CN113774295A - Al-Ni-Zr-Y-Co high-entropy amorphous alloy and preparation method thereof - Google Patents
Al-Ni-Zr-Y-Co high-entropy amorphous alloy and preparation method thereof Download PDFInfo
- Publication number
- CN113774295A CN113774295A CN202111118671.4A CN202111118671A CN113774295A CN 113774295 A CN113774295 A CN 113774295A CN 202111118671 A CN202111118671 A CN 202111118671A CN 113774295 A CN113774295 A CN 113774295A
- Authority
- CN
- China
- Prior art keywords
- amorphous alloy
- alloy
- entropy amorphous
- entropy
- vacuum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
-
- 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
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Continuous Casting (AREA)
Abstract
The invention provides an Al-Ni-Zr-Y-Co high-entropy amorphous alloy and a preparation method thereof, wherein the chemical formula of the Al-Ni-Zr-Y-Co high-entropy amorphous alloy is (Al)1/4Ni1/4Zr1/4Y1/4)100‑xCoxWherein x is 5 to 25, and Al, Ni, Zr, Y are in equal atomic ratios. The invention also provides a preparation method of the high-entropy amorphous alloy. The corrosion resistance of the Al-Ni-Zr-Y-Co high-entropy amorphous alloy prepared by the method is far higher than that of common steel materials, and the corrosion resistance requirement of large-scale equipment in a marine corrosion environment can be met on the premise of ensuring the mechanical property; the alloy components selected by the design of the invention have moderate price, and the preparation method is simple and easy to implement, and is a raw material for preparing the protective coating with marine corrosion resistance.
Description
Technical Field
The invention belongs to the field of amorphous alloy materials, and particularly relates to a high-entropy amorphous alloy with higher hardness and good corrosion resistance and a preparation method thereof.
Background
The earth surface of human life is covered by 70% of the ocean, which is the life's cradle, treasury of resources, and the fate of traffic. The 21 st century is the "ocean century", the development of the ocean industry has become a wide consensus all over the world, and the reasonable development and utilization of ocean resources are the common concern of all countries in the world. Nowadays, ocean science and technology has entered the frontier of global science and technology competition and become one of the focuses of comprehensive strength among countries. The development of ocean science and technology is not independent of the continuous development of ocean engineering materials, and faces to the severe ocean service environment, the research and application of high-performance ocean corrosion resistant materials become hot spots pursued in the industry at present, and the development of equipment materials with higher ocean corrosion resistance is more urgent.
At present, metal materials for ocean engineering comprise common T10 steel, No. 45 steel and the like, but the wide development of the metal materials is severely restricted by adverse factors such as high steel density, poor corrosion resistance, poor abrasion resistance, high engineering cost of stainless steel under the condition of large-scale use and the like.
Amorphous alloys (MGs) are obtained for the first time in the 60 s of the 20 th century by the professor Duwez of the united states through a melt spinning method, the atomic arrangement of the amorphous alloys has the characteristics of long-range disorder and short-range order, the amorphous alloys are macroscopically isotropic, the defects of common dislocation, grain boundaries and the like in crystalline materials do not exist, and the amorphous alloys generally have the characteristics of ultrahigh fracture toughness, excellent corrosion resistance, unique self-repairing capability and the like.
The concept of high-entropy alloys (HEAs) was formally proposed by samouria leaf in 2004: a solid solution alloy composed of 5 or more than 5 elements in equal atomic ratio or near equal atomic ratio, wherein the atomic fraction of each principal element is between 5% and 35%; it is based on "chemical disorder" development new material, and it has broken through the restriction of traditional alloy material primitive, creatively develops and researches the alloy material from the angle of entropy, has opened up the brand-new research field of metallic material.
High-entropy amorphous alloys (HE-MGs) are novel materials developed in recent years, the concept of the high-entropy amorphous alloys is firstly proposed in 2011 by Wangwawa academy of sciences theme of the Chinese academy of sciences, and meanwhile, the bulk high-entropy amorphous alloy Zn which has a disordered structure and can show thermoplastic deformation behavior similar to that of a high polymer at room temperature is prepared20Ca20Sr20Yb20(Li0.55Mg0.45)20. Shortly afterwards, Takeuchi et al at northeast university of Japan prepared high-entropy amorphous alloy Pd simultaneously containing metal elements and nonmetal elements20Pt20Cu20Ni20P20. It comprehensively utilizes the design concept of high-entropy alloy and amorphous alloy, combines the performance characteristics of 'chemical disorder' of the high-entropy alloy and 'structural disorder' of the amorphous alloy, and has the characteristics of 1+1>2, the development and application thereof are attracting attention. In recent 10 years, scholars at home and abroad preliminarily explore the materials, deepen the understanding of the basic performance of the materials and widen the application range of the high-entropy amorphous alloy as a functional material.
Therefore, the development of the high-entropy amorphous alloy which is suitable for large-area popularization and application and has both mechanical property and corrosion resistance has natural advantages in the aspect of service protection of large-scale marine equipment.
Disclosure of Invention
In order to solve the problems, the invention provides the Al-Ni-Zr-Y-Co high-entropy amorphous alloy which has higher hardness and corrosion resistance and can be used as a raw material for preparing a protective coating of large equipment in a marine environment.
The invention also aims to provide the preparation method of the Al-Ni-Zr-Y-Co high-entropy amorphous alloy, which has the advantages of simple and feasible operation steps and easily controlled process, and can obtain the high-entropy amorphous alloy with uniform components, outstanding mechanical properties and better corrosion resistance.
In order to achieve the aim, the invention provides an Al-Ni-Zr-Y-Co high-entropy amorphous alloy, and the chemical formula of the corrosion-resistant high-entropy amorphous alloy is (Al)1/4Ni1/4Zr1/4Y1/4)100-xCoxWherein x is 5 to 25, and Al, Ni, Zr, Y are in equal atomic ratios.
