CN115679234A - Method for improving wear resistance and corrosion resistance of zirconium-based amorphous alloy - Google Patents
Method for improving wear resistance and corrosion resistance of zirconium-based amorphous alloy Download PDFInfo
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- CN115679234A CN115679234A CN202211515158.3A CN202211515158A CN115679234A CN 115679234 A CN115679234 A CN 115679234A CN 202211515158 A CN202211515158 A CN 202211515158A CN 115679234 A CN115679234 A CN 115679234A
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- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 65
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 55
- 238000005260 corrosion Methods 0.000 title claims abstract description 38
- 230000007797 corrosion Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 abstract description 10
- 239000000956 alloy Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
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Abstract
The invention discloses a method for improving wear resistance and corrosion resistance of a zirconium-based amorphous alloy, and belongs to the technical field of preparation of wear-resistant and corrosion-resistant amorphous alloy materials. The zirconium-based amorphous alloy comprises, by mass percent, 40 to 41.2% of Zr,13 to 13.8% of Ti,12 to 12.5% of Cu,9.5 to 10% of Ni,22 to 22.5% of Be and inevitable impurities; the heat treatment process for regulating and controlling the short-range order of the zirconium-based amorphous alloy to improve the wear resistance and corrosion resistance comprises the processes of heating the zirconium-based amorphous by a heating furnace, circulating alternating current pulse and direct current pulse heat treatment and rapid cooling; finally, the obtained atomic entropy is increased, the long-range full disorder of the amorphous sample is realized, and the short-range order tends to the (111) crystal orientation, so that the aim of improving the wear resistance and corrosion resistance of the zirconium-based amorphous alloy is fulfilled.
Description
Technical Field
The invention relates to a method for improving wear resistance and corrosion resistance of a zirconium-based amorphous alloy, and belongs to the technical field of preparation of wear-resistant and corrosion-resistant amorphous alloy materials.
Background
The corrosive wear behavior is a widely existing problem in the material application process, and causes great harm to the economic development of the society. The difficulty and the key point of the research in the field of materials at the present stage are to solve and delay the equipment damage caused by the corrosive wear, research the corrosive wear mechanism of the materials and improve the wear resistance and corrosion resistance of the materials. Due to the special atomic structure in the zirconium-based bulk amorphous, the zirconium-based bulk amorphous has the advantages of high strength, high elastic limit, high corrosion resistance and the like, and is widely applied to wear-resistant and corrosion-resistant equipment.
At present, a great number of scholars research the wear resistance and corrosion resistance of the zirconium-based amorphous alloy. The results of research performed by current researchers indicate that the properties of amorphous materials mainly include: has excellent mechanical performance. Research shows that the rupture strength of the Zr-based amorphous material reaches 2070 MPa respectively. Compared with the traditional crystal material, the amorphous phase exists, so that the corrosion-resistant material has better corrosion resistance and can be used for a long time under some complex and harsh working conditions. The trace element adding method is widely applied to the field of amorphous alloy manufacturing. The glass forming ability and properties of the amorphous alloy have a great influence on the chemical composition thereof, so that the properties of the amorphous alloy can be well adjusted by microalloying. Researches find that 0.1% of boron, 0.2% of silicon and 0.1% of lead can effectively reduce the adverse effect of oxygen on the amorphous alloy; proper addition of N can promote glass formation by inhibiting the formation of competing crystals in Zr and Ti based bulk amorphous alloys; the Cr and Nb coatings promote the formation of a continuous compact oxide film on the friction surface, and the wear rate of the amorphous coating is obviously reduced. However, the microalloying method increases the manufacturing cost of the amorphous material and does not meet the economic benefit index. The electric pulse method can improve the wear resistance and corrosion resistance of the zirconium-based amorphous alloy, thereby effectively reducing the production cost. At present, the main structural relaxation means of the amorphous alloy is heat treatment, the traditional heat treatment process has high cost and long time consumption, and the traditional isothermal annealing process is often difficult to obtain the required structural relaxation effect. Therefore, a new heat treatment method is developed to meet the requirement of realizing the rapid structural relaxation of the zirconium-based amorphous alloy and improving the wear-resisting and corrosion-resisting properties of the zirconium-based amorphous alloy.
Disclosure of Invention
The invention aims to provide a method for improving the wear resistance and corrosion resistance of a zirconium-based amorphous alloy, which achieves the aim of improving the wear resistance and corrosion resistance of the zirconium-based amorphous alloy by regulating the short-range order of the zirconium-based amorphous alloy through electric pulses and combining low-temperature annealing and water quenching processes, and specifically comprises the following steps:
(1) Heating the zirconium-based amorphous to 180-200 ℃ by using an open heating furnace;
(2) Alternating current pulse is introduced, the pulse width is 1-20 mus, the pulse interval is 10-100 mus, and the pulse current density is 50-1000A/mm 2 The temperature of the sample is regulated and controlled below the crystallization temperature, and the atom entropy is increased, so that the sample is more disordered in long range.
(3) Introducing direct current pulse with the pulse frequency of 1-10 Hz, the pulse interval of 50-100 mus and the pulse current density of 500-1000A/mm 2 The temperature of the sample is controlled below the crystallization temperature, so that the sample is short-range to (111) crystal orientation.
(4) Performing circulating alternating current pulse and direct current pulse heat treatment on the zirconium-based amorphous sample, wherein the circulating times are not less than 5 times, and the time of each pulse heat treatment is not less than 10 s;
(5) And (3) carrying out water quenching cooling on the zirconium-based amorphous sample subjected to pulse heat treatment.
Preferably, the zirconium-based amorphous alloy comprises, by mass, 40-41.2% of Zr, 13-13.8% of Ti, 12-12.5% of Cu, 9.5-10% of Ni, 22-22.5% of Be and inevitable impurities.
Preferably, in step (4) of the present invention, when the temperature of the pulse heat treatment is 350 ℃ or higher, the electric pulse cycle is stopped.
The principle of the invention is as follows:
applying pulse current in the annealing treatment process of the amorphous alloy can relax the amorphous structure, change the atomic structure, and implement the heat treatment of circulating alternating current pulse and direct current pulse, wherein the temperature of the heat treatment of the pulse is close to the crystallization transformation area of the amorphous alloy, the entropy value of amorphous atoms is obviously increased by the circulating alternating current pulse, the atomic arrangement is more disordered, the long-range disorder is improved, and the hardness and the strength of the material are improved; the direct current pulse treatment enables amorphous atoms to form an orientation relation in a short-range order, the atoms tend to be arranged in a (111) crystal orientation, and the wear resistance and corrosion resistance of the amorphous alloy are improved.
The application effect of the invention is as follows:
(1) The invention adjusts and controls the short-range order of the zirconium-based amorphous alloy through electric pulse, and combines the low-temperature annealing and water quenching processes to obtain the zirconium-based amorphous alloy with the short-range order orientation being (111) crystal orientation, thereby achieving the purpose of improving the wear resistance and corrosion resistance of the zirconium-based amorphous alloy.
(2) Compared with the conventional zirconium-based amorphous alloy production process, the method has two characteristics, namely, the circulating alternating current pulse and the direct current pulse heat treatment are added, the entropy value of amorphous atoms is obviously increased due to the circulating alternating current pulse, the atom arrangement is more disordered, the long-range disorder is realized, and the hardness and the strength of the material are improved; the direct current pulse treatment enables amorphous atoms to form an orientation relation in a short-range order, the atoms tend to be arranged in a (111) crystal orientation, and the wear resistance and the corrosion resistance of the amorphous alloy are improved. And secondly, the conventional annealing process is adopted to accelerate the rapid cooling quenching, so that the heat-treated structure is stable at room temperature and does not change any more, the treatment time is short, the crystallization of the amorphous alloy is avoided, and the performance regulation and control requirements are met. The invention has the advantages of simple operation process and easy implementation for enterprises.
Drawings
Fig. 1 is a schematic view of a production process of the thermal treatment process for regulating and controlling the short-range order of the zirconium-based amorphous alloy of the present invention.
FIG. 2 is a controlled atomic model of short-range order and long-range disorder of the zirconium-based amorphous alloy.
Detailed description of the preferred embodiments
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the examples.
Example 1
The chemical composition of the zirconium based amorphous alloy according to the present example is shown in table 1.
TABLE 1 chemical composition (wt%) of zirconium based amorphous alloy according to the present embodiment
A method for improving wear resistance and corrosion resistance of a zirconium-based amorphous alloy specifically comprises the following steps:
(1) Smelting and water-cooling copper mold casting are carried out according to the components in the table 1 to obtain the zirconium-based amorphous alloy.
(2) Connecting the positive and negative electrodes of a pulse power supply to two ends of a sample, putting the zirconium-based amorphous alloy into an open heating furnace to heat the zirconium-based amorphous alloy to 180 ℃, and then introducing alternating current pulses, wherein the pulse width is 10 mu s, the pulse interval is 50 mu s, and the pulse current density is 50A/mm 2 The processing time is 30 s, and the temperature of the sample is controlled below the crystallization temperature, so that the sample is more disordered in long range.
(3) Introducing direct current pulse with the pulse frequency of 5 Hz, the pulse interval of 50 mus and the pulse current density of 500A/mm 2 The temperature of the sample is regulated to be below the crystallization temperature, the zirconium-based amorphous sample is subjected to circulating alternating current pulse and direct current pulse heat treatment, the circulating times are 5 times, and the heat treatment temperature is lower than 300 ℃.
(4) And performing water quenching treatment on the zirconium-based amorphous sample subjected to the pulse heat treatment to obtain the wear-resistant and corrosion-resistant zirconium-based amorphous material.
The hardness and the wear rate of the sample are measured by adopting a micro Vickers hardness and a reciprocating wear machine to represent the wear resistance of the material, and the corrosion resistance of the material is measured by adopting the open circuit potential and the self-corrosion current density of the sample measured by electrochemistry as shown in Table 2.
TABLE 2 hardness, wear rate, open circuit potential and corrosion current density performance results for zirconium-based amorphous materials
Example 2
The chemical composition of the zirconium based amorphous alloy according to the present example is shown in table 3.
Table 3 chemical composition (wt%) of zirconium based amorphous alloy of this example
A method for improving wear resistance and corrosion resistance of a zirconium-based amorphous alloy specifically comprises the following steps:
(1) Smelting and water-cooling copper mold casting are carried out according to the components in the table 3 to obtain the zirconium-based amorphous alloy, and the zirconium-based amorphous alloy is heated to 190 ℃ by adopting an open heating furnace.
(2) Connecting the positive and negative electrodes of a pulse power supply to two ends of a sample, and then introducing alternating current pulse with the pulse width of 10 mus, the pulse interval of 50 mus and the pulse current density of 500A/mm 2 The processing time is 20s, and the temperature of the sample is controlled to be lower than the crystallization temperature, so that the sample is disordered in long distance.
(3) Introducing direct current pulse with the pulse frequency of 50 Hz, the pulse interval of 100 mus and the pulse current density of 800A/mm 2 And regulating the temperature of the sample to be below the crystallization temperature, and performing circulating alternating current pulse and direct current pulse heat treatment on the zirconium-based amorphous sample for 6 times.
(4) And performing water quenching treatment on the zirconium-based amorphous sample subjected to the pulse heat treatment to obtain the wear-resistant and corrosion-resistant zirconium-based amorphous material.
The hardness and wear rate of the samples measured by a micro Vickers hardness and a reciprocating wear machine are used for representing the wear resistance of the material, and the corrosion resistance of the material measured by the open-circuit potential and the self-corrosion current density of the samples measured by electrochemistry is shown in Table 4.
TABLE 4 hardness, wear rate, open circuit potential and corrosion current density performance results for the zirconium-based amorphous material of this example
Example 3
The chemical composition of the zirconium based amorphous alloy according to the present example is shown in table 5.
Table 5 chemical composition (wt%) of zirconium-based amorphous alloy according to the embodiment of the present invention
A method for improving wear resistance and corrosion resistance of a zirconium-based amorphous alloy specifically comprises the following steps:
(1) Smelting and water-cooling copper mold casting are carried out according to the components in the table 5 to obtain the zirconium-based amorphous alloy; and heating the zirconium-based amorphous alloy to 200 ℃ by adopting an open heating furnace.
(2) Connecting the positive and negative electrodes of a pulse power supply to two ends of a sample, and then introducing alternating current pulse, wherein the pulse width is 20 mus, the pulse interval is 100 mus, and the pulse current density is 1000A/mm 2 The processing time is 60 s, and the temperature of the sample is controlled below the crystallization temperature, so that the sample is more disordered in long range.
(3) Introducing direct current pulse with pulse frequency of 10Hz, pulse interval of 100 mus and pulse current density of 500A/mm 2 And regulating the temperature of the sample to be below the crystallization temperature, and performing circulating alternating current pulse and direct current pulse heat treatment on the zirconium-based amorphous sample, wherein the circulating times are 5 times, and the heat treatment temperature is less than 300 ℃.
(4) And performing water quenching treatment on the zirconium-based amorphous sample subjected to the pulse heat treatment to obtain the wear-resistant and corrosion-resistant zirconium-based amorphous material.
The hardness and the wear rate of the sample are measured by adopting a micro Vickers hardness and a reciprocating wear machine to represent the wear resistance of the material, and the corrosion resistance of the material is measured by adopting the open-circuit potential and the self-corrosion current density of the sample measured by electrochemistry as shown in the table 6.
TABLE 6 hardness, wear rate, open circuit potential and corrosion current density performance results of the zirconium-based amorphous material of this example
Claims (3)
1. A method for improving wear resistance and corrosion resistance of a zirconium-based amorphous alloy is characterized by comprising the following steps: regulating and controlling the zirconium-based amorphous alloy by electric pulse to ensure that the zirconium-based amorphous alloy has short-range order,
(1) Heating the zirconium-based amorphous to 180-200 ℃ by using an open heating furnace;
(2) Alternating current pulse is introduced, the pulse width is 1-20 mus, the pulse interval is 10-100 mus, and the pulse current density is 50-1000A/mm 2 The temperature of the sample is regulated below the crystallization temperature, so that the length of the sample is more disordered;
(3) Introducing direct current pulse with the pulse frequency of 1-10 Hz, the pulse interval of 50-100 mus and the pulse current density of 500-1000A/mm 2 The temperature of the sample is controlled to be below the crystallization temperature, so that the sample tends to a (111) crystal orientation in a short range;
(4) Performing circulating alternating current pulse and direct current pulse heat treatment on the zirconium-based amorphous sample, wherein the circulating times are not less than 5 times, and the time of each pulse heat treatment is not less than 10 s;
(5) And carrying out water quenching and cooling on the zirconium-based amorphous sample subjected to the pulse heat treatment.
2. The method for improving the wear resistance and corrosion resistance of the zirconium-based amorphous alloy according to claim 1, wherein the method comprises the following steps: the zirconium-based amorphous alloy comprises, by mass, 40-41.2% of Zr, 13-13.8% of Ti, 12-12.5% of Cu, 9.5-10% of Ni, 22-22.5% of Be and inevitable impurities.
3. The method for improving the wear resistance and corrosion resistance of the zirconium-based amorphous alloy according to claim 1, wherein the method comprises the following steps: and (4) stopping the electric pulse circulation when the temperature of the pulse heat treatment is more than or equal to 350 ℃.
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