463535A (en) * | 2025-07-11 | 2025-08-12 | 浙江大学杭州国际科创中心 | Preparation method and application of high-orientation, low-dielectric coating on silicon carbide surface |
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| WO2013119806A1 (en) * | 2012-02-07 | 2013-08-15 | Kansas State University Research Foundation | Boron-modified silazanes for synthesis of sibnc ceramics |
| CN111689778A (en) * | 2020-06-30 | 2020-09-22 | 哈尔滨工业大学 | High-density SiBCN ceramic material and preparation method thereof |
| CN116947490A (en) * | 2023-07-31 | 2023-10-27 | 哈尔滨工业大学 | Low-temperature sintered compact block ceramic material and preparation method thereof |
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| WO2013119806A1 (en) * | 2012-02-07 | 2013-08-15 | Kansas State University Research Foundation | Boron-modified silazanes for synthesis of sibnc ceramics |
| CN111689778A (en) * | 2020-06-30 | 2020-09-22 | 哈尔滨工业大学 | High-density SiBCN ceramic material and preparation method thereof |
| CN116947490A (en) * | 2023-07-31 | 2023-10-27 | 哈尔滨工业大学 | Low-temperature sintered compact block ceramic material and preparation method thereof |
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| CN119569464A (en) * | 2024-12-05 | 2025-03-07 | 哈尔滨工业大学 | Amorphous SiBCN ceramic block with high density and excellent oxidation resistance and preparation method thereof |
| CN120463535A (en) * | 2025-07-11 | 2025-08-12 | 浙江大学杭州国际科创中心 | Preparation method and application of high-orientation, low-dielectric coating on silicon carbide surface |
| CN120463535B (en) * | 2025-07-11 | 2025-10-03 | 浙江大学杭州国际科创中心 | Preparation method and application of high-orientation, low-dielectric coating on silicon carbide surface |
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