CN106810236B - Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder - Google Patents
Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder Download PDFInfo
- Publication number
- CN106810236B CN106810236B CN201710046647.1A CN201710046647A CN106810236B CN 106810236 B CN106810236 B CN 106810236B CN 201710046647 A CN201710046647 A CN 201710046647A CN 106810236 B CN106810236 B CN 106810236B
- Authority
- CN
- China
- Prior art keywords
- powder
- solid solution
- mixture
- composite solid
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/405—Iron group metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
Abstract
The invention discloses a preparation method of superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder. Firstly, the superfine TiO is treated2Dispersing the powder and then dispersing the dispersed TiO2Powder, graphite powder, dicyanodiamine and MoO3Powder, WO3The powder is used as a main raw material, a small amount of Ni powder is added to prepare a mixture, and the mixture is placed in a vacuum furnace for reduction and nitridation after mixing, drying, sieving and boat pressing treatment to obtain the superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder. The powder prepared by the method has fine particles, uniform particle size distribution and controllable N/C ratio, and the introduction of Mo and W alloy elements can effectively improve the high-temperature stability of the obtained composite solid solution. The preparation method has the advantages of low price of raw materials, low synthesis temperature, no need of consuming extra nitrogen source, simple process, greatly reduced cost and suitability for mass industrial production.
Description
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to a preparation method of superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder.
Background
The Ti (C, N) -based cermet is a multi-phase composite material which takes (TiC + TiN) or Ti (C, N) solid solution as a hard phase and takes Ni/Co as a bonding phase and is added with other carbides, not only has higher obdurability, but also has a series of advantages of high red hardness, good wear resistance, strong high-temperature creep resistance and oxidation resistance, low intermetallic friction coefficient and the like, so that the cermet has wide application prospect in a plurality of fields such as cutters, molds, wear-resistant parts, corrosion-resistant devices and the like. Meanwhile, the precious metal elements such as W, Co, Ta and the like consumed in the production process of the metal ceramic are few, the density is only about half of that of the hard alloy, and the metal ceramic becomes an ideal upgraded substitute material of the hard alloy.
In recent years, the preparation of Ti (C, N) -based cermets with higher nitrogen content has become a major development trend in the cermet industry of all countries in the world, because increasing the N content can improve the plasticity of Ti (C, N) ceramic particles, inhibit the growth of crystal grains during sintering, thereby improving the hardness and toughness of the material, and at the same time, can improve the high-temperature strength, high-temperature hardness and high-temperature plastic deformation resistance of the material, and improve the thermal conductivity and thermal shock resistance of the material. However, it is difficult to increase the nitrogen content in the sintered cermet body only by increasing the content of TiN in the mixture because TiN undergoes a significant denitrification reaction during high-temperature sintering, resulting in a sharp increase in porosity in the sintered body, thereby deteriorating the properties of the material. Relatively speaking, Ti (C, N) solid solution has better high temperature stability than TiN, and the high temperature denitrification tendency is less severe than TiN. However, the wettability between the Ti (C, N) solid solution and the metal binder phase in the cermet is poor, and the mixture must be added with alloying elements such as Mo and W to form a thin (Ti, Mo, W) (C, N) ring phase on the surface thereof by a dissolution precipitation mechanism to improve the wettability between the hard particles and the metal liquid phase. The thickness and the coating integrity degree of the annular phase are greatly influenced by components and process parameters, and the cermet can obtain a more uniform microstructure and better comprehensive performance only when the annular phase has moderate thickness and complete coating. Therefore, the raw material composition formula and the tolerance range of sintering process parameters of the high-nitrogen-content Ti (C, N) -based cermet are very narrow, and small deviations in the production process can cause the performance of the cermet to be reduced.
