CN115652162A - High-temperature wear-resistant Mo-Si-B-zirconium boride composite material and preparation method thereof - Google Patents
High-temperature wear-resistant Mo-Si-B-zirconium boride composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-temperature wear-resistant Mo-Si-B-zirconium boride composite material, which comprises the following raw materials in percentage by mass: 3.7 to 4.2 percent of Si powder, 1.0 to 1.2 percent of B powder and 1.0 to 1.1 percent of CeO 2 Powder, 2.5 to 10 percent of ZrB 2 Powder, and the balance of Mo powder. Meanwhile, the invention also discloses a preparation method of the composite material. The invention realizes the rapid and efficient preparation of Mo-Si-B/ZrB by adopting a mechanical alloying combined discharge plasma sintering method 2 The composite material can simultaneously improve the strength, the high-temperature oxidation resistance and the abrasion resistance of the Mo-Si-B alloy, and meet the requirements of Mo-Si-B/ZrB 2 The wear-resisting property of the composite material at room temperature to 800 ℃ is required.
Description
Technical Field
The invention relates to the field of refractory material preparation, in particular to a high-temperature wear-resistant Mo-Si-B-zirconium boride composite material and a preparation method thereof.
Background
The development of the high-temperature alloy plays a crucial role in the development of the fields of aviation, aerospace, nuclear power, petroleum, chemical engineering and the like. With the rapid development of tip technologies of aeroengines, gas turbines and the like, severer requirements are put on the service temperature and the service performance of high-temperature alloys. The Mo-Si-B alloy has the advantages of high melting point, stable high-temperature structure, excellent high-temperature mechanics and oxidation resistance and the like, and is expected to become a candidate material for replacing the nickel-based high-temperature alloy.
In order to take the strength and the fracture toughness of the Mo-Si-B alloy into consideration, the patent CN108034875A prepares the Mo-Si-B alloy doped with rare earth oxide with excellent strength and fracture toughness by combining mechanical alloying with a hot-pressing sintering method. For the high-temperature strength of the Mo-Si-B alloy, the CN102424928A adds W element in the Mo-Si-B alloy, and adopts mechanical alloy and hot-pressing sintering to prepare the Mo-Si-B-W alloy, thereby improving the high-temperature strength and the tensile elongation of the alloy. In order to improve the oxidation resistance of the Mo-Si-B alloy, the CN114406284A patent prepares the Mo-Si-B-Ti alloy with high strength, light weight and high temperature oxidation resistance integrated by adding Ti element into the Mo-Si-B alloy, reduces the density of the material while maintaining the high melting point and high strength of the Mo-Si-B alloy, and obviously improves the high temperature oxidation resistance.
However, the main defects of the Mo-Si-B alloy are that the medium temperature (800 to 1000 ℃) oxidation resistance is poor, and PEST oxidation is easy to occur. In addition, mo-Si-B alloy has the disadvantages of high friction coefficient and high wear rate, and the problem of high-temperature oxidation wear caused by PEST oxidation. Therefore, the existing Mo-Si-B alloy can not completely meet the performance requirements of oxidation resistance and abrasion resistance, and the development of a novel Mo-Si-B alloy and a composite material thereof is urgently needed to solve the abrasion resistance problem of relevant moving parts under extreme harsh environments such as high load, high speed, high temperature and the like. In addition, the existing preparation method of the Mo-Si-B alloy mainly adopts a mechanical alloying combined hot-pressing sintering method, but the preparation method has the defects of high sintering temperature (1500-1700 ℃) and long heat preservation time (1-3h).
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-temperature wear-resistant Mo-Si-B-zirconium boride composite material with good mechanical property and tribological property.
The invention also aims to provide a preparation method of the high-temperature wear-resistant Mo-Si-B-zirconium boride composite material.
In order to solve the problems, the high-temperature wear-resistant Mo-Si-B-zirconium boride composite material is characterized in that: the composite material comprises the following raw materials in percentage by mass: 3.7 to 4.2 percent of Si powder, 1.0 to 1.2 percent of B powder and 1.0 to 1.1 percent of CeO 2 Powder, 2.5 to 10 percent of ZrB 2 Powder, and the balance of Mo powder.
The preparation method of the high-temperature wear-resistant Mo-Si-B-zirconium boride composite material is characterized by comprising the following steps of: firstly, weighing according to the proportion; then Mo powder, si powder, B powder and CeO powder 2 Mixing the powder in a high-energy ball mill to obtain Mo-Si-B alloying powder; the Mo-Si-B alloyed powder and ZrB 2 Uniformly mixing the powder in a low-energy ball mill to obtain mixed powder; and finally, placing the mixed powder in a discharge plasma sintering furnace for sintering, and cooling the sintered mixed powder to room temperature along with the furnace to obtain the material.
The mixing conditions of the high-energy ball mill are that the ball-to-material ratio is 1 to 3, the rotating speed is 200 to 300 r/min, the ball milling time is 8 to 16 h, a milling pot and a milling ball are made of tungsten carbide hard alloy, and argon is filled before the ball milling is started.
The mixing condition of the low-energy ball mill is that the ball-material ratio is 1 to 2, the rotating speed is 250 to 300 r/min, the ball milling time is 6 to 8 hours, and the milling pot and the milling ball are made of stainless steel.
The discharge plasma sintering condition is that the vacuum degree is (5 to 20) multiplied by 10 -2 Pa, the temperature rise speed is 100 to 150 ℃, the sintering temperature is 1450 to 1550 ℃, the applied pressure is 30 to 40 MPa, and the heat preservation time is 5 to8 min。
Compared with the prior art, the invention has the following advantages:
1. the invention adds ZrB into the Mo-Si-B alloy 2 And the strength of the material is improved, the density of the material is reduced, the oxidation resistance at 800 ℃ is improved, and the abrasion resistance of the material is improved.
2. The invention adopts a rapid sintering technology-spark plasma sintering method (rapid temperature rise and short sintering time) to further improve the high-temperature wear-resistant Mo-Si-B/ZrB 2 Hardness and strength of the composite material.
3. The invention has simple preparation process, can regulate and control the material performance by adjusting the formula and the process parameters, and the prepared material meets the multifunctional requirements of high strength, oxidation resistance, wear resistance and the like.
4. Tests prove that the high-temperature wear-resistant Mo-Si-B/ZrB prepared by the invention 2 The composite material has good mechanical property and tribological property, particularly has excellent self-lubricating property at 600-800 ℃, is suitable for solving the problem of wear resistance of the molybdenum alloy in a wide temperature range (room temperature-800 ℃) environment, and has important application prospect in the aerospace field as a high-strength refractory material.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows Mo-Si-B/ZrB prepared in example 1 of the invention 2 XRD spectrum of the composite material.
FIG. 2 shows Mo-Si-B/ZrB prepared in example 2 of the invention 2 Coefficient of friction curves of the composite at different temperatures.
Detailed Description
A high-temperature wear-resistant Mo-Si-B-zirconium boride composite material is composed of the following raw materials in percentage by mass (g): 3.7 to 4.2 percent of Si powder, 1.0 to 1.2 percent of B powder and 1.0 to 1.1 percent of CeO 2 Powder, 2.5 to 10 percent of ZrB 2 Powder, and the balance of Mo powder.
Wherein: zrB 2 The powder is prepared by a high temperature self-propagating process.
The high-temperature wear-resistant Mo-Si-B-boronThe preparation method of the zirconium composite material comprises the following steps: firstly, weighing according to the proportion; then Mo powder, si powder, B powder and CeO powder 2 Putting the powder into a high-energy ball mill, wherein a milling pot and a milling ball are made of tungsten carbide hard alloy, filling argon, and uniformly mixing under the conditions that the ball-to-material ratio is 1 to 3 2 Putting the powder into a low-energy ball mill, wherein a milling pot and a milling ball are made of stainless steel, and uniformly mixing the stainless steel and the stainless steel under the conditions that the ball-to-material ratio is 1 to 2, the rotating speed is 250 to 300 r/min, and the ball milling time is 6 to 8 hours to obtain mixed powder; and finally, placing the mixed powder in a discharge plasma sintering furnace for sintering, wherein the sintering parameters are as follows: the vacuum degree is (5 to 20) multiplied by 10 -2 Pa, the temperature rising speed is 100-150 ℃, the sintering temperature is 1450-1550 ℃, the applied pressure is 30-40 MPa, and the heat preservation time is 5-8 min. Cooling to room temperature along with the furnace after sintering is finished to obtain the Mo-Si-B/ZrB 2 A composite material.
EXAMPLE 1A high temperature, wear resistant Mo-Si-B-zirconium boride composite consisting of 89.0g of Mo powder, 3.9g of Si powder, 1.1g of B powder, 1.0g of CeO 2 Powder, 5.0g of ZrB 2 And (3) powder composition.
The preparation method comprises the following steps: firstly, weighing according to the proportion; then Mo powder, si powder, B powder and CeO powder 2 Placing the powder in a high-energy ball mill, filling argon gas into the high-energy ball mill, mixing the powder with a ball-to-material ratio of 2:1 and 16 h under the condition of a rotating speed of 250 r/min to obtain Mo-Si-B alloying powder, wherein the Mo-Si-B alloying powder and ZrB are mixed 2 Putting the powder into a low-energy ball mill, and uniformly mixing the powder under the conditions that the ball-material ratio is 1:1, the rotating speed is 250 r/min and the ball milling time is 8 hours to obtain mixed powder; and finally, placing the mixed powder in a discharge plasma sintering furnace for sintering, wherein the sintering parameters are as follows: vacuum degree of 15X 10 -2 Pa, the temperature rise speed is 140 ℃, the sintering temperature is 1480 ℃, the applied pressure is 30 MPa, and the heat preservation time is 5 min. Cooling to room temperature along with the furnace after sintering is finished to obtain the Mo-Si-B/ZrB 2 A composite material. The XRD spectrum of the composite material is shown in figure 1, and the phase composition of the composite material is alpha-Mo and Mo 5 SiB 2 , Mo 3 Si and ZrB 2 。
Using Archimedes origin for the obtained composite materialThe density was measured and found to be 8.9 g/cm 3 。
The hardness of the resulting composite material was measured using a Vickers hardness tester, and the result was 1103.8 HV.
And testing the bending strength of the obtained composite material by using a universal material testing machine under the following test conditions: the loading speed was 0.05 mm/min, the span was 20mm. The bending strength is 544.8 MPa.
And evaluating the friction and wear performance of the obtained composite material by adopting an HT-1000 high-temperature friction and wear tester. And (3) testing conditions are as follows: the dual balls are Al 2 O 3 Ceramic, load of 5N, sliding linear velocity of 0.2 m/s, friction radius of 5 mm, run time of 30 min. The results show that: the friction coefficient of the composite material is 0.34 to 0.80 within the temperature range of room temperature to 800 ℃, and the wear rate is (1.17 to 8.51) multiplied by 10 -5 mm 3 in/Nm. The friction coefficient of the lubricating oil at 600 to 800 ℃ is as low as 0.34 to 0.42, and the lubricating oil shows excellent self-lubricating performance.
EXAMPLE 2A high temperature, wear resistant Mo-Si-B-zirconium boride composite material comprised of 86.6g of Mo powder, 3.8g of Si powder, 1.1g of B powder, 1.0g of CeO 2 Powder, 7.5g of ZrB 2 And (3) powder composition.
The preparation method comprises the following steps: firstly, weighing according to the proportion; then Mo powder, si powder, B powder and CeO powder 2 Placing the powder in a high-energy ball mill, filling argon gas into the high-energy ball mill, wherein the ball-to-material ratio is 2:1, and mixing the powder with 12 h under the condition of the rotating speed of 250 r/min to obtain Mo-Si-B alloying powder, wherein the Mo-Si-B alloying powder and ZrB are mixed 2 Putting the powder into a low-energy ball mill, and uniformly mixing the powder under the conditions that the ball-material ratio is 1:1, the rotating speed is 300 r/min and the ball milling time is 6 hours to obtain mixed powder; and finally, placing the mixed powder in a discharge plasma sintering furnace for sintering, wherein the sintering parameters are as follows: vacuum degree of 12X 10 -2 Pa, the temperature rise speed of 130 ℃, the sintering temperature of 1500 ℃, the applied pressure of 30 MPa and the heat preservation time of 5 min. Cooling to room temperature along with the furnace after sintering is finished to obtain the Mo-Si-B/ZrB 2 A composite material.
The density of the obtained composite material was measured by the Archimedes principle, and the result was 8.7 g/cm 3 。
The hardness of the resulting composite material was measured using a Vickers hardness tester, and the result was 1172.0 HV.
And testing the bending strength of the obtained composite material by using a universal material testing machine under the following test conditions: the loading speed was 0.05 mm/min, the span was 20mm. The bending strength is 552.3 MPa.
And evaluating the friction and wear performance of the obtained composite material by adopting an HT-1000 high-temperature friction and wear tester. And (3) testing conditions: the dual balls are Al 2 O 3 Ceramic, load of 5N, sliding linear velocity of 0.2 m/s, friction radius of 5 mm, run time of 30 min. The results show that: the friction coefficient of the composite material is 0.36 to 0.85 within the temperature range of room temperature to 800 ℃, and the wear rate is (4.85 to 75.18) multiplied by 10 -6 mm 3 in/Nm. The friction coefficient curves of the composite material at different temperatures are shown in figure 2, the friction coefficient at room temperature to 400 ℃ is 0.75 to 0.85, and the friction coefficient at 600 to 800 ℃ is as low as 0.36 to 0.40, so that the composite material has excellent self-lubricating performance.
EXAMPLE 3A high temperature, wear resistant Mo-Si-B-zirconium boride composite consisting of 4.3g of Mo powder, 3.7g of Si powder, 1.0g of B powder, 1.0g of CeO 2 Powder, 10.0g of ZrB 2 And (3) powder composition.
The preparation method comprises the following steps: firstly, weighing according to the proportion; then Mo powder, si powder, B powder and CeO powder 2 Placing the powder in a high-energy ball mill, filling argon gas into the high-energy ball mill, mixing the powder with a ball-to-material ratio of 2:1 and 16 h under the condition of a rotating speed of 250 r/min to obtain Mo-Si-B alloying powder, wherein the Mo-Si-B alloying powder and ZrB are mixed 2 Putting the powder into a low-energy ball mill, and uniformly mixing the powder under the conditions that the ball-material ratio is 2:1, the rotating speed is 250 r/min and the ball milling time is 6 hours to obtain mixed powder; and finally, placing the mixed powder in a discharge plasma sintering furnace for sintering, wherein the sintering parameters are as follows: vacuum degree of 15X 10 -2 Pa, the temperature rise speed of 150 ℃ per minute, the sintering temperature of 1550 ℃, the applied pressure of 32 MPa and the heat preservation time of 5 min. Cooling to room temperature along with the furnace after sintering is finished to obtain the Mo-Si-B/ZrB 2 A composite material.
The density of the obtained composite material was measured by the Archimedes principle, and the result was 8.4 g/cm 3 。
The hardness of the resulting composite material was measured using a Vickers hardness tester, and the result was 1250.4 HV.
And testing the bending strength of the obtained composite material by using a universal material testing machine under the following test conditions: the loading speed was 0.05 mm/min, the span was 20mm. The bending strength is 600.2 MPa.
And evaluating the friction and wear performance of the obtained composite material by adopting an HT-1000 high-temperature friction and wear tester. And (3) testing conditions: the dual balls are Al 2 O 3 Ceramic, load of 5N, sliding linear velocity of 0.2 m/s, friction radius of 5 mm, run time of 30 min. The results show that: the friction coefficient of the composite material is 0.35 to 0.86 in the temperature range from room temperature to 800 ℃, and the wear rate is (3.75 to 72.49) multiplied by 10 -6 mm 3 in/Nm. The friction coefficient of the self-lubricating oil is as low as 0.35 to 0.50 at the temperature of 600 to 800 ℃, and the self-lubricating oil shows excellent self-lubricating performance.
Claims (5)
1. A high-temperature wear-resistant Mo-Si-B-zirconium boride composite material is characterized in that: the composite material comprises the following raw materials in percentage by mass: 3.7 to 4.2 percent of Si powder, 1.0 to 1.2 percent of B powder and 1.0 to 1.1 percent of CeO 2 Powder, 2.5 to 10 percent of ZrB 2 Powder, and the balance of Mo powder.
2. The preparation method of the high-temperature wear-resistant Mo-Si-B-zirconium boride composite material as claimed in claim 1, wherein the preparation method comprises the following steps: firstly, weighing according to the proportion; then Mo powder, si powder, B powder and CeO 2 Mixing the powder in a high-energy ball mill to obtain Mo-Si-B alloying powder; the Mo-Si-B alloyed powder and ZrB 2 Uniformly mixing the powder in a low-energy ball mill to obtain mixed powder; and finally, placing the mixed powder in a discharge plasma sintering furnace for sintering, and cooling the sintered mixed powder to room temperature along with the furnace to obtain the material.
3. The preparation method of the high-temperature wear-resistant Mo-Si-B-zirconium boride composite material as claimed in claim 2, wherein the preparation method comprises the following steps: the mixing condition of the high-energy ball mill is that the ball-to-feed ratio is 1 to 3, the rotating speed is 200 to 300 r/min, the ball milling time is 8 to 16 h, a milling pot and a milling ball are made of tungsten carbide hard alloy, and argon is filled before the ball milling is started.
4. The preparation method of the high-temperature wear-resistant Mo-Si-B-zirconium boride composite material as claimed in claim 2, wherein the preparation method comprises the following steps: the mixing condition of the low-energy ball mill is that the ball-material ratio is 1 to 2, the rotating speed is 250 to 300 r/min, the ball milling time is 6 to 8 hours, and the milling pot and the milling ball are made of stainless steel.
5. The preparation method of the high-temperature wear-resistant Mo-Si-B-zirconium boride composite material as claimed in claim 2, wherein the preparation method comprises the following steps: the discharge plasma sintering condition is that the vacuum degree is (5 to 20) multiplied by 10 -2 Pa, the temperature rising speed is 100 to 150 ℃, the sintering temperature is 1450 to 1550 ℃, the applied pressure is 30 to 40 MPa, and the heat preservation time is 5 to 8 min.
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