CN111348919A

CN111348919A - TiN-NbC composite material and preparation method thereof

Info

Publication number: CN111348919A
Application number: CN202010177281.3A
Authority: CN
Inventors: 李艳国; 邹芹; 王明智; 邹娟; 党赏
Original assignee: Yanshan University
Current assignee: Yanshan University
Priority date: 2020-03-13
Filing date: 2020-03-13
Publication date: 2020-06-30

Abstract

The invention provides a TiN-NbC composite material and a preparation method thereof, wherein the TiN-NbC composite material comprises niobium carbide micro powder and TiNx, wherein x is more than or equal to 0.3 and less than or equal to 0.9, or x is 1.1-1.3. The volume percentage of the niobium carbide micro powder is 10-40 vol.%. During preparation, mixing niobium carbide micro powder and TiNx powder in a ball mill according to different volume ratios; uniformly mixing, filling the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 100-500 MPa, and the prepressing is 10-30 s; and then putting the pre-pressed sample into a graphite mold for hot-pressing sintering, wherein the sintering pressure is 20-50 MPa, the sintering temperature is 1100-2000 ℃, and the temperature is kept for 10-120 min, so that the TiN-NbC composite material is prepared. The invention utilizes the vacancy in the TiNx to reduce the sintering temperature, improve the hardness and fracture toughness, solve the problem that the transition carbide is difficult to sinter, and obtain the TiN-NbC composite material with higher hardness through hot-pressing sintering.

Description

TiN-NbC composite material and preparation method thereof

Technical Field

The invention relates to the technical field of composite materials, in particular to a TiN-NbC composite material and a preparation method thereof.

Background

TiN is often applied to cutting tools, which makes the tool material have better hardness, toughness, chipping resistance and plastic deformation resistance, less affinity with iron element, and more excellent cutting performance, which is completely superior to the traditional WC tools [ aixing, liuzhang, development of high-speed cutting tool material and future [ J ]. manufacturing technology and machine tools, 2001(8):21-25 ]. TiNx is a vacancy type solid solution with a wide composition range, the composition range of N atoms can be changed within a certain range, and the value of x can be 0.26-1.16. When the number of N atoms in TiNx is higher than that of Ti atoms, the content of N is high and Ti is low, and the TiNx is a Ti-deficient solid solution, and the TiNx mainly exhibits the property of covalent compound, which results in the property of TiNx being different from that of the stoichiometric compound TiN [ Chenyuqing, Liangou, concept of non-stoichiometric and solid solution and the progress [ J ] ceramics science, 1998,19(2):115-118 ]. Because high-concentration N vacancies exist in the TiNx crystal, the N element in the N-rich environment around the TiNx can fill the N vacancies in the TiNx crystal by the characteristic, and therefore, the N element in the PcBN crystal can be well combined with the TiNx. In addition, the radius of the C atoms is equivalent to that of the N atoms, and the C atoms can also fill N vacancies in the TiNx, so that nitrides or carbides can be added into the TiNx to improve the toughness of the TiNx, thereby meeting the application requirement of the TiNx as a PcBN tool binding agent and prolonging the service life of the PcBN. Research shows that in the hard alloy added with NbC, the grains of the hard phase are refined, and the hot hardness, the thermal shock resistance and the thermal oxidation resistance of the cutter are all improved to a certain extent. NbC is also a main raw material of composite ceramics, and can control the thickness of the shell in the Ti (C, N) -based cermet core-shell structure, thereby affecting the performance of the cermet, and meanwhile, the addition of NbC can effectively reduce the sintering temperature of a sintered body [ QingN, nanqing, LiZ, et al.

The TiN powder is used as raw material for preparing TiN ceramics and related composite materials, so that the properties of the powder not only influence the process selection for preparing the TiN ceramics and the related composite materials, but also directly influence the performances of the related products. For example, the particle size, particle size distribution range, particle morphology, impurity content and the like of the titanium nitride powder all have certain influence on the subsequent process flow. How to prepare TiN powder with proper particle size and shape, narrow particle size distribution range and as little impurity content as possible is always the main research direction. In addition, TiN compositely sintered with NbC powder is non-stoichiometric TiNx, and a large number of vacancies exist in the structure, so that the TiN powder has the effects of promoting diffusion and reducing the sintering temperature in sintering, and a sintered body with higher densification degree and better performance can be obtained at lower temperature.

