TiB2 / TiCN ceramic composite powder and preparation method thereof

Abstract

The invention particularly relates to TiB2 / TiCN ceramic composite powder and a preparation method thereof.The preparation method of the TiB2 / TiCN ceramic composite powder comprises the following steps that melamine and boric acid are dispersed in deionized water, a boric acid solution is dropwise added into melamine turbid liquid to generate white precipitates, and the precipitates are collected and dried; carrying out heat treatment on the obtained precipitate in an inert atmosphere, and then carrying out calcination treatment to obtain BCxN ternary powder; and mixing the obtained BCxN ternary powder with Ti powder, rapidly heating by using a Joule heater, and carrying out heat preservation treatment to obtain the TiB2 / TiCN ceramic composite powder. The TiB2 / TiCN ceramic body powder is formed by compounding TiB2 and TiCN, and the composition phase of the TiB2 / TiCN ceramic composite powder is the superposition of TiB2 (JPCDS No: 35-0741) and TiCN (JPCDS No: 42-1488). The preparation method of the TiB2 / TiCN ceramic composite powder is simple and rapid, the raw materials are economical, the production cost of the composite ceramic is greatly reduced, and the TiB2 / TiCN ceramic composite powder can be widely applied to ceramic production and has a better commercial application prospect.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of cermet powder preparation, in particular to a TiB2 / TiCN ceramic composite powder and a preparation method thereof. BACKGROUND

[0002] TiBCN series ceramic composite powders are generally developed from TiN, TiB and TiC which have the same crystal structure (face-centered cubic lattice point array, wherein Ti atoms occupy the vertex position of the face-centered cubic lattice point array, and N, C and B atoms occupy the (1 / 2, 0, 0) position of the face-centered cubic lattice point array). Therefore, pure TiBCN can be regarded as a solid solution of TiN, TiB and TiC. It is a non-oxidizing ceramic material combining the advantages of high melting point, high hardness, low friction coefficient, excellent thermal and electrical conductivity, oxidation resistance and corrosion resistance. Since the ceramic cutter has good electrical conductivity, it can be processed by wire cutting and a good quality processing surface can be obtained, which solves the problem of difficult processing of superhard cutters and makes it an ideal choice for cutting tool materials.

[0003] At present, most of the TiBCN powder preparation and sintered ceramic researches use C powder, B powder, Ti powder, TiN powder and other powders as raw materials to obtain TiBCN powder through mechanical ball milling. However, oxidation of raw materials and introduction of impurities will inevitably occur during the ball milling process.

[0004] Due to the complexity of the TiBCN cermet system, it is difficult to prepare pure phase powders. Some scholars expect to prepare Ti-B-C-N system composite ceramics with the same excellent performance as TiBCN ceramics from TiB2, TiCN, TiC and other ceramics to meet the purpose of industrial application. However, how to solve the problem of performance decline caused by agglomeration of TiB2, TiCN, TiC and other powders during mixing and sintering has become a key point restricting the application of Ti-B-C-N system composite ceramics. In 2016, Zhao successfully prepared TiCN-TiB2-Co cermet from Co-Ti-C-BN system through in-situ reaction hot processing. Although the addition of Co leads to the decline of the performance of the ceramic, it is proved that in-situ reaction can avoid the problem of powder agglomeration.

[0005] At present, the main methods for preparing TiB-C-N ceramic composite powders are: mechanical ball milling of TiB2 / TiCN powders, adding BN, B4C and other B sources to TiCN and adding Co as a catalyst to reduce the TiB2 generation temperature. The preparation cycle of ball milling mixed powder is long, and it is difficult to avoid the occurrence of agglomeration; the addition of catalyst will inevitably reduce the mechanical properties of the final ceramic block. SUMMARY

[0006] In view of the problems existing in the prior art, the application provides a TiB2 / TiCN ceramic composite powder and a preparation method thereof.

[0007] In order to achieve the above-mentioned purpose, the technical scheme of the application is as follows:

[0008] A preparation method of a TiB2 / TiCN ceramic composite powder comprises the following steps:

[0009] (1) melamine and boric acid are respectively dispersed in deionized water and heated and dispersed and dissolved, the boric acid solution is added dropwise into the melamine suspension to generate white precipitate, and the precipitate is collected and dried;

[0010] The melamine is an alkaline nitrogen-containing compound, which is slightly soluble in cold water and has increased solubility when heated; the boric acid solution (acidic) is added dropwise into the melamine suspension (weakly alkaline) to initiate an acid-base neutralization reaction, and the amino group of the melamine and the hydroxyl group of the boric acid form a stable complex through hydrogen bonding:

[0011] C3H6N6+H3BO3→C3H6N6·H3BO3↓.

[0012] (2) the precipitate obtained in step (1) is subjected to heat treatment in an inert atmosphere, and then calcination treatment is performed to obtain BC x N ternary powder;

[0013] (3) the BC x N ternary powder obtained in step (2) is mixed with Ti powder, and then a joule heating instrument is used for rapid heating and heat preservation treatment to obtain the TiB2 / TiCN ceramic composite powder.

[0014] Further, the heating temperature in step (1) is 50-70 DEG C, and the time is 20-40 min.

[0015] Further, the molar ratio of the melamine to the boric acid in step (1) is 1:(1-2), and the temperature for drying the precipitate is 70-90 DEG C; preferably, the molar ratio of the melamine to the boric acid is 1:(1.3-2), and more preferably, the molar ratio of the melamine to the boric acid is 1:(1.3-1.8).

[0016] Further, the inert atmosphere in step (2) comprises nitrogen, argon or helium; and the heat treatment process parameters are as follows: first, heat preservation at a temperature of 250-350 DEG C for 40-90 min, and then heating to 500-600 DEG C and heat preservation for 3-5 h.

[0017] First, the dehydration of H3BO3 is completed at 250-350℃, releasing crystal water and part of the hydroxyl group, preventing the subsequent high-temperature weight loss from causing bubbling; at 500-600℃, under the condition of solid-phase melting-polycondensation, the melamine ring and boron oxide (B2O3) undergo high-temperature condensation and B-N crosslinking to generate high-crosslinking C3N4 / BN prepolymers or g-C3N4 / BN composite networks or boron nitride carbide.

[0018] Further, the temperature of the calcination treatment in step (2) is 1600-1800℃, the time is 20-40min, and the heating rate is 3-6℃ / min. The C3N4 / BN prepolymers or g-C3N4 / BN composite networks that have been formed are converted into high-crystallinity ternary B-C-N ceramic powders. Long-time high-temperature promotes grain growth and pore shrinkage, and finally high-density, high-crystallinity, and uniform-particle-size B-C-N ceramic powders are obtained.

[0019] Further, in step (3), the BC x The mass ratio of the N ternary powder to Ti powder is (5-7):(13-15), the mixing method is grinding or ball milling, and the mixing time is 20-40min.

[0020] Further, in step (3), the temperature of the heating by the Joule heating instrument is 1800-2300℃, and the holding time is 30-60s. Preferably, the temperature of the heating by the Joule heating instrument is 2000-2300℃, and more preferably, the temperature of the heating by the Joule heating instrument is 2000-2200℃.

[0021] Further, in step (3), the rapid heating rate of the Joule heating instrument is 2444-3143℃ / s, and the time is 700ms-900ms.

[0022] Further, the TiB2 / TiCN ceramic composite powder prepared by the above method is composed of TiB2 and TiCN powders, and the composition phase of the TiB2 / TiCN ceramic powder is the superposition of TiB2 (JPCDS No: 35-0741) and TiCN (JPCDS No: 42-1488). The mass percentage (or mass ratio) of TiB2 and TiCN is 40%-60% and 40%-60% respectively. The D50 particle size of the TiB2 / TiCN ceramic powder is 0.5-2μm. The TiB2 / TiCN ceramic composite powder has uniform element distribution and less agglomeration.

[0023] Further, the TiB2 / TiCN ceramic composite powder is applied in superhard materials.

[0024] Further, the application of the TiB2 / TiCN ceramic composite powder in lithium batteries, supercapacitors, fuel cells, photovoltaic cells and energy storage collectors.

[0025] Advantages of the application:

[0026] 1. The application provides a preparation process of TiB2 / TiCN cermet composite powder, optimizes the preparation path, uses melamine (C3H6N6) and boric acid (H3BO3) as raw materials, and generates BC x N ternary powder through liquid phase mixing and pyrolysis reaction, reacts the BC x N ternary compound with Ti powder to generate TiB2 / TiCN ceramic composite powder in situ, and avoids the problem of uneven dispersion caused by agglomeration in the conventional method of mixing borides of Ti and carbonitrides of Ti.

[0027] 2. The preparation method has an extremely fast heating rate of about 2222-3143 DEG C / s, obtains a super-high temperature (1800-2300 DEG C) heating time of only 700-900 milliseconds, can effectively avoid the problem that low-temperature phases (such as TiB2) grow preferentially and then cause inconsistent particle sizes and single-phase agglomeration between different phases such as TiB2 and TiCN in the in-situ reaction process due to a large difference in generation temperature, and realizes the composite ceramic powder with consistent grain size and uniform phase.

[0028] 3. The TiB2 / TiCN ceramic composite powder prepared by the application is composed of TiB2 and TiCN composite powder, the EDS proves that the element distribution of the obtained cermet powder is relatively uniform, the crystal phase of the TiB2 / TiCN ceramic composite powder is close to the 2θ peak position of TiB2 crystal and TiCN crystal, it can be seen that the ceramic powder obtained by the method has sufficient reaction, and the grain sizes of different phases are uniform. And the SEM verifies that the particle size of the obtained cermet powder is uniform.

[0029] 4. The preparation method uses low-cost raw materials such as melamine, boric acid and micron-sized Ti powder, has fast reaction speed, short production cycle, simple and efficient preparation process, greatly reduces the production cost of the composite ceramic, and can be widely applied to the production of Ti-B-C-N cermet composite powder.

[0030] 5. The preparation method has an extremely short heating and cooling time (the heating time is 700-900 milliseconds, and the cooling time is 1000-3000 milliseconds), effectively inhibits the growth of grains at high temperature, and can obtain ceramic powder of different sizes (submicron, micron) by controlling the holding time, can meet different application requirements, and does not need to be treated twice. BRIEF DESCRIPTION OF DRAWINGS

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 The image shows the XRD phase diagram of the TiB2 / TiCN ceramic composite powder prepared in Example 1.

[0033] Figure 2 The image shows a scanning electron microscope (SEM) image of the TiB2 / TiCN ceramic composite powder prepared in Example 1.

[0034] Figure 3 The energy dispersive spectroscopy (EDS) image (right) shows the elemental distribution of the TiB2 / TiCN ceramic composite powder prepared in Example 1.

[0035] Figure 4 The image shows the XRD phase diagram of the TiB2 / TiCN ceramic composite powder prepared in Example 2.

[0036] Figure 5 SEM image of the ceramic composite powder prepared in Comparative Example 1.

[0037] Figure 6 SEM image of the ceramic composite powder prepared in Comparative Example 2. Detailed Implementation

[0038] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] Testing instruments for the materials prepared in this invention:

[0040] Phase analysis of the composite powder was performed using a fully automated X-ray diffractometer from Rigaku, Japan, model: Ultima IV.

[0041] The microstructure and energy dispersive spectroscopy of the composite powder were analyzed by SEM using an Apreo 2C HiVac instrument.

[0042] Example 1

[0043] This embodiment prepares a TiB2 / TiCN ceramic composite powder, including the following preparation steps:

[0044] (1) Preparation: melamine 12.6 g, boric acid 9.6 g (molar ratio 1:1.5) were weighed;

[0045] (2) BC x N precursor preparation: melamine and boric acid were dispersed in deionized water respectively. After stirring at 60°C water bath for 30 minutes, the boric acid solution was poured into the melamine suspension to generate white precipitate rapidly. The obtained precipitate was placed in an oven at 80°C for drying. The dried powder was placed in a high temperature furnace and calcined at 300°C for 1 hour, 550°C for 4 hours and 1700°C for 30 minutes (all at a heating rate of 5°C / min) under nitrogen atmosphere to obtain BC x N ternary powder.

[0046] (3) Ti-B-C-N powder mixing: BC x N powder 0.3 g, Ti powder 0.7 g were weighed and mixed by hand grinding for 30 minutes.

[0047] (4) Rapid preparation of TiB2 / TiCN ceramic composite powder: the mixed Ti-B-C-N powder was placed in a graphite tube, and a CIS-JH4.0 type joule heating instrument was used to rapidly heat (700ms-900ms) to 2200°C at a heating rate of 2444-3143°C / s and keep for 60s to obtain TiB2 / TiCN ceramic composite powder with uniform phase distribution and uniform particle size (2um).

[0048] The XRD pattern of the obtained TiB2 / TiCN ceramic composite powder is shown in Figure 1 The powder composition phase is TiB2(JPCDS No:35-0741), TiCN(JPCDS No:42-1488). The scanning electron micrograph (SEM) and energy spectrum micrograph (EDS) of the composite powder are shown in Figure 2 、 3 It can be seen that the composite powder has uniform morphology and uniform particle size, and the elements Ti, B, C and N are uniformly distributed, indicating that the rapid preparation technology of the powder can obtain TiB2 / TiCN ceramic composite precursor powder with uniform phase distribution.

[0049] Example 2

[0050] This example prepares a TiB2 / TiCN ceramic composite powder, which includes the following preparation steps:

[0051] (1) Preparation: melamine 12.3 g, boric acid 9.6 g (molar ratio 1:1.5) were weighed

[0052] (2) BC xN Precursor preparation: melamine and boric acid were dispersed in deionized water respectively. After stirring at 60°C water bath for 30 minutes, the boric acid solution was poured into the melamine suspension to generate white precipitate rapidly. The obtained precipitate was placed in an oven at 80°C for drying. The dried powder was placed in a high temperature furnace and calcined at 300°C for 1 hour, 550°C for 4 hours and 1700°C for 30 minutes (the heating rate was 5°C / min) under nitrogen atmosphere to obtain BC x N Ternary powder.

[0053] (3) Ti-B-C-N powder mixing: BC x N 0.3g of powder and 0.7g of Ti powder were mixed by hand grinding for 30 minutes.

[0054] (4) Rapid preparation of TiB2 / TiCN-ceramic composite powder: the mixed Ti-B-C-N powder was placed in a graphite tube, and a CIS-JH4.0 type joule heating instrument was used to rapidly (700ms-900ms) heat to 2000°C at a heating rate of 2222-2857°C / s, and heat preservation for 60s, to obtain TiB2 / TiCN-ceramic composite powder with uniform phase distribution and uniform particle size (1.5um).

[0055] The XRD pattern of the obtained TiB2 / TiCN-ceramic composite powder is shown in Figure 4 The powder composition phase is TiB2(JPCDS No: 35-0741) and TiCN(JPCDS No: 42-1488).

[0056] Example 3

[0057] This example prepares a TiB2 / TiCN ceramic composite powder, which includes the following preparation steps:

[0058] (1) Preparation of materials: 12.6g of melamine and 6.2g of boric acid (molar ratio 1:1) were weighed;

[0059] (2) BC x N Precursor preparation: melamine and boric acid were dispersed in deionized water respectively. After stirring at 50°C water bath for 40 minutes, the boric acid solution was poured into the melamine suspension to generate white precipitate rapidly. The obtained precipitate was placed in an oven at 90°C for drying. The dried powder was placed in a high temperature furnace and calcined at 250°C for 1.5h, 600°C for 3 hours and 1600°C for 40 minutes (the heating rate was 3°C / min) under nitrogen atmosphere to obtain BC x N Ternary powder.

[0060] (3) Ti-B-C-N powder mixing: BC xN powder 0.35 g, Ti powder 0.65 g, manual grinding and mixing for 20 minutes.

[0061] (4) Rapid preparation of TiB2 / TiCN-ceramic composite powder: the mixed Ti-B-C-N powder was placed in a graphite tube, and a CIS-JH4.0 type joule heating instrument was used to rapidly (700 ms-900 ms) heat to 2300℃ at a heating rate of 2222-2857℃ / s, and heat preservation for 30s, to obtain a TiB2 / TiCN-ceramic composite powder with uniform phase distribution and uniform particle size (1.5um).

[0062] The composition of the obtained TiB2 / TiCN-ceramic composite powder is TiB2(JPCDS No:35-0741) and TiCN(JPCDS No:42-1488).

[0063] Example 4

[0064] This embodiment prepares a TiB2 / TiCN ceramic composite powder, including the following preparation steps:

[0065] (1) Preparation of materials: weigh melamine 12.6 g, boric acid 12.4 g (molar ratio 1:2);

[0066] (2) BC x N precursor preparation: melamine and boric acid were dispersed in deionized water respectively. After 20 minutes of heating and stirring in a 70℃ water bath, the boric acid solution was poured into the melamine suspension to quickly generate white precipitate. The obtained precipitate was placed in an oven at 70℃ for drying. The dried powder was placed in a high temperature furnace, and was heat treated at 350℃ for 40 min, 500℃ for 5 hours, and 1800℃ for 20 min (heating rate was 6℃ / min) under argon atmosphere to obtain BC x N ternary powder;

[0067] (3) Ti-B-C-N powder mixing: weigh BC x N powder 0.35 g, Ti powder 0.65 g, manual grinding and mixing for 20 minutes;

[0068] (4) Rapid preparation of TiB2 / TiCN-ceramic composite powder: the mixed Ti-B-C-N powder was placed in a graphite tube, and a CIS-JH4.0 type joule heating instrument was used to rapidly (700 ms-900 ms) heat to 2300℃ at a heating rate of 2222-2857℃ / s, and heat preservation for 30s, to obtain a TiB2 / TiCN-ceramic composite powder with uniform phase distribution and uniform particle size (1.5um).

[0069] The composition phases of the obtained TiB2 / TiCN-ceramic composite powder are TiB2(JPCDS No: 35-0741) and TiCN(JPCDS No: 42-1488).

[0070] Comparative Example 1

[0071] The present comparative example provides a preparation method of a TiB2 / TiCN ceramic composite powder, which is different from Example 1 in that the heating rate in the preparation process is different, comprising the following preparation steps:

[0072] (1) Preparation of raw materials: 12.3 g of melamine and 9.6 g of boric acid (molar ratio 1:1.5) were weighed;

[0073] (2) BC x N precursor preparation: melamine and boric acid were dispersed in deionized water respectively. After stirring at 60°C water bath for 30 minutes, the boric acid solution was poured into the melamine suspension to form white precipitate rapidly. The obtained precipitate was placed in an oven at 80°C for drying. The dried powder was placed in a high temperature furnace and calcined at 300°C for 1 hour, 550°C for 4 hours and 1700°C for 30 minutes (heating rate was 5°C / min) under nitrogen atmosphere to obtain BC x N ternary powder;

[0074] (3) Ti-B-C-N powder mixing: 0.3 g of BC x N powder and 0.7 g of Ti powder were weighed and manually ground and mixed for 30 minutes;

[0075] (4) Rapid preparation of TiB2 / TiCN ceramic composite powder: the mixed Ti-B-C-N powder was placed in a graphite tube, and a CIS-JH4.0 type joule heating instrument was used to rapidly (30s) heat to 2200°C at a heating rate of 73-74°C / s and keep for 60s to obtain TiB2 / TiCN-ceramic composite powder. The results are shown in Figure 5 As can be seen from the figure, the heating rate of the present comparative example is slower than that of Example 1, and obvious phase separation and agglomeration occur, which is due to the slow heating rate, and the low-temperature phase (such as TiB2) grows preferentially, thereby causing inconsistent particle size and single-phase agglomeration.

[0076] Comparative Example 2

[0077] The present comparative example provides a preparation method of a TiB2 / TiCN ceramic composite powder, which is different from Example 2 in that the heating rate in the preparation process is different, comprising the following preparation steps:

[0078] (1) Preparation of raw materials: 12.3 g of melamine and 9.6 g of boric acid (molar ratio 1:1.5) were weighed;

[0079] (2) BCx N precursor preparation: melamine and boric acid were dispersed in deionized water respectively. After stirring at 60°C water bath for 30 minutes, the boric acid solution was poured into the melamine suspension to form white precipitate rapidly. The obtained precipitate was placed in an oven at 80°C for drying. The dried powder was placed in a high temperature furnace, and calcined at 300°C for 1 hour, 550°C for 4 hours and 1700°C for 30 minutes (all at a heating rate of 5°C / min) under nitrogen atmosphere to obtain BC x N ternary powder;

[0080] (3) Ti-B-C-N powder mixing: 0.3 g of BC x N powder and 0.7 g of Ti powder were mixed by manual grinding for 30 minutes;

[0081] (4) Rapid preparation of TiB2 / TiCN-ceramic composite powder: the mixed Ti-B-C-N powder was placed in a graphite tube, and heated rapidly (30 s) to 2000°C at a heating rate of 66-67°C / s using a CIS-JH4.0 type joule heating instrument, and kept for 60 s to obtain TiB2 / TiCN-ceramic composite powder. The results are shown in Figure 6 As can be seen from the figure, the heating rate of the present comparative example is slower than that of Example 2, and obvious phase separation and agglomeration phenomena (such as fibrous TiB2 region and durian shell-like TiCN region) occur, which is due to the slow heating rate, the low temperature phase (such as TiB2) grows preferentially and then causes the particle size to be inconsistent and the single phase to agglomerate.

[0082] The above only describes the preferred embodiments of the present application and should not be used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing TiB2 / TiCN ceramic composite powder, characterized in that: Includes the following steps: (1) Disperse melamine and boric acid in deionized water and heat to disperse them. Add boric acid solution dropwise to melamine suspension to generate white precipitate. Collect the precipitate and dry it. (2) In an inert atmosphere, the precipitate obtained in step (1) is heat-treated and then calcined to obtain BC. x N ternary powder; (3) The BC obtained in step (2) x After mixing N ternary powder with Ti powder, the mixture is rapidly heated and held at that temperature using a Joule heater to obtain TiB2 / TiCN ceramic composite powder.

2. The method for preparing TiB2 / TiCN ceramic composite powder according to claim 1, characterized in that: The heating temperature in step (1) is 50-70℃ and the heating time is 20-40min.

3. The method for preparing TiB2 / TiCN ceramic composite powder according to claim 2, characterized in that: In step (1), the molar ratio of melamine to boric acid is 1:(1-2), and the temperature for drying the precipitate is 70-90℃.

4. The method for preparing TiB2 / TiCN ceramic composite powder according to claim 1, characterized in that: The inert atmosphere in step (2) includes nitrogen, argon or helium; the heat treatment parameters are: first, keep at a temperature of 250-350℃ for 40-90 minutes, then raise the temperature to 500-600℃ and keep at that temperature for 3-5 hours.

5. The method for preparing TiB2 / TiCN ceramic composite powder according to claim 1, characterized in that: In step (2), the calcination temperature is 1600-1800℃, the time is 20-40min, and the heating rate is 3-6℃ / min.

6. The method for preparing TiB2 / TiCN ceramic composite powder according to claim 1, characterized in that: In step (3), BC x The mass ratio of N ternary powder to Ti powder is (5-7):(13-15), and the mixing method is grinding or ball milling, with a mixing time of 20-40 min.

7. The method for preparing TiB2 / TiCN ceramic composite powder according to claim 1, characterized in that: In step (3), the Joule heating device heats the temperature to 1800-2300℃ and holds the temperature for 30-60 seconds.

8. The method for preparing TiB2 / TiCN ceramic composite powder according to claim 1, characterized in that: In step (3), the Joule heating device has a rapid heating rate of 2444-3143℃ / s and a time of 700ms-900ms.

9. The TiB2 / TiCN ceramic composite powder prepared by the method according to any one of claims 1-8, characterized in that, The TiB2 / TiCN ceramic composite powder is composed of TiB2 and TiCN, and the phase composition of the TiB2 / TiCN ceramic composite powder is a superposition of TiB2 crystal and TiCN crystal phases.

10. The TiB2 / TiCN ceramic composite powder according to claim 9, characterized in that, The D50 particle size of the TiB2 / TiCN ceramic powder is 1-2 μm; the mass percentages of TiB2 and TiCN are 40%-60% and 40-60%, respectively.

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