That is, it means that the atomic fraction of Co is 5 to 25%, the sum of the atomic fractions of Al, Ni and Y is 75 to 95%, and Al, Ni, Zr and Y are equal atomic ratios, each representing 1/4 of the atomic fractions.
The invention also provides a preparation method of the Al-Ni-Zr-Y-Co high-entropy amorphous alloy, which comprises the following steps:
1) weighing Al, Ni, Zr, Y and Co particles or block raw materials with required mass according to the atomic fraction in the chemical formula of the alloy and carrying out surface treatment;
2) smelting the raw materials required in the step 1) in a vacuum arc furnace with the smelting current of 150-180A to prepare a master alloy ingot;
3) crushing the master alloy ingot in the step 2), then placing the crushed master alloy ingot in a quartz tube, placing the quartz tube in an induction coil of a vacuum melt-spun machine to melt the master alloy ingot, and spraying liquid alloy on the surface of a copper roller rotating at high speed in the vacuum melt-spun machine to rapidly cool to obtain the strip-shaped high-entropy amorphous alloy.
Further, the surface treatment in the step 1) is to mechanically polish the granular or bulk raw material to remove surface scale, and then perform ultrasonic cleaning for 30 seconds by using acetone or alcohol, and repeat the cleaning for 1-3 times.
Further, the degree of vacuum in the vacuum arc furnace in the step 2) is 4.5 × 10-3Pa～5.0×10- 3Pa。
Further, in the step 2), the smelting is repeated for 3 to 5 times during the smelting in the vacuum arc furnace.
Further, the degree of vacuum in the melt-spun machine in the step 3) was 6.5 × 10-3Pa～7.5×10-3And Pa, filling argon, repeatedly vacuumizing to ensure that no impurity gas exists in the furnace cavity, and adjusting the pressure difference between the inside and the outside of the quartz tube to be 0.02 Pa. .
Furthermore, the surface linear speed of the copper roller in the step (3) is 25-40 m/s.
Furthermore, the thickness of the strip-shaped high-entropy amorphous alloy is 30-40 μm, and the width of the strip-shaped high-entropy amorphous alloy is 1.5-2.5 mm.
The invention also provides an application of the Al-Ni-Zr-Y-Co high-entropy amorphous alloy as a surface protection material for steel for ocean engineering.
In the preparation process, the smelting current range limited in the step 2) ensures the complete melting of the raw materials, if the current is too small, the element particles cannot be completely melted, and if the current is too large, the low-melting-point element Al is easy to volatilize, so that the alloy components have larger errors. And smelting is carried out repeatedly for 3-5 times, so that the components of the master alloy ingot are uniform, and the large difference in the components is avoided as much as possible.
According to the Al-Ni-Zr-Y-Co high-entropy amorphous alloy provided by the invention, the selected corrosion-resistant element Al can form a compact oxide film, so that the corrosion resistance of the alloy is improved; the elements Ni and Co with higher hardness and good wear resistance are selected, and the elements Ni and Co can play the roles of solid solution strengthening and fine grain strengthening; the rare earth element Y for promoting the formation of the amorphous is selected, and can play a role in purifying the melt, degassing and removing impurities and improving the microstructure. Zr can enhance the mechanical property of the alloy, has powerful deoxidizing and denitrifying capabilities and is an element with high melting point and corrosion resistance.
The invention adopts the high-vacuum single-roller rotary quenching strip-spinning technology to prepare the strip Al-Ni-Zr-Y-Co high-entropy amorphous alloy, on one hand, the size difference among all element atoms is large, so that the lattice distortion is easily caused, on the other hand, the metal atoms are arranged in a disordered state through the rapid quenching process of the single-roller strip-spinning machine, and the defects of non-uniform local structures such as crystal boundary, stacking fault, segregation and the like of crystalline metal are avoided, so the Al-Ni-Zr-Y-Co high-entropy amorphous alloy obtained by the method has excellent corrosion resistance. Generally speaking, high cooling speed is favorable for rapid cooling solidification, and amorphous alloys with different morphologies are prepared. At present, the cooling rate of the amorphous alloy strip prepared by the melt spinning process can reach 105～106K/s is slightly lower than the cooling rate (more than 10) of the small-size amorphous materials such as amorphous alloy powder prepared by an atomization method6K/s). Therefore, when the prepared band is judged to be in an amorphous structure condition through XRD diffractionThen, the powder is prepared by adopting a gas atomization process with higher cooling rate, and amorphous alloy powder can be obtained. Therefore, the high-entropy amorphous alloy material can be used as a surface protection material to well protect a base material in extreme ocean severe environment.
The high-entropy amorphous alloy obtained by the invention is of a complete amorphous structure in structure; the alloy has the characteristic of 'chemical disorder' typical of high-entropy alloy in composition. The high-entropy amorphous alloy provided by the invention has the design of equal atomic ratio and unequal atomic ratio, and the atomic radius difference between Y and other elements is increased by adding Y with the atomic radius of 181pm (r (Al) 143.1pm, r (Ni) 124.6pm, r (Co) 125.3pm and r (Zr) 160pm), so that the alloy is more prone to generate an amorphous structure, and further structural defects such as dislocation, twin crystal and the like are avoided, and better corrosion resistance can be obtained.
The invention selects the light element Al as the alloy component, can effectively reduce the density of the alloy, and controls the density of each alloy to be 5.85kg/m3Within. Meanwhile, the average Vickers microhardness of the series of alloys is higher than 495HV0.1And the self-corrosion current density is 2-3 orders of magnitude lower than that of T10 steel, which shows that the actual corrosion degree is lower. The discovery of the high-entropy amorphous alloy is applied to the protection aspect of relevant important equipment in the future, and is beneficial to realizing the dual targets of light weight and long-acting corrosion resistance.