Disclosure of Invention

Aiming at the defects of the prior art, the invention mixes non-stoichiometric TiNx prepared by a mechanical alloying Method (MA) with refined niobium carbide powder, adopts hot-pressing sintering (HP) to prepare a metal-free bonding phase TiN-NbC composite material, utilizes the vacancy in the TiNx to reduce the sintering temperature to promote the sintering, and forms the metal-free bonding agent TiN-NbC composite material by compositely sintering with niobium carbide and other transition group refractory carbides on the basis, thereby overcoming the defect of performance failure caused by high-temperature softening of the traditional TiN-based hard alloy and simultaneously improving the hardness and fracture toughness.

The technical means adopted by the invention are as follows:

the TiN-NbC composite material comprises raw materials of niobium carbide micro powder and TiNx, wherein x is more than or equal to 0.3 and less than or equal to 0.9 or x is 1.1-1.3, the volume percentage of the niobium carbide micro powder is 10-40 vol.%, and the volume percentage of the TiNx is 60-90 vol.%.

The purity of the niobium carbide micro powder is more than 99 percent, and the granularity is 150nm and is fine; the particle size of TiNx is 150nm to be fine.

A preparation method of a TiN-NbC composite material comprises the following steps:

s1, performing ball milling on raw material powder consisting of titanium powder and urea, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 350-600 r/min, the ball milling is performed for 20-60 h, the ball milling is stopped for 20min every rotation for 60min, and then the TiNx with the granularity of 150nm and fine is prepared;

s2, performing ball milling and refining on the niobium carbide powder, wherein the mass ratio of ball materials is 10: 1-20: 1, the rotating speed is 250-450 r/min, the ball milling is performed for 10-40 h, 60min is performed every time, the machine is stopped for 10min for heat dissipation, and then the fine niobium carbide micro powder with the granularity of 150nm is prepared;

s3, adding the niobium carbide micro powder into the TiNx, performing ball milling and mixing, wherein the volume percentage of the niobium carbide micro powder is 10-40 vol%, the ball material mass ratio is 5: 1-10: 1, the ball milling rotation speed is 250-350 r/min, the ball milling is performed for 10h, 60min is performed every rotation, the machine is stopped for 20min to perform heat dissipation, the mixing of the TiNx and the niobium carbide micro powder is completed, the mixture of the mixed TiNx and the niobium carbide micro powder is filled into a hard alloy die to perform pre-pressing, the pre-pressing pressure is 100-500 MPa, 10-30S of pre-pressing is performed, a pre-pressed sample is obtained, then the pre-pressed sample is filled into a graphite die to perform hot-pressing sintering, the sintering pressure is 20-50 MPa, the sintering temperature is 1100-2000 ℃, the heat preservation is 10-120 min, and then the temperature is reduced and pressure is relieved, so.

Further, in the step S1, the molar ratio of the titanium powder to the urea powder in the raw material is 6:1, or 5:1, or 4:1, or 10:3, or 20:7, or 5:2, or 20:9, or 20:11, or 5:3, or 20: 13.

Furthermore, the particle size of the titanium powder is less than 30 μm, and the purity is more than 99.5%.

Furthermore, the dispersing agent is industrial ethanol with analytical purity of more than or equal to 99.7%, and 0.2-0.5 mL of dispersing agent is added into every 10g of powder.

Furthermore, the particle size of the niobium carbide powder is 1-3 mu m, and the purity is more than 99%.

Further, the ball milling processes of steps S1, S2 and S3 all use two kinds of WC cemented carbide balls of 5mm and 8 mm.

Further, the sintering process in step S3 is specifically: firstly, slowly applying pressure to a pre-pressed sample to 20-50 MPa; then, heating from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, and preserving the heat at 1000 ℃ for 10 min; and then heating the mixture from 1000 ℃ to 1100-2000 ℃ at a heating rate of 20 ℃/min, preserving the heat for 10-120 min, cooling the mixture along with the furnace to obtain a blank, and carrying out surface grinding and deburring treatment on the prepared blank to finally obtain the metal-free bonding phase non-stoichiometric TiN-NbC composite material. (ii) a

And in the sintering process, the vacuum degree in the furnace is 10-40 Pa before the furnace temperature is 400 ℃, and after the furnace temperature is heated to 400 ℃, the furnace is filled with nitrogen for protection.