In order to solve the above difficulties, it is necessary to develop (Ti, Mo, W) (C, N) composite solid solution powder. At present, the research on the preparation of (Ti, Mo, W) (C, N) composite solid solution powder at home and abroad is very little. Recently, S, Park et al reported that "nanocrystals (Ti, M)1,M2) Synthesis of (CN) -Ni powder "(Synthesis of (Ti, M1, M2)(CN)–Ni nanocrystallinepowders. International Journal of Refractory Metals&Hard Materials, 2006, Vol24, P115-121), mixing the alloy elements of W, Mo, Nb and the like with TiO in the form of corresponding oxides2Preparing a mixture, and preparing the (Ti, M) rich in alloy elements through mechanical alloying, carbothermic reduction and high-temperature nitridation processes1,M2) (CN) composite solid solution powder. The composite solid solution powder prepared by the method can effectively improve the wettability between the Ti (C, N) solid solution and the binding phase, and can avoid the problem that the annular phase is difficult to control in the sintering process. However, this method was used to prepare (Ti, M)1,M2) When the (CN) composite solid solution powder is used, nitrogen is required to be filled in a high-temperature stage, long-time carbonization and nitridation treatment is required, energy consumption is high, meanwhile, the planetary high-energy ball milling is required to be used for refining and mechanical alloying treatment of raw materials, production efficiency is low, and the powder is difficult to be used for large-scale industrial production.
In view of this, there is a need for a method for preparing a composite solid solution powder for cermet, which has good high-temperature stability, uniform particle size, low cost, and is suitable for industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder, so that the superfine (Ti, Mo, W) (C, N) composite solid solution powder can be used for preparing nitrogen-containing metal ceramics with uniform tissues and better comprehensive mechanical properties.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder sequentially comprises the following steps:
step (1), adopting an ultrasonic oscillation method to carry out treatment on superfine TiO2Dispersing the powder;
step (2) of dispersing the ultrafine TiO2Powder, graphite powder, dicyanodiamine and MoO3Powder, WO3The powder and the Ni powder are used as raw materials to prepare a mixture, and the mixture comprises the following components in parts by mass:
the ultrafine TiO being226.43 to 42.77 of powder, 20.05 to 23.86 of graphite powder and 20.05 to 23.86 of dicyanodiamine7.88~11.32，MoO38.45-17.99 of powder and WO314.48-27.20% of powder and 0.33-0.75% of Ni powder;
step (3), placing the mixture and the hard alloy balls into a stirring ball mill for ball milling;
step (4), drying, screening and pressing the ball-milled mixture in sequence, and then placing the mixture in a vacuum furnace for reduction and nitridation to obtain superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder;
the reduction and nitridation are carried out in a vacuum furnace with a vacuum degree higher than 0.1Pa, and comprise three stages: firstly, heating the mixture subjected to boat pressing treatment to 700-800 ℃ at the speed of 3 ℃/min, and preserving heat for 30-60 min; then heating to 900-1000 ℃ at the speed of 5 ℃/min, and preserving heat for 60-90 min; finally, the temperature is rapidly reduced to below 400 ℃ at the speed of 20 ℃/min, and then the furnace is cooled.
The relevant content in the above technical solution is explained as follows:
1. in the above scheme, the preferable scheme is that the superfine TiO in the step (1) is treated2The powder is subjected to dispersion treatment by dispersing TiO2The powder is placed in a 1.2kw ultrasonic oscillator, the dispersion medium is absolute ethyl alcohol, the purity of the used ethyl alcohol is more than or equal to 99.5%, and the dispersion time is 30-50 min.
2. In the above scheme, the preferable scheme is that the superfine TiO in the step (2)2Providing a Ti source, wherein the grain diameter is 0.2-0.4 mu m, and the purity is more than or equal to 99.5%; dicyanodiamine provides an N source and a part of C source, the particle size is 0.4-0.6 mu m, and the purity is more than or equal to 99.0%; graphite powder provides part of C source, the particle size is 0.6-0.8 mu m, and the purity is more than or equal to 99.0%; MoO3Providing a Mo source, wherein the grain diameter is 3.8-4.2 mu m, and the purity is more than or equal to 99.0%; WO3Providing a W source by powder, wherein the particle size is 4.8-5.2 mu m, and the purity is more than or equal to 99.0%; ni powder is used as a trace additive and has a catalytic effect, the particle size is 2.0 mu m, and the purity is more than or equal to 99.0%.
