CN112239360A - Boron oxide, magnesium oxide and reaction product thereof synergistically toughened tungsten carbide composite material and preparation thereof - Google Patents

Boron oxide, magnesium oxide and reaction product thereof synergistically toughened tungsten carbide composite material and preparation thereof Download PDF

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CN112239360A
CN112239360A CN202011009853.3A CN202011009853A CN112239360A CN 112239360 A CN112239360 A CN 112239360A CN 202011009853 A CN202011009853 A CN 202011009853A CN 112239360 A CN112239360 A CN 112239360A
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composite material
tungsten carbide
sintering
mgo
magnesium oxide
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李小强
赖佳明
李京懋
曹廷
吴祖骥
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of tungsten carbide materials, and discloses a tungsten carbide composite material toughened by boron oxide, magnesium oxide and reaction products thereof in a synergistic manner and a preparation method thereof. The composite material is prepared from tungsten carbide WC and B2O3Is prepared by mixing with MgO; wherein the content of tungsten carbide is 90-98 wt%, and the balance is B2O3With MgO and unavoidable impurities, B2O3And MgO is used in an amount such that the atomic ratio of Mg to B is 1: (0.9-1.1). The invention also discloses a preparation method of the composite material. According to the invention, by adding the boron oxide and the magnesium oxide, the sintering temperature of the composite material is obviously reduced, and the fracture toughness of the composite material is improved. The prepared WC composite material without any metal binding phase has high hardness, toughness and wear resistanceGood performance, oxidation resistance and better corrosion resistance.

Description

Boron oxide, magnesium oxide and reaction product thereof synergistically toughened tungsten carbide composite material and preparation thereof
Technical Field
The invention belongs to the technical field of alloy materials, and particularly relates to a tungsten carbide composite material toughened by boron oxide, magnesium oxide and reaction products thereof in a synergistic manner and a preparation method thereof.
Background
The tungsten carbide-cobalt (WC-Co) hard alloy has high hardness, high wear resistance and excellent fracture toughness, so that the tungsten carbide-cobalt (WC-Co) hard alloy is widely applied to the fields of mining, oil drilling, metal cutting and the like which are closely combined with national economic development, and is the most widely applied hard alloy at present. The WC-Co hard alloy mainly comprises a hard phase WC and a binder phase Co, the Co has excellent wettability to WC, the addition of the Co is favorable for obtaining the high-density WC-based hard alloy, but the addition of the Co inevitably causes the reduction of the hardness, the oxidation resistance, the corrosion resistance and other properties of the WC-based hard alloy, and the Co is easy to soften at high temperature, and the defects limit the application of the WC-Co hard alloy under the severer working condition. With the continuous development of science and technology, the application working condition of WC-based hard alloy becomes worse, and the traditional WC-Co hard alloy cannot adapt to the increasing use requirement more and more, so that the development of the binderless WC hard alloy which can adapt to the bad working condition becomes the key point of research in the field.
WC is a very hard and very wear-resistant substance, is mainly bonded by covalent bonds, and therefore has high strength and melting point, and also has the intrinsic brittleness of a ceramic material. The pure WC material has high sintering temperature, high brittleness and poor toughness of only 4-6 Mpa.m1/2(Tang W.,Zhang L.,Zhu J.F.,et al.Effect of direct current patterns on densification and mechanical properties of binderless tungsten carbides fabricated by the spark plasma sintering system[J].International Journal of Refractory Metals&Hard Materials,2517,64:90-97), the compactness is relatively low, and the defects limit the application of pure WC Materials, so that a strengthening and toughening means of the WC material must be explored, and the toughness of the WC material is improved by using a second phase, so that the WC material can meet the requirements of practical application.