The raw material ratio of TiNx is shown in the following table:

TABLE 1 preparation of TiN_xThe raw materials and the mass ratio thereof

TABLE 2 preparation of TiN_1.1-1.3The raw materials and the mass ratio thereof

Compared with the prior art, the invention has the following advantages:

the invention mixes non-stoichiometric TiNx prepared by a mechanical alloying Method (MA) with refined niobium carbide powder, adopts hot-pressing sintering (HP) to prepare the metal-free bonding phase TiN-NbC composite material, utilizes the vacancy in the TiNx to reduce the sintering temperature to promote sintering, and forms the metal-free bonding agent TiN-NbC composite material by composite sintering with niobium carbide and other transition group refractory carbides on the basis, thereby overcoming the defect of performance failure caused by high-temperature softening of the traditional TiN-based hard alloy and simultaneously improving the hardness and fracture toughness of the TiN-based hard alloy.

For the reasons, the invention can be widely popularized in the fields of material synthesis and the like.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 shows 70 vol.% TiN at a sintering temperature of 1300-1600 ℃ in accordance with one embodiment of the present invention_0.3-30 vol.% NbC sintered body XRD spectrum.

FIG. 2 shows TiN with different NbC additions at 1500 ℃ in accordance with an embodiment of the present invention_0.3SEM images of fractures of NbC composite sintered bodies, wherein a) and e) represent 10 vol.%, b) and f) represent 20 vol.%, c) and g) represent 30 vol.%, d) and h) represent 40 vol.%.

Detailed Description

It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. Any specific values in all examples shown and discussed herein are to be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.

In the description of the present invention, it is to be understood that the orientation or positional relationship indicated by the directional terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal" and "top, bottom", etc., are generally based on the orientation or positional relationship shown in the drawings, and are used for convenience of description and simplicity of description only, and in the absence of any contrary indication, these directional terms are not intended to indicate and imply that the device or element so referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore should not be considered as limiting the scope of the present invention: the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.

Spatially relative terms, such as "above … …," "above … …," "above … …," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial relationship to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is turned over, devices described as "above" or "on" other devices or configurations would then be oriented "below" or "under" the other devices or configurations. Thus, the exemplary term "above … …" can include both an orientation of "above … …" and "below … …". The device may be otherwise variously oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

It should be noted that the terms "first", "second", and the like are used to define the components, and are only used for convenience of distinguishing the corresponding components, and the terms have no special meanings unless otherwise stated, and therefore, the scope of the present invention should not be construed as being limited.

Example 1

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_0.3The formula table of the raw materials is as follows:

TABLE 3 raw materials prescription Table (40g)

s1, putting raw material powder consisting of 33.1g of titanium powder and 6.9g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, the ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the ball mill into an operation cavity of the ball mill, covering a sealing cover, taking the ball mill into the ball mill under the condition of ensuring that the ball mill rotates at the speed of 350r/min and rotates for 60min every time, stopping the machine for 20min for heat dissipation, and ball milling for 60h to obtain TiN_0.3；

S2, ball milling and thinning the niobium carbide powder, wherein the ball-material ratio is 10:1, the rotating speed is 300r/min, ball milling is carried out for 40h, each rotation is 60min, the machine is stopped for 10min for heat dissipation, and the thinned niobium carbide micro powder with the particle size of 150nm is prepared;

s3, mixing 28g of TiN_0.3Mixing the powder and 12g of refined NbC micro powder in a ball mill for 10h at a ball-to-material ratio of 5:1 and a ball milling rotation speed of 300r/min, and putting TiN in a glove box_0.3And filling the mixture of the niobium carbide micro powder and the niobium carbide micro powder into a hard alloy die for prepressing, wherein the prepressing pressure is 100MPa, the prepressing time is 10s, and then putting the prepressed sample into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the temperature rise rate of 20 ℃/min, preserving the heat for 10min at the temperature of 1000 ℃, raising the temperature from 1000 ℃ to 1300 ℃ at the temperature rise rate of 20 ℃/min, slowly applying pressure to the sintered body to 20MPa, and preserving the heat for 120min to obtain the TiN_0.3-NbC。