The invention has the beneficial effects that:
the invention provides an Al-Ni-Zr-Y-Co high-entropy amorphous alloy which has higher hardness and excellent corrosion resistance compared with common marine steel materials, has low raw material cost, simple and easy operation steps and easily controlled process, can obtain the high-entropy amorphous alloy with uniform components, outstanding mechanical properties and better corrosion resistance, and can be used as a raw material for preparing large equipment protective materials in a marine environment.
Drawings
FIG. 1 is an XRD pattern of the high-entropy amorphous alloy strips prepared in examples 1-5.
FIG. 2 is a DSC curve of the high entropy amorphous alloy ribbons prepared in examples 1-5.
FIG. 3 shows the hardness of the high-entropy amorphous alloy ribbons prepared in examples 1 to 5.
FIG. 4 is a potentiodynamic polarization curve obtained from electrochemical testing of the high-entropy amorphous alloy strips prepared in examples 1-5.
Detailed Description
The following detailed and complete description of the embodiments of the present invention is provided to enable those skilled in the art to more easily understand the advantages and features of the present invention, and to clearly and clearly define the scope of the present invention. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The amorphous alloy is characterized by "single principal component" or "dual principal component", for example, the atomic fraction of the single principal component is more than 80% (such as Fe-based amorphous alloy and Al-based amorphous alloy), or the atomic fractions of the dual principal component amorphous alloys are more than 30% (such as Ti: Ti, etc.)32.8Zr30.2Be22.7Cu9Ni5.3And Zr52Cu33Ni4Al8.5Ag1.5Nb1Amorphous alloys). The high-entropy alloy is emphasized to be the concept of multi-principal element, and the high-entropy amorphous alloy is based on the high-entropy alloy as a design basis, so that the high-entropy amorphous alloy is represented by the multi-principal element of the high-entropy alloy instead of the single principal element or the double principal elements of the amorphous alloy.
The Al, Ni, Zr, Y and Co raw materials used for preparing the cast ingot are all commercially available raw materials, and the purity is higher than 99.9 wt%.
The electric arc melting furnace used in the invention is a rotary vacuum copper mold melting system of NMS-DRII model developed by Chengdu Zhongke new material science and technology engineering Limited company.
The vacuum melt-spun machine used in the invention is particularly a swing type small vacuum induction melting and rapid quenching system produced by the Chinese science instrument company, wherein a water-cooling circulating system is arranged below a copper roller of the vacuum melt-spun machine, so that the temperature of the copper roller can be ensured, and the cooling rate of melting amorphous alloy to generate strips can reach 105～106K/s。
Examples 1-4 preparation of (Al)1/4Ni1/4Zr1/4Y1/4)95Co5，(Al1/4Ni1/4Zr1/4Y1/4)90Co10，(Al1/ 4Ni1/4Zr1/4Y1/4)80Co20And (Al)1/4Ni1/4Zr1/4Y1/4)75Co25. Meanwhile, to compare the (Al) content with other Co contents1/4Ni1/4Zr1/4Y1/4)100-xCox(x is 5 to 25) high entropy amorphous alloy, example 5, (Al) was selected1/4Ni1/4Zr1/4Y1/4)98Co2The composition is used as a comparison case, and the performance of the composition is researched and characterized.
Example 1 (Al)1/4Ni1/4Zr1/4Y1/4)95Co5Preparation of high-entropy amorphous alloy strip
The method comprises the steps of firstly converting the atomic fraction of the high-entropy amorphous alloy into mass percent, selecting high-purity aluminum particles, nickel particles, zirconium particles, yttrium blocks and cobalt particles (the purity is not lower than 99.9%) as raw materials, polishing oxide skins, then carrying out ultrasonic cleaning by using acetone or alcohol, and batching by using a high-precision balance with the precision of 0.0001 g. The mass of the melting ingot is 20g, so the named masses of the elements are w (al) 1.9409g, w (ni) 4.2189g, w (zr) 6.5572g, w (y) 6.3911g, and w (co) 0.8919 g.
(Al1/4Ni1/4Zr1/4Y1/4)95Co5Has a theoretical melting point of about 1380 ℃ and is therefore maintained above (Al) during the melting process1/4Ni1/4Zr1/4Y1/4)95Co5Under the condition of the theoretical melting point of the raw materials, the raw materials are uniformly mixed and completely smelted.
Preparing a master alloy ingot by an arc melting method under the conditions of vacuum and argon protection, and repeatedly vacuumizing for three times to 4.5 multiplied by 10-3Pa, then feeding high-purity argon with the purity of 99.999 percent to a vacuum bin with the pressure of-0.8 MPa and the heightPure argon gas is used as a protective gas and an arc medium, the smelting current is 170A, cooling water is introduced during smelting to prevent the water-cooled copper plate from being melted by overheating, and the residual impurity gas is firstly adsorbed by the titanium sponge. After the gas adsorption is finished, the sample is smelted, the component uniformity of the alloy ingot is ensured by repeatedly re-smelting for 4 times, and the (Al) is obtained after cooling1/4Ni1/4Zr1/4Y1/4)95Co5A master alloy ingot; the actual density of the alloy was 5.362g/cm as measured by a Sadoris electronic analytical balance using a drainage method3。
Will be (Al)1/4Ni1/4Zr1/4Y1/4)95Co5Crushing the master alloy ingot, putting 5g of the crushed master alloy ingot into a quartz tube, and placing the quartz tube into an induction coil of a melt spinning machine, wherein the diameter of a nozzle of the quartz tube is 1mm, and the distance between the nozzle and a copper roller is 0.4 mm. Wherein the vacuum degree is 7.0 × 10- 3And Pa, then filling argon, repeating the vacuum pumping operation to ensure that no impurity gas exists in the furnace cavity, and adjusting the pressure difference between the inside and the outside of the quartz tube to be 0.02 Pa. Heating the alloy by a copper coil, spraying the liquid alloy onto a copper roller which moves at a high speed after the alloy is melted to obtain the alloy strip, wherein the surface linear velocity of the copper roller is 30m/s, (Al)1/4Ni1/4Zr1/4Y1/4)95Co5The thickness of the high-entropy amorphous alloy strip is 35 +/-5 mu m.