3. In the above scheme, the ball milling in the step (3) preferably means that the mixture and absolute ethyl alcohol are placed in a stirring ball mill together according to a ratio of 1:1, the stirring speed is 90-150 r/min, the mass ratio of the hard alloy balls to the mixture is 10:1, and the time is 24-36 hours.
4. In the above scheme, the boat pressing process in step (3) refers to placing the mixture in a graphite boat for compaction.
5. In the above scheme, when the mass ratio of dicyandiamide to graphite powder in step (2) is controlled to be 0.33: 1-0.56: 1, the ultra-fine grain (Ti, Mo, W) (C, N) composite solid solution powder has an N/C ratio of 4: 6-6: 4 in the middle.
The design principle of the invention is as follows: in the preparation method of the invention, firstly, ultrafine TiO is treated2Dispersing the powder and then dispersing the dispersed TiO2Powder, graphite powder, dicyanodiamine (molecular formula C)2H4N4）、MoO3Powder, WO3The powder is used as a main raw material, a small amount of Ni powder is added to prepare a mixture, and the mixture is placed in a vacuum furnace for reduction and nitridation after mixing, drying, sieving and boat pressing treatment to obtain the superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder. The C content added in the form of dicyandiamide and graphite powder is such that complete reduction of MoO is ensured3、WO3And TiO2And can generate Mo through a carbonization process2C. WC and TiC. Oxygen has been considered as a harmful impurity in cermets in the past, and the oxygen content in the powder has been reduced as much as possible in the production of the cermet powder material because oxygen increases the wetting angle between the hard phase and the binder phase during liquid phase sintering, reduces the wettability thereof, and thus deteriorates the texture and properties of the material. Although the invention takes oxide as raw material, the invention provides C source with corresponding content by introducing dicyanodiamine and graphite powder, and reasonably controls sintering process to completely remove oxygen through carbothermic reduction reaction. Meanwhile, the reductive gas CO released in the carbothermic reduction process can ensure that the adsorbed oxygen on the surface of the powder is removed more thoroughly, and further purify the ceramic phase particles. In the subsequent reaction stage, the Mo obtained is reduced with increasing temperature2C. WC and TiC will continue to react with C2H4N4The provided N further generates (Ti, Mo, W) (C, N) composite solid solution through combination reaction. And by adjusting C2H4N4The ratio of the graphite powder to the graphite powder can control the N/C ratio in the mixture, thereby controlling the generation of (Ti, Mo)W) (C, N) nitrogen content in the composite solid solution. On the other hand, the invention introduces a small amount of Ni powder as a catalyst for synthesizing solid solution powder and a transmission medium for element diffusion, wherein Ni is one of the necessary raw materials of the metal ceramic, and the micro introduction of Ni does not deteriorate the structure and the performance of the metal ceramic like other impurities, but can greatly reduce the reaction temperature and shorten the reaction process, so that the finally synthesized (Ti, Mo, W) (C, N) composite solid solution particles still basically keep the original TiO2The shape and the particle size of the powder are different, so that the solid solution powder with low oxygen content, fine particles and uniform particle size distribution is obtained.
In the step (4) of the production method, the reduction and nitridation are performed in a vacuum furnace having a degree of vacuum higher than 0.1Pa, and include three stages. Firstly, heating the powder subjected to boat pressing treatment to 700-800 ℃ at the speed of 3 ℃/min, and preserving heat for 30-60 min, so as to fully remove oxygen contained in molybdenum trioxide and tungsten trioxide through carbothermic reduction reaction, and simultaneously enable generated gas to smoothly escape from a sintered body through an opening; then raising the temperature to 900-1000 ℃ at the speed of 5 ℃/min, and preserving the temperature for 60-90 min so as to reduce and carbonize titanium dioxide and thermally reduce various carbides and C obtained by carbothermic reduction2H4N4The provided N further generates (Ti, Mo, W) (C, N) composite solid solution through combination reaction; and finally, rapidly cooling to below 400 ℃ at the speed of 20 ℃/min, and then cooling along with the furnace, so as to rapidly reduce the furnace temperature after the reaction is finished, and prevent the generated (Ti, Mo, W) (C, N) composite solid solution powder from further growing up due to overlong retention time at high temperature.