After grinding and polishing the TiN0.3-NbC composite material sample subjected to hot-pressing sintering, carrying out tissue and performance detection, wherein the obtained sintered block has the following technical parameters:

table 4 technical parameters and specific values of composite sintered body in example 1

Example 2

A TiN-NbC composite material, which has the same raw material ratio as that in example 1, and the manufacturing method thereof is different from that in example 1 in step S3:

28g of TiN were added as shown in Table 3_0.3Mixing the powder and 12g of refined NbC powder in a ball mill for 10h at a ball-to-material ratio of 5:1 and a ball milling rotation speed of 300r/min, and adding TiN in a glove box_0.3And the niobium carbide powder mixture is filled into a hard alloy die for prepressing, the prepressing pressure is 100MPa, the prepressing time is 10s, and then the prepressed sample is filled into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the temperature rise rate of 20 ℃/min, preserving heat for 10min at the temperature of 1000 ℃, raising the temperature from 1000 ℃ to 1400 ℃ at the temperature rise rate of 20 ℃/min, slowly applying pressure to the sintered body to 20MPa, and preserving heat for 90min to obtain the TiN_0.3-NbC composite material.

TiN after hot pressing sintering_0.3And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 5 technical parameters and specific values of composite sintered body in example 2

Example 3

28g of TiN were added as shown in Table 3_0.3Mixing the powder and 12g of refined NbC micro powder in a ball mill for 10h at a ball-to-material ratio of 5:1 and a ball milling rotation speed of 300r/min, and putting TiN in a glove box_0.3And filling the mixture of the niobium carbide micro powder and the niobium carbide micro powder into a hard alloy die for prepressing, wherein the prepressing pressure is 100MPa, the prepressing time is 10s, and then putting the prepressed sample into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: heating from room temperature to 1000 deg.C at a rate of 20 deg.C/min, maintaining at 1000 deg.C for 10min, heating from 1000 deg.C to 1500 deg.C at a rate of 20 deg.C/min, slowly applying pressure to the sintered body to 20MPa, and maintaining for 60min to obtain TiN_0.3-NbC composite material.

TABLE 6 technical parameters and specific values of composite sintered body in example 3

Example 4

28g of TiN were added as shown in Table 3_0.3Powder with 12g ofMixing the refined NbC micro powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 300r/min, and adding TiN in a glove box_0.3And filling the mixture of the niobium carbide micro powder and the niobium carbide micro powder into a hard alloy die for prepressing, wherein the prepressing pressure is 200MPa, the prepressing time is 10s, and then putting the prepressed sample into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, preserving the heat for 10min at 1000 ℃, raising the temperature from 1000 ℃ to 1600 ℃ at the heating rate of 20 ℃/min, and meanwhile slowly applying pressure to the sintered body to 20MPa, and preserving the heat for 30 min.

TABLE 7 technical parameters and specific values of composite sintered body in example 4

Example 5

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_0.4The formula table of the raw materials is as follows:

TABLE 8 raw materials prescription Table (40g)

s1, putting raw material powder consisting of 32g of titanium powder and 8g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, a ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the ball mill into an operation cavity of the ball mill, covering a sealing cover with the used gas, taking the ball mill into the ball mill under the condition of ensuring that the gas in the tube is argon, enabling the ball mill to rotate at the speed of 400r/min, rotating for 60min every time, stopping the machine for 20min for heat dissipation, and performing ball milling for 20h to obtain TiN_0.4；

S2, ball milling and thinning the niobium carbide powder, wherein the ball-material ratio is 10:1, the rotating speed is 400r/min, ball milling is carried out for 20h, each rotation is 60min, the machine is stopped for 10min for heat dissipation, and the thinned niobium carbide micro powder with the particle size of 150nm is prepared;

s3, mixing 36g of TiN_0.4Mixing the powder and 4g of refined NbC micro powder in a ball mill for 10h at a ball-to-material ratio of 5:1 and a ball milling rotation speed of 350r/min, and putting TiN in a glove box_0.4And filling the mixture of the niobium carbide micro powder and the niobium carbide micro powder into a hard alloy die for prepressing, wherein the prepressing pressure is 200MPa, the prepressing time is 20s, and then putting the prepressed sample into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: heating from room temperature to 1000 deg.C at a rate of 20 deg.C/min, maintaining at 1000 deg.C for 10min, heating from 1000 deg.C to 1500 deg.C at a rate of 20 deg.C/min, slowly applying pressure to the sintered body to 40MPa, and maintaining for 60min to obtain TiN_0.4-NbC composite material.

TiN after hot pressing sintering_0.4And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 9 technical parameters and specific values of composite sintered body in example 5

Example 6

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_0.5The formula table of the raw materials is as follows:

TABLE 10 raw materials prescription Table (40g)

s1, putting raw material powder consisting of 30.48g of titanium powder and 9.52g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 10:1, and ball milling media are hard materials with the diameters of 8mm and 5mmRepeatedly washing the alloy balls in a glove box transition bin, putting the alloy balls into an operation cavity of a ball mill, covering a sealing cover with argon gas, taking the alloy balls out under the condition of ensuring that the alloy balls in the tube are in an argon gas environment, putting the alloy balls into the ball mill, performing ball milling at the rotating speed of 450r/min for 60min every time, stopping the ball mill for 20min for heat dissipation, and preparing TiN after ball milling for 40h_0.5；

S2, ball milling and thinning the niobium carbide powder, wherein the ball-material ratio is 10:1, the rotating speed is 450r/min, ball milling is carried out for 20h, each rotation is 60min, the machine is stopped for 10min for heat dissipation, and 130nm thinned niobium carbide micro powder is prepared;

s3, mixing 32g of TiN_0.5Mixing the powder and 8g of refined NbC micro powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 350r/min, and adding TiN in a glove box_0.5And filling the mixture of the niobium carbide micro powder and the niobium carbide micro powder into a hard alloy die for prepressing, wherein the prepressing pressure is 300MPa, the prepressing time is 20s, and then putting the prepressed sample into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at a heating rate of 20 ℃/min, preserving the heat at 1000 ℃ for 10min, raising the temperature from 1000 ℃ to 1500 ℃ at a heating rate of 20 ℃/min, slowly applying pressure to the sintered body to 50MPa, and preserving the heat for 60min to obtain TiN_0.5-NbC composite material.

TiN after hot pressing sintering_0.5And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 11 technical parameters and specific values of composite sintered body in example 6

Example 7

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_0.6The formula table of the raw materials is as follows:

TABLE 12 raw materials prescription Table (40g)

s1, putting raw material powder consisting of 29.09g of titanium powder and 10.91g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball material ratio is 10:1, a ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the mixture into an operation cavity of a ball mill, covering a sealing cover, taking the mixture out of the ball mill under the condition of ensuring that the argon gas in a tube is in the environment, putting the mixture into the ball mill at the ball milling speed of 600r/min, performing heat dissipation after each rotation for 60min, stopping the ball mill for 20 hours to prepare TiC_0.6；

S2, ball milling and thinning the niobium carbide powder, wherein the ball-material ratio is 10:1, the rotating speed is 450r/min, ball milling is carried out for 30h, each rotation is 60min, the machine is stopped for 10min for heat dissipation, and the thinned niobium carbide micro powder with the particle size of 110nm is prepared;

s3, mixing 24g of TiN_0.6Mixing the powder and 16g of refined NbC powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 350r/min, and adding TiN in a glove box_0.6And the niobium carbide powder mixture is filled into a hard alloy die for prepressing, the prepressing pressure is 300MPa, the prepressing time is 10s, and then the prepressed sample is filled into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, preserving the heat for 10min at 1000 ℃, raising the temperature from 1000 ℃ to 1600 ℃ at the heating rate of 20 ℃/min, and simultaneously slowly applying pressure to the sintered body to 30MPa, and preserving the heat for 60 min.

TiN after hot pressing sintering_0.6And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 13 technical parameters and specific values of composite sintered body in example 7

Example 8

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_0.7The formula table of the raw materials is as follows:

TABLE 14 raw materials prescription Table (40g)

s1, putting raw material powder consisting of 27.83g of titanium powder and 12.17g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, the ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the ball mill into an operation cavity of the ball mill, covering a sealing cover, taking the ball mill into the ball mill under the condition of ensuring that the ball mill rotates at the speed of 600r/min and rotates for 60min every time, stopping the machine for 20min for heat dissipation, and ball milling for 30h to obtain TiN_0.7；

