CN115679234B - Method for improving wear-resistant and corrosion-resistant properties of zirconium-based amorphous alloy - Google Patents
Method for improving wear-resistant and corrosion-resistant properties of zirconium-based amorphous alloy Download PDFInfo
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- CN115679234B CN115679234B CN202211515158.3A CN202211515158A CN115679234B CN 115679234 B CN115679234 B CN 115679234B CN 202211515158 A CN202211515158 A CN 202211515158A CN 115679234 B CN115679234 B CN 115679234B
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Abstract
The invention discloses a method for improving wear-resistant and corrosion-resistant performance 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, 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 unavoidable impurities; the heat treatment process for regulating and controlling the zirconium-based amorphous alloy to improve the wear resistance and corrosion resistance in a short-range order comprises a heating furnace for heating the zirconium-based amorphous alloy, a circulating alternating current pulse and direct current pulse heat treatment process and a rapid cooling process; finally, the atomic entropy is increased, the amorphous sample is fully disordered in long-range, 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-resistant and corrosion-resistant performance 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 corrosion and abrasion behavior is a widely existing problem in the material application process, and causes great harm to the economic development of society. Solving and delaying equipment damage caused by corrosion and abrasion, researching the corrosion and abrasion mechanism of the material, and improving the wear resistance and the corrosion resistance of the material is the difficulty and the key point of the research in the field of the material at the present stage. Because of the special atomic structure in the amorphous inner part of the zirconium-based block, the zirconium-based block 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 deal of scholars research the wear resistance and corrosion resistance of zirconium-based amorphous alloys. The results of studies conducted by current researchers indicate that the properties of amorphous materials mainly include: has excellent mechanical properties. It was found that the fracture strength of the Zr-based amorphous material had reached 2070 MPa, respectively. Compared with the traditional crystal material, the amorphous phase exists, so that the amorphous phase has better corrosion resistance and can be used for a long time under some complicated and severe working conditions. The trace element addition method is widely applied to the field of amorphous alloy manufacturing. The glass forming ability and properties of amorphous alloys have a great influence on their chemical composition, so microalloying can well adjust the properties of amorphous alloys. Research shows that 0.1% boron +0.2% silicon +0.1% lead can effectively reduce the adverse effect of oxygen on amorphous alloys; proper addition of N can promote glass formation by inhibiting formation of competing crystals in Zr and Ti based bulk amorphous alloys; the Cr and Nb coatings promote the formation of a continuous dense oxide film on the friction surface, and the wear rate of the amorphous coating is remarkably reduced. However, the microalloying method increases the manufacturing cost of the amorphous material, and does not meet the economic benefit index. The wear resistance and corrosion resistance of the zirconium-based amorphous alloy can be improved by an electric pulse method, so that the production cost can be effectively reduced. At present, the main structural relaxation means of the amorphous alloy is to perform heat treatment, the traditional heat treatment process has higher cost and longer time consumption, and the traditional isothermal annealing process is difficult to obtain the required structural relaxation effect. Therefore, a novel heat treatment method is developed to meet the requirements of realizing rapid structural relaxation of the zirconium-based amorphous alloy and improving the wear resistance and corrosion resistance 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 adjusts and controls the short-range order of the zirconium-based amorphous alloy through electric pulse and combines low-temperature annealing and water quenching processes, thereby achieving the purpose of improving the wear resistance and corrosion resistance of the zirconium-based amorphous alloy, and specifically comprises the following steps:
(1) Heating the zirconium-based amorphous material to 180-200 ℃ by adopting an open heating furnace;
（2) Introducing alternating current pulse with pulse width of 1-20 mu s, pulse interval of 10-100 mu s and pulse current density of 50-1000A/mm 2 The temperature of the sample is regulated and controlled below the crystallization temperature, and the atomic entropy is increased, so that the sample is more disordered for a long distance.
(3) Introducing direct current pulse with pulse frequency of 1-10 Hz, pulse interval of 50-100 μs and pulse current density of 500-1000A/mm 2 The temperature of the sample is controlled below the crystallization temperature, so that the sample tends to the (111) crystal orientation in a short range.
(4) Carrying out cyclic alternating current pulse and direct current pulse heat treatment on the zirconium-based amorphous sample, wherein the cycle times are not less than 5 times, and the heat treatment time of each pulse is not less than 10 s;
(5) And carrying out water quenching cooling on the zirconium-based amorphous sample subjected to pulse heat treatment.
