CN112876253B - Low-temperature sintered high-toughness wear-resistant WC ceramic and preparation method thereof - Google Patents
Low-temperature sintered high-toughness wear-resistant WC ceramic and preparation method thereof Download PDFInfo
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Abstract
A low-temperature sintered high-toughness wear-resistant WC ceramic and a preparation method thereof relate to a ceramic material and a preparation method thereof. Aims at solving the problems of overhigh sintering temperature, poor toughness and insufficient wear resistance of the conventional WC ceramic. ZrO (zinc oxide) of high-toughness wear-resistant WC (Wt) ceramic with mass fraction of 4-10% 2 (Y 2 O 3 )‑Al 2 O 3 The composite powder, 0.1-1% of expanded graphite and the balance of WC powder. The method comprises the following steps: adding expanded graphite into liquid medium, ultrasonic stirring, and adding WC powder and ZrO 2 (Y 2 O 3 )‑Al 2 O 3 Compounding the powder to obtain a mixed solution; ball milling the mixed solution to obtain ceramic slurry, drying and screening to obtain ceramic powder; and sintering the ceramic powder to obtain the high-toughness wear-resistant WC ceramic. The invention adds the low-cost expanded graphite, reduces the cost and makes the industrial application field wider. The prepared WC ceramic is compact, and the fracture toughness and the wear resistance are improved.
Description
Technical Field
The invention relates to a ceramic material and a preparation method thereof.
Background
The tungsten carbide ceramic is a material with stable physical and chemical properties, high temperature resistance, wear resistance and extremely high hardness, and has wide application in cutting tools, mining, machinery and precise key parts under high temperature and high load. Although the tungsten carbide ceramic has excellent performance, the tungsten carbide ceramic has the problems of overhigh sintering temperature and poor toughness, so that the traditional WC material is sintered by adopting Co as a binder, and the hardness and strength of the WC material are severely reduced due to softening of a binder phase Co at high temperature although the sintering temperature is effectively reduced and the toughness is improved, so that the application of the traditional WC-Co material is greatly limited.
At present, the non-binding phase WC ceramic is developed at home and abroad to replace WC-Co material, although the WC ceramic can meet the requirements of special environments such as application fields of high temperature and high pressure, the pure WC material is high in sintering temperature and is difficult to sinter compactly, and based on the pure WC material, the compact sintering of the WC ceramic is realized through hot-press sintering and hot isostatic pressing processes by the preparation method of the tungsten carbide ceramic material (publication No. CN 107522490A), but the sintering temperature is as high as 1900-2000 ℃ and the toughness is lower. In order to improve the mechanical properties of the composite ceramic material and balance the properties of the composite ceramic material in all aspects, the patent of a high-performance tungsten carbide ceramic material (publication No. CN 106631024A) and a preparation method thereof (publication No. CN 105801120A) discloses that the mechanical properties of the composite ceramic material are improved by adding a second relative component into a WC system, but the toughness improvement is not obvious, and the problem of friction and abrasion in the application process is not considered. In order to further improve toughness and wear resistance, the patent 'self-generated silicon nitride whisker toughened tungsten carbide composite material and a preparation method thereof' (publication No. CN 102701773A) discloses that the mechanical properties of the self-generated silicon nitride whisker toughened tungsten carbide composite material are improved in an in-situ whisker generation mode, and although the toughness is obviously improved, the hardness is obviously reduced, and the requirements of practical application are hardly met. The binding-phase-free WC-based hard alloy cutter material and the preparation method thereof (publication No. CN 111056852A) have the advantages that the multielement components comprise oxides, carbides, carbon nanotubes, graphene and the like, the toughness and the wear resistance are enhanced, but the preparation process is complex, the cost is high, and the effective popularization and application are difficult. Therefore, the WC ceramic which is low in cost, compact in sintering at a lower temperature and excellent in mechanical property and wear resistance is particularly necessary.
Disclosure of Invention
Aiming at the problems of overhigh sintering temperature, poor toughness and insufficient wear resistance of the conventional WC ceramic, the invention provides a low-temperature sintered high-toughness wear-resistant WC ceramic and a preparation method thereof.
The invention has the advantages of low-temperature sintering, high toughness and high resistanceThe mass fraction of the ZrO of the ground WC ceramic is 4-10 percent 2 (Y 2 O 3 )-Al 2 O 3 The composite powder, 0.1-1% of expanded graphite and the balance of WC powder.
The preparation method of the low-temperature sintered high-toughness wear-resistant WC ceramic comprises the following steps:
step one: weighing 4-10% of ZrO according to mass fraction 2 (Y 2 O 3 )-Al 2 O 3 Composite powder, 0.1-1% of expanded graphite and the balance of WC powder;
the average grain diameter of the WC powder is less than or equal to 300nm, and the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The average grain diameter of the composite powder is less than or equal to 300nm.
The purity of the WC powder is more than or equal to 99.9wt percent, and the ZrO powder is prepared by the following steps of 2 (Y 2 O 3 )-Al 2 O 3 Al in the composite powder 2 O 3 The content of (C) is 20wt%, Y 2 O 3 The content of (3-4 wt.%), zrO 2 +Y 2 O 3 +Al 2 O 3 ≥99.9wt％；
The ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder is prepared by taking zirconium oxychloride, aluminum chloride and yttrium chloride as raw materials and adopting a hydrothermal method;
the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The preparation method of the composite powder comprises the following steps:
weighing ZrOCl 2 ·8H 2 O、YCl 3 ·6H 2 O and AlCl 3 ·6H 2 The O is prepared into a salt solution with the solute concentration of 0.2mol/L, the mole percentage of Al element in the solute of the salt solution is 37.6 percent, the mole percentage of Y element is 2.5-3.4 percent, and the balance is Zr element. Adding absolute ethyl alcohol and polyethylene glycol into a salt solution, wherein the absolute ethyl alcohol and the salt solution have the same volume, the adding amount of the polyethylene glycol in the salt solution is 20g/L, stirring for 2 hours by using a constant-temperature magnetic stirrer after uniform mixing, adding ammonia water to generate white flocculent gel, and repeatedly washing the flocculent gel with deionized water until no Cl exists - Production ofWashing with absolute ethanol for three times to obtain a precursor solution, then dropwise adding nitric acid and ammonia water to adjust the pH=10 of the precursor solution, continuously stirring for 30min to obtain a precursor solution with uniform chemical components, filling the precursor solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 5h at 180 ℃; filtering the product obtained by the reaction, repeatedly washing with deionized water, washing with absolute ethyl alcohol for three times, and drying at 70 ℃ for 24 hours to obtain uniform ZrO 2 (Y 2 O 3 )-Al 2 O 3 Calcining the precursor powder at 1000 ℃ for 3 hours to obtain ZrO with average grain diameter less than or equal to 300nm 2 (Y 2 O 3 )-Al 2 O 3 Composite powder;
step two: firstly, adding expanded graphite into a liquid medium for ultrasonic stirring, and then adding WC powder and ZrO 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again after the powder is compounded, so as to obtain a mixed solution;
the liquid medium is absolute ethyl alcohol, industrial alcohol or deionized water;
the expanded graphite is ultrasonically stirred in a liquid medium for 1h, and WC powder and ZrO are added 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again for 1h after the powder is compounded;
step three: ball milling the mixed solution to obtain ceramic slurry, drying and screening to obtain ceramic powder;
the ball milling time of the mixed solution is 24 hours; sieving with 80 mesh sieve;
the ball milling adopts a planetary ball mill, the grinding ball is made of tungsten carbide, and the mass ratio of the mixed solution to the grinding ball is 1 (3-10);
step four: sintering the ceramic powder to obtain high-toughness wear-resistant WC ceramic;
the ceramic powder sintering process comprises the following steps: sintering by adopting oscillating pressure: the temperature rising speed is 10 ℃/min, the sintering temperature is 1700-1800 ℃, the sintering time is 60-90 min, the constant pressure of 10MPa is applied to the sintering object before the temperature is 1200 ℃, the constant pressure and the oscillating pressure are applied to the sintering object after the temperature exceeds 1200 ℃, the constant pressure is 20-60 MPa, the oscillating pressure is +/-2- +/-6 MPa, the oscillating frequency is 1-4 Hz, and the sintering atmosphere is vacuum or high-purity argon atmosphere.
The invention has the principle and beneficial effects that:
1. the dynamic pressure in the oscillation pressure sintering process improves the sintering driving force in the sintering process, can eliminate closed pores in the ceramic as much as possible, promotes the densification behavior of the WC ceramic matrix, improves the reliability and enhances the mechanical property; the ball-milled expanded graphite is completely converted into flaky graphene oxide nano sheets, the dynamic pressure promotes the sliding of the graphene oxide nano sheets, the densification of the matrix is promoted, the matrix is completely densified due to the reasons above, and the fracture toughness is promoted.
2. Under the condition of oscillation pressure, the graphene oxide nano sheets are arranged in an oriented mode, and energy for crack expansion is consumed by pulling out the graphene oxide nano sheets and deflecting cracks of the graphene oxide nano sheets in crack expansion; at the same time Y 2 O 3 Stabilized ZrO 2 Maintaining t-ZrO after cooling 2 The phase of the alloy is phase-changed and toughened, effectively inhibits the expansion of cracks, and Al 2 O 3 Particle dispersion toughening also effectively improves toughness and is due to ZrO 2 -Al 2 O 3 The particle action forms a 'crack bridging', more 'crack deflection' is caused, and the like consume energy to effectively improve the fracture toughness, so that the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder and the graphene oxide nanosheets cooperate to further improve fracture toughness and strength.
2. Because the flaky graphene oxide nano-sheets are embedded in the particles and serve as friction layers, the graphene oxide nano-sheets have good lubricity, and the relative wear resistance of the lubrication is improved. Meanwhile, as the mechanical properties, especially the strength and toughness, are improved, the generation and the extension of cracks in the friction process are effectively limited, the wear resistance is improved, the service life is prolonged, and the industrial application field is wider.
3. The invention adopts oxide ZrO 2 (Y 2 O 3 )-Al 2 O 3 As sintering aid, is remarkableThe compact sintering temperature of WC-based ceramics is reduced. The invention adds the low-cost expanded graphite, reduces the cost and makes the industrial application field wider.
4. The WC-based ceramic prepared by the method is simple and low in cost, has good toughness and excellent wear resistance, and has the product density of more than 99% and high reliability. The prepared WC-based ceramic has excellent mechanical properties, wherein the Vickers hardness reaches 25-28 GPa, and the fracture toughness reaches 8-11 MPa.m 1/2 The bending strength can reach 1200-1500 MPa. The GCr15 bearing steel ball friction ball is adopted to apply load 80N, the friction coefficient is only 0.2-0.4, and the wear rate is 1 multiplied by 10 -7 ～6×10 -7 mm 3 N -1 m -1 Meets the application requirement of WC ceramics at high temperature and high pressure.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also comprises any reasonable combination of the specific embodiments.
The first embodiment is as follows: the low-temperature sintered high-toughness wear-resistant WC ceramic of the embodiment comprises 4-10% of ZrO by mass percent 2 (Y 2 O 3 )-Al 2 O 3 The composite powder, 0.1-1% of expanded graphite and the balance of WC powder.
According to the embodiment, the added expanded graphite is completely converted into the flaky graphene oxide nano sheets after ball milling, the dynamic pressure promotes the sliding of the graphene oxide nano sheets, the densification of the matrix is promoted, the matrix is completely densified due to the above reasons, and the fracture toughness is promoted. Because the flaky graphene oxide nano-sheets are embedded in the particles and serve as friction layers, the graphene oxide nano-sheets have good lubricity, and the relative wear resistance of the lubrication is improved. Meanwhile, as the mechanical properties, especially the strength and toughness, are improved, the generation and the extension of cracks in the friction process are effectively limited, the wear resistance is improved, the service life is prolonged, and the industrial application field is wider.
In the present embodiment, oxide ZrO is used 2 (Y 2 O 3 )-Al 2 O 3 As a burnAnd the sintering temperature of the WC-based ceramic is obviously reduced by the aid of the junction agent. The expanded graphite with low price is added in the method, so that the cost is reduced, and the industrial application field is wider.
The WC-based ceramic method is simple and low in cost, has good toughness and excellent wear resistance, and has the product density reaching more than 99% and high reliability. The prepared WC-based ceramic has excellent mechanical properties, wherein the Vickers hardness reaches 25-28 GPa, and the fracture toughness reaches 8-11 MPa.m 1/2 The bending strength can reach 1200-1500 MPa. The GCr15 bearing steel ball friction ball is adopted to apply load 80N, the friction coefficient is only 0.2-0.4, and the wear rate is 1 multiplied by 10 -7 ～6×10 -7 mm 3 N -1 m -1 Meets the application requirement of WC ceramics at high temperature and high pressure.
The second embodiment is as follows: the preparation method of the low-temperature sintered high-toughness wear-resistant WC ceramic in the embodiment comprises the following steps:
step one: weighing 4-10% of ZrO according to mass fraction 2 (Y 2 O 3 )-Al 2 O 3 Composite powder, 0.1-1% of expanded graphite and the balance of WC powder;
step two: firstly, adding expanded graphite into a liquid medium for ultrasonic stirring, and then adding WC powder and ZrO 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again after the powder is compounded, so as to obtain a mixed solution;
step three: ball milling the mixed solution to obtain ceramic slurry, drying and screening to obtain ceramic powder;
step four: sintering the ceramic powder to obtain high-toughness wear-resistant WC ceramic;
the ceramic powder sintering process comprises the following steps: sintering by adopting oscillating pressure: the temperature rising speed is 10 ℃/min, the sintering temperature is 1700-1800 ℃, the sintering time is 60-90 min, the constant pressure of 10MPa is applied to the sintering object before the temperature is 1200 ℃, the constant pressure and the oscillating pressure are applied to the sintering object after the temperature exceeds 1200 ℃, the constant pressure is 20-60 MPa, the oscillating pressure is +/-2- +/-6 MPa, the oscillating frequency is 1-4 Hz, and the sintering atmosphere is vacuum or high-purity argon atmosphere.
1. The dynamic pressure in the oscillation pressure sintering process of the embodiment promotes the sintering driving force in the sintering process, can eliminate closed pores in the ceramic as much as possible, promotes the densification behavior of the WC ceramic matrix, improves the reliability and enhances the mechanical property; the ball-milled expanded graphite is completely converted into flaky graphene oxide nano sheets, the dynamic pressure promotes the sliding of the graphene oxide nano sheets, the densification of the matrix is promoted, the matrix is completely densified due to the reasons above, and the fracture toughness is promoted.
2. Under the condition of oscillation pressure, the graphene oxide nano sheets are arranged in an oriented mode, and energy for crack expansion is consumed by pulling out the graphene oxide nano sheets and deflecting cracks of the graphene oxide nano sheets in crack expansion; at the same time Y 2 O 3 Stabilized ZrO 2 Maintaining t-ZrO after cooling 2 The phase of the alloy is phase-changed and toughened, effectively inhibits the expansion of cracks, and Al 2 O 3 Particle dispersion toughening also effectively improves toughness and is due to ZrO 2 -Al 2 O 3 The particle action forms a 'crack bridging', more 'crack deflection' is caused, and the like consume energy to effectively improve the fracture toughness, so that the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder and the graphene oxide nanosheets cooperate to further improve fracture toughness and strength.
2. Because the flaky graphene oxide nano-sheets are embedded in the particles and serve as friction layers, the graphene oxide nano-sheets have good lubricity, and the relative wear resistance of the lubrication is improved. Meanwhile, as the mechanical properties, especially the strength and toughness, are improved, the generation and the extension of cracks in the friction process are effectively limited, the wear resistance is improved, the service life is prolonged, and the industrial application field is wider.
3. In the present embodiment, oxide ZrO is used 2 (Y 2 O 3 )-Al 2 O 3 As a sintering aid, the compact sintering temperature of the WC-based ceramic is remarkably reduced. The expanded graphite with low price is added in the method, so that the cost is reduced, and the industrial application field is wider.
4. The WC-based ceramic prepared by the method is simple and low in cost, has good toughness and excellent wear resistance, and has the product density reaching more than 99% and high reliability. The prepared WC-based ceramic has excellent mechanical properties, wherein the Vickers hardness reaches 25-28 GPa, and the fracture toughness reaches 8-11 MPa.m 1/2 The bending strength can reach 1200-1500 MPa. The GCr15 bearing steel ball friction ball is adopted to apply load 80N, the friction coefficient is only 0.2-0.4, and the wear rate is 1 multiplied by 10 -7 ～6×10 - 7 mm 3 N -1 m -1 Meets the application requirement of WC ceramics at high temperature and high pressure.
And a third specific embodiment: the second difference between this embodiment and the second embodiment is that: the average grain diameter of the WC powder is less than or equal to 300nm, and the ZrO is prepared by the following steps 2 (Y 2 O 3 )-Al 2 O 3 The average grain diameter of the composite powder is less than or equal to 300nm.
The specific embodiment IV is as follows: this embodiment differs from the second or third embodiment in that: the purity of the WC powder is more than or equal to 99.9wt percent, and the ZrO is prepared by the following steps 2 (Y 2 O 3 )-Al 2 O 3 Al in the composite powder 2 O 3 The content of (C) is 20wt%, Y 2 O 3 The content of (3-4 wt.%), zrO 2 +Y 2 O 3 +Al 2 O 3 ≥99.9wt％。
Fifth embodiment: the present embodiment differs from the second to fourth embodiments in that: step one the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder is prepared by taking zirconium oxychloride, aluminum chloride and yttrium chloride as raw materials and adopting a hydrothermal method.
Specific embodiment six: the fifth difference between this embodiment and the third embodiment is that: the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The preparation method of the composite powder comprises the following steps: weighing ZrOCl 2 ·8H 2 O、YCl 3 ·6H 2 O and AlCl 3 ·6H 2 O is prepared into a salt solution with the solute concentration of 0.2mol/L, and the solute of the salt solution contains Al element37.6 mol percent of element, 2.5-3.4 mol percent of Y element and the balance of Zr element; adding absolute ethyl alcohol and polyethylene glycol into a salt solution, wherein the absolute ethyl alcohol and the salt solution have the same volume, the adding amount of the polyethylene glycol in the salt solution is 20g/L, stirring for 2 hours by using a constant-temperature magnetic stirrer after uniform mixing, adding ammonia water to generate white flocculent gel, and repeatedly washing the flocculent gel with deionized water until no Cl exists - Generating, washing with absolute ethyl alcohol for three times to obtain a precursor liquid, then dropwise adding nitric acid and ammonia water to adjust the pH=10 of the precursor liquid, continuously stirring for 30min to obtain a precursor liquid with uniform chemical components, filling the precursor liquid into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 5h at 180 ℃; filtering the product obtained by the reaction, repeatedly washing with deionized water, washing with absolute ethyl alcohol for three times, and drying at 70 ℃ for 24 hours to obtain uniform ZrO 2 (Y 2 O 3 )-Al 2 O 3 Calcining the precursor powder at 1000 ℃ for 3 hours to obtain ZrO with average grain diameter less than or equal to 300nm 2 (Y 2 O 3 )-Al 2 O 3 And (5) compounding powder.
Seventh embodiment: this embodiment differs from one of the second to sixth embodiments in that: and step two, the liquid medium is absolute ethyl alcohol, industrial alcohol or deionized water.
Eighth embodiment: this embodiment differs from one of the second to seventh embodiments in that: step two, the expanded graphite is ultrasonically stirred in a liquid medium for 1h, and WC powder and ZrO are added 2 (Y 2 O 3 )-Al 2 O 3 And after the powder is compounded, stirring again by ultrasonic for 1h.
Detailed description nine: this embodiment differs from one of the second to eighth embodiments in that: step three, ball milling is carried out on the mixed solution for 24 hours; and screening the mixture by a 80-mesh screen.
Detailed description ten: this embodiment differs from one of the second to ninth embodiments in that: and step three, the ball milling adopts a planetary ball mill, the grinding ball is made of tungsten carbide, and the mass ratio of the mixed solution to the grinding ball is 1 (3-10).
Example 1:
the preparation method of the low-temperature sintered high-toughness wear-resistant WC ceramic comprises the following steps:
step one: weighing 10% ZrO by mass 2 (Y 2 O 3 )-Al 2 O 3 Composite powder, 0.4% of expanded graphite and the balance of WC powder;
the average grain diameter of the WC powder is less than or equal to 300nm, and the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The average grain diameter of the composite powder is less than or equal to 300nm.
The purity of the WC powder is more than or equal to 99.9wt percent, and the ZrO powder is prepared by the following steps of 2 (Y 2 O 3 )-Al 2 O 3 Al in the composite powder 2 O 3 The content of (C) is 20wt%, Y 2 O 3 The content of (3.9 wt%, zrO) 2 +Y 2 O 3 +Al 2 O 3 ≥99.9wt％；
The ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder is prepared by taking zirconium oxychloride, aluminum chloride and yttrium chloride as raw materials and adopting a hydrothermal method;
the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The preparation method of the composite powder comprises the following steps:
weighing ZrOCl 2 ·8H 2 O、YCl 3 ·6H 2 O and AlCl 3 ·6H 2 O is prepared into a salt solution with the solute concentration of 0.2mol/L, the mole percentage of Al element in the solute of the salt solution is 37.6 percent, the mole percentage of Y element is 3.0 percent, and the balance is Zr element. Adding absolute ethyl alcohol and polyethylene glycol into a salt solution, wherein the absolute ethyl alcohol and the salt solution have the same volume, the adding amount of the polyethylene glycol in the salt solution is 20g/L, stirring for 2 hours by using a constant-temperature magnetic stirrer after uniform mixing, adding ammonia water to generate white flocculent gel, and repeatedly washing the flocculent gel with deionized water until no Cl exists - Generating, washing with absolute ethanol for three times to obtain a precursor solution, then dropwise adding nitric acid and ammonia water to adjust the pH value of the precursor solution to be 10, continuously stirring for 30min to obtain a precursor solution with uniform chemical components, and loading the precursor solution into a high-pressure reactionIn the kettle, carrying out hydrothermal reaction for 5h at 180 ℃; filtering the product obtained by the reaction, repeatedly washing with deionized water, washing with absolute ethyl alcohol for three times, and drying at 70 ℃ for 24 hours to obtain uniform ZrO 2 (Y 2 O 3 )-Al 2 O 3 Calcining the precursor powder at 1000 ℃ for 3 hours to obtain ZrO with average grain diameter less than or equal to 300nm 2 (Y 2 O 3 )-Al 2 O 3 Composite powder;
step two: firstly, adding expanded graphite into a liquid medium for ultrasonic stirring, and then adding WC powder and ZrO 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again after the powder is compounded, so as to obtain a mixed solution;
the liquid medium is absolute ethyl alcohol;
the expanded graphite is ultrasonically stirred in a liquid medium for 1h, and WC powder and ZrO are added 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again for 1h after the powder is compounded;
step three: ball milling the mixed solution to obtain ceramic slurry, drying and screening to obtain ceramic powder;
the ball milling time of the mixed solution is 24 hours; sieving with 80 mesh sieve;
the ball milling adopts a planetary ball mill, the grinding ball is made of tungsten carbide, and the mass ratio of the mixed solution to the grinding ball is 1:5;
step four: sintering the ceramic powder to obtain high-toughness wear-resistant WC ceramic;
the ceramic powder sintering process comprises the following steps: sintering by adopting oscillating pressure: the heating speed is 10 ℃/min, the sintering temperature is 1700 ℃, the sintering time is 90min, a constant pressure of 10MPa is applied to a sintering object before the temperature is 1200 ℃, the constant pressure and the oscillating pressure are applied to the sintering object after the temperature exceeds 1200 ℃, the constant pressure and the oscillating pressure are 60MPa, the oscillating pressure is +/-3 MPa, the oscillating frequency is 1Hz, and the sintering atmosphere is a vacuum atmosphere;
according to the embodiment, the research shows that the graphene oxide nanosheets can be obtained after ball milling of the expanded graphite, the expanded graphite is uniformly dispersed by ultrasonic stirring, and ball milling is carried outThe graphene oxide nano-sheets with uniform length and size can be obtained. The density of the WC ceramic prepared by the embodiment is up to 99%, the Vickers hardness is 26.9GPa, and the fracture toughness is up to 10.8 MPa.m 1/2 The bending strength is 1340MPa, the wear resistance is excellent, the load applied by adopting GCr15 bearing steel ball friction ball is 80N, the friction coefficient is 0.31, and the wear rate is 4.6X10 -7 mm 3 N -1 m -1 。
Example 2:
the preparation method of the low-temperature sintered high-toughness wear-resistant WC ceramic comprises the following steps:
step one: weighing 8% ZrO by mass 2 (Y 2 O 3 )-Al 2 O 3 Composite powder, 1% of expanded graphite and the balance of WC powder;
the average grain diameter of the WC powder is less than or equal to 300nm, and the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The average grain diameter of the composite powder is less than or equal to 300nm.
The purity of the WC powder is more than or equal to 99.9wt percent, and the ZrO powder is prepared by the following steps of 2 (Y 2 O 3 )-Al 2 O 3 Al in the composite powder 2 O 3 The content of (C) is 20wt%, Y 2 O 3 The content of (3.9 wt%, zrO) 2 +Y 2 O 3 +Al 2 O 3 ≥99.9wt％；
The ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder is prepared by taking zirconium oxychloride, aluminum chloride and yttrium chloride as raw materials and adopting a hydrothermal method;
the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The preparation method of the composite powder comprises the following steps:
weighing ZrOCl 2 ·8H 2 O、YCl 3 ·6H 2 O and AlCl 3 ·6H 2 O is prepared into a salt solution with the solute concentration of 0.2mol/L, the mole percentage of Al element in the solute of the salt solution is 37.6 percent, the mole percentage of Y element is 3.0 percent, and the balance is Zr element. . Adding absolute ethyl alcohol and polyethylene glycol into salt solution, and adding absolute ethyl alcohol and polyethylene glycol into salt solutionAdding 20g/L polyethylene glycol into the salt solution, uniformly mixing, stirring for 2h by using a constant-temperature magnetic stirrer, adding ammonia water to generate white flocculent gel, and repeatedly washing the flocculent gel with deionized water until no Cl exists - Generating, washing with absolute ethyl alcohol for three times to obtain a precursor liquid, then dropwise adding nitric acid and ammonia water to adjust the pH=10 of the precursor liquid, continuously stirring for 30min to obtain a precursor liquid with uniform chemical components, filling the precursor liquid into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 5h at 180 ℃; filtering the product obtained by the reaction, repeatedly washing with deionized water, washing with absolute ethyl alcohol for three times, and drying at 70 ℃ for 24 hours to obtain uniform ZrO 2 (Y 2 O 3 )-Al 2 O 3 Calcining the precursor powder at 1000 ℃ for 3 hours to obtain ZrO with average grain diameter less than or equal to 300nm 2 (Y 2 O 3 )-Al 2 O 3 Composite powder;
step two: firstly, adding expanded graphite into a liquid medium for ultrasonic stirring, and then adding WC powder and ZrO 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again after the powder is compounded, so as to obtain a mixed solution;
the liquid medium is deionized water;
the expanded graphite is ultrasonically stirred in a liquid medium for 1h, and WC powder and ZrO are added 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again for 1h after the powder is compounded;
step three: ball milling the mixed solution to obtain ceramic slurry, drying and screening to obtain ceramic powder;
the ball milling time of the mixed solution is 24 hours; sieving with 80 mesh sieve;
the ball milling adopts a planetary ball mill, the grinding ball is made of tungsten carbide, and the mass ratio of the mixed solution to the grinding ball is 1:10;
step four: sintering the ceramic powder to obtain high-toughness wear-resistant WC ceramic;
the ceramic powder sintering process comprises the following steps: sintering by adopting oscillating pressure: the heating speed is 10 ℃/min, the sintering temperature is 1740 ℃, the sintering time is 80min, a constant pressure of 10MPa is applied to a sintering object before the temperature is 1200 ℃, the constant pressure and the oscillating pressure are applied to the sintering object after the temperature exceeds 1200 ℃, the constant pressure and the oscillating pressure are 50MPa, the oscillating pressure is +/-5 MPa, the oscillating frequency is 2Hz, and the sintering atmosphere is high-purity nitrogen atmosphere;
the density of the WC ceramic prepared by the embodiment is up to 99%, the Vickers hardness is 25.5GPa, and the fracture toughness is up to 10.1 MPa.m 1/2 The bending strength is 1250MPa, the wear resistance is excellent, the load applied by adopting GCr15 bearing steel ball friction ball is 80N, the friction coefficient is 0.23, and the wear rate is 1.8X10 -7 mm 3 N -1 m -1 。
Example 3:
step one: weighing 6% ZrO by mass 2 (Y 2 O 3 )-Al 2 O 3 Composite powder, 0.1% of expanded graphite and the balance of WC powder;
the average grain diameter of the WC powder is less than or equal to 300nm, and the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The average grain diameter of the composite powder is less than or equal to 300nm.
The purity of the WC powder is more than or equal to 99.9wt percent, and the ZrO powder is prepared by the following steps of 2 (Y 2 O 3 )-Al 2 O 3 Al in the composite powder 2 O 3 The content of (C) is 20wt%, Y 2 O 3 The content of (3.9 wt%, zrO) 2 +Y 2 O 3 +Al 2 O 3 ≥99.9wt％；
The ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder is prepared by taking zirconium oxychloride, aluminum chloride and yttrium chloride as raw materials and adopting a hydrothermal method;
the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The preparation method of the composite powder comprises the following steps:
weighing ZrOCl 2 ·8H 2 O、YCl 3 ·6H 2 O and AlCl 3 ·6H 2 O is prepared into a salt solution with the solute concentration of 0.2mol/L, the mole percentage of Al element in the solute of the salt solution is 37.6 percent, and the mole percentage of Y element is3.0% and the balance Zr element. . Adding absolute ethyl alcohol and polyethylene glycol into a salt solution, wherein the absolute ethyl alcohol and the salt solution have the same volume, the adding amount of the polyethylene glycol in the salt solution is 20g/L, stirring for 2 hours by using a constant-temperature magnetic stirrer after uniform mixing, adding ammonia water to generate white flocculent gel, and repeatedly washing the flocculent gel with deionized water until no Cl exists - Generating, washing with absolute ethyl alcohol for three times to obtain a precursor liquid, then dropwise adding nitric acid and ammonia water to adjust the pH=10 of the precursor liquid, continuously stirring for 30min to obtain a precursor liquid with uniform chemical components, filling the precursor liquid into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 5h at 180 ℃; filtering the product obtained by the reaction, repeatedly washing with deionized water, washing with absolute ethyl alcohol for three times, and drying at 70 ℃ for 24 hours to obtain uniform ZrO 2 (Y 2 O 3 )-Al 2 O 3 Calcining the precursor powder at 1000 ℃ for 3 hours to obtain ZrO with average grain diameter less than or equal to 300nm 2 (Y 2 O 3 )-Al 2 O 3 Composite powder;
step two: firstly, adding expanded graphite into a liquid medium for ultrasonic stirring, and then adding WC powder and ZrO 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again after the powder is compounded, so as to obtain a mixed solution;
the liquid medium is absolute ethyl alcohol;
the expanded graphite is ultrasonically stirred in a liquid medium for 1h, and WC powder and ZrO are added 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again for 1h after the powder is compounded;
step three: ball milling the mixed solution to obtain ceramic slurry, drying and screening to obtain ceramic powder;
the ball milling time of the mixed solution is 24 hours; sieving with 80 mesh sieve;
the ball milling adopts a planetary ball mill, the grinding ball is made of tungsten carbide, and the mass ratio of the mixed solution to the grinding ball is 1:3;
step four: sintering the ceramic powder to obtain high-toughness wear-resistant WC ceramic;
the ceramic powder sintering process comprises the following steps: sintering by adopting oscillating pressure: the heating speed is 10 ℃/min, the sintering temperature is 1760 ℃, the sintering time is 70min, a constant pressure of 10MPa is applied to a sintering object before the temperature is 1200 ℃, the constant pressure and the oscillating pressure are applied to the sintering object after the temperature exceeds 1200 ℃, the constant pressure and the oscillating pressure are 20MPa, the oscillating pressure is +/-2 MPa, the oscillating frequency is 3Hz, and the sintering atmosphere is a vacuum atmosphere;
the density of the WC ceramic prepared by the embodiment is up to 99%, the Vickers hardness is 27.6GPa, and the fracture toughness is 9.2 MPa.m 1/2 The bending strength is 1390MPa, the wear resistance is excellent, the load applied by adopting GCr15 bearing steel ball friction ball is 80N, the friction coefficient is 0.37, and the wear rate is 5.8X10 -7 mm 3 N -1 m -1 。
Example 4:
the preparation method of the low-temperature sintered high-toughness wear-resistant WC ceramic comprises the following steps:
step one: weighing 4% ZrO by mass 2 (Y 2 O 3 )-Al 2 O 3 Composite powder, 0.7% of expanded graphite and the balance of WC powder;
the average grain diameter of the WC powder is less than or equal to 300nm, and the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The average grain diameter of the composite powder is less than or equal to 300nm.
The purity of the WC powder is more than or equal to 99.9wt percent, and the ZrO powder is prepared by the following steps of 2 (Y 2 O 3 )-Al 2 O 3 Al in the composite powder 2 O 3 The content of (C) is 20wt%, Y 2 O 3 The content of (3.9 wt%, zrO) 2 +Y 2 O 3 +Al 2 O 3 ≥99.9wt％；
The ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder is prepared by taking zirconium oxychloride, aluminum chloride and yttrium chloride as raw materials and adopting a hydrothermal method;
the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The preparation method of the composite powder comprises the following steps:
weighing ZrOCl 2 ·8H 2 O、YCl 3 ·6H 2 O and AlCl 3 ·6H 2 O is prepared into a salt solution with the solute concentration of 0.2mol/L, the mole percentage of Al element in the solute of the salt solution is 37.6 percent, the mole percentage of Y element is 3.0 percent, and the balance is Zr element. Adding absolute ethyl alcohol and polyethylene glycol into a salt solution, wherein the absolute ethyl alcohol and the salt solution have the same volume, the adding amount of the polyethylene glycol in the salt solution is 20g/L, stirring for 2 hours by using a constant-temperature magnetic stirrer after uniform mixing, adding ammonia water to generate white flocculent gel, and repeatedly washing the flocculent gel with deionized water until no Cl exists - Generating, washing with absolute ethyl alcohol for three times to obtain a precursor liquid, then dropwise adding nitric acid and ammonia water to adjust the pH=10 of the precursor liquid, continuously stirring for 30min to obtain a precursor liquid with uniform chemical components, filling the precursor liquid into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 5h at 180 ℃; filtering the product obtained by the reaction, repeatedly washing with deionized water, washing with absolute ethyl alcohol for three times, and drying at 70 ℃ for 24 hours to obtain uniform ZrO 2 (Y 2 O 3 )-Al 2 O 3 Calcining the precursor powder at 1000 ℃ for 3 hours to obtain ZrO with average grain diameter less than or equal to 300nm 2 (Y 2 O 3 )-Al 2 O 3 Composite powder;
step two: firstly, adding expanded graphite into a liquid medium for ultrasonic stirring, and then adding WC powder and ZrO 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again after the powder is compounded, so as to obtain a mixed solution;
the liquid medium is absolute ethyl alcohol;
the expanded graphite is ultrasonically stirred in a liquid medium for 1h, and WC powder and ZrO are added 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again for 1h after the powder is compounded;
step three: ball milling the mixed solution to obtain ceramic slurry, drying and screening to obtain ceramic powder;
the ball milling time of the mixed solution is 24 hours; sieving with 80 mesh sieve;
the ball milling adopts a planetary ball mill, the grinding ball is made of tungsten carbide, and the mass ratio of the mixed solution to the grinding ball is 1:7;
step four: sintering the ceramic powder to obtain high-toughness wear-resistant WC ceramic;
the ceramic powder sintering process comprises the following steps: sintering by adopting oscillating pressure: the heating speed is 10 ℃/min, the sintering temperature is 1800 ℃, the sintering time is 60min, a constant pressure of 10MPa is applied to a sintering object before the temperature is 1200 ℃, the constant pressure and the oscillating pressure are applied to the sintering object after the temperature exceeds 1200 ℃, the constant pressure and the oscillating pressure are 30MPa, the oscillating pressure is +/-6 MPa, the oscillating frequency is 4Hz, and the sintering atmosphere is high-purity nitrogen atmosphere;
the density of the WC ceramic prepared by the embodiment is up to 99%, the Vickers hardness is 26.2GPa, and the fracture toughness is up to 8.6 MPa.m 1/2 The bending strength is 1450MPa, the wear resistance is excellent, the load applied by adopting a GCr15 bearing steel ball friction ball is 80N, the friction coefficient is 0.28, and the wear rate is 2.7X10 -7 mm 3 N -1 m -1 。
Claims (8)
1. A low-temperature sintered high-toughness wear-resistant WC ceramic is characterized in that: the low-temperature sintered high-toughness wear-resistant WC ceramic comprises 4-10% of ZrO by mass percent 2 (Y 2 O 3 )-Al 2 O 3 The composite powder, 0.1-1% of expanded graphite and the balance of WC powder are prepared;
the preparation method of the low-temperature sintered high-toughness wear-resistant WC ceramic comprises the following steps:
step one: weighing 4-10% of ZrO according to mass fraction 2 (Y 2 O 3 )-Al 2 O 3 Composite powder, 0.1-1% of expanded graphite and the balance of WC powder;
the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The preparation method of the composite powder comprises the following steps: weighing ZrOCl 2 ·8H 2 O、YCl 3 ·6H 2 O and AlCl 3 ·6H 2 The O is prepared into a salt solution with the solute concentration of 0.2mol/L, the mole percentage of Al element in the solute of the salt solution is 37.6%, the mole percentage of Y element is 2.5-3.4%, and the balance is Zr element; adding absolute ethanol and poly (ethylene glycol) to the salt solutionEthylene glycol, absolute ethyl alcohol and a salt solution with the same volume, wherein the adding amount of polyethylene glycol in the salt solution is 20g/L, stirring for 2 hours by using a constant-temperature magnetic stirrer after uniform mixing, adding ammonia water to generate white flocculent gel, and repeatedly washing the flocculent gel with deionized water until no Cl exists - Generating, washing with absolute ethyl alcohol for three times to obtain a precursor liquid, then dropwise adding nitric acid and ammonia water to adjust the pH=10 of the precursor liquid, continuously stirring for 30min to obtain a precursor liquid with uniform chemical components, filling the precursor liquid into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 5h at 180 ℃; filtering the product obtained by the reaction, repeatedly washing with deionized water, washing with absolute ethyl alcohol for three times, and drying at 70 ℃ for 24 hours to obtain uniform ZrO 2 (Y 2 O 3 )-Al 2 O 3 Calcining the precursor powder at 1000 ℃ for 3 hours to obtain ZrO with average grain diameter less than or equal to 300nm 2 (Y 2 O 3 )-Al 2 O 3 Composite powder;
step two: firstly, adding expanded graphite into a liquid medium for ultrasonic stirring, and then adding WC powder and ZrO 2 (Y 2 O 3 )-Al 2 O 3 Ultrasonic stirring is carried out again after the powder is compounded, so as to obtain a mixed solution;
step three: ball milling the mixed solution to obtain ceramic slurry, drying and screening to obtain ceramic powder;
step four: sintering the ceramic powder to obtain high-toughness wear-resistant WC ceramic;
the ceramic powder sintering process comprises the following steps: sintering by adopting oscillating pressure: the temperature rising speed is 10 ℃/min, the sintering temperature is 1700-1800 ℃, the sintering time is 60-90 min, constant pressure of 10MPa is applied to a sintering object before 1200 ℃, constant pressure and oscillation pressure are applied to the sintering object after the temperature exceeds 1200 ℃, the constant pressure is 20-60 MPa, the oscillation pressure is +/-2- +/-6 MPa, the oscillation frequency is 1-4 Hz, and the sintering atmosphere is vacuum or high-purity argon atmosphere.
2. The low temperature sintered high toughness wear resistant WC ceramic according to claim 1 wherein: and step one, the average particle size of the WC powder is less than or equal to 300nm.
3. The low temperature sintered high toughness wear resistant WC ceramic according to claim 1 wherein: the purity of the WC powder is more than or equal to 99.9wt percent, and the ZrO is prepared by the following steps 2 (Y 2 O 3 )-Al 2 O 3 Al in the composite powder 2 O 3 The content of (C) is 20wt%, Y 2 O 3 The content of (3-4 wt.%), zrO 2 +Y 2 O 3 +Al 2 O 3 ≥99.9wt%。
4. The low temperature sintered high toughness wear resistant WC ceramic according to claim 1 wherein: step one the ZrO 2 (Y 2 O 3 )-Al 2 O 3 The composite powder is prepared by taking zirconium oxychloride, aluminum chloride and yttrium chloride as raw materials and adopting a hydrothermal method.
5. The low temperature sintered high toughness wear resistant WC ceramic according to claim 1 wherein: and step two, the liquid medium is absolute ethyl alcohol, industrial alcohol or deionized water.
6. The low temperature sintered high toughness wear resistant WC ceramic according to claim 1 wherein: step two, the expanded graphite is ultrasonically stirred in a liquid medium for 1h, and WC powder and ZrO are added 2 (Y 2 O 3 )-Al 2 O 3 And after the powder is compounded, stirring again by ultrasonic for 1h.
7. The low temperature sintered high toughness wear resistant WC ceramic according to claim 1 wherein: step three, ball milling is carried out on the mixed solution for 24 hours; and screening the mixture by a 80-mesh screen.
8. The low temperature sintered high toughness wear resistant WC ceramic according to claim 1 wherein: and thirdly, a planetary ball mill is adopted for ball milling, the material of the grinding balls is tungsten carbide, and the mass ratio of the mixed solution to the grinding balls is 1 (3-10).
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