At present, the research on strengthening and toughening of WC materials mainly focuses on two aspects, one is to adopt a mode of adding second-phase ceramic particles to improve the fracture toughness of the WC materials and simultaneously keep higher hardness, and the ceramic particles mainly comprise MgO and Al2O3And ZrO2Ceramic particle toughening machineThe principle is crack deflection, crystal-crossing fracture, phase change toughening and the like; secondly, the fracture toughness of the WC material is improved by adopting a whisker toughening mode, the crack propagation length is reduced by utilizing the bridging effect of the whisker on the crack, the energy consumption of pulling out the whisker during fracture, the crack penetrating through the whisker and the like, so that the fracture toughness is improved, and the commonly used whisker mainly comprises SiC and Si3N4And the like. Both of these strengthening ways can improve the fracture toughness of WC materials to some extent, but these second phases are mainly oxides or carbides, which have very high melting points and thus require very high temperatures to sinter the materials densely, and the sintering temperature will be close to 1800 ℃ (Zheng D, Li X, Li Y, et al. in-situ bonded β -Si3N4 grains sintered WC composites one/two-step sintered plate sintering [ J ] J].Materials Science&Engineering A Structural Materials Properties Microstructure&Processing,2513,561(none), which is much higher than the sintering temperature (1400-1500 ℃) of the traditional WC-Co hard alloy, and is a great challenge to the application of the non-bonding phase WC hard alloy.
The invention introduces a small amount of B into WC powder2O3With MgO powder, using B2O3Magnesium borate whisker generated by reacting with MgO at low temperature improves the fracture toughness of WC material to a great extent, and B2O3The liquid phase generated in the sintering process can improve the sintering performance of the composite material and the bonding performance of a WC and MgO particle interface, and the WC composite material with high compactness and high bonding strength is obtained at lower temperature.
Disclosure of Invention
In order to solve the defects of over high sintering temperature and poor fracture toughness of the binderless WC material, the invention firstly aims to provide a binder B2O3WC composite material toughened by cooperation with MgO and reaction products thereof.
It is another object of the present invention to provide the above-mentioned uses B2O3A method for preparing WC composite material toughened by cooperation with MgO and reaction products thereof.
The purpose of the invention is realized by the following technical scheme:
by means of B2O3WC composite material (namely, tungsten carbide composite material toughened by boron oxide, magnesium oxide and reaction products thereof) synergistically with MgO and reaction products thereof is prepared from tungsten carbide and B2O3Is prepared by mixing with MgO; wherein the content of tungsten carbide is 90-98 wt%, and the balance is B2O3With MgO and unavoidable impurities, B2O3And MgO is used in an amount such that the atomic ratio of Mg to B is 1: (0.9-1.1).
Above mentioned adopt B2O3The preparation method of the WC composite material toughened by cooperating with MgO and reaction products thereof comprises the following steps:
(1) mixing WC powder, MgO powder and B2O3Performing wet ball milling on the powder to obtain slurry; an organic solvent is adopted in the wet ball milling;
(2) removing the solvent in the slurry to obtain composite powder; the particle size of the composite powder is less than or equal to 65 mu m; removing the solvent in the slurry, and sieving to obtain composite powder with the particle size of less than or equal to 65 mu m;
(3) and sintering the composite powder to obtain the tungsten carbide composite material toughened by the boron oxide, the magnesium oxide and the reaction product thereof in a synergistic manner.
The sintering in the step (3) is sintering by adopting a spark plasma sintering technology; the specific sintering conditions were as follows:
the type of the sintering current is direct current pulse current;
sintering pressure: 30-50 MPa;
sintering atmosphere: the low vacuum is less than or equal to 6 Pa;
the heating rate is as follows: 50-250 ℃/min;
sintering temperature: 1250-1550 ℃;
and (3) heat preservation time: 5-30 min.
The sintering temperature is preferably 1400 ℃.
And (2) during the wet ball milling in the step (1), the organic solvent adopted is ethanol. The wet ball milling time is more than 25 h.
The step (2) of removing the solvent in the slurry is drying until the residual mass of the solvent is less than or equal to 2 percent.
The composite material and the preparation method have the following advantages and beneficial effects:
(1) the invention adds B into pure WC2O3And MgO, B2O3Can form liquid phase at lower temperature, the flow of the liquid phase is helpful for the densification of the composite material, and the liquid phase B2O3The magnesium borate crystal whisker can be generated in situ by reacting with MgO in the flowing process, and the generation of the crystal whisker can greatly improve the fracture toughness of the WC material;
(2) the invention introduces B into the cemented carbide without binding phase2O3After being mixed with MgO, the mixture can form a liquid phase at a low temperature, so that the sintering temperature of the WC hard alloy without the metal binding phase can be greatly reduced, and the hard alloy material without the metal binding phase with higher comprehensive mechanical property can be obtained at a lower temperature;
(3) the WC composite material prepared by the invention adopts B2O3The WC composite material which is toughened by the MgO and the reaction product, namely the magnesium borate whisker, and does not contain any metal binding phase has high hardness and high toughness, good wear resistance, oxidation resistance, corrosion resistance and the like, and is suitable for being used as a cutter material or a die material.
Drawings
FIG. 1 shows the results obtained in example 2 using B2O3A tissue back scattering scanning electron microscope photograph of the WC composite material toughened by cooperation with MgO and reaction products thereof;
FIG. 2 shows the result of example 5, wherein B is2O3Growing a back scattering scanning electron microscope photo of the magnesium borate crystal whisker with a certain length-diameter ratio with the MgO and the reaction product thereof for toughening the WC composite material cooperatively;
FIG. 3 shows the result of example 6, wherein B is used2O3And (3) performing a back scattering Scanning Electron Microscope (SEM) picture on the WC composite material structure toughened by cooperation of the MgO and the reaction product thereof to grow coarse magnesium borate whiskers.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
One kind of this embodiment adopts B2O3The WC composite material toughened by cooperating with MgO and reaction products thereof is prepared by the following method:
(1) 98g of WC (0.8 μm, purity)>99.9%, mansion heron limited), 0.92g B2O3(AR>98 percent of alatin), 1.08g of MgO (45um, Zhongnuo new materials Co., Ltd.) is poured into a 250ml hard alloy tank, ethanol is added as a solvent (the volume of the obtained mixed slurry does not exceed 2/3 of the volume of a ball milling tank) to obtain mixed slurry, and then the ball milling tank is placed on a planetary ball mill for wet ball milling (the rotating speed is 300r/min, the ball milling time is 30h) to obtain ball milling slurry;
(2) placing the ball-milling slurry in a vacuum drying oven to dry until the residual amount of the solvent is less than or equal to 2%, taking out the dried powder, grinding and sieving to obtain composite powder with the particle size of less than or equal to 65 mu m;
(3) 25g of composite powder is taken and filled into the inner diameter
Figure BDA0002697217590000041
And outer diameter
Figure BDA0002697217590000042
In the cylindrical graphite die, the powder, the female die and the punch are separated by graphite paper for demolding, and the female die is coated with a layer of graphite felt with the thickness of 10mm to reduce heat radiation loss; placing the graphite mould filled with the composite powder in a spark plasma sintering furnace for sintering to obtain a material B2O3And the WC composite material is toughened by cooperating with MgO and reaction products thereof. The sintering parameters are as follows: the type of the sintering current is direct current pulse current, the sintering atmosphere is low vacuum (less than or equal to 6Pa), the sintering pressure is 50MPa, the heating rate is 50 ℃/min, the temperature measurement mode is infrared temperature measurement (more than or equal to 570 ℃), the sintering temperature is 1250 ℃, and the heat preservation time is 25 min.
Obtained by this example Using B2O3In conjunction with MgO and reaction products thereofThe hardness of the WC composite material with the same toughness is HV measured1019.73 GPa; according to Vickers hardness indentation, the fracture toughness is calculated to be 8.73 MPa.m by adopting an indentation method1/2。
Example 2
One kind of this embodiment adopts B2O3The WC composite material toughened by cooperating with MgO and reaction products thereof is prepared by the following method:
(1) 94g of WC (0.8 μm, purity)>99.9%, mansion heron limited), 2.76g B2O3(AR>98 percent of alatin) and 3.24g of MgO (45um, Zhongnuo new materials Co., Ltd.) are poured into a 250ml hard alloy tank, ethanol is added as a solvent (the volume of the obtained mixed slurry does not exceed 2/3 of the volume of a ball milling tank) to obtain mixed slurry, and then the ball milling tank is placed on a planetary ball mill for wet ball milling (the rotating speed is 300r/min, the ball milling time is 30h) to obtain ball milling slurry;
(2) placing the ball-milling slurry in a vacuum drying oven to dry until the residual amount of the solvent is less than or equal to 2%, taking out the dried powder, grinding and sieving to obtain composite powder with the particle size of less than or equal to 65 mu m;
(3) 25g of composite powder is taken and filled into the inner diameter
Figure BDA0002697217590000051
And outer diameter
Figure BDA0002697217590000052
In the cylindrical graphite die, the powder, the female die and the punch are separated by graphite paper for demolding, and the female die is coated with a layer of graphite felt with the thickness of 10mm to reduce heat radiation loss; placing the graphite mould filled with the composite powder in a spark plasma sintering furnace for sintering to obtain a material B2O3WC composite material toughened by cooperation with MgO and reaction products thereof. The sintering parameters are as follows: the type of the sintering current is direct current pulse current, the sintering atmosphere is low vacuum (less than or equal to 6Pa), the sintering pressure is 40MPa, the heating rate is 250 ℃/min, the temperature measurement mode is infrared temperature measurement (more than or equal to 570 ℃), the sintering temperature is 1350 ℃, and the heat preservation time is 10 min.
Obtained by this example Using B2O3The hardness of the WC composite material toughened by the cooperation of the MgO and the reaction product is HV1017.22 GPa; according to Vickers hardness indentation, the fracture toughness of 9.91 MPa-m is calculated by adopting an indentation method1/2。
Obtained by this example Using B2O3The scanning electron microscope image of the WC composite material toughened by cooperating with MgO and the reaction product thereof is shown in figure 1.
Example 3
One kind of this embodiment adopts B2O3The WC composite material toughened by cooperating with MgO and reaction products thereof is prepared by the following method:
steps (1) to (2) are the same as in example 1;
(3) 25g of composite powder is taken and filled into the inner diameter
Figure BDA0002697217590000061
And outer diameter
Figure BDA0002697217590000062
In the cylindrical graphite die, the powder, the female die and the punch are separated by graphite paper for demolding, and the female die is coated with a layer of graphite felt with the thickness of 10mm to reduce heat radiation loss; placing the graphite mould filled with the composite powder in a spark plasma sintering furnace for sintering to obtain a material B2O3And the WC composite material is toughened by cooperating with MgO and reaction products thereof. The sintering parameters are as follows: the type of the sintering current is direct current pulse current, the sintering atmosphere is low vacuum (less than or equal to 6Pa), the sintering pressure is 30MPa, the heating rate is 150 ℃/min, the temperature measurement mode is infrared temperature measurement (more than or equal to 570 ℃), the sintering temperature is 1450 ℃, and the heat preservation time is 25 min.
Obtained by this example Using B2O3The hardness of the WC composite material toughened by cooperating with MgO and reaction products thereof is HV through measurement and calculation1017.62GPa and fracture toughness of 8.4 MPa.m1/2。
Example 4
One kind of this embodiment adopts B2O3The WC composite material toughened by cooperating with MgO and reaction products thereof is prepared by the following method:
steps (1) to (2) are the same as in example 1;
(3) 25g of composite powder is taken and filled into the inner diameter
Figure BDA0002697217590000063
And outer diameter
Figure BDA0002697217590000064
In the cylindrical graphite die, the powder, the female die and the punch are separated by graphite paper for demolding, and the female die is coated with a layer of graphite felt with the thickness of 10mm to reduce heat radiation loss; placing the graphite mould filled with the composite powder in a spark plasma sintering furnace for sintering to obtain a material B2O3And the WC composite material is toughened by cooperating with MgO and reaction products thereof. The sintering parameters are as follows: the type of the sintering current is direct current pulse current, the sintering atmosphere is low vacuum (less than or equal to 6Pa), the sintering pressure is 30MPa, the heating rate is 100 ℃/min, the temperature measurement mode is infrared temperature measurement (more than or equal to 570 ℃), the sintering temperature is 1550 ℃, and the heat preservation time is 15 min.
Obtained by this example Using B2O3The hardness of the WC composite material toughened by the cooperation of the MgO and the reaction product is HV1017.78GPa and fracture toughness of 10.08 MPa.m1/2。
Example 5
Adoption of this example B2O3The WC composite material toughened by cooperating with MgO and reaction products thereof is prepared by the following method:
(1) 92g of WC (0.8 μm, purity)>99.9%, mansion heron limited), 3.68g B2O3(AR>98 percent of alatin), 4.32g of MgO (45um, Zhongnuo new materials Co., Ltd.) is poured into a 250ml hard alloy tank, ethanol is added as a solvent (the volume of the obtained mixed slurry does not exceed 2/3 of the volume of a ball milling tank) to obtain mixed slurry, and then the ball milling tank is placed on a planetary ball mill for wet ball milling (the rotating speed is 300r/min, the ball milling time is 30h) to obtain ball milling slurry;
(2) placing the ball-milling slurry in a vacuum drying oven to dry until the residual amount of the solvent is less than or equal to 2%, taking out the dried powder, grinding and sieving to obtain composite powder with the particle size of less than or equal to 65 mu m;
(3) 25g of composite powder is taken and filled into the inner diameter
Figure BDA0002697217590000071
And outer diameter
Figure BDA0002697217590000072
In the cylindrical graphite die, the powder, the female die and the punch are separated by graphite paper for demolding, and the female die is coated with a layer of graphite felt with the thickness of 10mm to reduce heat radiation loss; placing the graphite mould filled with the composite powder in a spark plasma sintering furnace for sintering to obtain a material B2O3And the WC composite material is toughened by cooperating with MgO and reaction products thereof. The sintering parameters are as follows: the type of the sintering current is direct current pulse current, the sintering atmosphere is low vacuum (less than or equal to 6Pa), the sintering pressure is 30MPa, the heating rate is 100 ℃/min, the temperature measurement mode is infrared temperature measurement (more than or equal to 570 ℃), the sintering temperature is 1400 ℃, and the heat preservation time is 5 min.
Obtained by this example Using B2O3WC composite material synergistically toughened with MgO and reaction product thereof and hardness of WC composite material is HV1018.15 GPa; according to Vickers hardness indentation, the fracture toughness is calculated to be 10.33 MPa.m by adopting an indentation method1/2。
Obtained by this example Using B2O3The back scattering scanning electron microscope image of the WC composite material toughened by cooperating with MgO and the reaction product thereof is shown in figure 2.
Example 6
One kind of this embodiment adopts B2O3The WC composite material toughened by cooperating with MgO and reaction products thereof is prepared by the following method:
(1) 90g of WC (0.8 μm, purity)>99.9%, mansion heron limited), 4.60g B2O3(AR>98% of alatin), 5.40g of MgO (45um, zhongnuo new materials ltd), poured into a 250ml cemented carbide jar, added with ethanol as a solvent (the volume of the resulting mixed slurry does not exceed 2/3 of the volume of the ball milling jar) to obtain a mixed slurry, and then the ball milling jar was placed on a planetary ball mill for wet ball milling (rotary milling)The speed is 300r/min, the ball milling time is 30h), and ball milling slurry is obtained;
(2) placing the ball-milling slurry in a vacuum drying oven to dry until the residual amount of the solvent is less than or equal to 2%, taking out the dried powder, grinding and sieving to obtain composite powder with the particle size of less than or equal to 65 mu m;
(3) 25g of composite powder is taken and filled into the inner diameter
Figure BDA0002697217590000081
And outer diameter
Figure BDA0002697217590000082
In the cylindrical graphite die, the powder, the female die and the punch are separated by graphite paper for demolding, and the female die is coated with a layer of graphite felt with the thickness of 10mm to reduce heat radiation loss; placing the graphite mould filled with the composite powder in a spark plasma sintering furnace for sintering to obtain a material B2O3And the WC composite material is toughened by cooperating with MgO and reaction products thereof. The sintering parameters are as follows: the type of the sintering current is direct current pulse current, the sintering atmosphere is low vacuum (less than or equal to 6Pa), the sintering pressure is 50MPa, the heating rate is 250 ℃/min, and the temperature measurement mode is infrared temperature measurement (more than or equal to 570 ℃, the sintering temperature is 1450 ℃, and the heat preservation time is 30 min.