The outstanding substantive features and remarkable progress of the technical scheme of the invention are mainly reflected in that:
(1) the invention adopts TiO with low cost2Powder, graphite powder, dicyanodiamine and MoO3Powder and WO3The powder is used as a main raw material, Mo and W alloy elements are directly introduced into the solid solution in the powder preparation process of the invention in the form of oxides, the process flow is simplified, the synthesis temperature is obviously reduced by introducing a small amount of Ni powder, and the superfine crystal (Ti, Mo, W) (C, N) composite solid solution can be obtained in one step;
(2) according to the invention, the dicyanodiamine powder is used for providing an N source, a large amount of nitrogen is not required to be introduced in the preparation process for high-temperature nitridation, the N/C ratio and the contents of Mo and W alloy elements in the obtained superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder are controllable, the residual oxygen content is low, the components are uniform, the high-temperature stability is good, and the denitrification reaction at the high-temperature stage can be effectively inhibited, so that the density and the stability of the nitrogen-containing metal ceramic prepared by using the superfine crystal as a raw material are improved;
(3) the invention has no special requirements on production equipment, only needs conventional equipment, has simple process, can greatly reduce the production cost and energy consumption, and is beneficial to industrial popularization and application.
Detailed Description
The invention is further described below and in the examples:
the technical effects of the present invention are further illustrated below with reference to examples. The starting material used in the following examples is TiO2Powder, graphite powder, dicyanodiamine (molecular formula C)2H4N4）、MoO3Powder, WO3Powder and Ni powder. Table 1 is a blend of 4 ingredient formulations.
Table 1 ingredient formula (wt.%) of the four mixes
| Composition (I) | WO3 | MoO3 | TiO2 | C | C2H4N4 | Ni |
| 1# | 15.52 | 9.64 | 42.77 | 23.86 | 7.88 | 0.33 |
| 2# | 14.48 | 17.99 | 34.93 | 22.40 | 9.73 | 0.47 |
| 3# | 27.20 | 8.45 | 32.80 | 21.33 | 9.68 | 0.54 |
| 4# | 25.57 | 15.88 | 26.43 | 20.05 | 11.32 | 0.75 |
Example 1:
1. by ultrasonic oscillation methodUltrafine TiO 22Dispersing the powder in a 1.2kw ultrasonic oscillator with absolute ethanol as dispersion medium, ethanol purity not less than 99.5%, and dispersing for 50 min;
2. respectively weighing 4 mixtures and superfine TiO according to the table 12Dispersing the powder to form suspension, and adding graphite powder, dicyandiamide and MoO3Powder, WO3Adding the powder and Ni powder into the mixture to form a mixed solution;
3. ball milling, putting the mixture and absolute ethyl alcohol into a stirring ball mill according to the proportion of 1:1, wherein the stirring speed is 90r/min, the ball-to-material ratio is 10:1, and the time is 36 hours;
4. drying in a vacuum drying oven at 75 deg.C for 2 h;
5. sieving, and sieving the dried powder with a 80-mesh sieve;
6. pressing the boat, namely placing the sieved mixture in a graphite boat for compaction;
7. reduction and nitridation, carried out in a vacuum furnace with a vacuum degree higher than 0.1Pa, comprising three stages: firstly, heating the powder subjected to boat pressing treatment to 700 ℃ at the speed of 3 ℃/min, and keeping the temperature for 60 min; then heating to 900 ℃ at the speed of 5 ℃/min, and preserving the heat for 90 min; and finally, rapidly cooling to below 400 ℃ at the speed of 20 ℃/min, and then cooling to room temperature along with the furnace to obtain the superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder. The molecular formulas of 1# -4 # ultrafine crystal (Ti, Mo, W) (C, N) composite solid solution powder in Table 1 are respectively (Ti0.8,Mo0.1,W0.1)(C0.6,N0.4)、(Ti0.7,Mo0.2,W0.1)(C0.5,N0.5)、(Ti0.7,Mo0.1,W0.2)(C0.5,N0.5) And (Ti)0.6,Mo0.2,W0.2)(C0.4,N0.6)。
The properties of the (Ti, Mo, W) (C, N) composite solid solution powder prepared from the mixture with different component ratios under the process conditions are shown in Table 2.
