A ternary composite ceramic material, a preparation method and application thereof

Abstract

The application discloses a ternary composite ceramic material and a preparation method and application thereof. The ternary composite ceramic material is obtained by sintering raw materials of silicon carbide, boron nitride and titanium diboride. The ternary composite ceramic material is prepared by the mass ratio of silicon carbide, boron nitride and titanium diboride in the ternary composite ceramic material, and the ternary composite ceramic material realizes stable heating up to 20 GPa and above 2000 K, and exhibits excellent physical and chemical stability, thermal stability and small temperature gradient characteristics.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite materials, and more particularly relates to a ternary composite ceramic material and a preparation method and application thereof. BACKGROUND

[0002] Large cavity press device originates from the high pressure technology developed in the early 20th century, including two-sided top press and multi-sided cavity device. Large cavity press is widely used in high temperature and high pressure experiments in physics, chemistry, materials, geology and other disciplines due to its precise control of temperature and pressure, and is commonly used in the research of synthesis, transformation and physical and chemical properties of materials under extreme conditions; in addition, it is also the main equipment for the synthesis of superhard materials such as diamond and cubic boron nitride (cBN) in China. Large cavity press uses resistance heating to maintain a high temperature environment under high pressure conditions, and the heating process of the sample in the cavity needs to be realized through a heating body of special material, so the heating body plays a crucial role in the heating process.

[0003] The common heating bodies at present include rhenium (Re), graphite, titanium carbide (TiC) based composite materials, LaCrO3 doped, EBN, etc. Among them, Re has a very wide temperature and pressure range, but the main problem is that it is expensive and easy to oxidize and deteriorate at high temperature for a long time, and the temperature gradient is large. Graphite heating body has uniform temperature distribution, stable performance and low price, but it is corrosive to tungsten carbide anvil, has poor heat storage property, low physical and chemical stability, is transformed into diamond at high temperature and pressure, loses the electric heating performance, and the application range is limited. TiC-based composite materials have chemical inertness and thermal stability, and can be used as X-ray transparent heating body by adjusting the resistance, which is an important research hotspot of heating body materials, but it is difficult to meet the application requirements by using traditional preparation process, and the commonly used polymer degradation process is complex and easy to introduce impurities. Boron-doped diamond is also a research hotspot of heating body, and such heating body has excellent performance, but the heating body material itself needs to be prepared under harsh high temperature and high pressure conditions, which is high in cost and difficult in process. LaCrO3 heating body has uniform temperature distribution, good heating stability and corrosion resistance at high temperature and high pressure up to 2700K, but it is difficult to be formed, the high activation energy of electric conduction leads to difficult start-up heating, and the high oxygen fugacity at high temperature easily changes the valence state of the sample. Researchers such as Xia Tao of Sun Yat-sen University have doped and modified LaCrO3, solved most of the problems of LaCrO3 heating body except oxygen fugacity, improved the problem of electric conduction activation energy to a certain extent, and pushed LaCrO3 heating body to a wider application prospect, but the chemical space doping improves the electrical conductivity while reducing the melting point and environmental compatibility of the heating body at high temperature, and the temperature limit under high pressure is about 2000K.

[0004] Titanium boride (TiB2) has high melting point, high hardness, low thermal expansion coefficient, good oxidation resistance and excellent chemical stability, etc., and is suitable for many high temperature environments. Hexagonal boron nitride (h-BN) has low density, high melting point, strong chemical inertness, good heat resistance, insulation and excellent processability, but due to its graphite layered structure and poor sintering performance, h-BN is difficult to sinter to be dense. The mixture of the two into TiB2-h-BN composite material can combine the advantages of both, make up for each other's shortcomings, not only can significantly improve the densification, but also can realize the adjustable mechanical properties and electrical conductivity.

[0005] EBN (material composed of TiB2, AlN and BN) composite material provided by Japan Electric Company is also an X-ray transparent commercial heating body raw material, which is processed by the user, and the operating current under high temperature and high pressure is lower than that of graphite, and is a market competitive alternative. But it will slightly corrode the WC anvil at high temperature, and the temperature rising range is limited (below 2000K). SUMMARY

[0006] In view of the above existing technical problems, the primary purpose of the present application is to provide a ternary composite ceramic material. The ternary composite ceramic material realizes stable heating up to 20GPa and above 2000K, and exhibits excellent physicochemical stability and thermal stability and small temperature gradient characteristics.

[0007] The second purpose of the present application is to provide a preparation method of the ternary composite ceramic material.

[0008] The third purpose of the present application is to provide an application of the ternary composite ceramic material in preparing heating body material.