Obtained by this example Using B2O3WC composite material synergistically toughened with MgO and reaction product thereof and hardness of WC composite material is HV1016.32 GPa; according to Vickers hardness indentation, the fracture toughness is calculated to be 10.69 MPa.m by adopting an indentation method1/2。
The back scattering scanning electron microscope picture of the material obtained in this example is shown in fig. 3, and the obtained structure is different from those of examples 2 and 5 due to different components, and the length and diameter of the whisker are lower.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. A tungsten carbide composite material toughened by boron oxide, magnesium oxide and reaction products thereof is characterized in that: from tungsten carbide WC, B2O3Is prepared by mixing with MgO; wherein the content of tungsten carbide is 90-98 wt%, and the balance is B2O3With MgO and unavoidable impurities, B2O3And MgO is used in an amount such that the atomic ratio of Mg to B is 1: (0.9-1.1).
2. The method for preparing the boron oxide and magnesium oxide and the reaction product thereof for synergistically toughening the tungsten carbide composite material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) mixing WC powder, MgO powder and B2O3Performing wet ball milling on the powder to obtain slurry;
(2) removing the solvent in the slurry to obtain composite powder;
(3) sintering the composite powder to obtain a tungsten carbide composite material toughened by boron oxide, magnesium oxide and reaction products of the boron oxide and the magnesium oxide;
the sintering in the step (3) is sintering by adopting a spark plasma sintering technology; the specific sintering conditions are as follows:
the type of the sintering current is direct current pulse current;
sintering pressure: 30-50 MPa;
sintering atmosphere: the low vacuum is less than or equal to 6 Pa;
the heating rate is as follows: 50-250 ℃/min;
sintering temperature: 1250-1550 ℃;
and (3) heat preservation time: 5-30 min.
3. The method for preparing the boron oxide and magnesium oxide and the reaction product thereof for synergistically toughening the tungsten carbide composite material according to claim 2, wherein the method comprises the following steps: the sintering temperature was 1400 ℃.
4. The method for preparing the boron oxide and magnesium oxide and the reaction product thereof for synergistically toughening the tungsten carbide composite material according to claim 2, wherein the method comprises the following steps: an organic solvent is adopted in the wet ball milling in the step (1);
the particle size of the composite powder in the step (2) is less than or equal to 65 mu m.
5. The method for preparing the boron oxide and magnesium oxide and the reaction product thereof for synergistically toughening the tungsten carbide composite material according to claim 4, wherein the method comprises the following steps: in the wet ball milling in the step (1), ethanol is used as an organic solvent; the wet ball milling time is more than or equal to 25 h.
6. The method for preparing the boron oxide and magnesium oxide and the reaction product thereof for synergistically toughening the tungsten carbide composite material according to claim 2, wherein the method comprises the following steps: and (3) removing the solvent in the slurry in the step (2), and sieving to obtain composite powder with the particle size of less than or equal to 65 mu m.
7. The method for preparing the boron oxide and magnesium oxide and the reaction product thereof for synergistically toughening the tungsten carbide composite material according to claim 2, wherein the method comprises the following steps: the step (2) of removing the solvent in the slurry is drying until the residual mass of the solvent is less than or equal to 2 percent.
CN202011009853.3A 2020-09-23 2020-09-23 Boron oxide, magnesium oxide and reaction product thereof synergistically toughened tungsten carbide composite material and preparation thereof Pending CN112239360A (en)

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