CN111196726A - SiBCN-Ta4HfC5Complex phase ceramic and preparation method thereof - Google Patents
SiBCN-Ta4HfC5Complex phase ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention provides SiBCN-Ta4HfC5The preparation method of the complex phase ceramic comprises the following steps: preparation of Ta4HfC5Single-phase nanocrystalline powder; subjecting said Ta4HfC5Mixing single-phase nanocrystalline powder, hexagonal boron nitride, cubic silicon powder and graphite, and performing high-energy ball milling to obtain amorphous-nanocrystalline composite powder; sintering the amorphous-nanocrystalline composite powder to obtain SiBCN-Ta4HfC5A complex phase ceramic. The invention uses two-step mechanical alloying to obtain Ta4HfC5Introducing into SiBCN series ceramics as additive phase, ultra-high temperature phase Ta4HfC5The nano-crystalline silicon-carbon composite ceramic is uniformly dispersed in an amorphous SiBCN matrix in a nano-crystalline form, so that the mechanical and high-temperature resistance of the composite ceramic is improved, and the composite ceramic can be used at a higher temperature.
Description
Technical Field
The invention relates to the field of ceramics, in particular to SiBCN-Ta4HfC5Complex phase ceramicAnd a method for preparing the same.
Background
Aerospace equipment is the centralized embodiment of the national manufacturing level and comprehensive strength, and is also an important guarantee of national economy and national safety, and silicon-boron-carbon-nitrogen series ceramics show good development prospect in the aerospace field due to good thermal stability and high-temperature oxidation resistance. With the development of aerospace technology, high-temperature structural materials and multifunctional heat-proof materials are required to be in service in more severe environments, which requires that the ablation resistance of silicon-boron-carbon-nitrogen series ceramics is further improved.
The tantalum-hafnium carbide alloy is an infinite solid solution formed by single phases of tantalum carbide and hafnium carbide, has good chemical stability and ablation resistance, and has a melting point which is the highest value in the ultrahigh-temperature ceramics reported at present. How to uniformly introduce the ultrahigh-temperature tantalum hafnium carbide ceramic as an additive phase into the silicon-boron-carbon-nitrogen series ceramic in a nanocrystalline form so as to improve the high-temperature and mechanical properties of the silicon-boron-carbon-nitrogen series ceramic is a problem to be solved at present.
Disclosure of Invention
The invention solves the problems that: how to improve the mechanical and ultrahigh temperature performance of the silicon-boron-carbon-nitrogen ceramic.
In order to solve the problems, the invention provides SiBCN-Ta4HfC5The preparation method of the complex phase ceramic comprises the following steps: preparation of Ta4HfC5Single-phase nanocrystalline powder; subjecting said Ta4HfC5Mixing single-phase nanocrystalline powder, hexagonal boron nitride, cubic silicon powder and graphite, and performing high-energy ball milling to obtain amorphous-nanocrystalline composite powder; sintering the amorphous-nanocrystalline composite powder to obtain SiBCN-Ta4HfC5A complex phase ceramic.
Alternatively, said Ta4HfC5The grain size of the single-phase nanocrystalline powder is 3-5 nm.
Alternatively, said Ta4HfC5The mass of the single-phase nanocrystalline powder accounts for 2.5-15% of the mass of the amorphous-nanocrystalline composite powder.
Optionally, the molar ratio of the cubic silicon powder, the hexagonal boron nitride, and the graphite is Si: BN: c ═ 1.8 to 2.2: (0.5-1.2): (2.8-3.2).
Alternatively, the preparation of Ta4HfC5Single-phase nanocrystalline powder, comprising:
under the protection of argon, placing tantalum carbide powder and hafnium carbide powder in a high-energy ball mill for high-energy ball milling to ensure that tantalum carbide crystal grains and hafnium carbide crystal grains are crushed, cold welded and solid-dissolved to prepare the Ta4HfC5Single-phase nanocrystalline powder.
Optionally, the molar ratio of the tantalum carbide powder to the hafnium carbide powder is 4: 1;
preparation of said Ta4HfC5The ball milling conditions of the single-phase nanocrystalline powder are as follows: ball-material ratio (10-30): 1, the rotation speed of the main disc is 200-.
Optionally, the sintering method of the amorphous-nanocrystalline composite powder includes: hot pressing sintering, spark plasma sintering, hot isostatic pressing sintering or ultrahigh pressure sintering.
Optionally, when the hot-pressing sintering is adopted, the process conditions of the hot-pressing sintering include: the sintering temperature is 1800-2200 ℃, the sintering pressure is 40-80Mpa, the sintering time is 20-90min, and the protective atmosphere is nitrogen or argon or vacuum condition.
