CN115286392B - Preparation of TiB 2 Method for preparing ternary complex phase ceramic of-TiC-SiC and its product - Google Patents

Preparation of TiB 2 Method for preparing ternary complex phase ceramic of-TiC-SiC and its product Download PDF

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CN115286392B
CN115286392B CN202210938342.2A CN202210938342A CN115286392B CN 115286392 B CN115286392 B CN 115286392B CN 202210938342 A CN202210938342 A CN 202210938342A CN 115286392 B CN115286392 B CN 115286392B
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朱建华
崔名芳
冉松林
岳晓君
龙红明
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Anhui University of Technology AHUT
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Abstract

The invention provides a method for preparing TiB 2 A method for preparing TiC-SiC ternary complex phase ceramic and a product thereof, relating to the field of ceramic composite materials; method bagComprises the following steps: obtaining a catalyst formed from Ti 3 SiC 2 Powder, B 4 Wet mixing the dried mixed raw materials of the C powder and the Ti powder according to a proportion, and sintering the mixed raw materials in a discharge plasma sintering furnace according to a preset condition to prepare the complex phase ceramic; the invention adopts a reaction discharge plasma sintering technology, simultaneously introduces TiC and SiC components, and the multi-component forms a novel multi-component synergistic toughened TiB under the reaction and external pressure induction 2 Base composite material having rod-like TiB with significantly preferential growth in its microstructure 2 Grains and TiB 2 the-TiC mutual cross-linked structure can greatly improve the fracture toughness and the bending strength of the material.

Description

Preparation of TiB 2 Method for preparing ternary complex phase ceramic of-TiC-SiC and its product
Technical Field
The invention relates to the technical field of ceramic composite materials, in particular to a method for preparing TiB 2 -TiC-SiC ternary complex phase ceramic and its product.
Background
TiB 2 The ceramic is a very important non-oxide advanced ceramic, has high strength, super hardness, abrasion resistance, impact resistance and excellent conductivity, and is widely applied to the fields of hard alloy, dies, aerospace and the like. On a microscopic scale, B atoms interact with each other through covalent bonds, and an ionic bond is formed between Ti and B; and the atomic planes of Ti and B are arranged alternately in space to form a two-dimensional network. TiB 2 Strong covalent and ionic bonds exist within the structure, which gives it ultra-high melting point, superior hardness, and excellent chemical stability characteristics. However, the superhard material has remarkable brittleness, the processing and sintering properties of the superhard material are limited to a great extent, and the popularization and the use of the superhard material in different engineering fields are influenced.
To solve the above problems, researchers often introduce new composite phases to improve TiB 2 The sintering performance of the material is improved, and the mechanical property of the material is improved. However, the single introduced phase is in TiB 2 The ceramic structure is mostly an independent and dispersed structure, and the toughening effect is poor. For this reason, researchers also often use the addition of multiple reinforcing phases to improve the firing of ceramics by the interaction between different phasesJunction performance while optimizing TiB 2 Based on the comprehensive mechanical property of the complex phase ceramic.
However, limited by the limited interactions between the different species, the toughening effect of the direct incorporation of the multi-component phase is often not ideal; the reaction sintering method can be used for preparing the complex phase ceramic, and unexpected effects can be achieved. In the reactive sintering process, a new material phase is generated through reaction, the growth of particles goes through a process from small to large, and the phenomenon of cross interpenetration exists among crystal grains, so that the effect of different material phases can be obviously improved, and further the comprehensive mechanical property of the complex phase ceramic is improved.
Disclosure of Invention
The invention aims to provide a method for preparing TiB 2 Method for preparing TiB by reaction discharge plasma sintering technology and product thereof 2 -TiC-SiC ternary complex phase ceramic, on a micro-scale, tiB 2 Grain along [001 ]]The direction has obvious preferential growth and forms a mutual cross-linking structure with TiC crystal grains, and the double-toughening novel structure obviously improves the mechanical properties of the composite ceramic, such as strength, toughness and the like.