[0009] The fourth purpose of the present application is to provide an application of the ternary composite ceramic material as heating body material in a multi-face top press.

[0010] In order to achieve the above purpose, the present application is realized by the following technical scheme:

[0011] The present application claims a ternary composite ceramic material, which is sintered from raw materials silicon carbide, boron nitride and titanium diboride, and according to mass percentage, the raw materials include: 25-35% of silicon carbide, 5-15% of boron nitride and 55-65% of titanium diboride.

[0012] The present application claims a ternary composite ceramic material, which is sintered from raw materials silicon carbide, boron nitride and titanium diboride, and according to mass percentage, the raw materials include: 25-35% of silicon carbide, 5-15% of boron nitride and 55-65% of titanium diboride.

[0013] The application claims a ternary composite ceramic material sintered from raw materials silicon carbide, boron nitride and titanium diboride, wherein the raw materials comprise 18-22% of silicon carbide, 8-22% of boron nitride and 58-72% of titanium diboride by mass percentage.

[0014] The application introduces SiC into the TiB2-h-BN binary system material and controls the content proportion of each component to develop a ternary composite ceramic material with excellent performance, which can be stably heated up to 20 GPa and 2000 K or above, and exhibits excellent physicochemical stability and thermal stability and small temperature gradient characteristics.

[0015] The ternary ceramic composite material has moderate resistance, low electrical conductivity activation energy, and realizes universal use in a wide temperature and pressure range. The ternary composite material has excellent processing performance, low cost, simple production, X-ray transparency, and is suitable as an experimental resistance tube heating body.

[0016] The application has found that the mass proportion of each component in the ternary composite ceramic material is very important. When the content of silicon carbide or boron nitride in the ternary composite ceramic material is increased or decreased, it is difficult to be stably heated above 1273 K.

[0017] The raw materials of the application are low in cost and easy to obtain without special preparation. The ternary composite ceramic material realizes adjustable resistance, ensures low working current, has low requirements for working cables, and widens the application range. In addition, after adding SiC, the sample can be densified and sintered by a tablet press, which solves the problem of poor mechanical processing performance of TiB2 and h-BN, and is convenient for storage, transportation and reprocessing.

[0018] Further, the application claims a preparation method of a ternary composite ceramic material, which comprises: pressing and forming a mixture of silicon carbide, boron nitride, titanium diboride and a solidifying agent, heating and solidifying, and sintering at 1100-1300 DEG C in an inert atmosphere to obtain the ternary composite ceramic material.

[0019] The application finally prepares the ternary composite ceramic material by solidifying the mixed raw materials at low temperature and then sintering in a normal pressure atmosphere. The method has the advantages of fast production speed, high yield, no pollution emission in the whole process, and no special requirements for process equipment performance. The preparation method does not involve the steps of impurity removal, laser, discharge, precursor conversion and other processes, and can be completed by using the most common oven and atmosphere sintering furnace in the industry.

[0020] Preferably, the curing agent is selected from one or more of phenol formaldehyde resin liquid paraffin, polyethylene butyl, polyethylene glycol. Further preferably, the curing agent is phenol formaldehyde resin.

[0021] Preferably, the temperature of the heating is 150-250℃. Further preferably, the temperature of the heating is 185-195℃.

[0022] Preferably, the sintering time is 5-15h.

[0023] Preferably, the boron nitride is selected from one or more of hexagonal boron nitride (h-BN), rhombohedral boron nitride (RBn) or wurtzite boron nitride (WBN).

[0024] Preferably, the inert atmosphere comprises one or both of nitrogen and argon.

[0025] Further, the present application claims a ternary composite ceramic material for use in the preparation of a heating body material.

[0026] Further, the present application claims a ternary composite ceramic material for use as a heating body material in a multi-anvil press. It is particularly suitable for use as a high temperature and high pressure experimental resistance tube heating body in a multi-anvil press.

[0027] Compared with the prior art, the present application has the following beneficial effects:

[0028] The present application provides a ternary composite ceramic material, which achieves stable heating up to 20GPa and 2000K or above, and exhibits excellent physicochemical stability and thermal stability and a small temperature gradient characteristic. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 Two standard specification diagrams of the finished heating body prepared in Example 1 and the matching electrodes of the same composition.

[0030] Figure 2 X-ray powder diffraction pattern of the ternary composite ceramic material prepared in Example 1.

[0031] Figure 3 Schematic diagram of the loading mode of the heating body sample.

[0032] Figure 4 Heating performance phase diagram of the heating body tested at 3GPa.

[0033] Figure 5 High temperature and high pressure test power-temperature curve of the heating body prepared in Example 1.

[0034] Figure 6High temperature and high pressure test temperature-resistance curve of the heating body prepared for Example 1.

[0035] Figure 7 Heating-cooling-heating test of the heating body prepared for Example 1 at 5 GPa, 7 GPa.

[0036] Figure 8 Thermal power-temperature curve and temperature-heating resistance curve of the heating body under the condition of 22 GPa, 2100 K.

[0037] Figure 9 Thermal power-temperature curve and temperature-heating resistance curve of the heating body prepared for each of the examples and comparative examples except Example 1.

[0038] Figure 10 Test results of the heating body prepared for Comparative Example 11 using the formula provided in Patent CN 113698210A as raw materials. DETAILED DESCRIPTION

[0039] The present application will be further described in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present application in any form. Unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the technical field.

[0040] The raw materials used in the examples and comparative examples of the present application are shown as follows.

[0041] TiB2, 99.99%, 1 um, Guangzhou Metal Metallurgical Group Co., Ltd.

[0042] SiC, 99.9%, 1-2 um, Shanghai Maikelin Biochemical Technology Co., Ltd.

[0043] h-BN, 99.9%, metal basis, 1-2 um, Shanghai Maikelin Biochemical Technology Co., Ltd.

[0044] Example 1

[0045] According to the mass percentage of 30% silicon carbide, 10% boron nitride and 60% titanium diboride, the powders are mixed, 100 μL / g of phenolic resin is added, and then transferred into a mold (the mold size is customized according to the required size of the heating body, and the mold size does not affect the preparation effect) to be formed under a tablet press with a pressure of 2 MPa. After heating to 190°C for curing, the heating body, i.e. ternary composite ceramic material, is obtained by sintering at 1300°C for 10 hours under argon. The appearance of the heating body prepared in Example 1 is shown in Figure 1 Different molds can be used for pressing according to different requirements, or the sintered block can be cut according to the requirements.

[0046] Examples 2-6

[0047] Examples 2-6 and Example 1 differ respectively in that:

[0048] Example 2: Mixed into a powder in mass percentages of 10% silicon carbide, 10% boron nitride, and 80% titanium diboride.

[0049] Example 3: Mixed into a powder in mass percentages of 10% silicon carbide, 20% boron nitride, and 70% titanium diboride.

[0050] Example 4: Mixed into a powder in mass percentages of 10% silicon carbide, 30% boron nitride, and 60% titanium diboride.

[0051] Example 5: Mixed into a powder in mass percentages of 20% silicon carbide, 10% boron nitride, and 70% titanium diboride.

[0052] Example 6: Mixed into a powder in mass percentages of 20% silicon carbide, 20% boron nitride, and 60% titanium diboride.

[0053] Comparative Examples 1-11

[0054] Comparative Examples 1-11 and Example 1 differ respectively in that:

[0055] Comparative Example 1: Mixed into a powder in mass percentages of 0% silicon carbide, 0% boron nitride, and 100% titanium diboride.

[0056] Comparative Example 2: Mixed into a powder in mass percentages of 0% silicon carbide, 10% boron nitride, and 90% titanium diboride.

[0057] Comparative Example 3: Mixed into a powder in mass percentages of 0% silicon carbide, 20% boron nitride, and 80% titanium diboride.

[0058] Comparative Example 4: Mixed into a powder in mass percentages of 10% silicon carbide, 0% boron nitride, and 90% titanium diboride.

[0059] Comparative Example 5: Mixed into a powder in mass percentages of 20% silicon carbide, 30% boron nitride, and 50% titanium diboride.

[0060] Comparative Example 6: Mixed into a powder in mass percentages of 30% silicon carbide, 20% boron nitride, and 50% titanium diboride.

[0061] Comparative Example 7: Mixed into a powder in mass percentages of 30% silicon carbide, 30% boron nitride, and 40% titanium diboride.

[0062] Comparative Example 8: Mixed into a powder in mass percentages of 30% silicon carbide, 0% boron nitride, and 70% titanium diboride.

[0063] Comparative Example 9: According to the mass percentage of 0% silicon carbide, 30% boron nitride, and 70% titanium diboride, a powder was mixed.

[0064] Comparative Example 10: According to the mass percentage of 20% silicon carbide, 0% boron nitride, and 80% titanium diboride, a powder was mixed.

[0065] Comparative Example 11: According to the ratio given in Patent Publication No. CN 113698210A: 3% silicon carbide, 72% boron nitride, and 25% titanium diboride, a powder was mixed.

[0066] Test Example 1

[0067] Figure 2 The X-ray powder diffraction pattern of the ternary composite ceramic material. From the Figure 2 It can be seen that the ternary composite ceramic material is a TiB2-SiC-BN structure containing trace impurities, and it is speculated that the impurities come from a small amount of oxygen mixed in the argon gas and the high-temperature reaction of the binder and the raw materials.

[0068] Test Example 2

[0069] Test method: The heating performance of the heating bodies prepared in the examples and comparative examples was tested at 3 GPa using a Walker-type multi-face anvil press. The specific operation was as follows: using the sample loading method shown in Figure 3 , the sample was sent into the cavity of the large-cavity press for ultrahigh-temperature and high-pressure heating performance test, and a hydraulic system-controlled six-face anvil and a resistance heating method were used to provide high pressure and high temperature environment. The performance image was drawn by summarizing the change law of the pressure, temperature, power, resistance, etc. data in the heating data obtained by test.

[0070] Figure 4 The heating performance phase diagram of the heating body tested at 3 GPa. Figure 4 , the gray cross represents that the sample resistance exceeds the range, and no test data can be obtained, so the application cannot be carried out. The green circle represents that the sample can pass the test to obtain ultrahigh-temperature and high-pressure heating data, so it also has a certain applicable temperature range (its high temperature limit is below 1400K, see Test Example 6 / Figure 9 ). The pentagram represents that the sample heating data is the best, and the heating temperature range obtained by testing at 3 GPa pressure is the widest (0-1467K), which is higher than that of other examples and comparative examples under the same conditions (<1400K), so it is the most suitable material for the required application scenario.

[0071] Test Example 3

[0072] The high temperature and high pressure application of the heating body prepared in Example 1 was tested by a Walker-type multi-surface top press machine, the pressure range was 3-20 GPa, the sample in-cavity heating speed could be freely set, in this paper, the test examples were all set to 150 K / min, the temperature detection selected a C-type W / Re alloy or R-type Pt / Rh made thermocouple wire, the detection range was 0-2500 K, a tungsten carbide anvil was used, and the pressure transmission medium selected an octahedron made of ARMC-646 or 584 powder.

[0073] Figure 5 The high pressure and temperature test results of the heating body prepared in Example 1 at 3-7 GPa, the heating temperature could be stably increased to about 2000 K. Figure 5 (d) The 3 times of continuous heating experiments showed that the performance of the heating body hardly changed after the first round of heating.

[0074] Figure 6 The high pressure resistance test results of the heating body prepared in Example 1 at 3-7 GPa. The heating body showed similar resistance change trends with temperature rise at different pressures, and all showed a turning point at 900-1100 K, and the temperature of the resistance turning point increased with the applied pressure. Figure 6 (d) The 3 times of continuous heating experiments, i.e. after each heating reached the highest power point, the heating power was immediately reduced to 0 W for natural annealing, the annealing speed was indefinite, about 800 K / min, the temperature detection showed that after dropping to 323 K, the next heating was immediately started, and the analysis results found that after the first heating, the turning point disappeared, and the resistance value tended to be stable.

[0075] Test Example 4

[0076] The same basic test method as described above was used, only the performance test was changed from one heating test to heating-annealing-heating test, the pressure applied to the sample was 5 GPa and 7 GPa respectively, the corresponding heating temperature was 1400 K and 1970 K respectively, the annealing was water cooling annealing, the cooling speed could be freely set, in this test, it was set to 100 K / min, the temperature detection showed that after dropping to 323 K, the second heating was immediately started.

[0077] Figure 7 The heating-annealing-heating test of the TBSB-631 heating body of different specifications at different pressures was shown, although there was more or less position and resistance deviation in each sample loading, Figure 7 The data and Figure 5 d、 Figure 6The results of multiple heating cycle experiments shown in d do not have significant differences, and the resistance curves of different heating bodies show similar trends during the test, including the upper limit of temperature rise, the stable correspondence of heating power and temperature rise, the sharp decrease and slow increase of resistance with temperature rise, and the disappearance of resistance turning point, proving the repeatability of the heating experiment and the stability of the heating body resistance in various heating tests.

[0078] Therefore, the heating body prepared in Example 1 exhibits good heating performance and stability under high temperature and high pressure tests, and is a high-performance heating element with excellent application value and wide application conditions.

[0079] Test Example 5

[0080] The test method is the same as that of Test Example 3, except that (1) Cr2O3 (5wt%) doped MgO is used instead of ARMC 646 as the pressure medium; (2) to reduce the stress area and achieve a larger pressure, a smaller cylindrical resistance tube heating body with an outer diameter of 2.5 mm, an inner diameter of 1.6 mm, and a length of 5-6 mm is prepared by a fine process; (3) to achieve better heat preservation effect and protect the heating body, a Re metal sheet with a thickness of 0.85 mm is covered on the exposed surface of the heating body electrode.

[0081] Figure 8 The heating power-temperature curve and the temperature-heating resistance curve of the heating body under the condition of 22GPa, 2100K are shown in Figure 8 The test results are shown in , which realizes excellent heating performance of stable temperature rise to 2100K under superhigh pressure above 20GPa, greatly widening the application pressure range of the heating body. At the same time, under superhigh pressure, the heating power and heating temperature of the heating body still maintain an approximately linear relationship, and the resistance change trend is also similar to the previous test examples, meaning that its physical and chemical properties have not changed significantly at high temperatures above 20GPa, and it is a reliable and practical heating body material.

[0082] Test Example 6

[0083] The test method is the same as that of Test Example 2.

[0084] Figure 9 The heating power-temperature curve and the temperature-heating resistance curve of the heating body under the condition of 22GPa, 2100K are shown in Figure 9 , wherein a, c, e in are the heating power-temperature curves of each example and the comparative example except Example 1; Figure 9 , wherein b, d, f in are the temperature-heating resistance curves of each example and the comparative example except Example 1.

[0085] Figure 9In the example, TBSB-730 corresponds to Example 8, TBSB-703 corresponds to Example 9, TBSB-802 corresponds to Example 10, TBSB-712 corresponds to Example 3, TBSB-721 corresponds to Example 5, TBSB-622 corresponds to Example 6, TBSB-613 corresponds to Example 4, and TBSB-811 corresponds to Example 2. Figure 4 The materials prepared in the comparative examples corresponding to the crosses in the diagram cannot be heated for testing due to their resistance exceeding the range, and therefore no meaningful performance curves can be obtained. They are not considered.

[0086] Overall, the other comparative examples and embodiments also have certain application potential in the field of ultra-high temperature and high pressure. However, the upper limit of the heating temperature of the comparative examples is significantly lower and can only be used for medium and low temperature heating. The embodiments other than Example 1 have shown certain valuable heating performance (the upper limit of temperature rise under 3GPa pressure is higher than 1273K), but their performance is slightly inferior to the heating body prepared in Example 1.

[0087] Test Example 7

[0088] The test method for Comparative Example 11 is exactly the same as that for Test Example 2. However, since it cannot heat up and therefore has no temperature or heating resistance data, the voltage-power data that has exceeded the range is shown.

[0089] like Figure 10 As shown, it was found that this material is almost impossible to conduct electricity, has extremely low operating power, and extremely high operating voltage, making it impossible to use as a heating element. Therefore, it cannot be used as a raw material for heating elements.

[0090] The foregoing examples are merely illustrative, used to explain some features of the method described in this invention. The appended claims are intended to claim the broadest possible scope, and the embodiments presented herein are demonstrated by the applicant's actual experimental results. Therefore, the applicant intends that the appended claims are not limited by the selection of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be interpreted as being covered by the appended claims where possible.

Claims

1. A ternary composite ceramic material, characterized by, The ternary composite ceramic material is obtained by sintering raw materials of silicon carbide, boron nitride and titanium diboride, wherein the raw materials comprise, in percentage by mass, 25-35% of silicon carbide, 5-15% of boron nitride and 55-65% of titanium diboride.

2. The method of making the ternary composite ceramic material of claim 1, wherein, The silicon carbide, boron nitride and titanium diboride are mixed in percentage by mass, and a solidifying agent is added; the mixture of the silicon carbide, boron nitride, titanium diboride and solidifying agent is pressure-formed, heated and solidified, and sintered at 1100-1300 ℃ in an inert atmosphere to obtain the ternary composite ceramic material.

3. The preparation method according to claim 2, characterized in that, The solidifying agent is selected from one or more of phenol formaldehyde resin, liquid paraffin and polyethylene glycol.

4. The preparation method according to claim 2, characterized in that, The temperature of the heating and solidification is 150-250 ℃.

5. The preparation method according to claim 2, characterized in that, The sintering time is 5-15 h.

6. The preparation method according to claim 2, characterized in that, The boron nitride is one or more of hexagonal boron nitride, rhombohedral boron nitride and wurtzite boron nitride.

7. Use of the ternary composite ceramic material of claim 1 in the preparation of a heating body material.

8. Use of the ternary composite ceramic material of claim 1 as a heating body material in a multi-face press.

Images