Preferably, the zirconium-based amorphous alloy component and the mass percentage thereof comprise 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 unavoidable impurities.
Preferably, in the step (4) of the present invention, when the pulse heat treatment temperature is 350 ℃ or higher, the electric pulse circulation is stopped.
The principle of the invention is as follows:
the amorphous alloy annealing treatment process has the advantages that the amorphous structure can be relaxed by applying pulse current, the atomic structure is changed, the cyclic alternating current pulse and direct current pulse heat treatment is implemented, the pulse heat treatment temperature is close to the amorphous alloy crystallization transition area, the cyclic alternating current pulse enables the entropy value of amorphous atoms to be obviously increased, the atomic arrangement is more disordered, the long-range is more disordered, 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 direction, and the wear resistance and corrosion resistance of the amorphous atoms are improved.
The application effect of the invention is as follows:
(1) The invention regulates and controls the short-range order of the zirconium-based amorphous alloy through electric pulse, and combines low-temperature annealing and water quenching processes to obtain the zirconium-based amorphous alloy with the short-range order oriented (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 cyclic alternating current pulse and direct current pulse heat treatment is added, the cyclic alternating current pulse enables the entropy value of amorphous atoms to be obviously increased, the atomic arrangement is more disordered, the long-range is more disordered, 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 direction, and the wear resistance and corrosion resistance of the amorphous atoms are improved. And secondly, the conventional annealing process is adopted to cool and quench rapidly, so that the heat-treated structure is stable and does not change at room temperature, the treatment time is short, the crystallization of 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 drawing of a process for controlling a short-range ordered heat treatment process for a zirconium-based amorphous alloy in accordance with the present invention.
FIG. 2 is a schematic diagram of a short range ordered long range disordered atomic model of a controlled 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 above.
Example 1
The chemical compositions of the zirconium based amorphous alloy described in this example are shown in table 1.
TABLE 1 chemical composition (wt%) of zirconium based amorphous alloy of the present invention
The method for improving the wear resistance and corrosion resistance of the zirconium-based amorphous alloy specifically comprises the following steps:
(1) Smelting and water-cooling copper mold casting are carried out according to the components shown in the table 1 to obtain the zirconium-based amorphous alloy.
(2) Positive and negative of pulse power supplyThe electrodes are connected with the two ends of the sample, the zirconium-based amorphous alloy is put into an open heating furnace to heat the zirconium-based amorphous alloy to 180 ℃, then alternating current pulse is introduced, the pulse width is 10 mu s, the pulse interval is 50 mu s, and the pulse current density is 50A/mm 2 The treatment time is 30 s, and the temperature of the sample is regulated and controlled below the crystallization temperature, so that the sample is more disordered for a long time.
(3) Introducing DC pulse with pulse frequency of 5 Hz, pulse interval of 50 μs and pulse current density of 500A/mm 2 The temperature of the sample is regulated and controlled below crystallization temperature, and the zirconium-based amorphous sample is subjected to cyclic alternating current pulse and direct current pulse heat treatment, wherein the cycle times are 5 times, and the heat treatment temperature is less than 300 ℃.
(4) And carrying out water quenching treatment on the zirconium-based amorphous sample subjected to pulse heat treatment to obtain the wear-resistant and corrosion-resistant zirconium-based amorphous material.
The hardness and wear rate of the samples were measured using a micro vickers hardness and reciprocating wear machine to characterize the wear resistance of the materials, and the open circuit potential and self-etching current density of the samples were measured electrochemically to measure the corrosion resistance of the materials 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 compositions of the zirconium based amorphous alloy described in this example are shown in table 3.
TABLE 3 chemical composition (wt%) of zirconium based amorphous alloy of the present example
The method for improving the wear resistance and corrosion resistance of the 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 table 3 to obtain a zirconium-based amorphous alloy, and an open heating furnace is adopted to heat the zirconium-based amorphous alloy to 190 ℃.
(2) The positive and negative electrodes of the pulse power supply are connected to the two ends of the sample, and then alternating current pulse with the pulse width of 10 mu s, the pulse interval of 50 mu s and the pulse current density of 500A/mm is introduced 2 The treatment time is 20s, and the temperature of the sample is regulated and controlled below the crystallization temperature, so that the sample is more disordered in a long-range.
(3) Introducing DC pulse with pulse frequency of 50 Hz and pulse interval of 100 μs and pulse current density of 800A/mm 2 And (3) carrying out cyclic alternating current pulse and direct current pulse heat treatment on the zirconium-based amorphous sample under the crystallization temperature by regulating the temperature of the sample, wherein the cycle times are 6 times.
(4) And carrying out water quenching treatment on the zirconium-based amorphous sample subjected to pulse heat treatment to obtain the wear-resistant and corrosion-resistant zirconium-based amorphous material.
The hardness and wear rate of the samples were measured using a micro vickers hardness and reciprocating wear machine to characterize the wear resistance of the materials, and the open circuit potential and self-etching current density of the samples were measured electrochemically to measure the corrosion resistance of the materials as shown in table 4.
TABLE 4 hardness, wear Rate, open circuit potential and Corrosion Current Density Performance results for the zirconium-based amorphous materials of this example
Example 3
The chemical compositions of the zirconium based amorphous alloy described in this example are shown in table 5.
TABLE 5 chemical composition (wt%) of zirconium based amorphous alloy of an embodiment of the present invention
The method for improving the wear resistance and corrosion resistance of the 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 a zirconium-based amorphous alloy; the zirconium-based amorphous phase is heated to 200 ℃ by an open heating furnace.
(2) The positive and negative electrodes of the pulse power supply are connected to the two ends of the sample, and then alternating current pulse with the pulse width of 20 mu s, the pulse interval of 100 mu s and the pulse current density of 1000A/mm is introduced 2 The treatment time is 60 s, and the temperature of the sample is regulated and controlled below the crystallization temperature, so that the sample is more disordered for a long time.
(3) Introducing DC pulse with pulse frequency of 10Hz, pulse interval of 100 μs and pulse current density of 500A/mm 2 The temperature of the sample is regulated and controlled below crystallization temperature, and the zirconium-based amorphous sample is subjected to cyclic alternating current pulse and direct current pulse heat treatment, wherein the cycle times are 5 times, and the heat treatment temperature is less than 300 ℃.
(4) And carrying out water quenching treatment on the zirconium-based amorphous sample subjected to pulse heat treatment to obtain the wear-resistant and corrosion-resistant zirconium-based amorphous material.
The hardness and wear rate of the samples were measured using a micro vickers hardness and reciprocating wear machine to characterize the wear resistance of the materials, and the open circuit potential and self-etching current density of the samples were measured electrochemically to measure the corrosion resistance of the materials as shown in table 6.
TABLE 6 hardness, wear Rate, open circuit potential and Corrosion Current Density Performance results for the zirconium-based amorphous materials of this example
Claims (2)
1. A method for improving wear resistance and corrosion resistance of zirconium-based amorphous alloy is characterized by comprising the following steps: the zirconium-based amorphous alloy is regulated and controlled by electric pulse to ensure that the zirconium-based amorphous alloy is in short-range order,
(1) Heating the zirconium-based amorphous material to 180-200 ℃ by adopting an open heating furnace;
(2) Introducing alternating current pulse with pulse width of 1-20 mu s, pulse interval of 10-100 mu s and pulse current density of 50-1000A/mm 2 The temperature of the sample is regulated and controlled below the crystallization temperature, so that the sample is more disordered for a long distance;
(3) Introducing direct current pulse with pulse frequency of 1-10 Hz, pulse interval of 50-100 μs and pulse current density of 500-1000A/mm 2 Regulating the temperature of the sample below the crystallization temperature to enable the sample to trend to the (111) crystal orientation in a short range;
(4) Carrying out cyclic alternating current pulse and direct current pulse heat treatment on the zirconium-based amorphous sample, wherein the cycle times are not less than 5 times, and the heat treatment time of each pulse is not less than 10 s;
(5) Carrying out water quenching cooling on the zirconium-based amorphous sample subjected to pulse heat treatment;
the zirconium-based amorphous alloy component 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 unavoidable impurities.
2. The method for improving the wear resistance and corrosion resistance of a zirconium based amorphous alloy according to claim 1, wherein: and (4) stopping the electric pulse circulation when the pulse heat treatment temperature is more than or equal to 350 ℃.
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