Example 2 (Al)1/4Ni1/4Zr1/4Y1/4)90Co10Preparation of high-entropy amorphous alloy strip
The method comprises the steps of firstly converting the atomic fraction of the high-entropy amorphous alloy into mass percent, selecting high-purity aluminum particles, nickel particles, zirconium particles, yttrium blocks and cobalt particles (the purity is not lower than 99.9%) as raw materials, polishing oxide skins, then carrying out ultrasonic cleaning by using acetone or alcohol, and batching by using a high-precision balance with the precision of 0.0001 g. The mass of the melting ingot is 20g, so the named masses of the elements are w (al) 1.8493g, w (ni) 4.0197g, w (zr) 6.2478g, w (y) 6.0892g, and w (co) 1.7940 g.
(Al1/4Ni1/4Zr1/4Y1/4)90Co10Has a theoretical melting point of about 1386 ℃ so that the temperature is maintained above (Al) during the melting process1/4Ni1/4Zr1/4Y1/4)90Co10Under the condition of the theoretical melting point of the raw materials, the raw materials are uniformly mixed and completely smelted.
Preparing a master alloy ingot by an arc melting method under the conditions of vacuum and argon protection, and repeatedly vacuumizing for three times to 4.5 multiplied by 10-3Pa, then feeding high-purity argon with the purity of 99.999 percent to a vacuum chamber with the pressure of-0.8 MPa, taking the high-purity argon as protective gas and an arc medium, smelting current as 170A, introducing cooling water during smelting to prevent a water-cooled copper disc from being melted by overheating, and firstly adsorbing the residual impurity gas by using titanium sponge. After the gas adsorption is finished, the sample is smelted, the component uniformity of the alloy ingot is ensured by repeatedly re-smelting for 4 times, and the (Al) is obtained after cooling1/4Ni1/4Zr1/4Y1/4)90Co10A master alloy ingot; the actual density of the alloy was 5.461g/cm as measured by a Sadoris electronic analytical balance using a drainage method3。
Will be (Al)1/4Ni1/4Zr1/4Y1/4)90Co10Crushing the mother alloy ingot, putting 5g of the crushed mother alloy ingot into a quartz tube respectively, and putting the quartz tube into an induction coil of a melt spinning machine, wherein the diameter of a nozzle of the quartz tube is 1mm, and the distance between the nozzle and a copper roller is 0.4 mm. Wherein the vacuum degree is 7.0 × 10-3And Pa, then filling argon, repeating the vacuum pumping operation to ensure that no impurity gas exists in the furnace cavity, and adjusting the pressure difference between the inside and the outside of the quartz tube to be 0.02 Pa. Heating the alloy by a copper coil, spraying the liquid alloy onto a copper roller which moves at a high speed after the alloy is melted to obtain the alloy strip, wherein the surface linear velocity of the copper roller is 30m/s, (Al)1/4Ni1/4Zr1/4Y1/4)90Co10The thickness of the high-entropy amorphous alloy strip is 35 +/-5 mu m.
Example 3 (Al)1/4Ni1/4Zr1/4Y1/4)80Co20Preparation of high-entropy amorphous alloy strip
The method comprises the steps of firstly converting the atomic fraction of the high-entropy amorphous alloy into mass fraction, selecting high-purity aluminum particles, nickel particles, zirconium particles, yttrium blocks and cobalt particles (the purity is not lower than 99.9%) as raw materials, polishing oxide skins, then carrying out ultrasonic cleaning by using acetone or alcohol, and batching by using a high-precision balance with the precision of 0.0001 g. The mass of the melting ingot is 20g, so the named masses of the elements are w (al) 1.6620g, w (ni) 3.6139g, w (zr) 5.6182g, w (y) 5.4760g, and w (co) 3.6299 g.
(Al1/4Ni1/4Zr1/4Y1/4)80Co20Has a theoretical melting point of about 1398 ℃ and is therefore kept above (Al) during the melting process1/4Ni1/4Zr1/4Y1/4)80Co20Under the condition of the theoretical melting point of the raw materials, the raw materials are uniformly mixed and completely smelted.
Preparing a master alloy ingot by an arc melting method under the conditions of vacuum and argon protection, and repeatedly vacuumizing for three times to 4.5 multiplied by 10-3Pa, then feeding high-purity argon with the purity of 99.999 percent to a vacuum chamber with the pressure of-0.8 MPa, taking the high-purity argon as protective gas and an arc medium, smelting current as 170A, introducing cooling water during smelting to prevent a water-cooled copper disc from being melted by overheating, and firstly adsorbing the residual impurity gas by using titanium sponge. After the gas adsorption is finished, the sample is smelted, the component uniformity of the alloy ingot is ensured by repeatedly re-smelting for 4 times, and the (Al) is obtained after cooling1/4Ni1/4Zr1/4Y1/4)80Co20A master alloy ingot; the actual density of the alloy was 5.679g/cm as measured by a Sadoris electronic analytical balance using a drainage method3。
Will be (Al)1/4Ni1/4Zr1/4Y1/4)80Co20Crushing the master alloy ingot, putting 5g of the crushed master alloy ingot into a quartz tube, and placing the quartz tube into an induction coil of a melt spinning machine, wherein the diameter of a nozzle of the quartz tube is 1mm, and the distance between the nozzle and a copper roller is 0.4 mm. Wherein the vacuum degree is 7.0 × 10- 3And Pa, then filling argon, repeating the vacuum pumping operation to ensure that no impurity gas exists in the furnace cavity, and adjusting the pressure difference between the inside and the outside of the quartz tube to be 0.02 Pa. Heating the alloy by a copper coil, spraying the liquid alloy onto a copper roller which moves at a high speed after the alloy is melted to obtain the alloy strip, wherein the surface linear velocity of the copper roller is 30m/s, (Al)1/4Ni1/4Zr1/4Y1/4)80Co20The thickness of the high-entropy amorphous alloy strip is 35 +/-5 mu m.