In order to achieve the above purpose, the invention provides the following technical scheme: preparation of TiB 2 The method of the-TiC-SiC ternary complex phase ceramic comprises the following steps:
1) Ti with the molar ratio of 2 (3-4) to 5 3 SiC 2 Powder, B 4 Wet mixing the C powder and the Ti powder, and then drying to obtain a mixed raw material with the particle size not more than 200 meshes;
2) Placing the mixed raw materials in a graphite mold, and sintering in a discharge plasma sintering furnace in vacuum according to preset conditions to obtain the complex phase ceramic;
wherein the preset conditions of the step 2) are as follows: heating to a target temperature of 1900-2100 deg.C at a rate of 100 deg.C/min, maintaining the temperature at the target temperature for 10min, and applying an external pressure of 50MPa in the heat preservation stage; after sintering, the sintered product was cooled at a rate of 50 ℃/min.
Further, 0.1 to 0.5wt% of B is added to the raw materials wet-mixed in the step 1) 2 O 3 。
Further, the raw material Ti in the reaction in the step 1) 3 SiC 2 Powder, B 4 The molar ratio of the C powder to the Ti powder is 2.
Further, the specific process of the step 1) is as follows: ti is weighed according to the molar ratio of 2 (3-4) to 5 3 SiC 2 Powder, B 4 C powder and Ti powder in ZrO 2 Wet mixing for 24h in the presence of balls and alcohol; and then, evaporating and drying the mixture by using a rotary evaporator, and sieving the dried mixture with a 200-mesh sieve to obtain a mixed raw material for later use.
Further, the complex phase ceramic forms TiB on a microscopic level 2 -TiC inter-linked reinforcing and toughening structure and along [001 ]]Rod-shaped TiB growing regularly in direction preference 2 And (4) crystal grains.
Furthermore, the bending strength, the fracture toughness and the Vickers hardness of the complex phase ceramic respectively reach 906 +/-8 MPa, 8.50 +/-0.43 MPa and 24.4 +/-0.47 GPa.
Further, B in the raw materials wet mixed in the step 1) 2 O 3 The amount of (B) added was 0.5wt%.
Further, the target temperature in the preset condition is 2000 ℃.
Further, the ZrO 2 The diameter of the ball is 5mm.
Another technical scheme of the invention provides a TiB 2 -TiC-SiC ternary complex phase ceramic prepared by the method for preparing TiB 2 A method for preparing TiC-SiC ternary complex phase ceramic.
According to the technical scheme, the technical scheme of the invention has the following beneficial effects:
the invention discloses a method for preparing TiB 2 The preparation method of the-TiC-SiC ternary complex phase ceramic comprises the following steps: obtaining a catalyst formed from Ti 3 SiC 2 Powder, B 4 Wet mixing the dried mixed raw materials of the C powder and the Ti powder according to a proportion, and sintering the mixed raw materials in a discharge plasma sintering furnace according to a preset condition to obtain the complex phase ceramic; wherein, the method firstly adopts a wet mixing mode to ensure that particles with different particle diameters and different chemical properties in the mixed raw materials are in spaceUniformly distributed, then adopting reaction discharge plasma sintering technology, simultaneously introducing TiC and SiC components, under the reaction and external pressure induction the multicomponent component can be formed into multicomponent synergistic toughened new type TiB 2 A base composite material; the microstructure of the prepared multiphase ceramic has rod-shaped TiB with obvious preferential growth 2 Grains and TiB 2 the-TiC mutual cross-linked structure can greatly improve the fracture toughness and the bending strength of the material.
The invention relates to a composite phase ceramic medium rod-shaped TiB 2 The formation of grains is closely related to the temperature of the reactive discharge plasma sintering process, and when the temperature reaches 2000 ℃, tiB 2 The grain orientation growth in the (001) plane reaches a higher value; at the same time, B is added into the mixed raw materials 2 O 3 So that the volatile component BO (g) generated during sintering synergistically promotes TiB 2 The crystal grains grow preferentially, and B is mixed with the raw materials 2 O 3 When the addition amount of (c) is 0.5wt%, the preferential growth of the (001) plane in the complex phase ceramic microstructure is significantly improved under the same preset conditions.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.
Drawings
The figures are not intended to be drawn to scale with true references. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is an XRD pattern of a sample of the complex phase ceramic prepared in example 1;
in fig. 2, a is an SEM photograph of a sample of the complex phase ceramic prepared in example 1, and b is an SEM picture of the complex phase ceramic prepared in comparative example 1;
FIG. 3 is an SEM photograph of crack propagation paths of the complex phase ceramic prepared in example 1;
FIG. 4 is an SEM photograph of a composite ceramic sample prepared in example 2;
FIG. 5 is an SEM photograph of a composite ceramic sample prepared in example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without inventive step, are within the scope of protection of the invention. Unless defined otherwise, technical or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The use of "first," "second," and similar terms in the description and in the claims of the present application does not denote any order, quantity, or importance, but rather the terms are used to distinguish one element from another. Similarly, the singular forms "a," "an," or "the" do not denote a limitation of quantity, but rather denote the presence of at least one, unless the context clearly dictates otherwise. The terms "comprises," "comprising," or the like, mean that the elements or items listed before "comprises" or "comprising" encompass the features, integers, steps, operations, elements, and/or components listed after "comprising" or "comprising," and do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Based on the introduction of single or multiple elements in the prior artPhase improved TiB 2 When the material has the problems of excellent hardness and high brittleness, limited interaction among different objects is realized, and the toughening effect of the ceramic material prepared by single or multiple introduction is not ideal; therefore, the present invention is directed to solving the above problems and providing a method for preparing TiB by reactive discharge plasma sintering 2 A method for preparing TiC-SiC ternary complex phase ceramic, wherein TiB is formed on the structure of the complex phase ceramic prepared by the method 2 -TiC cross-linked structure and rod-like TiB with significantly preferred growth 2 Crystal grains, the structure greatly improves the fracture toughness and the bending strength of the material.
In particular, the invention discloses a method for preparing TiB 2 The method of the-TiC-SiC ternary complex phase ceramic comprises the following steps: 1) Ti is weighed according to the molar ratio of 2 (3-4) to 5 3 SiC 2 Powder, B 4 C powder and Ti powder in ZrO 2 Wet mixing for 24h in the presence of balls and alcohol; then, evaporating and drying the mixture by a rotary evaporator, and sieving the dried mixture with a 200-mesh sieve to obtain a mixed raw material for later use; 2) Placing the mixed raw materials in a graphite mold, and sintering in a discharge plasma sintering furnace in vacuum according to preset conditions to obtain the complex phase ceramic; wherein the preset conditions are as follows: heating to a target temperature of 1900-2100 ℃ at a temperature of 100 ℃/min, preserving the temperature at the target temperature for 10min, and applying external pressure of 50MPa in the heat preservation stage; after sintering, the sintered product was cooled at a rate of 50 ℃/min.
The reason why the method adopts wet mixing and drying to obtain the mixed raw material is that the tank body adopted by the wet mixing is plastic, so that the method not only can ensure that particles with different particle sizes and different chemical properties are uniformly distributed in space when in use, but also is beneficial to forming a new phase in the subsequent sintering process; secondly, can effectively prevent the pollution of ball-milling in-process, because the jar body is plastics in this scheme, can not with the ZrO that plays the compounding effect 2 The balls form large collision, thereby avoiding bringing in ZrO 2 And (4) pollution.
The invention is disclosed below with reference to the specific embodiments shown in the drawings for preparing TiB 2 The method of-TiC-SiC ternary complex phase ceramic and the product thereof are further described in detail.
Ti described in the examples below 3 SiC 2 The powder is purchased from Ningbo Jinlei nanometer material science and technology Limited company, the average grain diameter is 478nm, and the purity is 99 percent; b is 4 The C powder is purchased from Suzhou Napo material science and technology Limited, the average grain diameter is 478nm, and the purity is 97.4-98.5%; the Ti powder is purchased from Beijing Gaokou New Material science and technology Limited, the average grain diameter is 700nm, and the purity is 98.4 percent; b is 2 O 3 The powder is obtained from Shanghai Naihou nanometer science and technology Limited company, and has an average particle diameter of 50nm and a purity of 99.9%.
Example 1
10.36g of Ti 3 SiC 2 、4.39g B 4 C, mixing the powder with 6.33g of Ti three raw materials in a molar ratio of 2; adding the dried mixed raw materials into a graphite mould, separating the powder from the mould and a pressure head by using graphite paper, and placing the mixture into a discharge plasma sintering furnace for vacuum sintering; the sintering conditions are as follows: heating to 1900 deg.C at a temperature rise rate of 100 deg.C/min, and maintaining for 10min; applying 50MPa pressure to the high-temperature section; after sintering, cooling the sample at the speed of 50 ℃/min to obtain a ceramic sample; the XRD pattern of the sample is shown in FIG. 1, and the SEM pattern of the sample is shown as a in FIG. 2.
Example 2
Example 2 differs from example 1 in that: when spark plasma sintering is adopted, the target temperatures of sintering conditions are different, the temperature is raised to 2000 ℃, and the constant temperature is kept for 10 minutes; SEM images of the samples are shown in fig. 4 and 5.
Example 3
Example 3 differs from example 1 in that: when wet mixed, B 4 The content of the C powder is increased to 5.85g, and the molar ratio of the three substances in the raw materials is 2.
Example 4
Example 4 differs from example 1 in that: when spark plasma sintering is adopted, the target temperature of sintering conditions is different, the temperature is raised to 2100 ℃, and the constant temperature is kept for 10 minutes.
Example 5
Example 5 differs from example 1 in that: when wet mixing, 0.5wt% of the mixture is addedB 2 O 3 Meanwhile, the target temperature for sintering by spark plasma is 2000 ℃, and the constant temperature is kept for 10 minutes.
Comparative example 1
Comparative example 1 differs from example 1 in that: step 1) adopting a direct mixing method, wherein raw materials Ti are directly mixed 3 SiC 2 Powder, B 4 The volume part ratio of the C powder to the Ti powder is 6 2 -TiC-SiC ternary complex phase ceramic; the SEM image of the sample is shown in fig. 2 b.
Referring to FIG. 1, the TiB prepared in example 1 2 Only TiB exists in the-TiC-SiC ternary complex phase ceramic sample 2 Three phases of TiC and SiC, and no other impurity peaks exist, which indicates that the raw material powder Ti 3 SiC 2 、B 4 After C and Ti are subjected to a reactive discharge plasma sintering (SPS) process, tiB can be generated 2 -TiC-SiC complex phase ceramic, and the crystallinity of the target ceramic is good. When the electron micrographs of example 1 and comparative example 1 shown in a and b in FIG. 2 are combined, the off-white color is TiB according to the energy spectrum analysis 2 TiC in bright white and SiC in black, tiB in sample 2 Grain edge [001 ]]The sample basically reaches complete compactness and can clearly observe TiB 2 -a TiC cross-linked structure. The ceramic sample prepared in comparative example 1 also contained three phases, but TiB 2 The crystal grains are irregular spherical, tiC is more aggregated, and TiC and TiB 2 The bonding of (a) is looser.
In conjunction with the crack propagation path of the complex phase ceramic of example 1 shown in FIG. 3, it can be clearly seen that the crack propagates along the grain boundaries, and the grain boundaries are distinct, further illustrating that the complex phase ceramic forms TiB 2 -a TiC cross-linked structure. TiB prepared in conjunction with example 2 shown in FIG. 4 2 SEM photograph of-TiC-SiC ternary complex phase ceramic, and TiB in the sample can be clearly observed 2 TiC crosslinked structure, but part TiB 2 The grain structure becomes irregular and the particles become large, which affects the mechanical properties of the ceramic sample to a large extent; in the embodiment 5, B is added as shown in FIG. 5 2 O 3 Is then prepared intoOf TiB 2 -TiC-SiC ternary complex phase ceramic in which structure TiB 2 Grain edge [001 ]]The directional growth is more pronounced due to the addition of B in the raw material 2 O 3 Generates a volatile component BO (g) during sintering, and the high temperature and the BO (g) synergistically promote TiB 2 Preferentially growing crystal grains; however, as shown in fig. 5, the presence of BO (g) also causes TiC to aggregate to some extent in the microstructure, resulting in an uneven distribution thereof within the ceramic structure.
Table 1 below is a TiB prepared in examples 1-5 2 -each mechanical property data of the TiC-SiC complex phase ceramic sample, wherein the actual density is carried out according to a method specified in the national standard GB/T1423-1996 test method for the density of the noble metal and the alloy thereof, and the calculation formula of the density D is as follows: d = ρ Practice of /ρ Theory of the invention X 100%, where ρ Practice of Representing the actual density, p Theory of the invention Represents the theoretical density; the Vickers hardness is measured by adopting an HVS-10 microhardness tester produced by Shanghai Shang material Co., ltd, and the magnitude of applied force is 19.61N; the fracture toughness is measured by adopting a traditional indentation method; the bending strength is tested by adopting a three-point bending method; the material mechanics tests are the average of 10 test data.
TABLE 1 TiB with different component contents 2 Various properties of-TiC-SiC complex phase ceramic
Figure GDA0004054762820000071
Figure GDA0004054762820000081
It is known that the bending strength of the ceramic obtained in comparative example 1 is 770. + -.14 MPa, the Vickers hardness is 22.31. + -. 0.74GPa, and the fracture toughness is 6.05. + -. 0.31 MPa.m 1/2 As shown in the table, the mechanical properties of the complex phase ceramics of any one of examples 1-5 of the present invention are superior to those of comparative example 1, and comparative example 1 is significantly lower than the ceramic sample prepared by reaction SPS sintering, therefore, tiB prepared by the present invention 2 the-TiC-SiC ternary complex phase ceramic can obviously improve the strength of the materialAnd (4) chemical properties. Further, as shown in the above table, when Ti is contained in the raw materials 3 SiC 2 Powder, B 4 And when the molar ratio of the C powder to the Ti powder is 2.
The invention provides a method for preparing TiB by adopting a reactive discharge plasma sintering technology 2 The method of the-TiC-SiC ternary complex phase ceramic can not only obtain a novel double-toughened ceramic structure, but also obviously improve the comprehensive mechanical properties with equal strength and toughness.
Although the invention has been described with reference to preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.

Claims (6)

1. Preparation of TiB 2 The method of the-TiC-SiC ternary complex phase ceramic is characterized by comprising the following steps:
1) Ti with the molar ratio of 2 (3 to 4) to 5 3 SiC 2 Powder, B 4 ZrO of C powder and Ti powder 2 Wet mixing the balls and alcohol for 24 hours in the presence of alcohol, then evaporating and drying the mixture by a rotary evaporator, and sieving the dried mixture with a 200-mesh sieve to obtain a mixture with the particle size not more than 200 meshes; 0.1 to 0.5wt% of B is added to the raw materials for wet mixing 2 O 3 ；
2) Placing the mixed raw materials in a graphite mold, and sintering in a discharge plasma sintering furnace in vacuum according to preset conditions to obtain the complex phase ceramic;
wherein the preset conditions of the step 2) are as follows: heating to a target temperature of 1900-2100 deg.C at a rate of 100 deg.C/min, maintaining the temperature at the target temperature for 10min, and applying an external pressure of 50MPa in the heat preservation stage; after sintering, cooling the sintered product at the speed of 50 ℃/min; the complex phase ceramic forms TiB on the micro scale 2 -TiC inter-linked reinforcing and toughening structure and along [001 ]]Rod-shaped TiB with regular direction preferred growth 2 A crystal grain; the bending strength of the complex phase ceramic,The fracture toughness and the Vickers hardness are 906 +/-8 MPa, 8.50 +/-0.43 MPa and 24.4 +/-0.47 GPa respectively.
2. Preparing TiB according to claim 1 2 The method of the-TiC-SiC ternary complex phase ceramic is characterized in that the raw material Ti in the reaction in the step 1) is 3 SiC 2 Powder, B 4 The molar ratio of the C powder to the Ti powder is 2.
3. Preparing TiB according to claim 1 2 The method of the-TiC-SiC ternary complex phase ceramic is characterized in that B in the wet mixed raw material in the step 1) 2 O 3 The amount of (B) added was 0.5wt%.
4. Preparing TiB according to claim 1 2 The method of the-TiC-SiC ternary complex phase ceramic is characterized in that the target temperature in the preset condition is 2000 ℃.
5. Preparing TiB according to claim 1 2 -TiC-SiC ternary complex phase ceramic, characterized in that the ZrO 2 2 The diameter of the ball is 5mm.
6. TiB 2 -TiC-SiC ternary complex phase ceramic, characterized in that said TiB 2 -TiC-SiC ternary complex phase ceramic prepared by the method of any one of claims 1-5 2 A method for preparing TiC-SiC ternary complex phase ceramic.
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