Compared with the prior art, the SiBCN-Ta of the invention4HfC5The preparation method of the complex phase ceramic has the following advantages:
the invention uses two-step mechanical alloying (i.e. high-energy ball milling) to mix Ta4HfC5Introducing into SiBCN series ceramics as additive phase, ultra-high temperature phase Ta4HfC5Uniformly dispersed in an amorphous SiBCN matrix in the form of nanocrystals, Ta4HfC5The ceramic composite material does not react with a SiBCN ceramic matrix, so that a strong bonding interface structure is prevented from being formed and the mechanical property of the composite ceramic is weakened; on the other hand, Ta4HfC5Dispersed in SiBCN matrix in the form of nanocrystalline and ultra-high temperature Ta4HfC5Has good physical and chemical compatibility with SiBCN crystal phase, and further improvesThe complex phase ceramic has mechanical and high temperature resistance, and can be used at higher temperature.
Another object of the present invention is to provide a SiBCN-Ta4HfC5The composite ceramic is used to raise the mechanical and superhigh temperature performance of available Si-B-C-N ceramic.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
SiBCN-Ta4HfC5The complex phase ceramic adopts the SiBCN-Ta4HfC5The preparation method of the complex phase ceramic.
Optionally, the SiBCN-Ta4HfC5The composite ceramic comprises SiBCN matrix phase, Ta4HfC5Single phase nanocrystals are distributed within the SiBCN matrix phase, and the Ta4HfC5The crystal grains of the single-phase nanocrystalline are mutually separated.
The SiBCN-Ta4HfC5Complex phase ceramic and SiBCN-Ta as described above4HfC5Compared with the prior art, the preparation method of the complex phase ceramic has the same advantages, and is not described in detail herein.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is SiBCN-Ta according to the present invention4HfC5A preparation flow chart of the complex phase ceramic;
FIG. 2 is an XRD pattern of TaC and HfC mixed powder after different time mechanization and gold deposition according to the present invention;
FIG. 3 shows SiBCN and different Ta according to the present invention4HfC5Added amount of SiBCN-Ta4HfC5XRD spectrum of the composite powder;
FIG. 4(a) is a HTEM plot of SiBCN powder after mechanical alloying; FIG. 4(b) is a TEM image of SiBCN powder after mechanical alloying; FIG. 4(c) is Ta4HfC5SiBCN-Ta in an amount of 10 wt%4HfC5HTEM image of the composite powder; FIG. 4(d) is Ta4HfC5SiBCN-Ta in an amount of 10 wt%4HfC5TEM image of the composite powder;
FIG. 5 shows SiBCN ceramic and different Ta after hot pressing sintering at 1900 ℃ and 60MPa according to the invention4HfC5Content of SiBCN-Ta4HfC5XRD pattern of the complex phase ceramic;
FIG. 6(a) is a TEM image of SiBCN ceramic after hot press sintering at 1900 ℃ and 60 MPa; FIG. 6(b) is a HTEM diagram of SiBCN ceramic after hot pressing sintering at 1900 ℃ and 60 MPa;
FIG. 7(c) is a graph showing the HADDF of SiBCN ceramic after hot press sintering at 1900 ℃ and 60 MPa; FIGS. 7(d) - (h) are diagrams of energy spectrum elements in SiBCN ceramics obtained after hot pressing sintering at 1900 ℃ and 60 MPa;
FIGS. 8(a) - (b) are SiBCN-Ta after hot pressing sintering at 1900 ℃ and 60MPa4HfC5TEM image of complex phase ceramic (STH10 complex phase ceramic);
FIG. 9(c) shows SiBCN-Ta after hot pressing sintering at 1900 ℃ and 60MPa4HfC5The HADDF diagram of complex phase ceramic (STH10 complex phase ceramic); FIGS. 9(d) - (j) are SiBCN-Ta obtained by hot pressing sintering at 1900 ℃ and 60MPa4HfC5Energy spectrum element diagram of complex phase ceramic (STH10 complex phase ceramic).
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In addition, the terms "comprising," "including," "containing," and "having" are intended to be non-limiting, i.e., that other steps and other ingredients can be added that do not affect the results. Materials, equipment and reagents are commercially available unless otherwise specified.
In addition, although the invention has described the forms of S1, S2, S3 and the like for each step in the preparation, the description is only for the convenience of understanding, and the forms of S1, S2, S3 and the like do not represent the limitation of the sequence of each step.
With the development of aerospace technology, hypersonic speed represents the development direction of the next generation of advanced aircrafts, and the high-speed motion of the aircrafts can cause nose cones, front edge stagnation points and the like on the surfaces of the aircrafts to generate high temperature of thousands of degrees centigrade or even thousands of degrees centigrade, so that the high-temperature structural stability needs to be maintained, and meanwhile, oxidation and chemical corrosion environments exist in the service process. In view of these severe conditions, further development of a heat shielding material more resistant to ultra-high temperature and ablation is required. The silicon boron carbon nitrogen (SiBCN) ceramic has the characteristics of good structure stability, good high-temperature creep resistance, good oxidation resistance and the like, is a better aerospace material, and however, the high-temperature performance of the SiBCN ceramic needs to be further improved due to the harsher service environment.