Example 4 (Al)1/4Ni1/4Zr1/4Y1/4)75Co25Preparation of high-entropy amorphous alloy strip
The method comprises the steps of firstly converting the atomic fraction of the high-entropy amorphous alloy into mass fraction, selecting high-purity aluminum particles, nickel particles, zirconium particles, yttrium blocks and cobalt particles (the purity is not lower than 99.9%) as raw materials, polishing oxide skins, then carrying out ultrasonic cleaning by using acetone or alcohol, and batching by using a high-precision balance with the precision of 0.0001 g. The mass of the melting ingot is 20g, so the named masses of the elements are w (al) 1.5680g, w (ni) 3.4083g, w (zr) 5.2974g, w (y) 5.1630g, and w (co) 4.5633 g.
(Al1/4Ni1/4Zr1/4Y1/4)75Co25Has a theoretical melting point of about 1404 ℃ so that the temperature is kept higher than (Al) during the melting process1/4Ni1/4Zr1/4Y1/4)75Co25Under the condition of the theoretical melting point of the raw materials, the raw materials are uniformly mixed and completely smelted.
Preparing a master alloy ingot by an arc melting method under the conditions of vacuum and argon protection, and repeatedly vacuumizing for three times to 4.5 multiplied by 10-3Pa, then feeding high-purity argon with the purity of 99.999 percent to a vacuum chamber with the pressure of-0.8 MPa, taking the high-purity argon as protective gas and an arc medium, smelting current as 170A, introducing cooling water during smelting to prevent a water-cooled copper disc from being melted by overheating, and firstly adsorbing the residual impurity gas by using titanium sponge. After the gas adsorption is finished, the sample is smelted, the component uniformity of the alloy ingot is ensured by repeatedly re-smelting for 4 times, and the (Al) is obtained after cooling1/4Ni1/4Zr1/4Y1/4)75Co25A master alloy ingot; the actual density of the alloy was 5.814g/cm as measured by a Sadoris electronic analytical balance using a drainage method3。
Will be (Al)1/4Ni1/4Zr1/4Y1/4)75Co25Crushing the master alloy ingot, taking 5g of the crushed master alloy ingot into a quartz tube, and mixing the crushed master alloy ingot with the quartz tubeThe quartz tube is arranged in an induction coil of the melt spinning machine, the diameter of a nozzle of the quartz tube is 1mm, and the height of the nozzle from a copper roller is 0.4 mm. Wherein the vacuum degree is 7.0 × 10-3And Pa, then filling argon, repeating the vacuum pumping operation to ensure that no impurity gas exists in the furnace cavity, and adjusting the pressure difference between the inside and the outside of the quartz tube to be 0.02 Pa. Heating the alloy by a copper coil, spraying the liquid alloy onto a copper roller which moves at a high speed after the alloy is melted to obtain the alloy strip, wherein the surface linear velocity of the copper roller is 30m/s, (Al)1/4Ni1/4Zr1/4Y1/4)75Co25The thickness of the high-entropy amorphous alloy strip is 35 +/-5 mu m.
Example 5 (Al)1/4Ni1/4Zr1/4Y1/4)98Co2Preparation of high-entropy amorphous alloy strip
The method comprises the steps of firstly converting the atomic fraction of the high-entropy amorphous alloy into mass fraction, selecting high-purity aluminum particles, nickel particles, zirconium particles, yttrium blocks and cobalt particles (the purity is not lower than 99.9%) as raw materials, polishing oxide skins, then carrying out ultrasonic cleaning by using acetone or alcohol, and batching by using a high-precision balance with the precision of 0.0001 g. The mass of the melting ingot is 20g, so the named masses of the elements are w (al) 1.9954g, w (ni) 4.3373g, w (zr) 6.7414g, w (y) 6.5704g, and w (co) 0.3555 g.
(Al1/4Ni1/4Zr1/4Y1/4)98Co2Has a theoretical melting point of about 1376 ℃, so that the temperature is kept higher than (Al) during the melting process1/4Ni1/4Zr1/4Y1/4)98Co2Under the condition of the theoretical melting point of the raw materials, the raw materials are uniformly mixed and completely smelted.
Preparing a master alloy ingot by an arc melting method under the conditions of vacuum and argon protection, and repeatedly vacuumizing for three times to 4.5 multiplied by 10-3Pa, then feeding high-purity argon with the purity of 99.999 percent to a vacuum chamber with the pressure of-0.8 MPa, taking the high-purity argon as protective gas and an arc medium, smelting current as 170A, introducing cooling water during smelting to prevent a water-cooled copper disc from being melted by overheating, and firstly adsorbing the residual impurity gas by using titanium sponge. After the gas adsorption is finished, the sample is smelted, and repeated remelting is needed for 4 timesEnsuring the component uniformity of the alloy ingot, and obtaining (Al) after cooling1/4Ni1/4Zr1/4Y1/4)98Co2A master alloy ingot; the actual density of the alloy measured by a Sadoris electronic analytical balance using a drainage method was 5.301g/cm3。
Will be (Al)1/4Ni1/4Zr1/4Y1/4)98Co2Crushing the master alloy ingot, putting 5g of the crushed master alloy ingot into a quartz tube, and placing the quartz tube into an induction coil of a melt spinning machine, wherein the diameter of a nozzle of the quartz tube is 1mm, and the distance between the nozzle and a copper roller is 0.4 mm. Wherein the vacuum degree is 7.0 × 10- 3And Pa, then filling argon, repeating the vacuum pumping operation to ensure that no impurity gas exists in the furnace cavity, and adjusting the pressure difference between the inside and the outside of the quartz tube to be 0.02 Pa. Heating the alloy by a copper coil, spraying the liquid alloy onto a copper roller which moves at a high speed after the alloy is melted to obtain the alloy strip, wherein the surface linear velocity of the copper roller is 30m/s, (Al)1/4Ni1/4Zr1/4Y1/4)98Co2The thickness of the high-entropy amorphous alloy strip is 35 +/-5 mu m.