S2, ball milling and thinning the niobium carbide powder, wherein the ball-material ratio is 20:1, the rotating speed is 300r/min, ball milling is carried out for 40h, each rotation is carried out for 60min, the machine is stopped for 10min, and the thinned niobium carbide micro powder with the particle size of 80nm is prepared;

s3, mixing 28g of TiN_0.7Mixing the powder and 12g of refined NbC powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 300r/min, and adding TiN in a glove box_0.7And the niobium carbide powder mixture is filled into a hard alloy die for prepressing, the prepressing pressure is 400MPa, the prepressing time is 20s, and then the prepressed sample is filled into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, preserving the heat for 10min at 1000 ℃, raising the temperature from 1000 ℃ to 1600 ℃ at the heating rate of 20 ℃/min, and meanwhile slowly applying pressure to the sintered body to 40MPa, and preserving the heat for 60 min.

TiN after hot pressing sintering_0.7And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 15 technical parameters and specific values of composite sintered body in example 8

Example 9

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_0.8The formula table of the raw materials is as follows:

TABLE 16 raw materials prescription Table (40g)

s1, putting raw material powder consisting of 26.67g of titanium powder and 13.33g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, the ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the ball mill into an operation cavity of the ball mill, covering a sealing cover, taking the ball mill into the ball mill under the condition of ensuring that the ball mill rotates at the speed of 600r/min and rotates for 60min every time, stopping the machine for 20min for heat dissipation, and preparing TiN after ball milling for 40h_0.8；

s3, mixing 28g of TiN_0.8Mixing the powder and 12g of refined NbC micro powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 350r/min, and adding TiN in a glove box_0.8And the niobium carbide powder mixture is filled into a hard alloy die for prepressing, the prepressing pressure is 500MPa, the prepressing time is 20s, and then the prepressed sample is filled into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: heating to 1000 deg.C at a heating rate of 20 deg.C/min, maintaining at 1000 deg.C for 10min, and heating to 20 deg.CThe temperature rise rate per minute is increased from 1000 ℃ to 1700 ℃, meanwhile, the pressure is slowly applied to the sintered body to 50MPa, and the temperature is kept for 60 minutes.

TiN after hot pressing sintering_0.8And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 17 technical parameters and specific values of composite sintered body in example 9

Example 10

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_0.9The formula table of the raw materials is as follows:

watch 18 raw material prescription table (40g)

S1, putting raw material powder consisting of 25.6g of titanium powder and 14.4g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, the ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the ball mill into an operation cavity of the ball mill, covering a sealing cover, taking the ball mill into the ball mill under the condition of ensuring that the ball mill rotates at the speed of 500r/min and rotates for 60min every time, stopping the machine for 20min for heat dissipation, and preparing TiN after ball milling for 40h_0.9；

S2, ball milling and thinning the niobium carbide powder, wherein the ball-material ratio is 20:1, the rotating speed is 450r/min, ball milling is carried out for 40h, each rotation is 60min, the machine is stopped for 10min for heat dissipation, and 80nm thinned niobium carbide micro powder is prepared;

s3, mixing 28g of TiN_0.9Mixing the powder and 12g of refined NbC micro powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 350r/min, and adding TiN in a glove box_0.9And the niobium carbide powder mixture is filled into a hard alloy die for prepressing with the prepressing pressure of 500MPa for 30s, and then the prepressed sample is filled into the dieAnd carrying out hot-pressing sintering in the graphite mould. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, preserving the heat for 10min at 1000 ℃, raising the temperature from 1000 ℃ to 1800 ℃ at the heating rate of 20 ℃/min, and meanwhile slowly applying pressure to the sintered body to 50MPa, and preserving the heat for 30 min.

TiN after hot pressing sintering_0.9And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 19 technical parameters and specific values of composite sintered body in example 10

Example 11

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_1.1The formula table of the raw materials is as follows:

watch 20 raw material prescription table (40g)

s1, putting raw material powder consisting of 23.16g of titanium powder and 16.84g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, the ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the ball mill into an operation cavity of the ball mill, covering a sealing cover, taking the ball mill into the ball mill under the condition of ensuring that the ball mill rotates at the speed of 600r/min and rotates for 60min every time, stopping the machine for 20min for heat dissipation, and performing ball milling for 40h to obtain TiN_1.1；

s3, mixing 28g of TiN_1.1Mixing the powder and 12g of refined NbC powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 350r/min, and adding TiN in a glove box_1.1And the niobium carbide powder mixture is filled into a hard alloy die for prepressing, the prepressing pressure is 500MPa, the prepressing time is 20s, and then the prepressed sample is filled into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at a heating rate of 20 ℃/min, preserving the heat for 10min at 1000 ℃, raising the temperature from 1000 ℃ to 1900 ℃ at a heating rate of 20 ℃/min, and meanwhile slowly applying pressure to the sintered body to 50MPa, and preserving the heat for 20 min.

TiN after hot pressing sintering_1.1And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 21 technical parameters and specific values of composite sintered body in example 11

Example 12

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_1.2The formula table of the raw materials is as follows:

TABLE 22 raw materials prescription Table (40g)

s1, putting a hard alloy tank into raw material powder consisting of 22.86g of titanium powder and 17.14g of urea, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, the ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the ball mill into an operation cavity of the ball mill, covering a sealing cover, taking the ball mill into the ball mill under the condition of ensuring that the ball mill rotates at the speed of 600r/min and rotates for 60min every time, stopping the machine for 20min for heat dissipation, and performing ball milling for 40h to obtain TiN_1.2；

s3, mixing 28g of TiN_1.2Mixing the powder and 12g of refined NbC powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 350r/min, and adding TiN in a glove box_1.2And the niobium carbide powder mixture is filled into a hard alloy die for prepressing, the prepressing pressure is 500MPa, the prepressing time is 30s, and then the prepressed sample is filled into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, preserving the heat for 10min at 1000 ℃, raising the temperature from 1000 ℃ to 1600 ℃ at the heating rate of 20 ℃/min, and meanwhile slowly applying pressure to the sintered body to 50MPa, and preserving the heat for 60 min.

TiN after hot pressing sintering_1.2And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 23 technical parameters and specific values of composite sintered body in example 12

Example 13

TABLE 24 raw materials prescription Table (40g)

s1, putting raw material powder consisting of 22.86g of titanium powder and 17.14g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, and the ball-milling medium is hard alloy with the diameter of 8mm and 5mmRepeatedly washing the balls in a glove box transition bin, putting the balls into an operation cavity of a ball mill, covering a sealing cover with argon gas, taking the balls out under the condition of ensuring that the argon gas in the tube is in an argon gas environment, putting the balls into the ball mill, performing ball milling at the rotating speed of 600r/min for 60min every time, stopping the ball mill for 20min for heat dissipation, and preparing TiN after ball milling for 40h_1.2；

s3, mixing 28g of TiN_1.2Mixing the powder and 12g of refined NbC powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 350r/min, and adding TiN in a glove box_1.2And the niobium carbide powder mixture is filled into a hard alloy die for prepressing, the prepressing pressure is 500MPa, the prepressing time is 30s, and then the prepressed sample is filled into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, preserving the heat for 10min at 1000 ℃, raising the temperature from 1000 ℃ to 2000 ℃ at the heating rate of 20 ℃/min, and meanwhile slowly applying pressure to the sintered body to 50MPa, and preserving the heat for 10 min.

TABLE 25 technical parameters and specific values of composite sintered body in example 13

Example 14

A TiN-NbC composite material is prepared from niobium carbide micropowder and TiN_1.3The formula table of the raw materials is as follows:

watch 26 raw material prescription table (40g)

s1, putting raw material powder consisting of 22.07g of titanium powder and 17.93g of urea into a hard alloy tank, adding industrial ethanol serving as a dispersing agent, wherein the ball-material ratio is 20:1, a ball milling medium is hard alloy balls with the diameters of 8mm and 5mm, repeatedly washing gas in a glove box transition bin, putting the ball mill into an operation cavity of the ball mill, covering a sealing cover, taking the ball mill into the ball mill under the condition of ensuring that the ball mill rotates at the speed of 600r/min and rotates for 60min every time, stopping the machine for 20min for heat dissipation, and preparing TiN after ball milling for 40h_1.3；

s3, mixing 28g of TiN_1.3Mixing the powder and 12g of refined NbC powder in a ball mill for 10h at a ball-to-material ratio of 10:1 and a ball milling rotation speed of 350r/min, and adding TiN in a glove box_1.3And the niobium carbide powder mixture is filled into a hard alloy die for prepressing, the prepressing pressure is 500MPa, the prepressing time is 30s, and then the prepressed sample is filled into a graphite die for hot-pressing sintering. Placing the graphite mold on a sintering table, wherein the temperature rising system is as follows: raising the temperature from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, preserving the heat for 10min at 1000 ℃, raising the temperature from 1000 ℃ to 1600 ℃ at the heating rate of 20 ℃/min, and meanwhile slowly applying pressure to the sintered body to 50MPa, and preserving the heat for 90 min.

TiN after hot pressing sintering_1.3And (3) carrying out tissue and performance detection on the-NbC composite material sample after grinding and polishing, wherein the obtained sintered block has the following technical parameters:

TABLE 26 technical parameters and specific values of composite sintered body in example 10

The data in the above embodiments show that:

it is clear from examples 1 to 14 that the sintering temperature and the TiNx content have a large influence on the properties of the composite material.

Through the examples 1, 5, 6, 7 and 10, it is known that the ball mill rotation speed, the operation time, the ball-material mass ratio and the alcohol addition amount have little influence on the performance of the composite material, and the main influence factors are the sintering temperature and the holding time.

It can be seen from examples 1 to 4 that as the sintering temperature is increased and the sintering time is decreased, the density and hardness of the composite material increase and the fracture toughness tends to increase.

It is clear from examples 4 to 7 that the density and hardness of the composite material increased with increasing NbC content, while the toughness remained almost unchanged.

It can be seen from examples 8 to 11 and 13 that the density, hardness and fracture toughness of the composite material increase with the increase of the sintering temperature, wherein the hardness increase is more obvious.

It is understood from examples 5, 10, 12 and 14 that the density, hardness and toughness of the composite material are reduced as the number of voids decreases as the x value increases in TiNx.

As is clear from examples 7, 8 and 9, the density, hardness and toughness of the composite material become higher as the sintering pressure becomes higher.

As can be seen from examples 3, 4, 6, 8 and 9, the density, hardness and toughness of the composite material become higher as the pre-stress increases.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. The TiN-NbC composite material is characterized in that raw materials of the TiN-NbC composite material comprise niobium carbide micro-powder and TiNx, wherein x is more than or equal to 0.3 and less than or equal to 0.9 or x is 1.1-1.3, the volume percentage of the niobium carbide micro-powder is 10-40 vol%, and the volume percentage of the TiNx is 60-90 vol%.

2. The TiN-NbC composite of claim 1, wherein: the purity of the niobium carbide micro powder is more than 99 percent, and the granularity is 150nm and is fine; the particle size of TiNx is 150nm to be fine.

3. A method for preparing the TiN-NbC composite material as claimed in any one of claims 1 to 2, wherein: the method comprises the following steps:

4. The method of claim 3, wherein the TiN-NbC composite material comprises: in the step S1, the molar ratio of the titanium powder to the urea powder in the raw material is 6:1, or 5:1, or 4:1, or 10:3, or 20:7, or 5:2, or 20:9, or 20:11, or 5:3, or 20: 13.

5. The method of claim 3, wherein the TiN-NbC composite material comprises: the grain size of the titanium powder is less than 30 mu m, and the purity is more than 99.5 percent.

6. The method of claim 3, wherein the TiN-NbC composite material comprises: in the step S1, a dispersant is used in the ball milling process, and the dispersant is industrial ethanol with an analytical purity of not less than 99.7%, and 0.2-0.5 mL of the dispersant is added to each 10g of the raw material powder.

7. The method of claim 3, wherein the TiN-NbC composite material comprises: the niobium carbide powder has a particle size of 1-3 mu m and a purity of more than 99%.

8. The TiN-NbC composite material according to claim 3, wherein: the ball milling process of the steps S1, S2 and S3 adopts two types of WC hard alloy balls of 5mm and 8 mm.

9. The method of claim 3, wherein the TiN-NbC composite material comprises: the sintering process in the step S3 includes: firstly, slowly applying pressure to a pre-pressed sample to 20-50 MPa; then, heating from room temperature to 1000 ℃ at the heating rate of 20 ℃/min, and preserving the heat at 1000 ℃ for 10 min; heating the mixture from 1000 ℃ to 1100-2000 ℃ at a heating rate of 20 ℃/min, preserving the heat for 10-120 min, cooling the mixture along with a furnace to obtain a blank, and grinding and deburring the surface of the prepared blank to obtain the TiN-NbC composite material;