In the prior art, an ultrahigh temperature enhancement item is introduced into a SiBCN matrix to improve the mechanical property and the ultrahigh temperature property of SiBCN series ceramics, and the method comprises the following steps: 1) lanthanum boride LaB6 was introduced into the SiBCN matrix by mechanical alloying, however, in a high temperature process, LaB6Reacting with SiBCN matrix to generate La2B2C6The strengthening and toughening effects of the additive phase and the matrix material are weakened due to the reaction of the additive phase and the matrix material, and the improvement on the high-temperature performance of the SiBCN series ceramics is limited; 2) the SiBCN-ZrB is prepared by adopting a mechanical alloying technology and combining a sol-gel method2The results of the composite ceramic show that zirconium boride ZrB generated by in-situ reaction2Improves the mechanical property and high temperature resistance of the SiBCN ceramic material to a certain extent, however, ZrB2The particle size of the composite material is relatively large (about 500 nanometers), so that the toughening effect of the composite material on a SiBCN base material is limited, and the improvement of the high-temperature performance of the SiBCN is limited due to the uneven distribution of the ultra-high temperature phase; 3) the microstructure evolution and the thermal stability of the SiBCN and ultra-high temperature phase composite ceramic prepared by adopting an organic precursor method are adopted to obtain PDCs-SiBCN/ZrB with high porosity2Or PDCs-SiBCN/HfN, however, the mechanical properties of the above composite ceramics have not been evaluated due to the limitation of the sample size.
The inventors have found that in selecting ultra high temperature ceramics to improve the high temperature and mechanical properties of SiBCN series ceramics, the following factors need to be considered: (1) the ultrahigh-temperature ceramic cannot react with the SiBCN ceramic matrix to form a strong bonding interface structure; (2) the ultrahigh-temperature ceramic should be uniformly dispersed in the SiBCN matrix in the form of nano crystals; (3) good physicochemical compatibility of the hyperthermal phase with the SiBCN crystalline phase.
In order to solve the problems, the invention provides SiBCN-Ta4HfC5The preparation method of (silicon boron carbon nitrogen-tantalum carbide) multiphase ceramic is characterized by that it uses tantalum hafnium carbide alloy (Ta)4HfC5) Introducing into SiBCN series ceramics as additive phase, ultra-high temperature phase Ta4HfC5The particles are uniformly dispersed in the amorphous silicon-boron-carbon-nitrogen matrix in a nanocrystalline form and do not react with the SiBCN matrix, so that the mechanical property and the high-temperature resistance of the complex phase ceramic are improved, and the complex phase ceramic can be used at a higher temperature.
It is understood that the mechanical alloying method is also called a high-energy ball milling method, and refers to a powder preparation technology for obtaining alloying powder by repeatedly generating cold welding and fracture of powder particles through long-time violent impact and collision between powder particles and milling balls in a high-energy ball mill, so that atoms in the powder particles are diffused.
Referring to FIG. 1, an embodiment of the present invention provides a SiBCN-Ta4HfC5The preparation method of the complex phase ceramic comprises the following steps:
s1: preparation of Ta4HfC5Single-phase nanocrystalline powder;
s2: mixing Ta4HfC5Mixing single-phase nanocrystalline powder, hexagonal boron nitride (h-BN), cubic silicon powder (c-Si) and graphite, and performing high-energy ball milling to obtain amorphous-nanocrystalline composite powder;
s3: sintering the amorphous-nanocrystalline composite powder to obtain SiBCN-Ta4HfC5A complex phase ceramic.
Thus, Ta is prepared by using a first mechanical alloying process (high energy ball milling)4HfC5Nanocrystalline and formed from c-Si, h-BN, graphite and Ta4HfC5Adopts a second-step mechanical alloying method to prepare SiBCN-Ta as raw materials4HfC5Amorphous nanocrystalline composite powder, and finally sintering the amorphous nanocrystalline composite powder to prepare SiBCN-Ta4HfC5A complex phase ceramic. The invention utilizes a two-step mechanical alloying method to obtain the ultra-high temperature Ta4HfC5The silicon-boron-carbon-nitrogen series ceramics are uniformly dispersed in an amorphous SiBCN matrix in a nanocrystalline form, so that the ultrahigh temperature and the mechanical property of the silicon-boron-carbon-nitrogen series ceramics are improved.