Example 6 determination of Properties of high entropy amorphous alloy strip
The Al-Ni-Zr-Y-Co high-entropy amorphous alloy strips prepared in examples 1 to 5 were subjected to property measurement of the alloy strips.
Using a Pasnake Empyrean X-ray diffractometer pair (Al)1/4Ni1/4Zr1/4Y1/4)98Co2，(Al1/4Ni1/ 4Zr1/4Y1/4)95Co5，(Al1/4Ni1/4Zr1/4Y1/4)90Co10，(Al1/4Ni1/4Zr1/4Y1/4)80Co20And (Al)1/4Ni1/4Zr1/ 4Y1/4)75Co25The phase analysis is respectively carried out on the high-entropy amorphous alloy strips, the working voltage and the current are respectively 45KV and 40mA, the X-ray source is a Cu Ka (lambda is 0.15406nm) ray, the scanning speed is 5 DEG/min, the scanning range is 20-80 DEG, and the result is shown in figure 1. From FIG. 1It can be seen that the 5 high-entropy amorphous alloys have typical diffuse scattering peaks of amorphous structures, indicating that the prepared ribbon indeed has an amorphous structure.
The DSC curve was measured by a differential scanning calorimeter (DSC404-F3 model) of Chi Kaishiki, and the results are shown in FIG. 2, (Al)1/4Ni1/4Zr1/4Y1/4)98Co2，(Al1/4Ni1/4Zr1/4Y1/4)95Co5，(Al1/4Ni1/4Zr1/4Y1/4)90Co10，(Al1/ 4Ni1/4Zr1/4Y1/4)80Co20And (Al)1/4Ni1/4Zr1/4Y1/4)75Co25Crystallization peak temperature T of high-entropy amorphous alloy stripp743K, 741K, 738K, 756K, 783K, respectively. The data show that the initial crystallization temperature of the materials is above 730K, which indicates that the materials can maintain an amorphous structure when working below the initial crystallization temperature, and can meet the requirement of service in a marine environment.
The results of the tests using an HVS-1000A model digital display automatic turret micro Vickers hardness tester are shown in FIG. 3, (Al)1/4Ni1/ 4Zr1/4Y1/4)98Co2Vickers hardness of high-entropy amorphous alloy is 563HV0.1；(Al1/4Ni1/4Zr1/4Y1/4)95Co5The Vickers hardness of the high-entropy amorphous alloy is 498.5HV0.1；(Al1/4Ni1/4Zr1/4Y1/4)90Co10The Vickers hardness of the high-entropy amorphous alloy is 523.5HV0.1；(Al1/4Ni1/4Zr1/4Y1/4)80Co20The Vickers hardness of the high-entropy amorphous alloy is 582HV0.1.；(Al1/4Ni1/4Zr1/ 4Y1/4)75Co25The Vickers hardness of the high-entropy amorphous alloy is 606.5HV0.1. Compared with the common Al-based amorphous alloy strip, the high-entropy amorphous alloy material provided by the inventionThe hardness of the material is higher than that of the traditional Al-based amorphous alloy strip, and the microhardness is about 2 times of that of the traditional Al-based amorphous alloy strip (for example: Al)86Ni6Y6Ce2The hardness of the amorphous alloy thin strip is 252HV0.1，Al86Ni7Y4.5Co1La1.5The hardness of the amorphous alloy thin strip is 271HV0.1)。
The alloys were subjected to corrosion resistance testing using a Shanghai Hua 660E model electrochemical workstation, in which the corrosive solution was a 3.5 wt.% NaCl solution simulating the ocean salt concentration, and the polarization curves of examples 1-5 are shown in FIG. 4.
In addition, the corrosion kinetics of the high-entropy Amorphous alloys prepared in examples 1-5 were compared with those of ordinary aluminum alloys in a 3.5 wt.% NaCl solution, and the test procedures are described in references (Cheng J B, Feng Y, Yan C, et Al. development and Characterization of Al-Based Amorphous Coating [ J ]. JOM,2020,72(3), 745. 753 HAN Z H, WANG Z, CHEN X H, et Al. Characterization and Characterization of Cu-Al high-purity Coating organic chemistry and vacuum-Characterization [ J ]. JOM,2020,72(3) 1254. 3. HUS B, Ta C J, CHEN Y, thermal and Characterization of pressing ceramic [ J ]. JOM,2020,72(3) 1254. U.S. J-S, Ta C J, Mo-Cu-Coating and Mo-V-Cu, 2019, 375: 802-809.) and the results are shown in table 1.
TABLE 1 electrochemical parameters of polarization curve fitting
The self-etching current density in Table 1 represents the actual etching rate, and the smaller the self-etching current density, the lower the etching degree under the same conditions; the self-corrosion potential represents corrosion tendency, the higher the self-corrosion potential is, the lower the corrosion tendency is, and the higher the polarization resistance is, the less corrosion is caused to the material under the same condition.
As can be seen from FIG. 4 and Table 1, (Al)1/4Ni1/4Zr1/4Y1/4)80Co20(may also be represented by Al)20Ni20Zr20Y20Co20) The self-corrosion current density of the high-entropy amorphous alloy is minimum although the self-corrosion potential is slightly higher than (Al)1/ 4Ni1/4Zr1/4Y1/4)95Co5、(Al1/4Ni1/4Zr1/4Y1/4)90Co10、(Al1/4Ni1/4Zr1/4Y1/4)85Co25But due to self-corrosion current density ratio (Al)1/4Ni1/4Zr1/4Y1/4)95Co5、(Al1/4Ni1/4Zr1/4Y1/4)90Co10、(Al1/4Ni1/4Zr1/4Y1/4)85Co25Is one order of magnitude lower, so the comprehensive corrosion resistance effect is the best.
(Al1/4Ni1/4Zr1/4Y1/4)95Co5、(Al1/4Ni1/4Zr1/4Y1/4)90Co10、(Al1/4Ni1/4Zr1/4Y1/4)85Co25The self-corrosion current density of the alloy is relatively small, and the self-corrosion potential of the alloy is higher than that of 45 steel and T10 steel, which shows that the high-entropy amorphous alloy material provided by the application has lower corrosion tendency and smaller actual corrosion rate in a corrosion environment of 3.5 wt.% NaCl solution than the existing material, so that the corrosion resistance effect is better.
For the quinary Al-Ni-Zr-Y-Co high-entropy amorphous alloy, because Co has the function of fine-grain strengthening, grains can be refined and an amorphous structure can be obtained by properly adding Co element, so that the corrosion resistance of the alloy can be further improved. However, when the content of Co element is too low, the comparative example (Al) shows1/4Ni1/4Zr1/4Y1/4)98Co2It can be seen that self-corrosion is causedThe current density is large and the self-corrosion potential is close to that of 45 steel and T10 steel, which indicates that the corrosion resistance effect of the high-entropy amorphous alloy cannot be improved due to the low content of Co element. And when the content of Co is too much, the high-entropy amorphous alloy strip is difficult to prepare, so that the high-entropy amorphous alloy strip is not suitable for being used as an ocean corrosion-resistant protective material. Therefore, the Co content selected by the invention is 5-25%. The corrosion resistance is further enhanced and the current density is smaller due to the addition of the Zr element.
It can be seen from the above embodiments that the high-entropy amorphous alloy provided by the invention has not only the strong corrosion resistance of the aluminum-based amorphous alloy, but also the high hardness of the high-entropy alloy, compared with the existing aluminum-based amorphous alloy, so that the high-entropy amorphous alloy can be applied to ships or marine large-scale equipment (such as marine oil platforms, sea-crossing bridges, etc.) which need to have both corrosion resistance and high hardness. Due to the limit of the preparation process of the high-entropy amorphous alloy, the yield cannot be too large, and therefore, the high-entropy amorphous alloy cannot be used as a main raw material of large-scale equipment of ships or oceans. However, due to the excellent performance of the high-entropy amorphous alloy, the high-entropy amorphous alloy can be used as a surface protective coating of ships or large ocean equipment to play a role in improving the hardness and the surface corrosion resistance of steel, so that the raw material does not need to be replaced in a large area, and chemical pollution caused by anticorrosive paint is avoided. The required raw materials are common raw materials in the field, the operation steps are simple and easy to implement, the process is easy to control, and the high-entropy amorphous alloy with uniform components, outstanding mechanical properties and better corrosion resistance can be obtained. The service life of the ship or the marine large-scale equipment can be prolonged through surface protection of the ship or the marine large-scale equipment, and the updating cost is reduced.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. An Al-Ni-Zr-Y-Co high-entropy amorphous alloy,the Al-Ni-Zr-Y-Co high-entropy amorphous alloy is characterized in that the chemical formula of the Al-Ni-Zr-Y-Co high-entropy amorphous alloy is (Al)1/4Ni1/4Zr1/4Y1/4)100-xCoxWherein x is 5 to 25, and Al, Ni, Zr, Y are in equal atomic ratios.
2. The preparation method of the Al-Ni-Zr-Y-Co high-entropy amorphous alloy according to claim 1, characterized by comprising the following steps:
1) weighing Al, Ni, Zr, Y and Co particles or block raw materials with required mass according to the atomic fraction in the chemical formula of the alloy and carrying out surface treatment;
2) smelting the raw materials required in the step 1) in a vacuum arc furnace with the smelting current of 150-180A to prepare a master alloy ingot;
3) crushing the master alloy ingot in the step 2), then placing the crushed master alloy ingot in a quartz tube, placing the quartz tube in an induction coil of a vacuum melt-spun machine to melt the master alloy ingot, and spraying liquid alloy on the surface of a copper roller rotating at high speed in the vacuum melt-spun machine to rapidly cool to obtain the strip-shaped high-entropy amorphous alloy.
3. The preparation method according to claim 2, wherein the surface treatment in step 1) is to mechanically polish the granular or bulk raw material to remove surface scale, and then to perform ultrasonic cleaning for 30 seconds with acetone or alcohol, and repeating the cleaning for 1-3 times.
4. The manufacturing method according to claim 2, wherein the degree of vacuum in the vacuum arc furnace in the step 2) is 4.5 x 10-3Pa～5.0×10-3And Pa, filling argon, repeatedly vacuumizing to ensure that no impurity gas exists in the furnace cavity, and adjusting the pressure difference between the inside and the outside of the quartz tube to be 0.02 Pa.
5. The production method according to claim 2, wherein in the step 2), the smelting is performed 3 to 5 times in the vacuum arc furnace.
6. The manufacturing method according to claim 2, wherein the degree of vacuum in the vacuum melt-spun machine in the step 3) is 6.5 x 10-3Pa～7.5×10-3Pa；。
7. The preparation method of claim 2, wherein the surface linear velocity of the copper roller in the step 3) is 25-40 m/s.
8. The method according to claim 2, wherein the thickness of the ribbon-shaped high-entropy amorphous alloy is 30 to 40 μm, and the width is 1.5 to 2.5 mm.
9. Use of the Al-Ni-Zr-Y-Co high-entropy amorphous alloy according to claim 1 as a surface protective material for steel for ocean engineering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111118671.4A CN113774295B (en) | 2021-09-24 | 2021-09-24 | Al-Ni-Zr-Y-Co high-entropy amorphous alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111118671.4A CN113774295B (en) | 2021-09-24 | 2021-09-24 | Al-Ni-Zr-Y-Co high-entropy amorphous alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113774295A true CN113774295A (en) | 2021-12-10 |
| CN113774295B CN113774295B (en) | 2022-05-17 |
Family
ID=78852951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111118671.4A Active CN113774295B (en) | 2021-09-24 | 2021-09-24 | Al-Ni-Zr-Y-Co high-entropy amorphous alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113774295B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334065A (en) * | 2013-06-06 | 2013-10-02 | 清华大学 | High-entropy amorphous alloy material and preparation method thereof |
| CN106756636A (en) * | 2016-11-28 | 2017-05-31 | 西安交通大学 | A kind of anti-corrosion amorphous high-entropy alloy high and preparation method thereof |
| EP3543368A1 (en) * | 2018-03-20 | 2019-09-25 | The Swatch Group Research and Development Ltd | High-entropy alloys for covering components |
| CN113025926A (en) * | 2021-03-03 | 2021-06-25 | 中国人民解放军军事科学院国防科技创新研究院 | High-entropy amorphous alloy material and preparation method thereof |
| CN113073273A (en) * | 2021-03-03 | 2021-07-06 | 浙江大学 | High-entropy amorphous alloy material and preparation method thereof |
-
2021
- 2021-09-24 CN CN202111118671.4A patent/CN113774295B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334065A (en) * | 2013-06-06 | 2013-10-02 | 清华大学 | High-entropy amorphous alloy material and preparation method thereof |
| CN106756636A (en) * | 2016-11-28 | 2017-05-31 | 西安交通大学 | A kind of anti-corrosion amorphous high-entropy alloy high and preparation method thereof |
| EP3543368A1 (en) * | 2018-03-20 | 2019-09-25 | The Swatch Group Research and Development Ltd | High-entropy alloys for covering components |
| CN113025926A (en) * | 2021-03-03 | 2021-06-25 | 中国人民解放军军事科学院国防科技创新研究院 | High-entropy amorphous alloy material and preparation method thereof |
| CN113073273A (en) * | 2021-03-03 | 2021-07-06 | 浙江大学 | High-entropy amorphous alloy material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| T. BENAMEUR等: "Crystalline to Amorphous Phase Transition in Al-Ni-Co System during Mechanical Alloying", 《MATERIALS TRANSACTIONS》 * |
| 张舒研等: "高熵非晶合金耐腐蚀性能研究进展", 《材料工程》 * |
| 杨铭等: "高熵非晶合金研究进展", 《中国科学:物理学 力学 天文学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113774295B (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108220742B (en) | Microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy and preparation method thereof | |
| CN111549270B (en) | Low-density high-strength high-plasticity high-entropy alloy material and preparation method thereof | |
| CN107739956B (en) | A kind of Nb microalloying Ni-Co-Fe-Cr-Al high-entropy alloy | |
| Zhang et al. | Recent progress in high-entropy alloys | |
| CN113073273B (en) | High-entropy amorphous alloy material and preparation method thereof | |
| CN110616341B (en) | CoCrNiNbx eutectic medium-entropy alloy and preparation method thereof | |
| CN104674103A (en) | CrFeCoNiNbx high-entropy alloy and preparation method thereof | |
| CN107527702B (en) | Iron-based amorphous alloy powder and preparation method and application thereof | |
| CN113025926B (en) | High-entropy amorphous alloy material and preparation method thereof | |
| CN109594002B (en) | Multi-principal-element medium-entropy alloy and preparation method thereof | |
| CN107142410A (en) | CrMoNbTiZr high entropy alloy materials and preparation method thereof | |
| CN104152781A (en) | A high-entropy alloy of AlCoFeNiSi and a preparation method thereof | |
| CN111647789A (en) | Alloying-method-based refined chromium-iron-cobalt-nickel-based high-entropy alloy crystal grain and preparation method thereof | |
| CN113151725A (en) | Method for enhancing wear resistance of refractory high-entropy alloy | |
| CN111676410A (en) | High-strength high-toughness CoFeNiTiV high-entropy alloy and preparation method thereof | |
| CN113122764A (en) | Preparation method of CuCrFeCoNixTi high-entropy alloy thin strip | |
| CN109468548B (en) | Wide supercooled liquid region zirconium-based amorphous alloy | |
| CN113774295B (en) | Al-Ni-Zr-Y-Co high-entropy amorphous alloy and preparation method thereof | |
| CN109355601B (en) | Cobalt-based bulk amorphous alloy and preparation method thereof | |
| CN115233076B (en) | CoNiAl magnetic control memory type eutectic medium entropy alloy and preparation method thereof | |
| CN108277418B (en) | MoNbTaTiHf high-entropy alloy material and preparation method thereof | |
| CN115433864B (en) | Hypoeutectic high-entropy alloy for friction material and preparation method thereof | |
| CN114717462B (en) | C-containing eutectic high-entropy alloy and preparation method thereof | |
| CN101195874A (en) | Method for improving amorphous alloy forming ability | |
| CN113755768B (en) | Al-Ni-Y-Co high-entropy amorphous alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |