CN112391587B - Preparation method and application of amorphous alloy material toughened in cryogenic cycle combined pre-deformation mode - Google Patents

Preparation method and application of amorphous alloy material toughened in cryogenic cycle combined pre-deformation mode Download PDF

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CN112391587B
CN112391587B CN202011070613.4A CN202011070613A CN112391587B CN 112391587 B CN112391587 B CN 112391587B CN 202011070613 A CN202011070613 A CN 202011070613A CN 112391587 B CN112391587 B CN 112391587B
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amorphous alloy
alloy
rolling
flexible coupling
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CN112391587A (en
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乔珺威
朱前勇
杨慧君
石晓辉
张敏
王雪姣
晋玺
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Taiyuan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D3/00—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive
    • F16D3/02—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive adapted to specific functions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D3/00—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive
    • F16D3/02—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive adapted to specific functions
    • F16D3/12—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive adapted to specific functions specially adapted for accumulation of energy to absorb shocks or vibration

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Abstract

The invention discloses a preparation method and application of a cryogenic cycle combined pre-deformation mode toughened amorphous alloy material, and belongs to the technical field of amorphous alloy application. The method comprises the steps of treating a flexible coupling diaphragm for toughening amorphous alloy in a cryogenic cycle combined pre-deformation mode, smelting by using a vacuum arc furnace, quickly suction casting a water-cooled copper mold into a plate-shaped amorphous alloy, carrying out cryogenic cycle treatment, carrying out rolling pre-deformation for 5%, and then carrying out rough machining and finish machining to obtain the required diaphragm. The amorphous alloy membrane toughened by the deep cooling circulation combined pre-deformation mode provided by the invention has the advantages of high elastic limit (2%), high hardness, high strength, wear resistance, long service life and the like. The flexible coupling diaphragm is made of Zr-based amorphous, so that the application of the flexible coupling in high-end, precise and special demand occasions is widened, and the high-precision flexible coupling diaphragm has high commercial use value.

Description

Preparation method and application of amorphous alloy material toughened in cryogenic cycle combined pre-deformation mode
Technical Field
The invention relates to a preparation method and application of a cryogenic cycle combined pre-deformation mode toughened amorphous alloy material, and belongs to the technical field of preparation and application of amorphous alloys.
Background
The amorphous alloy has many excellent performances, such as large elastic limit (elastic limit 2%), high breaking strength, high hardness, good corrosion resistance, friction resistance and the like, due to the unique structural characteristics of long-range disorder, short-range order, no grain boundary and the like, and is a structural material with wide application prospect. These unique properties provide excellent elastic behavior, which is rare in crystalline metals. However, the plastic deformation of room temperature amorphous alloys is limited to shear bands of the order of 10 nm, and the amorphous alloys exhibit brittle fracture due to the rapid propagation of a single shear band. Room temperature brittleness seriously hinders the practical application of amorphous alloys as structural materials. In recent years, researchers find that the room temperature brittleness of the amorphous alloy can be effectively improved by performing Deep cryogenic cycle treatment (DCT for short) on the amorphous alloy. Cryogenic cyclic treatment is a method of cyclic "hot" treatment between room temperature and low temperature. Compared with toughening treatment methods such as surface shot blasting, notch forming, radiation treatment and the like, the cryogenic circulating treatment has the advantages of low cost, simplicity in operation, no size limitation, no damage to samples, no crystallization and the like. Cryogenic cyclic treatment is considered an effective "hot" treatment method to improve the toughness of amorphous alloys. Meanwhile, the mode of increasing the toughness of the amorphous alloy by the pre-deformation mode has been widely researched. Amorphous alloys with large elastic limit and high strength have been used in the fields of golf clubs (drivers, push rods), watches, mobile phone electromagnetic device housings, optical lenses, and the like. In the mechanical transmission equipment devices in various industries at present, the flexible coupling well solves the problem of damage to equipment caused by impact generated by frequent acceleration and deceleration of the equipment on different occasions. The most important accessory on the flexible coupling is the diaphragm, and when the flexible coupling is transmitted to the diaphragm in the acceleration and deceleration process of the equipment, the diaphragm can well absorb impact to play a role in buffering; but also angular and axial deviations can be compensated for by the membrane. Zero gyration clearance, the same gyration characteristic is had in the same direction of flow transmission. This drives the need for membranes having high elasticity, high stiffness, wear resistance, fatigue resistance, etc. In the prior art, the flexible coupling diaphragm is mostly made of stainless steel, and although the stainless steel diaphragm is higher in strength and more wear-resistant compared with an early carbon steel diaphragm, the flexible coupling diaphragm cannot meet the requirements of customers in occasions with high precision, high rotating speed and special requirements. The amorphous alloy flexible coupling diaphragm toughened by the cryogenic circulating treatment well makes up the defects of the stainless steel diaphragm in the aspect.
Disclosure of Invention
The invention aims to provide a preparation method of an amorphous alloy material toughened by a cryogenic cycle combined predeformation mode and application of the amorphous alloy material in preparing a flexible coupling diaphragm, wherein the amorphous alloy diaphragm toughened by the cryogenic cycle combined predeformation mode has the advantages of high elastic limit (2%), high hardness, high strength, wear resistance, long service life and the like; the application of the flexible coupling in high-precision and special-demand occasions is widened.
The invention uses deep cooling circulation combined predeformation mode to process toughened flexible coupling diaphragm, and the high elastic diaphragm of the flexible coupling adopts Zr55Al10Ni5Cu29Y1Manufacturing an amorphous alloy; for the problems of high element purity, high smelting vacuum degree, amorphous forming capability and the like of amorphous alloy preparation, the Y element is added into a Zr-Al-Ni-Cu amorphous alloy system to improve the amorphous forming capability and reduce the cost of amorphous alloy smelting preparation; the toughness of the amorphous alloy subjected to the deep cooling circulation combined with the pre-deformation treatment is improved.
The invention provides a method for preparing a cryogenic circulation combined pre-deformation mode toughened amorphous alloy material, which comprises the following steps:
step one, pretreatment: respectively cleaning the amorphous alloy raw materials of Zr, Al, Ni, Cu and Y metals by a file, then respectively putting the raw materials into ultrasonic cleaning equipment filled with absolute ethyl alcohol for ultrasonic cleaning for 10-20 minutes to remove oil stains and impurities on the surfaces of the raw materials, and then drying the required raw materials by a drying oven;
step two, batching: according to the atomic percentage of Zr, Al, Ni, Cu and Y elements of 55: 10: 5: 29: 1, calculating the mass required by each pure metal raw material;
step three, smelting and suction casting:
(1) putting the pure metal raw materials weighed in the step two into the same copper mold crucible from bottom to top in sequence according to the sequence of the melting points of the elements from low to high, and ensuring that the high-melting-point raw materials can be completely melted; placing the titanium sponge block for testing the oxygen content into another copper mold crucible, and then closing a furnace door of the crucible;
(2) pumping the cavity to below 5 Pa by using a first-stage mechanical pump, closing a closing valve, opening a second-stage mechanical pump and a molecular pump to make the interior of the furnace chamber reach a high vacuum state, and when the vacuum degree of the furnace chamber reaches 1 × 10-3When Pa, closing a valve at the molecular pump; then filling high-purity argon to ensure that the pressure of the furnace chamber is 0.5 atm;
(3) firstly, smelting a titanium sponge block to check the oxygen content in the furnace, and smelting alloy after the titanium sponge block is smelted and cooled and has no color change, wherein the smelting process adopts electric arc smelting, and an alloy ingot is repeatedly turned and smelted for 5 times to ensure uniform components;
(4) placing alloy ingots with uniform components at the edge of a crucible, cutting the alloy ingots into alloy mother ingots with the mass of 30-40 g suitable for suction casting by using electric arcs, moving the alloy mother ingots into a suction casting copper mold crucible by using a mechanical arm, smelting the alloy ingots by using the electric arcs, quickly opening a suction casting valve switch after the alloy ingots are completely molten, quickly suction casting the alloy into a water-cooling copper mold by using pressure difference, and quickly cooling the alloy by the water-cooling copper mold to obtain plate-shaped amorphous alloys with the length, the width and the thickness of 85 multiplied by 30 multiplied by 2 mm;
step four, primary processing:
sequentially grinding and polishing the plate-shaped amorphous alloy obtained in the step three by using sand paper of different types of 240 #, 400 #, 600 #, 800 #, 1000 #, 1500 # and 2000 #, and removing oil stains and impurities by using ultrasonic waves; simultaneously, mechanically polishing the side surface of the plate-shaped test sample by using diamond polishing paste, and then cleaning the test sample by using ultrasonic waves;
step five, cryogenic circulating treatment:
in order to improve the mechanical property of the amorphous alloy and enable the amorphous alloy to be in a higher energy state, the amorphous alloy is subjected to cryogenic circular treatment. Carrying out cryogenic circulating treatment on the amorphous alloy in the fourth step: firstly, placing an amorphous alloy sample into a liquid nitrogen container for 5 minutes, then quickly placing the amorphous alloy sample into a boiled water container for 1 minute, heating to 50-80 ℃, and then standing in a room-temperature environment for 4 minutes; performing cyclic subzero treatment for 20-60 times respectively by using the above step as subzero cyclic treatment; and obtaining the amorphous alloy material.
In the second step of the preparation method, the clean pure metal raw material processed in the first step is weighed by using an electronic balance with the precision of 0.001g, and the weighing mass error range is ensured to be within the range of +/-0.003 g.
In the preparation method, the purity of the argon in the third step is 99.999%.
In the third step of the preparation method, the current is controlled to be 180-200 mA during arc melting.
The invention provides application of the amorphous alloy material prepared by the preparation method in a flexible coupling diaphragm.
The application specifically comprises the following steps:
(1) rolling and pre-deforming:
in order to further improve the amorphous toughness, the plate-shaped sample obtained after the deep cooling circulating treatment is rolled by adopting an ATMR series electric miniature reversible two-high mill, and the rolling process is finished in multiple passes; the rolling process adopts a longitudinal rolling two-dimensional rolling mode, after each rolling pass is finished, the sample is horizontally rotated by 180 degrees, and the two directions are alternately rolled until the required 5 percent of pre-deformation amount is obtained;
(2) finish machining:
polishing the alloy surface after the pre-deformation treatment to a thickness of 0.3-0.5 mm of a diaphragm, polishing, and removing oil stains by using ultrasonic cleaning equipment; then, according to a design dimension drawing of the flexible coupling diaphragm, precisely perforating the diaphragm by using the rotating heads with different diameters so as to install a fixing bolt; using a rotary head to open holes according to the principle of opening holes from small to large successively; then, accurately cutting according to the design size drawing and the structure and precision requirements by using a low-speed precision cutting machine; then, utilizing a polishing machine to polish the side surface and the front surface and the back surface of the membrane into mirror surfaces by water grinding; cleaning oil stains and impurities on the finished membrane by using ultrasonic cleaning equipment; and manufacturing the flexible coupling diaphragm.
Furthermore, in the rolling pre-deformation process, the reduction of each roller is not allowed to exceed 0.01mm, the rolling frequency is not less than 15 rolling processes, and the reduction of each pass is 0.01 mm.
Further, the diameters of the used rotor heads are 2, 3, 4, 5 and 6mm respectively.
The invention has the beneficial effects that:
the flexible coupling diaphragm for treating toughened amorphous alloy by using the deep cooling circulation combined pre-deformation mode has the advantages of high elastic limit (elastic limit is 2%), high hardness, high strength, wear resistance, long service life and the like. Compared with a flexible coupling diaphragm made of stainless steel, the flexible coupling diaphragm has wider application range, widens the application field of the flexible coupling in occasions with high-end precision and special requirements, and has very high commercial use value.
Drawings
FIG. 1 is stress-strain curves of compressive mechanical properties of amorphous alloys before and after treatment with combined pre-deformation of cryogenic cycles (0, 20, 40, 60 cycles) in example 1, and it is found by comparison that the toughness of amorphous alloys is improved with the increase of the number of cryogenic cycles.
FIG. 2 is a comparison XRD chart before and after the treatment of the deep cooling cycle (0, 20, 40, 60 cycles) combined with the pre-deformation mode in example 1, and it can be seen that the sample is still in an amorphous structure after the cast state deep cooling treatment.
Fig. 3 is DSC curves before and after the treatment in the combined pre-deformation mode of the cryogenic cycles (0, 20, 40, 60 cycles) in example 1, and it was found by curve calculation that the enthalpy value of release before and after the treatment in the combined pre-deformation mode of the cryogenic cycles was increased, that is, the content of free volume in the material before and after the treatment in the combined pre-deformation mode of the cryogenic cycles was increased.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
this example is a deep cooling circulation combined pre-deformation mode for treating toughened Zr55Al10Ni5Cu29Y1A preparation method and application of amorphous alloy material.
This embodiment is a deep coolingThe Zr-Al-Ni-Cu-Y amorphous alloy material treated and toughened in a circulating combined pre-deformation mode consists of five elements of Zr, Al, Ni, Cu and Y, wherein the atomic percent of the Zr-Al-Ni-Cu-Y amorphous alloy material is Zr55Al10Ni5Cu29Y1Wherein Ti, Zr, V, Cu and Be are subjected to smelting and suction casting to form plate-shaped amorphous alloy after removing oxides from blocky Zr, Al, Ni, Cu and Y with the purity of more than or equal to 99.999 percent by a file, cleaning by alcohol and drying by an oven, and then performing cryogenic circulating treatment and pre-deformation rolling.
Zr proposed in this example55Al10Ni5Cu29Y1The preparation process of the diaphragm of the amorphous alloy flexible coupling toughened by the deep cooling circulation combined pre-deformation mode treatment comprises the following steps:
step one, pretreatment: respectively cleaning oxide skins of Zr, Al, Ni, Cu and Y metals serving as amorphous alloy raw materials by using a file, then respectively putting the raw materials into ultrasonic cleaning equipment filled with absolute ethyl alcohol for ultrasonic cleaning for 10-20 minutes to remove oil stains and impurities on the surfaces of the raw materials, and then drying the required raw materials by using a drying oven.
Step two, batching: according to the atomic percentage of Zr, Al, Ni, Cu and Y elements of 55: 10: 5: 29: 1 calculating the mass required for each raw material pure metal. And weighing the clean pure metal raw material processed in the step one by adopting an electronic balance with the precision of 0.001g, wherein the weighing mass error range is ensured to be less than +/-0.003 g.
Step three, smelting and suction casting:
(1) putting the pure metal raw materials weighed in the step two into the same copper mold crucible from bottom to top in sequence according to the sequence of the melting points of the elements from low to high, and ensuring that the high-melting-point raw materials can be completely melted; placing the titanium sponge block for testing the oxygen content into another copper mold crucible, and then closing the furnace door;
(2) pumping the cavity to below 5 Pa by using a first-stage mechanical pump, closing a closing valve, opening a second-stage mechanical pump and a molecular pump to make the interior of the furnace chamber reach a high vacuum state, and when the vacuum degree of the furnace chamber reaches 1 × 10-3When Pa, closing a valve at the molecular pump; then is filled into highPure argon makes the pressure of the furnace chamber 0.5 atm;
(3) firstly, smelting a titanium sponge block to check the oxygen content in the furnace, and smelting alloy after the titanium sponge block is smelted and cooled and has no color change, wherein the smelting process adopts electric arc smelting (the current is controlled to be 180 mA), and an alloy ingot is repeatedly turned and smelted for 5 times to ensure uniform components;
(4) placing an alloy ingot with uniform components at the edge of a crucible, cutting the alloy ingot into alloy mother ingots with the mass of 30g and suitable for suction casting by using an electric arc, moving the alloy mother ingots into a suction casting copper mold crucible by using a mechanical arm, smelting the alloy ingots by using the electric arc (the control current is 180 mA), quickly opening a suction casting valve switch after the alloy ingots are completely molten, quickly suction casting the alloy into a water-cooling copper mold by using pressure difference, and quickly cooling the alloy by using the water-cooling copper mold to obtain the plate-shaped amorphous alloy with the length, width and thickness of 85 multiplied by 30 multiplied by 2 mm.
Step four, primary processing:
sequentially grinding and polishing the plate-shaped amorphous alloy obtained in the step three by using sand paper of different types of 240 #, 400 #, 600 #, 800 #, 1000 #, 1500 # and 2000 #, and removing oil stains and impurities by using ultrasonic waves; simultaneously, mechanically polishing the side surface of the plate-shaped test sample by using diamond polishing paste, and then cleaning the test sample by using ultrasonic waves;
step five, cryogenic circulating treatment:
in order to improve the mechanical property of the amorphous alloy and enable the amorphous alloy to be in a higher energy state, the amorphous alloy is subjected to cryogenic circular treatment. And D, carrying out deep cooling circulation treatment on the amorphous alloy in the fourth step. Firstly, an amorphous alloy sample is put into a liquid nitrogen container for 5 minutes, then is quickly put into a boiled water container for 1 minute to be heated to 50 ℃, and then is kept still in a room temperature environment for 4 minutes. The treatment is a cryogenic cycle treatment, and 20, 40 and 60 cycles of cryogenic treatment are respectively carried out.
Step six, rolling and pre-deforming:
in order to further improve the amorphous toughness, after the deep cooling cycle treatment, an ATMR series electric miniature reversible two-roll mill is adopted for rolling, and the rolling process is completed in multiple steps: the reduction of each roller is not allowed to exceed 0.01mm, the reduction frequency of the roller is not less than 15 times of rolling processes, and the reduction of each pass is 0.01 mm. And a longitudinal rolling two-dimensional rolling mode is adopted in the rolling process, after each rolling pass is finished, the sample is horizontally rotated by 180 degrees, and the two directions are alternately rolled until the required 5% pre-deformation amount is obtained.
Step seven, fine machining:
and (3) polishing the alloy surface treated by the deep cooling circulation combined predeformation mode to the thickness of 0.3 mm of the diaphragm, polishing, and removing oil stains by using ultrasonic cleaning equipment. And then, according to a flexible coupling diaphragm design size drawing, utilizing the rotary heads with different diameters to precisely open holes in the diaphragm so as to install the fixing bolts. And (4) using a rotary head to perform hole opening according to the principle of opening holes from small to large successively. The diameter specifications of the rotating head are respectively 2, 3, 4, 5 and 6 mm. And then, accurately cutting according to the structure and the precision requirement by using a low-speed precision cutting machine according to the design dimension drawing. And then, polishing the side surface and the front surface and the back surface of the membrane into a mirror surface by using a polishing machine. And (4) cleaning oil stains and impurities of the finished membrane by using ultrasonic cleaning equipment.
And (3) carrying out a performance detection process on the obtained product and according to the following steps:
(1) selecting a 2X 4mm cuboid compression sample from the finished sample, and performing quasi-static compression test by using an Instron5696 electronic mechanical testing machine, wherein the compression rate is 1X 10-4s-1Therefore, the change of the mechanical property of the material after the combined pre-deformation treatment of the cryogenic cycle (0, 20, 40 and 60 times) of the amorphous material is analyzed and compared, as shown in figure 1.
(2) A 3 × 3mm rectangular piece is taken from the finished sample and tested by an XRD device at a scanning rate of 10 °/min and a test angle ranging from 10 ° to 90 °, so as to analyze and compare the change of the crystal structure of the material after the amorphous material deep cooling cycle (0, 20, 40 and 60 times) combined pre-deformation treatment, as shown in FIG. 2.
(3) And taking 20mg of sample from the finished sample to carry out DSC test, and selecting 20K/min as the heating rate so as to analyze and compare the change of the thermodynamic property of the material after the amorphous material is subjected to combined pre-deformation treatment in cryogenic cycles (0, 20, 40 and 60 times), as shown in figure 3.
And (3) performance test results:
in fig. 1, stress-strain curves of compressive mechanical properties of the amorphous alloy before and after the treatment in the deep cooling cycle (0, 20, 40, and 60 times) combined pre-deformation mode are compared, and it is found that the toughness of the amorphous alloy is improved with the increase of the number of times of the deep cooling cycle treatment.
In fig. 2, XRD comparison patterns before and after the deep cooling cycle (0, 20, 40, and 60 times) combined pre-deformation treatment show that the sample is still amorphous compared to the sample after the as-cast state cryogenic treatment.
In the DSC curves before and after the deep cooling cycle (0, 20, 40, 60 times) combined pre-deformation mode treatment in fig. 3, it is found through curve calculation that the enthalpy value of release increases before and after the deep cooling cycle combined pre-deformation mode treatment, that is, the free volume content in the material increases before and after the deep cooling cycle combined pre-deformation mode treatment.
Example 2:
this example is a deep cooling circulation combined pre-deformation mode for treating toughened Zr55Al10Ni5Cu29Y1A preparation method and application of amorphous alloy material.
The embodiment is that the Zr-Al-Ni-Cu-Y amorphous alloy material toughened by the deep cooling circulation combined pre-deformation mode treatment consists of five elements of Zr, Al, Ni, Cu and Y, wherein the atomic percent of the Zr-Al-Ni-Cu-Y amorphous alloy material is Zr55Al10Ni5Cu29Y1Wherein Ti, Zr, V, Cu and Be are subjected to smelting and suction casting to form plate-shaped amorphous alloy after removing oxides from blocky Zr, Al, Ni, Cu and Y with the purity of more than or equal to 99.999 percent by a file, cleaning by alcohol and drying by an oven, and then performing cryogenic circulating treatment and pre-deformation rolling.
Zr proposed in this example55Al10Ni5Cu29Y1The preparation process of the diaphragm of the amorphous alloy flexible coupling toughened by the deep cooling circulation combined pre-deformation mode treatment comprises the following steps:
step one, pretreatment: respectively cleaning oxide skins of Zr, Al, Ni, Cu and Y metals serving as amorphous alloy raw materials by using a file, then respectively putting the raw materials into ultrasonic cleaning equipment filled with absolute ethyl alcohol for ultrasonic cleaning for 10-20 minutes to remove oil stains and impurities on the surfaces of the raw materials, and then drying the required raw materials by using a drying oven.
Step two, batching: according to the atomic percentage of Zr, Al, Ni, Cu and Y elements of 55: 10: 5: 29: 1 calculating the mass required for each raw material pure metal. And weighing the clean pure metal raw material processed in the step one by adopting an electronic balance with the precision of 0.001g, wherein the weighing mass error range is ensured to be less than +/-0.003 g.
Step three, smelting and suction casting:
(1) putting the pure metal raw materials weighed in the step two into the same copper mold crucible from bottom to top in sequence according to the sequence of the melting points of the elements from low to high, and ensuring that the high-melting-point raw materials can be completely melted; placing the titanium sponge block for testing the oxygen content into another copper mold crucible, and then closing the furnace door;
(2) pumping the cavity to below 5 Pa by using a first-stage mechanical pump, closing a closing valve, opening a second-stage mechanical pump and a molecular pump to make the interior of the furnace chamber reach a high vacuum state, and when the vacuum degree of the furnace chamber reaches 1 × 10-3When Pa, closing a valve at the molecular pump; then filling high-purity argon to ensure that the pressure of the furnace chamber is 0.5 atm;
(3) firstly, smelting a titanium sponge block to check the oxygen content in the furnace, and smelting alloy after the titanium sponge block is smelted and cooled and has no color change, wherein the smelting process adopts electric arc smelting (the current is controlled to be 190 mA), and an alloy ingot is repeatedly turned and smelted for 5 times to ensure uniform components;
(4) placing an alloy ingot with uniform components at the edge of a crucible, cutting the alloy ingot into alloy mother ingots with the mass of about 35g suitable for suction casting by using an electric arc, moving the alloy mother ingots into a suction casting copper mold crucible by using a mechanical arm, smelting the alloy ingots by using the electric arc (the control current is 190 mA), quickly opening a suction casting valve switch after the alloy ingots are completely molten, quickly suction casting the alloy into a water-cooling copper mold by using pressure difference, and quickly cooling the alloy by the water-cooling copper mold to obtain the plate-shaped amorphous alloy with the length, the width and the thickness of 85 multiplied by 30 multiplied by 2 mm.
Step four, primary processing:
sequentially grinding and polishing the plate-shaped amorphous alloy obtained in the step three by using sand paper of different types of 240 #, 400 #, 600 #, 800 #, 1000 #, 1500 # and 2000 #, and removing oil stains and impurities by using ultrasonic waves; simultaneously, mechanically polishing the side surface of the plate-shaped test sample by using diamond polishing paste, and then cleaning the test sample by using ultrasonic waves;
step five, cryogenic circulating treatment:
in order to improve the mechanical property of the amorphous alloy and enable the amorphous alloy to be in a higher energy state, the amorphous alloy is subjected to cryogenic circular treatment. And D, carrying out deep cooling circulation treatment on the amorphous alloy in the fourth step. Firstly, an amorphous alloy sample is put into a liquid nitrogen container for 5 minutes, then is quickly put into a boiled water container for 1 minute to be heated to 65 ℃, and then is kept still in a room temperature environment for 4 minutes. The treatment is a cryogenic cycle treatment, and 40 cycles of cryogenic treatment are carried out.
Step six, rolling and pre-deforming:
in order to further improve the amorphous toughness, after the deep cooling cycle treatment, an ATMR series electric miniature reversible two-roll mill is adopted for rolling, and the rolling process is completed in multiple steps: the reduction of each roller is not allowed to exceed 0.01mm, the reduction frequency of the roller is not less than 15 times of rolling processes, and the reduction of each pass is 0.01 mm. And a longitudinal rolling two-dimensional rolling mode is adopted in the rolling process, after each rolling pass is finished, the sample is horizontally rotated by 180 degrees, and the two directions are alternately rolled until the required 5% pre-deformation amount is obtained.
Step seven, fine machining:
and (3) polishing the alloy surface treated by the deep cooling circulation combined predeformation mode to the thickness of 0.4 mm of the diaphragm, polishing, and removing oil stains by using ultrasonic cleaning equipment. And then, according to a flexible coupling diaphragm design size drawing, utilizing the rotary heads with different diameters to precisely open holes in the diaphragm so as to install the fixing bolts. And (4) using a rotary head to perform hole opening according to the principle of opening holes from small to large successively. The diameter specifications of the rotating head are respectively 2, 3, 4, 5 and 6 mm. And then, accurately cutting according to the structure and the precision requirement by using a low-speed precision cutting machine according to the design dimension drawing. And then, polishing the side surface and the front surface and the back surface of the membrane into a mirror surface by using a polishing machine. And (4) cleaning oil stains and impurities of the finished membrane by using ultrasonic cleaning equipment.
Example 3:
this example is a deep cooling circulation combined pre-deformation mode for treating toughened Zr55Al10Ni5Cu29Y1A preparation method and application of amorphous alloy material.
The embodiment is that the Zr-Al-Ni-Cu-Y amorphous alloy material toughened by the deep cooling circulation combined pre-deformation mode treatment consists of five elements of Zr, Al, Ni, Cu and Y, wherein the atomic percent of the Zr-Al-Ni-Cu-Y amorphous alloy material is Zr55Al10Ni5Cu29Y1Wherein Ti, Zr, V, Cu and Be are subjected to smelting and suction casting to form plate-shaped amorphous alloy after removing oxides from blocky Zr, Al, Ni, Cu and Y with the purity of more than or equal to 99.999 percent by a file, cleaning by alcohol and drying by an oven, and then performing cryogenic circulating treatment and pre-deformation rolling.
Zr proposed in this example55Al10Ni5Cu29Y1The preparation process of the diaphragm of the amorphous alloy flexible coupling toughened by the deep cooling circulation combined pre-deformation mode treatment comprises the following steps:
step one, pretreatment: respectively cleaning oxide skins of Zr, Al, Ni, Cu and Y metals serving as amorphous alloy raw materials by using a file, then respectively putting the raw materials into ultrasonic cleaning equipment filled with absolute ethyl alcohol for ultrasonic cleaning for 10-20 minutes to remove oil stains and impurities on the surfaces of the raw materials, and then drying the required raw materials by using a drying oven.
Step two, batching: according to the atomic percentage of Zr, Al, Ni, Cu and Y elements of 55: 10: 5: 29: 1 calculating the mass required for each raw material pure metal. And weighing the clean pure metal raw material processed in the step one by adopting an electronic balance with the precision of 0.001g, wherein the weighing mass error range is ensured to be less than +/-0.003 g.
Step three, smelting and suction casting:
(1) putting the pure metal raw materials weighed in the step two into the same copper mold crucible from bottom to top in sequence according to the sequence of the melting points of the elements from low to high, and ensuring that the high-melting-point raw materials can be completely melted; placing the titanium sponge block for testing the oxygen content into another copper mold crucible, and then closing the furnace door;
(2) pumping the cavity to below 5 Pa by using a first-stage mechanical pump, closing a closing valve, opening a second-stage mechanical pump and a molecular pump to make the interior of the furnace chamber reach a high vacuum state, and when the vacuum degree of the furnace chamber reaches 1 × 10-3When Pa, closing a valve at the molecular pump; then filling high-purity argon to ensure that the pressure of the furnace chamber is 0.5 atm;
(3) firstly, smelting a titanium sponge block to check the oxygen content in the furnace, and smelting alloy after the titanium sponge block is smelted and cooled and has no color change, wherein the smelting process adopts electric arc smelting (the current is controlled to be 200 mA), and an alloy ingot is repeatedly turned and smelted for 5 times to ensure uniform components;
(4) placing an alloy ingot with uniform components at the edge of a crucible, cutting the alloy ingot into alloy mother ingots with the mass of about 40g suitable for suction casting by using an electric arc, moving the alloy mother ingots into a suction casting copper mold crucible by using a mechanical arm, smelting the alloy ingots by using the electric arc (the control current is 200 mA), quickly opening a suction casting valve switch after the alloy ingots are completely molten, quickly suction casting the alloy into a water-cooling copper mold by using pressure difference, and quickly cooling the alloy by the water-cooling copper mold to obtain the plate-shaped amorphous alloy with the length, width and thickness of 85 multiplied by 30 multiplied by 2 mm.
Step four, primary processing:
sequentially grinding and polishing the plate-shaped amorphous alloy obtained in the step three by using sand paper of different types of 240 #, 400 #, 600 #, 800 #, 1000 #, 1500 # and 2000 #, and removing oil stains and impurities by using ultrasonic waves; simultaneously, mechanically polishing the side surface of the plate-shaped test sample by using diamond polishing paste, and then cleaning the test sample by using ultrasonic waves;
step five, cryogenic circulating treatment:
in order to improve the mechanical property of the amorphous alloy and enable the amorphous alloy to be in a higher energy state, the amorphous alloy is subjected to cryogenic circular treatment. And D, carrying out deep cooling circulation treatment on the amorphous alloy in the fourth step. Firstly, an amorphous alloy sample is put into a liquid nitrogen container for 5 minutes, then is quickly put into a boiled water container for 1 minute to be heated to 80 ℃, and then is kept stand in a room temperature environment for 4 minutes. The treatment is a cryogenic cycle treatment, and 60 cycles of cryogenic treatment are carried out.
Step six, rolling and pre-deforming:
in order to further improve the amorphous toughness, after the deep cooling cycle treatment, an ATMR series electric miniature reversible two-roll mill is adopted for rolling, and the rolling process is completed in multiple steps: the reduction of each roller is not allowed to exceed 1 scale value (1 scale value is 0.01 mm) of the dividing plate, the reduction frequency of the roller is not less than 15 times of rolling processes, and the reduction of each pass is 0.01 mm. And a longitudinal rolling two-dimensional rolling mode is adopted in the rolling process, after each rolling pass is finished, the sample is horizontally rotated by 180 degrees, and the two directions are alternately rolled until the required 5% pre-deformation amount is obtained.
Step seven, fine machining:
and (3) polishing the alloy surface treated by the deep cooling circulation combined predeformation mode to the thickness of 0.5mm of the diaphragm, polishing, and removing oil stains by using ultrasonic cleaning equipment. And then, according to a flexible coupling diaphragm design size drawing, utilizing the rotary heads with different diameters to precisely open holes in the diaphragm so as to install the fixing bolts. And (4) using a rotary head to perform hole opening according to the principle of opening holes from small to large successively. The diameter specifications of the rotating head are respectively 2, 3, 4, 5 and 6 mm. And then, accurately cutting according to the structure and the precision requirement by using a low-speed precision cutting machine according to the design dimension drawing. And then, polishing the side surface and the front surface and the back surface of the membrane into a mirror surface by using a polishing machine. And (4) cleaning oil stains and impurities of the finished membrane by using ultrasonic cleaning equipment.

Claims (5)

1. A method for preparing a flexible coupling diaphragm made of amorphous alloy materials toughened in a cryogenic cycle combined pre-deformation mode is characterized in that the toughened amorphous alloy materials are treated in the cryogenic cycle combined pre-deformation mode, and the amorphous alloy materials are Zr55Al10Ni5Cu29Y1(ii) a The addition of Y element in the Zr-Al-Ni-Cu amorphous alloy system improves the amorphous forming ability and reduces the cost of amorphous alloy smelting preparation; pre-changing by deep cooling circulationThe toughness of the amorphous alloy subjected to shape treatment is improved; the preparation method comprises the following steps:
step one, pretreatment: respectively cleaning the amorphous alloy raw materials of Zr, Al, Ni, Cu and Y metals by a file, then respectively putting the raw materials into ultrasonic cleaning equipment filled with absolute ethyl alcohol for ultrasonic cleaning for 10-20 minutes to remove oil stains and impurities on the surfaces of the raw materials, and then drying the required raw materials by a drying oven;
step two, batching: according to the atomic percentage of Zr, Al, Ni, Cu and Y elements of 55: 10: 5: 29: 1, calculating the mass required by each pure metal raw material;
step three, smelting and suction casting:
(1) putting the pure metal raw materials weighed in the step two into the same copper mold crucible from bottom to top in sequence according to the sequence of the melting points of the elements from low to high, and ensuring that the high-melting-point raw materials can be completely melted; placing the titanium sponge block for testing the oxygen content into another copper mold crucible, and then closing a furnace door of the crucible;
(2) pumping the cavity to below 5 Pa by using a first-stage mechanical pump, closing a closing valve, opening a second-stage mechanical pump and a molecular pump to make the interior of the furnace chamber reach a high vacuum state, and when the vacuum degree of the furnace chamber reaches 1 × 10-3When Pa, closing a valve at the molecular pump; then filling high-purity argon to ensure that the pressure of the furnace chamber is 0.5 atm;
(3) firstly, smelting a titanium sponge block to check the oxygen content in the furnace, and smelting alloy after the titanium sponge block is smelted and cooled and has no color change, wherein the smelting process adopts electric arc smelting, and an alloy ingot is repeatedly turned and smelted for 5 times to ensure uniform components; during arc melting, controlling the current to be 180-200 mA;
(4) placing an alloy ingot with uniform components at the edge of a crucible, cutting the alloy ingot into alloy mother ingots with the mass of 30-40 g and suitable for suction casting by using electric arcs, moving the alloy mother ingots into a suction casting copper mold crucible by using a mechanical arm, smelting the alloy ingots by using the electric arcs, quickly opening a suction casting valve switch to quickly suction cast the alloy into a water-cooling copper mold by using pressure difference after the alloy ingots are completely molten, and quickly cooling the alloy by using the water-cooling copper mold to obtain the plate-shaped amorphous alloy with the length, width and thickness of 85 multiplied by 30 multiplied by 2 mm;
step four, primary processing:
sequentially grinding and polishing the plate-shaped amorphous alloy obtained in the step three by using sand paper of different types of 240 #, 400 #, 600 #, 800 #, 1000 #, 1500 # and 2000 #, and removing oil stains and impurities by using ultrasonic waves; simultaneously, mechanically polishing the side surface of the plate-shaped test sample by using diamond polishing paste, and then cleaning the test sample by using ultrasonic waves;
step five, cryogenic circulating treatment:
carrying out cryogenic circulating treatment on the amorphous alloy in the fourth step: firstly, placing an amorphous alloy sample into a liquid nitrogen container for 5 minutes, then quickly placing the amorphous alloy sample into a boiled water container for 1 minute, heating to 50-80 ℃, and then standing in a room-temperature environment for 4 minutes; performing cyclic subzero treatment for 20-60 times respectively by using the above step as subzero cyclic treatment; preparing a plate-shaped sample which is obtained by suction casting of the amorphous alloy material copper mold;
step six, rolling and pre-deforming:
rolling the amorphous alloy material plate-shaped sample subjected to the cryogenic circulating treatment by adopting an ATMR series electric miniature reversible two-roll mill, wherein the rolling process is completed in multiple passes; the rolling process adopts a longitudinal rolling two-dimensional rolling mode, after each rolling pass is finished, the sample is horizontally rotated by 180 degrees, and the two directions are alternately rolled until the required 5 percent of pre-deformation amount is obtained;
step seven, fine machining:
polishing the alloy surface after the pre-deformation treatment to a thickness of 0.3-0.5 mm of a diaphragm, polishing, and removing oil stains by using ultrasonic cleaning equipment; then, according to a design dimension drawing of the flexible coupling diaphragm, precisely perforating the diaphragm by using the rotating heads with different diameters so as to install a fixing bolt; using a rotary head to open holes according to the principle of opening holes from small to large successively; then, accurately cutting according to the design size drawing and the structure and precision requirements by using a low-speed precision cutting machine; then, utilizing a polishing machine to polish the side surface and the front surface and the back surface of the membrane into mirror surfaces by water grinding; cleaning oil stains and impurities on the finished membrane by using ultrasonic cleaning equipment; and manufacturing the flexible coupling diaphragm.
2. The method for preparing the flexible coupling diaphragm made of the amorphous alloy material toughened in the cryogenic cycle combined predeformation mode according to claim 1, is characterized in that: in the second step, the clean pure metal raw materials processed in the first step are weighed by adopting an electronic balance with the precision of 0.001g, and the weighing mass error range is ensured to be within the range of +/-0.003 g.
3. The method for preparing the flexible coupling diaphragm made of the amorphous alloy material toughened in the cryogenic cycle combined predeformation mode according to claim 1, is characterized in that: in the third step, the purity of the argon gas is 99.999 percent.
4. The method for preparing the flexible coupling diaphragm made of the amorphous alloy material toughened in the cryogenic cycle combined predeformation mode according to claim 1, is characterized in that: in the rolling pre-deformation process, the rolling reduction of each time is not allowed to exceed 0.01mm, the rolling reduction frequency is not less than 15 times of rolling processes, and the rolling reduction of each time is 0.01 mm.
5. The method for preparing the flexible coupling diaphragm made of the amorphous alloy material toughened in the cryogenic cycle combined predeformation mode according to claim 1, is characterized in that: the diameters of the used rotary heads are respectively 2, 3, 4, 5 and 6 mm.
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