In step S1, Ta is prepared4HfC5The single-phase nanocrystalline powder comprises the following steps: under the protection of argon, placing tantalum carbide powder and hafnium carbide powder in a high-energy ball mill for ball milling, and crushing, cold welding and solid dissolving tantalum carbide crystal grains and hafnium carbide crystal grains to obtain the Ta4HfC5Single-phase nanocrystalline powder.
Specifically, weighing a certain amount of tantalum carbide powder and hafnium carbide powder in a glove box filled with argon, putting the weighed tantalum carbide powder and hafnium carbide powder into a ball milling tank, adding grinding balls into the ball milling tank, filling 99.9% of high-purity argon into the ball milling tank, sealing, taking out the ball milling tank from the glove box, mounting the ball milling tank on a planetary high-energy ball mill for first ball milling, taking down the ball milling tank and placing the ball milling tank in the glove box after ball milling is finished, taking out the prepared powder, and obtaining Ta4HfC5Single-phase nanocrystalline powder.
Wherein, the molar ratio of the tantalum carbide powder to the hafnium carbide powder is 4:1, and when TaC and HfC are in the molar ratio of 4:1, an infinite solid solution phase Ta4Hf C5 with a melting point of 3942 ℃ can be formed.
The grinding balls added in the first ball milling are silicon nitride balls (Si)3N4) And the ball material ratio is (10-30): 1, the rotating speed of the main disc is 200-.
In step S2, Ta prepared in step S1 is subjected to mechanical alloying technology4HfC5Uniformly mixing single-phase nanocrystalline powder, hexagonal boron nitride (h-BN), cubic silicon powder (c-Si) and graphite, and then carrying out high-energy ball milling. Specifically, Ta prepared in step S1 was weighed in a glove box filled with argon gas4HfC5Single-phase nano-crystalline powder, hexagonal boron nitride, cubic silicon powder and graphite, and weighing Ta4HfC5Putting the single-phase nanocrystalline powder, hexagonal boron nitride, cubic silicon powder and graphite into a ball-milling tank together, adding grinding balls into the ball-milling tank, and sealing the ball-milling tankAnd sealing, taking out the powder from the glove box, mounting the ball milling tank on a planetary high-energy ball mill for secondary ball milling, realizing non-crystallization of the raw material powder and chemical reaction between elements by repeated high-energy collision between the grinding balls and the powder and between the powder and the tank wall, finally placing the ball milling tank in the glove box, and taking out the powder to obtain the SiBCN-Ta4HfC amorphous-nanocrystalline composite powder.
Wherein, Ta4HfC5The mass of the single-phase nanocrystalline powder accounts for 2.5-15% of the mass of the amorphous-nanocrystalline composite powder. The mol ratio of the cubic silicon powder, the hexagonal boron nitride and the graphite is Si: BN: c ═ 1.8 to 2.2: (0.5-1.2): (2.8-3.2). The purity of the cubic silicon powder is 99-99.9%, and the particle size is 1-20 μm. The purity of the hexagonal nitriding powder is 99-99.9%, and the grain diameter is 0.5-20 μm. The purity of the graphite powder is 99-99.9%, and the particle size is 0.5-20 μm.
The ball milling conditions of the second ball milling are the same as those of the first ball milling in the step S1, and are: the added grinding balls are silicon nitride balls (Si)3N4) The ball-material ratio is (10-30): 1, the rotating speed of the main disc is 200-.
In step S3, the sintering method of the amorphous-nanocrystalline composite powder includes: hot pressing sintering, spark plasma sintering, hot isostatic pressing sintering or ultrahigh pressure sintering. Each sintering mode has different advantages and disadvantages, and in the embodiment of the invention, the amorphous-nanocrystalline composite powder is prepared into SiBCN-Ta through hot-pressing sintering4HfC5A complex phase ceramic. Specifically, the method comprises the following steps:
the SiBCN-Ta4HfC amorphous-nanocrystalline composite powder prepared in the step S2 is filled into a graphite mold, the assembled mold is placed into a high-temperature sintering furnace, hot-pressing sintering is carried out in a hot-pressing furnace under the inert atmosphere, and after sintering is finished, post-processing treatment such as cooling, demolding, cutting and grinding is carried out to prepare solid ceramic with certain strength and shape, namely the SiBCN-Ta4HfC5A complex phase ceramic.
Wherein, the technological conditions of the hot-pressing sintering comprise: the sintering temperature is 1800-2200 ℃, the sintering pressure is 40-80Mpa, the sintering time is 20-90min, and the protective atmosphere is nitrogen or argon or vacuum condition.
In the embodiment of the invention, silicon boron carbon nitrogen ceramic is taken as a substrate, and Ta is added4HfC5Preparing a reinforcing phase into SiBCN-Ta4HfC5Multiphase ceramic, ultra high temperature phase Ta4HfC5Uniformly dispersed in an amorphous SiBCN matrix in the form of nanocrystals, can play a role in pinning crack propagation, improve the mechanical property of SiBCN ceramics, and simultaneously Ta4HfC5The ultra-high temperature material reinforces the SiBCN ceramic, improves the high temperature resistance of the complex phase ceramic material, and enables the complex phase ceramic material to be in service at higher temperature.
Therefore, the SiBCN-Ta provided by the embodiment of the invention4HfC5The preparation method of the complex phase ceramic comprises the step of alloying Ta by two steps4HfC5Is introduced into SiBCN series ceramics as an additive phase, on one hand, Ta is in ultrahigh temperature in the preparation process4HfC5The ceramic composite material does not react with a SiBCN ceramic matrix, so that a strong bonding interface structure is prevented from being formed and the mechanical property of the composite ceramic is weakened; on the other hand, Ta4HfC5Dispersed in SiBCN matrix in the form of nanocrystalline and ultra-high temperature Ta4HfC5Has good physical and chemical compatibility with SiBCN crystal phase, which is beneficial to improving the mechanical property of SiBCN ceramics.
The embodiment of the invention also provides a SiBCN-Ta4HfC5A complex phase ceramic of SiBCN-Ta4HfC5The multiphase ceramic is based on the above SiBCN-Ta4HfC5The preparation method of the complex phase ceramic.
The SiBCN-Ta4HfC5The composite ceramic comprises SiBCN matrix phase, Ta4HfC5Single phase nanocrystals distributed in the SiBCN matrix phase, and Ta4HfC5The crystal grains of the single-phase nanocrystalline are mutually separated. The SiBCN matrix phase includes SiC and BN (C) phases, the BN (C) phases are distributed around the SiC crystal grains, and the BN (C) phases are turbulent laminar structures which are distributed around the SiC crystal grains and isolate the SiC crystal grains from each other. And a part of Ta4HfC5With smaller grains distributed in BN (C) phase to form Ta4HfC5-a bn (c) area; another part of Ta4HfC5Uniformly dispersed throughout the SiBCN matrix phase. Ta4HfC5The turbulent layer structure composed of-BN (C) can be coated on the surface of the SiC crystal grains, thereby inhibiting element diffusion and avoiding abnormal growth of the SiC crystal grains, and the special distribution form ensures that the nanocrystalline tantalum carbide reinforced silicon-boron-carbon-nitrogen composite ceramic material keeps a nanocrystalline-amorphous structure.
In the present example, Ta prepared in step S14HfC5The size of single-phase nanocrystalline grain is 3-5nm, and the SiBCN-Ta is prepared by hot-pressing sintering4HfC5Ta in bulk ceramics4HfC5Grain size of 5-50nm, i.e. Ta distributed in the SiBCN matrix phase4HfC5The single-phase nanocrystalline grain size is smaller.
It is understood that the smaller the size of the grains, the higher the strength of the material. Thus, by introducing ultra-high temperature Ta in SiBCN ceramics4HfC5The single-phase nanocrystalline powder has good strengthening effect on a counter system, so that SiBCN-Ta4HfC5The complex phase ceramic has higher density, mechanical property and high temperature resistance.
The technical solutions of the present invention will be further described below with reference to several exemplary embodiments (not all embodiments), so as to clarify the objects and advantages of the present invention. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by weight.
Example 1
The embodiment of the invention provides a SiBCN-Ta4HfC5The preparation method of the complex phase ceramic specifically comprises the following steps:
s1 preparation of Ta4HfC5Single-phase nanocrystalline powder
Putting mixed powder of TaC and HfC with a molar ratio of 4:1 and Si3N4 grinding balls into a high-energy ball milling tank with a ball-to-material ratio of 20:1, and filling 99.9 percent of the high-energy ball milling tankThen putting the high-energy ball milling tank filled with the argon into a high-energy ball mill for mechanical alloying treatment to obtain Ta4HfC5Single-phase nanocrystalline powder. Wherein, the rotating speed of the main rotating disk is set to 350 r/min, and the rotating speed of the planetary disk is set to 800 r/min.
In addition, to further characterize the effective time of ball milling for the preparation of Ta4HfC5The influence of single-phase nanocrystalline powder, ball-milling effective time for setting for 9 time points, respectively: 0h, 0.5h, 1h, 1.5h, 3h, 5h, 10h, 15h and 30 h. Thus, Ta after different ball milling time can be obtained4HfC5Single-phase nanocrystalline powder.
Referring to fig. 2, fig. 2 is an X-ray diffraction (XRD) pattern of the TaC and HfC mixed powder after 9 ball milling times under the same other conditions, and it can be seen from the pattern that with the increase of the mechanical alloying time (i.e. the increase of the effective time of ball milling), the TaC and HfC gradually undergo a solid solution reaction, and after 10h of mechanical alloying, the TaC and HfC are completely solid-dissolved to form a single-phase Ta4HfC5(ii) a Also can obtain single-phase nanocrystalline Ta4HfC5The mechanical alloying time points of (1) are 10h, 15h and 30 h. SiBCN-Ta to avoid incomplete reaction of TaC and HfC4HfC5The multiphase ceramic has adverse effect, and in the following preparation process, the effective ball milling time of TaC and HfC is 30 h.
S2 SiBCN-Ta is prepared by adopting a mechanical alloying method4HfC5Amorphous-nanocrystalline composite powder
C-Si, h-BN and graphite are added into a ball milling tank according to the molar ratio of Si to BN to C of 2 to 1 to 3, and Ta mechanically alloyed for 30 hours in the step S1 is added into the ball milling tank4HfC5Adding Si3N4 grinding balls into the powder in a ball-milling tank, wherein the ball-to-material ratio is set to be 20: 1; filling 99.9 percent of high-purity argon into a high-energy ball milling tank, then putting the high-energy ball milling tank filled with the argon into a high-energy ball milling machine for mechanical alloying treatment to obtain the SiBCN-Ta4HfC5Amorphous-nanocrystalline composite powder. Wherein, the rotating speed of the main rotating disc is set to 350 r/min, the rotating speed of the planetary disc is set to 650r/min, and the effective ball milling time is 20 h.
In addition, to further characterize the added UHT enhancement phase Ta4HfC5For prepared SiBCN-Ta4HfC5Influence of Complex phase ceramics, adding Ta4HfC5The content is set as 4 proportions which are respectively as follows: ta4HfC5Accounting for 2.5 wt%, 5 wt%, 10 wt% and 15 wt% of the total weight of the powder. For convenience of description, 2.5 wt% Ta4HfC5Content of SiBCN-Ta4HfC5The amorphous-nanocrystalline composite powder is marked as STH2.5 powder, and the corresponding SiBCN-Ta4HfC5 bulk ceramic after hot-pressing sintering is marked as STH10 composite ceramic; 5 wt% Ta4HfC5Content of SiBCN-Ta4HfC5The amorphous-nanocrystalline composite powder is marked as STH5 powder, and the corresponding SiBCN-Ta4HfC5 bulk ceramic after hot-pressing sintering is marked as STH5 composite ceramic; 10 wt% Ta4HfC5Content of SiBCN-Ta4HfC5The amorphous-nanocrystalline composite powder is marked as STH10 powder, and the corresponding SiBCN-Ta4HfC5 bulk ceramic after hot-pressing sintering is marked as STH10 composite ceramic; 15 wt% a4HfC5Content of SiBCN-Ta4HfC5The amorphous-nanocrystalline composite powder is marked as STH15 powder, and the corresponding SiBCN-Ta4HfC5 bulk ceramic after hot-pressing sintering is marked as STH15 composite ceramic.
Referring to FIG. 3, FIG. 3 shows the X-ray diffraction (XRD) patterns of STH2.5 powder, STH5 powder, STH10 powder and STH15 powder under the same conditions, wherein after the mechanical alloying in step S2, SiBCN has an amorphous structure, and Ta 2 has an amorphous structure4HfC5The nanocrystalline structure is still maintained.
S3 SiBCN-Ta4HfC5Preparation of complex phase ceramics
Ta obtained in step S24HfC5Filling STH2.5, STH5, STH10 and STH15 powders with different contents into a graphite mould, and carrying out hot-pressing sintering to obtain Ta4HfC5SiBCN-Ta with different contents4HfC5A complex phase ceramic. The hot-pressing sintering process comprises the following steps: the temperature is 1900 deg.C, the pressure is 60Mpa, the time is 60min, and the sintering atmosphere is vacuum.
FIG. 8(a) - (A)b) Is SiBCN-Ta after hot-pressing sintering4HfC5TEM image of a complex phase ceramic (STH10 complex phase ceramic) from which it can be seen that a portion of Ta4HfC5Distributed in BN (C) to form Ta4HfC5Region of BN (C), Ta4HfC5Regions of-BN (C) are uniformly distributed in the STH10 composite ceramic, and another portion of Ta4HfC5Uniformly distributed in the STH10 composite ceramic in the form of single-phase nanocrystals.
FIGS. 9(c) - (j) are SiBCN-Ta after hot press sintering4HfC5HADDF and energy spectrum element diagram of complex phase ceramic (STH10 complex phase ceramic), Ta4HfC5Distributed in STH10 composite ceramic in two structures, part of Ta4HfC5With smaller grains distributed in BN (C) to form Ta4HfC5-a bn (c) area; and the rest of Ta4HfC5Uniformly dispersed throughout the composite ceramic. In conclusion, Ta can be shown4HfC5Does not react with the SiBCN matrix and is uniformly dispersed in the SiBCN phase.
Example 2
This example is a comparative example of example 1 and differs from example 1 in that it produces a SiBCN ceramic without the addition of ultra-high temperature Ta4HfC5The reinforced phase is prepared by the following specific steps:
s1, preparing SiBCN amorphous powder
Adding C-Si, h-BN and graphite into a ball milling tank according to the molar ratio of Si to BN to C being 2:1:3, adding Si3N4 grinding balls into the ball milling tank, and setting the ball-material ratio to be 20: 1; and (3) filling 99.9% of high-purity argon into the high-energy ball milling tank, and then putting the high-energy ball milling tank filled with the argon into a high-energy ball mill for mechanical alloying treatment to obtain the SiBCN amorphous composite powder. Wherein, the rotating speed of the main rotating disc is set to 350 r/min, the rotating speed of the planetary disc is set to 650r/min, and the effective ball milling time is 20 h.
Preparation of S2 SiBCN complex phase ceramic
And (5) loading the SiBCN amorphous powder obtained in the step (S1) into a graphite die, and carrying out hot-pressing sintering to obtain the SiBCN complex-phase ceramic. The hot-pressing sintering process comprises the following steps: the temperature is 1900 deg.C, the pressure is 60Mpa, the time is 60min, and the sintering atmosphere is vacuum.
Fig. 6 and 7 show XRD, TEM, HTEM patterns and element plane distributions of the SiBCN ceramic after hot press sintering in example 2 (comparative example). As can be seen from fig. 6(a), during the hot-pressing sintering process, the SiBCN amorphous powder achieves densification sintering and crystallization behavior, and the crystallized product contains SiC and bn (c), wherein bn (c) is distributed on the grain boundary of the SiC grains. As can be seen from fig. 6(b), the bn (c) phase is a turbulent laminar structure that is distributed around and isolates SiC grains from each other. From fig. 7(c) - (h), it can be seen that the element plane distribution of the SiBCN ceramic, in which the Si element is mainly distributed in the SiC grains, and B, C and the N element are distributed in the form of a bn (c) phase at the SiC grain boundaries, suppresses the diffusion of the elements, avoiding abnormal growth of SiC grains.
FIG. 4(a) is a high resolution transmission electron microscopy (HTEM) image of the SiBCN powder after mechanical alloying, as shown in FIG. 4; FIG. 4(b) is a Transmission Electron Microscope (TEM) image of SiBCN powder after mechanical alloying; as can be seen from the figure, in step S1 of example 2, after mechanical alloying for 20h, the SiBCN powder has an amorphous structure.
FIG. 4(c) is Ta4HfC5SiBCN-Ta in an amount of 10 wt%4HfC5HTEM image of the composite powder; FIG. 4(d) is Ta4HfC5SiBCN-Ta in an amount of 10 wt%4HfC5TEM image of the composite powder; as can be seen from the figure, Ta4HfC5Distributed in the form of nanocrystals in the SiBCN amorphous powder, which is consistent with the XRD characterization results of fig. 3.
FIG. 5, taken in conjunction with FIG. 5, is a graph of the different Ta's obtained in example 14HfC5Content of SiBCN-Ta4HfC5XRD contrast patterns of the complex phase ceramic, and the SiBCN ceramic prepared in example 2; as can be seen from the figure, the SiBCN ceramic phases after hot press sintering are mainly BN (C), 3C-SiC and 6H-SiC, while SiBCN-Ta4HfC5The multiphase ceramic phase mainly comprises BN (C), 3C-SiC, 6H-SiC and Ta4HfC5. This shows that the SiBCN-Ta provided by the embodiment of the invention4HfC5Preparation method of complex phase ceramic and use thereofSiBCN-Ta prepared by combining two-step mechanical alloying method with hot-pressing sintering technology4HfC5Ta in multiphase ceramics4HfC5Does not react with the SiBCN matrix and does not form a strong bonding interface structure, i.e., the ultra-high temperature Ta is illustrated from the side4HfC5Can be used as a reinforcing phase to be added into SiBCN ceramics and can improve the mechanical property of the complex phase ceramics.
Example 3
The difference between this example and example 1 is that the SiBCN-Ta provided in this example4HfC5The preparation method of the complex phase ceramic comprises the following steps:
in step S1, the ball milling conditions were: ball material ratio 10: 1, the rotating speed of the main disc is 200r/min, the rotating speed of the planetary disc is 650r/min, and the ball milling time is 20 h.
In step S2, C-Si, h-BN, the molar ratio of graphite Si to BN to C being 1.8:0.5: 2.8; ta4HfC5The mass of the single-phase nanocrystalline powder accounts for 10% of the mass of the amorphous-nanocrystalline composite powder; the ball milling conditions are as follows: ball material ratio 10: 1, the rotating speed of the main disc is 200r/min, the rotating speed of the planetary disc is 650r/min, and the ball milling time is 10 h.
In step S3, the hot-pressing sintering process includes: the temperature is 1800 ℃, the sintering pressure is 40Mpa, and the sintering time is 90 min.
Example 4
The difference between this example and example 1 is that the SiBCN-Ta provided in this example4HfC5The preparation method of the complex phase ceramic comprises the following steps:
in step S1, the ball milling conditions were: ball material ratio 30: 1, the rotating speed of a main disc is 400r/min, the rotating speed of a planetary disc is 850r/min, and the ball milling time is 20 h.
In step S2, C-Si, h-BN, wherein the molar ratio of Si to BN to C is 202:1.2: 3.2; ta4HfC5The mass of the single-phase nanocrystalline powder accounts for 10% of the mass of the amorphous-nanocrystalline composite powder; the ball milling conditions are as follows: ball material ratio 30: 1, the rotating speed of the main disc is 200r/min, the rotating speed of the planetary disc is 650r/min, and the ball milling time is 30 h.
In step S3, the hot-pressing sintering process includes: the temperature is 2200 ℃, the sintering pressure is 80Mpa, and the sintering time is 20 min.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (10)
1. SiBCN-Ta4HfC5The preparation method of the complex phase ceramic is characterized by comprising the following steps:
preparation of Ta4HfC5Single-phase nanocrystalline powder;
subjecting said Ta4HfC5Mixing single-phase nanocrystalline powder, hexagonal boron nitride, cubic silicon powder and graphite, and performing high-energy ball milling to obtain amorphous-nanocrystalline composite powder;
sintering the amorphous-nanocrystalline composite powder to obtain SiBCN-Ta4HfC5A complex phase ceramic.
2. The SiBCN-Ta of claim 14HfC5The preparation method of the complex phase ceramic is characterized in that the grain size of the Ta4HfC5 single-phase nanocrystalline powder is 3-5 nm.
3. The SiBCN-Ta of claim 14HfC5The preparation method of the complex phase ceramic is characterized in that the Ta4HfC5The mass of the single-phase nanocrystalline powder accounts for 2.5-15% of the mass of the amorphous-nanocrystalline composite powder.
4. The SiBCN-Ta of claim 34HfC5The preparation method of the multiphase ceramic is characterized in that the molar ratio of the cubic silicon powder, the hexagonal boron nitride and the graphite is Si: BN: c ═ 1.8 to 2.2: (0.5-1.2): (2.8-3.2).
5. The SiBCN-Ta of any one of claims 1-44HfC5The preparation method of the complex phase ceramic is characterized in that the Ta preparation method is used for preparing Ta4HfC5Single phase nano-meterA crystalline powder comprising:
under the protection of argon, placing tantalum carbide powder and hafnium carbide powder in a high-energy ball mill for high-energy ball milling to ensure that tantalum carbide crystal grains and hafnium carbide crystal grains are crushed, cold welded and solid-dissolved to prepare the Ta4HfC5Single-phase nanocrystalline powder.
6. The SiBCN-Ta of claim 54HfC5The preparation method of the complex phase ceramic is characterized in that the molar ratio of the tantalum carbide powder to the hafnium carbide powder is 4: 1;
preparation of said Ta4HfC5The high-energy ball milling conditions of the single-phase nanocrystalline powder are as follows: ball-material ratio (10-30): 1, the rotation speed of the main disc is 200-.
7. The SiBCN-Ta of any one of claims 1-44HfC5The preparation method of the complex phase ceramic is characterized in that the mode of sintering the amorphous-nanocrystalline composite powder comprises the following steps: hot pressing sintering, spark plasma sintering, hot isostatic pressing sintering or ultrahigh pressure sintering.
8. The SiBCN-Ta of claim 74HfC5The preparation method of the complex phase ceramic is characterized in that when the hot-pressing sintering is adopted, the process conditions of the hot-pressing sintering comprise the following steps: the sintering temperature is 1800-2200 ℃, the sintering pressure is 40-80Mpa, the sintering time is 20-90min, and the protective atmosphere is nitrogen or argon or vacuum condition.
9. SiBCN-Ta4HfC5Complex phase ceramics, characterized in that SiBCN-Ta according to any of claims 1-8 is used4HfC5The preparation method of the complex phase ceramic.
10. The SiBCN-Ta of claim 94HfC5Complex phase ceramic, characterized in that said SiBCN-Ta4HfC5The composite ceramic comprises SiBCN matrix phase, Ta4HfC5Single phase nanocrystals are distributed within the SiBCN matrix phase, and the Ta4HfC5The crystal grains of the single-phase nanocrystalline are mutually separated.
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