Table 2 chemical composition (wt.%) and average particle size (μm) of the composite solid solution prepared using the process of example 1
| Composition (I) | Ti | Mo | W | C | N | O | Ni | Average particle size |
| 1# | 48.03 | 12.02 | 23.10 | 9.05 | 7.04 | 0.13 | 0.63 | 0.36 |
| 2# | 39.50 | 22.62 | 21.53 | 7.07 | 8.25 | 0.15 | 0.88 | 0.42 |
| 3# | 35.69 | 10.25 | 39.27 | 6.40 | 7.48 | 0.11 | 0.80 | 0.39 |
| 4# | 29.04 | 19.40 | 37.05 | 4.85 | 8.43 | 0.22 | 1.01 | 0.44 |
Example 2:
1. ultrasonic oscillation method is adopted to process superfine TiO2Dispersing the powder in a 1.2kw ultrasonic oscillator with absolute ethanol as dispersion medium, ethanol purity not less than 99.5%, and dispersing for 40 min;
2. respectively weighing 4 mixtures and superfine TiO according to the table 12Dispersing the powder to form suspension, and adding graphite powder, dicyandiamide and MoO3Powder, WO3Adding the powder and Ni powder into the mixture to form a mixed solution;
3. ball milling, putting the mixture and absolute ethyl alcohol into a stirring ball mill according to the proportion of 1:1, wherein the stirring speed is 120r/min, the ball-to-material ratio is 10:1, and the time is 30 hours;
4. drying in a vacuum drying oven at 75 deg.C for 2 h;
5. sieving, and sieving the dried powder with a 80-mesh sieve;
6. pressing the boat, namely placing the sieved mixture in a graphite boat for compaction;
7. reduction and nitridation, carried out in a vacuum furnace with a vacuum degree higher than 0.1Pa, comprising three stages: firstly, heating the powder subjected to boat pressing treatment to 750 ℃ at the speed of 3 ℃/min, and preserving heat for 40 min; then heating to 950 ℃ at the speed of 5 ℃/min, and preserving the heat for 70 min; and finally, rapidly cooling to below 400 ℃ at the speed of 20 ℃/min, and then cooling to room temperature along with the furnace to obtain the superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder. The molecular formulas of 1# -4 # ultrafine crystal (Ti, Mo, W) (C, N) composite solid solution powder in Table 1 are respectively (Ti0.8,Mo0.1,W0.1)(C0.6,N0.4)、(Ti0.7,Mo0.2,W0.1)(C0.5,N0.5)、(Ti0.7,Mo0.1,W0.2)(C0.5,N0.5) And (Ti)0.6,Mo0.2,W0.2)(C0.4,N0.6)。
The properties of the (Ti, Mo, W) (C, N) composite solid solution powders prepared from the mixtures with different component ratios under the above process conditions are shown in Table 3.
Table 3 chemical composition (wt.%) and average particle size (μm) of the composite solid solution prepared using the process of example 2
| Composition (I) | Ti | Mo | W | C | N | O | Ni | Average particle size |
| 1# | 49.00 | 11.54 | 22.58 | 9.01 | 7.08 | 0.14 | 0.65 | 0.34 |
| 2# | 40.40 | 22.14 | 21.01 | 7.08 | 8.29 | 0.21 | 0.87 | 0.37 |
| 3# | 36.79 | 9.57 | 38.75 | 6.64 | 7.34 | 0.13 | 0.78 | 0.41 |
| 4# | 29.94 | 18.92 | 36.53 | 4.92 | 8.52 | 0.19 | 0.98 | 0.44 |
Example 3:
1. ultrasonic oscillation method is adopted to process superfine TiO2Dispersing the powder in a 1.2kw ultrasonic oscillator with absolute ethanol as dispersion medium, ethanol purity not less than 99.5%, and dispersing for 30 min;
2. respectively weighing 4 mixtures and superfine TiO according to the table 12Dispersing the powder to form suspension, and adding graphite powder, dicyandiamide and MoO3Powder, WO3Adding the powder and Ni powder into the mixture to form a mixed solution;
3. ball milling, putting the mixture and absolute ethyl alcohol into a stirring ball mill according to the proportion of 1:1, wherein the stirring speed is 150r/min, the ball-to-material ratio is 10:1, and the time is 24 hours;
4. drying in a vacuum drying oven at 75 deg.C for 2 h;
5. sieving, and sieving the dried powder with a 80-mesh sieve;
6. pressing the boat, namely placing the sieved mixture in a graphite boat for compaction;
7. reduction and nitridation, carried out in a vacuum furnace with a vacuum degree higher than 0.1Pa, comprising three stages: firstly, heating the powder material after the boat pressing treatment to 800 ℃ at the speed of 3 ℃/min,preserving the heat for 30 min; then raising the temperature to 1000 ℃ at the speed of 5 ℃/min, and preserving the temperature for 60 min; and finally, rapidly cooling to below 400 ℃ at the speed of 20 ℃/min, and then cooling to room temperature along with the furnace to obtain the superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder. The molecular formulas of 1# -4 # ultrafine crystal (Ti, Mo, W) (C, N) composite solid solution powder in Table 1 are respectively (Ti0.8,Mo0.1,W0.1)(C0.6,N0.4)、(Ti0.7,Mo0.2,W0.1)(C0.5,N0.5)、(Ti0.7,Mo0.1,W0.2)(C0.5,N0.5) And (Ti)0.6,Mo0.2,W0.2)(C0.4,N0.6)。
The properties of the (Ti, Mo, W) (C, N) composite solid solution powders prepared from the mixtures with different component ratios under the above process conditions are shown in Table 4.
Table 4 chemical composition (wt.%) and average particle size (mum) of the composite solid solution prepared using the process of example 3
| Composition (I) | Ti | Mo | W | C | N | O | Ni | Average particle size |
| 1# | 49.23 | 11.31 | 21.76 | 9.42 | 7.46 | 0.15 | 0.67 | 0.37 |
| 2# | 41.25 | 21.54 | 20.49 | 7.26 | 8.37 | 0.17 | 0.92 | 0.39 |
| 3# | 37.85 | 9.12 | 37.63 | 6.76 | 7.57 | 0.24 | 0.83 | 0.46 |
| 4# | 30.61 | 18.26 | 35.87 | 5.14 | 8.81 | 0.26 | 1.05 | 0.42 |
In the above examples, even though the same raw material formula is adopted in each of examples 1, 2 and 3, the solid solution degree is different due to the different process parameters used in the three examples, and thus, the chemical components and molecular formulas of the obtained ultra-fine grain (Ti, Mo, W) (C, N) composite solid solution powder have slight differences.
Within the value range of the claim, the second stage of reduction and nitridation has relatively large influence on the average particle size of the obtained (Ti, Mo, W) (C, N) composite solid solution powder, and only when the heat preservation temperature and the heat preservation time of the stage are reasonably matched (the heat preservation time is properly shortened when the heat preservation temperature is relatively high), the mixture of the above formula of the components can obtain the (Ti, Mo, W) (C, N) composite solid solution with fine particle size, uniform components and stable N/C ratio. In summary, within the value range of the present claims, the influence on the properties of the (Ti, Mo, W) (C, N) composite solid solution is limited.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (2)
1. A preparation method of superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder is characterized by sequentially comprising the following steps:
step (1), adopting an ultrasonic oscillation method to carry out treatment on superfine TiO2Dispersing the powder; in the step (1), ultrafine TiO is treated2The powder is subjected to dispersion treatment by dispersing TiO2Putting the powder into a 1.2kw ultrasonic oscillator, wherein the dispersion medium is absolute ethyl alcohol, the purity of the used ethyl alcohol is more than or equal to 99.5%, and the dispersion time is 30-50 min;
step (2) of dispersing the ultrafine TiO2Powder, graphite powder, dicyanodiamine and MoO3Powder, WO3The powder and the Ni powder are used as raw materials to prepare a mixture, and the mixture comprises the following components in parts by mass:
the ultrafine TiO being226.43 to 42.77 of powder, 20.05 to 23.86 of graphite powder, 7.88 to 11.32 of dicyanodiamide and MoO38.45-17.99 of powder and WO314.48-27.20% of powder and 0.33-0.75% of Ni powder; the superfine TiO in the step (2)2The particle size of the product is 0.2-0.4 mu m, and the purity is more than or equal to 99.5%; the particle size of dicyanodiamine is 0.4-0.6 mu m, and the purity is more than or equal to 99.0 percent; the particle size of the graphite powder is 0.6-0.8 mu m, and the purity is more than or equal to 99.0%; MoO3The particle size of the product is 3.8-4.2 mu m, and the purity is more than or equal to 99.0%; WO3The particle size of the powder is 4.8-5.2 mu m, and the purity is more than or equal to 99.0%; the particle size of the Ni powder is 2.0 mu m, and the purity is more than or equal to 99.0 percent; when the mass ratio of dicyandiamide to graphite powder in the step (2) is controlled to be 0.33: 1-0.56: 1, the ultra-fine grain (Ti, Mo, W) (C, N) composite solid solution powder has an N/C ratio of 4: 6-6: 4;
step (3), placing the mixture and the hard alloy balls into a stirring ball mill for ball milling;
step (4), drying, screening and pressing the ball-milled mixture in sequence, and then placing the mixture in a vacuum furnace for reduction and nitridation to obtain superfine crystal (Ti, Mo, W) (C, N) composite solid solution powder;
the reduction and nitridation are carried out in a vacuum furnace with a vacuum degree higher than 0.1Pa, and comprise three stages: firstly, heating the mixture subjected to boat pressing treatment to 700-800 ℃ at the speed of 3 ℃/min, and preserving heat for 30-60 min; then heating to 900-1000 ℃ at the speed of 5 ℃/min, and preserving heat for 60-90 min; finally, the temperature is rapidly reduced to below 400 ℃ at the speed of 20 ℃/min, and then the furnace is cooled.
2. The method for preparing ultrafine grained (Ti, Mo, W) (C, N) composite solid solution powder according to claim 1, characterized in that: the ball milling in the step (3) is to place the mixture and absolute ethyl alcohol in a stirring ball mill according to the proportion of 1:1, the stirring speed is 90-150 r/min, the mass ratio of the hard alloy balls to the mixture is 10:1, and the time is 24-36 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710046647.1A CN106810236B (en) | 2017-01-22 | 2017-01-22 | Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710046647.1A CN106810236B (en) | 2017-01-22 | 2017-01-22 | Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106810236A CN106810236A (en) | 2017-06-09 |
| CN106810236B true CN106810236B (en) | 2020-03-27 |
Family
ID=59111246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710046647.1A Active CN106810236B (en) | 2017-01-22 | 2017-01-22 | Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106810236B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114438361B (en) * | 2022-01-25 | 2023-02-28 | 苏州新锐合金工具股份有限公司 | Preparation method of surface fine-grain functionally-gradient cobalt-free titanium-based cermet |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006035535A1 (en) * | 2004-09-28 | 2006-04-06 | Murata Manufacturing Co., Ltd | Dielectric ceramic, process for producing the same, and laminated ceramic capacitor |
| CN1888104A (en) * | 2006-07-14 | 2007-01-03 | 北京工业大学 | Prepn process of high-performance superfine crystal hard WC-10 wt.% Co alloy |
| CN101020971A (en) * | 2007-04-06 | 2007-08-22 | 北京科技大学 | Process of making superfine crystal hard alloy without adhesive |
| CN101210291A (en) * | 2006-12-26 | 2008-07-02 | 四川理工学院 | Method for producing ultra-fine crystal particle cermet |
| CN102534340A (en) * | 2012-01-13 | 2012-07-04 | 四川大学 | Nitrogen-containing hard alloy based on multi-element composite titanium carbonitride solid solution and preparation method for nitrogen-containing hard alloy |
-
2017
- 2017-01-22 CN CN201710046647.1A patent/CN106810236B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006035535A1 (en) * | 2004-09-28 | 2006-04-06 | Murata Manufacturing Co., Ltd | Dielectric ceramic, process for producing the same, and laminated ceramic capacitor |
| CN1888104A (en) * | 2006-07-14 | 2007-01-03 | 北京工业大学 | Prepn process of high-performance superfine crystal hard WC-10 wt.% Co alloy |
| CN101210291A (en) * | 2006-12-26 | 2008-07-02 | 四川理工学院 | Method for producing ultra-fine crystal particle cermet |
| CN101020971A (en) * | 2007-04-06 | 2007-08-22 | 北京科技大学 | Process of making superfine crystal hard alloy without adhesive |
| CN102534340A (en) * | 2012-01-13 | 2012-07-04 | 四川大学 | Nitrogen-containing hard alloy based on multi-element composite titanium carbonitride solid solution and preparation method for nitrogen-containing hard alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106810236A (en) | 2017-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108637268B (en) | Method for preparing composite Ti (C, N) metal ceramic powder by microwave carbothermic reduction | |
| CN107552802B (en) | Titanium carbonitride-based solid solution powder for metal ceramics and preparation method thereof | |
| CN109487141B (en) | Preparation method of platy carbide solid solution toughened mixed crystal Ti (C, N) -based metal ceramic | |
| CN1321768C (en) | Preparation of warm pressed diffusing particle reinforced iron-based powder metallized composite materials | |
| CN112222419B (en) | Method for preparing nano molybdenum powder by regulating nucleation and growth processes and application | |
| CN113122747B (en) | Cu- (WC-Y) with excellent mechanical property2O3) Method for preparing composite material | |
| CN112662929B (en) | Refractory high-entropy alloy and preparation method thereof | |
| CN109261980A (en) | A kind of preparation method of heavy alloy tungsten powder | |
| CN104674098B (en) | Cermet material based on TiCN-(Ti,M)CN core mixed structure and preparation method thereof | |
| CN114438361B (en) | Preparation method of surface fine-grain functionally-gradient cobalt-free titanium-based cermet | |
| CN110732801A (en) | Cu-Ni-Mn alloy solder powder and its preparing process | |
| CN106756599A (en) | The preparation method of cBN High Speed Steel Composites and cBN High Speed Steel Composites | |
| CN115044794B (en) | Cu- (Y) with excellent performance 2 O 3 -HfO 2 ) Alloy and preparation method thereof | |
| CN109576546A (en) | A kind of preparation method of the high-strength tenacity without magnetic Ti (C, N) based ceramic metal | |
| CN102251130B (en) | Preparation method of superfine grain cemented carbide | |
| CN101210291B (en) | Method for producing ultra-fine crystal particle cermet | |
| US9028583B2 (en) | Process for producing refractory metal alloy powders | |
| CN106810236B (en) | Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder | |
| CN115635097B (en) | High-entropy alloy composite material with stable cellular structure and preparation method thereof | |
| JP5618364B2 (en) | Method for producing ultrafine and homogeneous titanium carbonitride solid solution powder | |
| CN112080661B (en) | Preparation method of superfine hard alloy | |
| JP2014077191A (en) | Synthesis method of carbide and carbonitride powder containing binder and cermet obtained thereby | |
| CN111455253A (en) | Titanium carbide-based metal ceramic thermal spraying powder and preparation method thereof | |
| KR101938471B1 (en) | Method of tantalum carbide for hard metal and tantalum carbide for hard metal using the same | |
| WO2023025251A1 (en) | Lightweight steel and preparation method therefor, steel structural member and electronic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |