Method of making a super-stable metallic glass

Abstract

This invention relates to the field of amorphous alloys, and more particularly to a method for preparing ultrastable metallic glasses, comprising: S1: melting alloy raw materials to obtain cast metallic glasses; S2: heat-treating the cast metallic glasses to induce a glass-glass transition without crystallization, thereby obtaining ultrastable metallic glasses; wherein the process parameters of the heat treatment are determined by differential scanning calorimetry (DSC) curves of the cast metallic glasses, and the temperature at which the glass-glass transition occurs without crystallization, determined by the exothermic peak in the DSC curves, is used as the final heating temperature of the heat treatment. The preparation method of this invention has advantages such as simple preparation method, high production efficiency, low cost, no size limitations, and wide applicability to alloy systems with glass-glass transition characteristics. The ultrastable metallic glasses prepared according to this invention have high anti-aging and anti-crystallization capabilities, better mechanical properties, and durability, making them suitable for various application scenarios.

Description

Technical Field

[0001] This invention relates to the field of amorphous alloys, and more particularly to a method for preparing ultrastable metallic glasses. Background Technology

[0002] In the field of amorphous alloys, traditional methods for preparing ultrastable metallic glasses mainly include physical vapor deposition (PVD). This method can produce ultrastable metallic glass films by adjusting the temperature of the deposition substrate (around 0.8 Tg) and the deposition rate. In addition, natural aging is another method for preparing ultrastable metallic glasses, relying on the natural relaxation process of the metallic glass over time to achieve a more stable structural state. However, the natural aging process is very slow, typically requiring several years or even decades.

[0003] Although PVD can prepare ultrastable glasses on a laboratory timescale, it has some significant limitations. First, PVD is primarily suitable for preparing thin film materials, typically only capable of producing two-dimensional films with thicknesses of tens to hundreds of nanometers, which limits its application in three-dimensional structures. Second, PVD-prepared films often exhibit strong anisotropy, which may affect the overall properties of the material. Furthermore, natural aging methods, due to their extremely long time spans, are practically unusable.

[0004] Therefore, it is essential to develop a new method for preparing ultrastable metallic glasses that is simple to prepare, has high production efficiency, low cost, and is not limited by size. Summary of the Invention

[0005] This invention aims to at least partially solve one of the technical problems existing in the prior art. To this end, this invention provides a method for preparing ultrastable metallic glasses. The preparation method of this invention has advantages such as simplicity, high production efficiency, low cost, no size limitations, and wide applicability to alloy systems with glass-glass transition properties. The ultrastable metallic glasses prepared according to this invention have no size limitations, high anti-aging properties, high anti-crystallization ability, better mechanical properties and durability, and are suitable for various application scenarios.

[0006] In a first aspect, the present invention provides a method for preparing ultrastable metallic glasses. According to an embodiment of the invention, the method includes: S1: melting alloy feedstock to obtain cast metallic glass; S2: heat-treating the cast metallic glass to induce a glass-glass transition without crystallization, thereby obtaining ultrastable metallic glass; wherein the process parameters of the heat treatment are determined by differential scanning calorimetry (DSC) of the cast metallic glass, and the temperature at which the glass-glass transition occurs without crystallization, determined by the exothermic peak in the DSC, is taken as the final temperature of the heat treatment. The inventors first prepare ordinary metallic glass through alloy melting and rapid cooling, then heat-treat the ordinary metallic glass to induce a glass-glass transition without crystallization, and then cool it to room temperature to obtain ultrastable metallic glass. The preparation method of the present invention has the advantages of simple preparation method, high production efficiency, low cost, no size limitation, and wide applicability to alloy systems with glass-glass transition properties. The ultra-stable metallic glass prepared according to the present invention has high anti-aging, high anti-crystallization ability, better mechanical properties and durability, and can be applied to different application scenarios.

[0007] According to embodiments of the present invention, the method for preparing ultrastable metallic glasses described above may further have the following additional technical features:

[0008] According to embodiments of the present invention, the alloy composition includes two or more of titanium, zirconium, hafnium, copper, nickel, beryllium, cobalt, aluminum, niobium, lanthanum, cerium, and cobalt.

[0009] According to embodiments of the present invention, the alloying ingredients include titanium, zirconium, copper, nickel, and beryllium. Therefore, the preparation method of the present invention is applicable to alloy systems comprising titanium, zirconium, copper, nickel, and beryllium alloying ingredients and exhibiting glass-glass transition properties.

[0010] According to an embodiment of the present invention, the alloy composition includes titanium, hafnium, copper, nickel and beryllium.

[0011] According to an embodiment of the present invention, the alloy composition includes titanium, zirconium, hafnium, copper, nickel, and beryllium.

[0012] According to an embodiment of the present invention, the smelting process includes the following steps: a. arc melting the alloy ingredients to obtain the master alloy ingot; b. induction melting the master alloy ingot and then cooling and solidifying it to obtain the cast metallic glass.

[0013] According to an embodiment of the present invention, the heat treatment further includes: heating the cast metallic glass to a temperature at which a glass-glass transition occurs but crystallization does not occur, and then cooling it to obtain an ultrastable metallic glass.

[0014] According to an embodiment of the present invention, the heat treatment further includes: heating the cast metallic glass to a preset temperature at which a glass-glass transition occurs but crystallization does not occur and then holding it at that temperature, followed by a cooling treatment to obtain an ultrastable metallic glass; wherein the preset temperature is lower than the final temperature of the heat treatment.

[0015] In a second aspect, the present invention provides an ultrastable metallic glass. According to an embodiment of the present invention, the ultrastable metallic glass is prepared according to the aforementioned method. The ultrastable metallic glass of the present invention has no size limitations, high resistance to aging, high resistance to crystallization, better mechanical properties and durability, and is suitable for various application scenarios.

[0016] According to embodiments of the present invention, the above-mentioned ultrastable metallic glass may also have the following additional technical features:

[0017] According to an embodiment of the present invention, the alloy composition of the ultrastable metallic glass, expressed as Ti (atomic percentage), is... a Zr b Cu c Ni d Be e Where: 19%≤a≤21%, 19%≤b≤21%, 19%≤c≤21%, 19%≤d≤21%, 16%≤e≤24%, a+b+c+d+e=100%.

[0018] According to an embodiment of the present invention, the alloy composition of the ultrastable metallic glass, expressed as Ti (atomic percentage), is... A Hf B Cu C Ni D Be E Where: 19%≤A≤21%, 19%≤B≤21%, 19%≤C≤21%, 19%≤D≤21%, 16%≤E≤24%, A+B+C+D+E=100%.

[0019] According to an embodiment of the present invention, the alloy composition of the ultrastable metallic glass, expressed as Ti (atomic percentage), is... I Zr II Hf III Cu IV Ni V Be VI , where: I=II=III, 12%≤I≤14%, IV=V=VI, 19%≤IV≤22%, I+II+III+IV+V+VI=100%.

[0020] The preparation method of the present invention has the advantages of simple preparation method, high production efficiency, low cost, no size limitation, and wide applicability to alloy systems with glass-glass transition properties. The ultra-stable metallic glass prepared according to the present invention has no size limitation, high anti-aging, high anti-crystallization ability, better mechanical properties and durability, and is suitable for different application scenarios. Attached Figure Description

[0021] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0022] Figure 1 The differential scanning calorimetry (DSC) curves of the cast metallic glass I and the ultrastable metallic glass I in Embodiment 1 of the present invention are shown, wherein the heating rate is 10 K min. -1 ;

[0023] Figure 2 The differential scanning calorimetry (DSC) curves of the cast metallic glass II and the ultrastable metallic glass II in Embodiment 2 of the present invention are shown, wherein the heating rate is 10 K min. -1 ;

[0024] Figure 3 The differential scanning calorimetry (DSC) curves of the as-cast metallic glass III and the ultrastable metallic glass III in Example 3 of this invention are shown, wherein the heating rate is 10 K min. -1 ;

[0025] Figure 4 The differential scanning calorimetry (DSC) curves of the cast metallic glass IV and the ultrastable metallic glass IV in Example 4 of this invention are shown, wherein the heating rate is 10 K min. -1 ;

[0026] Figure 5 The differential scanning calorimetry (DSC) curves of the as-cast metallic glass V and the ultrastable metallic glass V in Embodiment 5 of the present invention are shown, wherein the heating rate is 10 K min. -1 ;

[0027] Figure 6 The XRD results are for the cast metallic glass I and the ultrastable metallic glass I in Embodiment 6 of the present invention;

[0028] Figure 7 The XRD results are those of the cast metallic glass II and the ultrastable metallic glass II in Example 6 of this invention;

[0029] Figure 8 The XRD results are those of the cast metallic glass III and the ultrastable metallic glass III in Example 6 of this invention;

[0030] Figure 9The XRD results are for the cast metallic glass IV and the ultrastable metallic glass IV in Example 6 of this invention;

[0031] Figure 10 The XRD results are for the cast metallic glass V and the ultrastable metallic glass V in Embodiment 6 of the present invention.

[0032] Figure 11 The images show the TEM results of the cast metallic glass I and the ultrastable metallic glass I in Embodiment 6 of the present invention, where (a) is a high-resolution transmission electron micrograph and selected area electron diffraction pattern of the cast metallic glass I, (b) is a high-angle annular dark-field image of the cast metallic glass I, (c) is a high-resolution transmission electron micrograph and selected area electron diffraction pattern of the ultrastable metallic glass I, and (d) is a high-angle annular dark-field image of the ultrastable metallic glass I.

[0033] Figure 12 The curves of the distribution function G(r) for the cast metallic glass I and the ultrastable metallic glass I in Embodiment 6 of the present invention are shown.

[0034] Figure 13 The flash DSC results for the cast metallic glass I and the ultrastable metallic glass I in Example 6 of this invention are shown, with a heating rate of 1000 K s. -1 ;

[0035] Figure 14 The results of density tests comparing cast metallic glass I and ultrastable metallic glass I in Embodiment 6 of the present invention are shown.

[0036] Figure 15 The ultra-stable metallic glass I in Embodiment 6 of the present invention is in its T g XRD patterns, DSC curves, and nanoindentation load-displacement curves of the ultrastable metallic glass I before and after annealing at +70K for 10 hours are shown. (a) shows the ultrastable metallic glass I at its T g XRD patterns before and after annealing at +70K for 10 hours, (b) shows the ultrastable metallic glass I at its T g DSC curves before and after annealing at +70K for 10 hours. (c) shows the DSC curves of the ultrastable metallic glass I at its T. g Nanoindentation load-displacement curves before and after annealing at +70K for 10 hours. Detailed Implementation

[0037] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0038] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0039] In this document, the terms “comprising” or “including” are open-ended expressions, meaning that they include the contents specified in this invention, but do not exclude other aspects.

[0040] In this document, the terms “optionally,” “optionally,” or “optionally” generally refer to an event or condition that may, but may not, occur, and the description includes both cases in which the event or condition occurs and cases in which the event or condition does not occur.

[0041] Terms and Definitions

[0042] In this paper, the term "glass-glass transition" refers to the transformation from one type of glass to another, in which the structure, properties, and energy state of the glass change, usually accompanied by heat release (an exothermic peak occurs when the temperature rises). In this invention, after undergoing a glass-glass transition, the original cast metallic glass is transformed into an ultrastable metallic glass.

[0043] In this document, the term "final temperature" refers to the highest temperature reached by a sample during a heating test or experiment. In this invention, it specifically refers to the temperature at which a cast metallic glass has been heated to the point where it has completely completed the glass-glass transition without crystallization.

[0044] In this paper, the term "ultra-stable metallic glass" refers to an amorphous metallic material with high thermodynamic and kinetic stability. Compared with traditional metallic glasses, it has a more stable amorphous structure, higher thermal stability, better anti-aging properties, better anti-crystallization ability, better mechanical properties and durability.

[0045] In this document, the term "master alloy ingot" refers to an alloy material containing the alloy components and composition, which is completely melted into an alloy melt and then cooled and solidified. The composition is very uniform, and the material has been repeatedly smelted and processed to ensure that its chemical composition and physical properties meet specific standards.

[0046] In this paper, the term "complete crystallization" refers to the process by which a material transforms from an amorphous or partially crystalline state to a completely ordered crystalline state. In amorphous metallic glasses, complete crystallization usually involves the transformation of atoms from a long-range disordered arrangement to a regular, periodic arrangement. The temperature range in which complete crystallization occurs can be determined by the crystallization start point and end point corresponding to the crystallization exothermic peak of the differential scanning calorimetry curve.

[0047] Methods for preparing ultrastable metallic glasses

[0048] This invention proposes a method for preparing ultrastable metallic glasses. According to an embodiment of the invention, the method includes: S1: melting alloy raw materials to obtain cast metallic glass; S2: heat-treating the cast metallic glass to induce a glass-glass transition without crystallization, thereby obtaining ultrastable metallic glass; wherein the process parameters of the heat treatment are determined by differential scanning calorimetry (DSC) curves of the cast metallic glass, and the temperature at which the glass-glass transition occurs without crystallization, determined by the exothermic peak in the DSC curve, is taken as the final temperature of the heat treatment. The inventors first prepare ordinary metallic glass through alloy melting and rapid cooling, then heat-treat the ordinary metallic glass to induce a glass-glass transition without crystallization, and then cool it to room temperature to obtain ultrastable metallic glass. The preparation method of this invention has advantages such as simple preparation method, high production efficiency, low cost, no size limitation, and wide applicability to alloy systems with glass-glass transition characteristics. The ultrastable metallic glass prepared according to this invention has high anti-aging and anti-crystallization capabilities, better mechanical properties and durability, and is suitable for different application scenarios.

[0049] According to embodiments of the present invention, the alloy composition includes two or more of titanium, zirconium, hafnium, copper, nickel, beryllium, cobalt, aluminum, niobium, lanthanum, cerium, and cobalt. Therefore, the preparation method of the present invention is widely applicable to alloy systems exhibiting glass-glass transition properties.

[0050] According to embodiments of the present invention, the alloying ingredients include titanium, zirconium, copper, nickel, and beryllium. Therefore, the preparation method of the present invention is applicable to alloy systems comprising titanium, zirconium, copper, nickel, and beryllium alloying ingredients and exhibiting glass-glass transition properties.

[0051] According to embodiments of the present invention, the alloy composition includes titanium, hafnium, copper, nickel, and beryllium. Therefore, the preparation method of the present invention is applicable to alloy systems comprising titanium, hafnium, copper, nickel, and beryllium alloy compositions and exhibiting glass-glass transition properties.

[0052] According to embodiments of the present invention, the alloy composition includes titanium, zirconium, hafnium, copper, nickel, and beryllium. Therefore, the preparation method of the present invention is applicable to alloy systems comprising titanium, zirconium, hafnium, copper, nickel, and beryllium alloy compositions and exhibiting glass-glass transition properties.

[0053] According to an embodiment of the present invention, the smelting process includes the following steps: a. arc melting the alloy batch to obtain the master alloy ingot; b. induction melting the master alloy ingot, followed by cooling and solidification to obtain the cast metallic glass. This ensures the uniformity of the alloy composition, providing a homogeneous base material for the subsequent glass-to-glass transition, thereby guaranteeing the consistency and reliability of the ultrastable metallic glass.

[0054] According to an embodiment of the present invention, the heat treatment further includes: heating the cast metallic glass to a temperature at which a glass-glass transition occurs without crystallization, followed by cooling to obtain an ultrastable metallic glass. Thus, an ultrastable metallic glass is prepared. Exemplarily, in method 1 of the present invention for preparing ultrastable metallic glass, after heating the cast metallic glass at a heating rate of 10 K / min to a temperature at which a glass-glass transition occurs without crystallization (the final temperature of the heat treatment), an immediate cooling treatment is performed to obtain an ultrastable metallic glass. Thus, an ultrastable metallic glass is prepared.

[0055] According to an embodiment of the present invention, the heat treatment further includes: heating the cast metallic glass to a preset temperature at which a glass-glass transition occurs without crystallization and holding it at that temperature, followed by a cooling treatment to obtain an ultrastable metallic glass; wherein the preset temperature is lower than the final temperature of the heat treatment. Exemplarily, in method 2 of the present invention for preparing ultrastable metallic glass, the cast metallic glass is heated at a heating rate of 10 K / min to a preset temperature at which a glass-glass transition occurs without crystallization (this temperature is 5-10 K lower than the final temperature of the heat treatment), held at the preset temperature for approximately 20 minutes, and then cooled; this method can also prepare an ultrastable metallic glass.

[0056] Therefore, both of the above methods can be used to produce ultra-stable metallic glasses with no size limitations, high resistance to aging and crystallization, better mechanical properties and durability.

[0057] It should be noted that the phrase "not limited by size" in this article means that the size of the ultrastable metallic glass prepared by the preparation method of this invention is completely determined by the size of the cast metallic glass. The size of the ultrastable metallic glass can be as large as the size of the cast metallic glass. The phrase "not limited by size" mainly refers to the fact that, compared to the PVD method, which can only prepare thin film ultrastable glasses, the ultrastable metallic glass prepared by the preparation method of this invention has no size limitation within the glass forming capability limit.

[0058] Ultra-stable metallic glass

[0059] This invention proposes an ultrastable metallic glass. According to an embodiment of the invention, the ultrastable metallic glass is prepared according to the aforementioned method. The ultrastable metallic glass of this invention has no size limitations, high anti-aging properties, high anti-crystallization ability, better mechanical properties and durability, and is suitable for various application scenarios.

[0060] According to an embodiment of the present invention, the alloy composition of the ultrastable metallic glass, expressed as Ti (atomic percentage), is... a Zr b Cu c Ni d Be e Where: 19%≤a≤21%, 19%≤b≤21%, 19%≤c≤21%, 19%≤d≤21%, 16%≤e≤24%, a+b+c+d+e=100%. Therefore, ultrastable metallic glasses within the above alloy composition range all possess advantages such as no size limitations, high anti-aging properties, high anti-crystallization ability, better mechanical properties, and durability. Exemplarily, according to an embodiment of the present invention, the obtained ultrastable metallic glass, when titanium, zirconium, copper, nickel, and beryllium are used as alloying ingredients, includes Ti... 20 Zr 20 Cu 20 Ni 20 Be 20 Ti 21 Zr 21 Cu 21 Ni 21 Be 16 Ti 19 Zr 19 Cu 19 Ni 19 Be 24 .

[0061] According to an embodiment of the present invention, the alloy composition of the ultrastable metallic glass, expressed as Ti (atomic percentage), is... A Hf B Cu C Ni D Be E Wherein: 19%≤A≤21%, 19%≤B≤21%, 19%≤C≤21%, 19%≤D≤21%, 16%≤E≤24%, A+B+C+D+E=100%. Therefore, ultrastable metallic glasses within the above alloy composition range possess advantages such as no size limitations, high anti-aging properties, high anti-crystallization ability, better mechanical properties, and durability. Exemplarily, according to an embodiment of the present invention, the ultrastable metallic glass prepared with titanium, hafnium, copper, nickel, and beryllium as alloying elements includes Ti... 20 Hf 20 Cu 20 Ni20 Be 20 .

[0062] According to an embodiment of the present invention, the alloy composition of the ultrastable metallic glass, expressed as Ti (atomic percentage), is... I Zr II Hf III Cu IV Ni V Be VI Where: I = II = III, 12% ≤ I ≤ 14%, IV = V = VI, 19% ≤ IV ≤ 22%, I + II + III + IV + V + VI = 100%. Therefore, ultrastable metallic glasses within the above alloy composition range possess advantages such as no size limitations, high anti-aging properties, high anti-crystallization ability, better mechanical properties, and durability. Exemplarily, according to an embodiment of the present invention, the obtained ultrastable metallic glass, when titanium, zirconium, hafnium, copper, nickel, and beryllium are used as alloying elements, includes (TiZrHf). 40 Cu 20 Ni 20 Be 20 .

[0063] The present invention will be explained below with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0064] Example 1: The chemical composition formula is Ti 20 Zr 20 Cu 20 Ni 20 Be 20 Preparation of ultrastable metallic glasses

[0065] The inventors utilized the glass-glass transition phenomenon in metallic glasses, and through heating and annealing, transformed ordinary metallic glasses into ultra-stable metallic glasses with superior anti-aging and anti-crystallization capabilities. The chemical composition formula is Ti. 20 Zr 20 Cu 20 Ni 20 Be 20 The preparation method of the ultrastable metallic glass (ultrastable metallic glass I) is as follows:

[0066] 1. Preparation of alloy ingredients

[0067] Titanium, zirconium, copper, nickel and beryllium blocks with a purity higher than 99.9 wt% were selected for alloy preparation, and weighed according to the atomic percentage Ti:Zr:Cu:Ni:Be=1:1:1:1:1 using a high-precision electronic balance with an accuracy of 0.0001g.

[0068] 2. Alloy smelting batching

[0069] In a vacuum environment, with a vacuum level better than 3×10 -3 Under the condition of Pa, high-purity argon gas with a volume fraction of ≥99.999% is introduced to prevent the alloy ingredients from being oxidized or reacting unnecessarily with other gases; under argon protection, the above alloy ingredients are subjected to arc melting for 1 minute, and the arc melting operation is repeated 4 times to ensure the uniformity of the alloy ingot and obtain a master alloy ingot with uniform composition.

[0070] 3. Preparation of Cast Metallic Glass I

[0071] Under the vacuum and high-purity argon environment described in step 2, the above-mentioned master alloy ingot is melted by induction melting and sprayed onto the surface of a high-speed rotating copper roller to cool it rapidly. The copper roller rotates at 3800 rpm (approximately 40 m / s), the spray pressure is 55.4 kPa, the bottom opening diameter of the quartz tube is 0.4 mm, and the current is approximately 19 A, resulting in a metallic glass strip, namely, cast metallic glass I.

[0072] 4. Determination of heating conditions

[0073] Take 20 mg of the above-mentioned metallic glass strip and heat it to complete crystallization using a differential scanning calorimeter (DSC) at a heating rate of 10 K / min. Based on the obtained differential scanning calorimetry curve (DSC curve), determine the exothermic peak corresponding to the glass-glass transition and its temperature range, including the onset temperature and the end temperature (or termination temperature), when the atomic percentage of the alloy composition is Ti:Zr:Cu:Ni:Be=1:1:1:1:1. Based on this, determine the heat treatment conditions under this condition.

[0074] The differential scanning calorimetry curve of the cast metallic glass I is visible. Figure 1 .

[0075] The results show that at a heating rate of 10 K / min, the glass-glass transition completion temperature of the as-cast metallic glass I is 781 K.

[0076] The above results indicate that when the atomic percentage of the alloy composition is Ti:Zr:Cu:Ni:Be=1:1:1:1:1, the heating condition is to heat to 781K at a heating rate of 10K / min.

[0077] 5. Preparation of ultrastable metallic glasses

[0078] (1) Preparation method of ultrastable metallic glass 1

[0079] Based on the temperature conditions obtained in step 4, take another 50 mg of the above-mentioned metallic glass strips, heat them to 781 K using a differential scanning calorimeter (DSC) at a heating rate of 10 K / min, and cool them to room temperature at a cooling rate of 50 K / min to obtain ultrastable metallic glass I.

[0080] (2) Preparation method of ultrastable metallic glass

[0081] Based on the temperature conditions obtained in step 4, take several more of the above-mentioned metallic glass strips, place them in a quartz tube protected by Ar gas, and then place them together with the quartz tube in a heat treatment annealing furnace. Heat them to 771K at a heating rate of 10K / min, and hold them at 771K for 20 minutes. Then take the quartz tube out and air-cool or water-cool it to room temperature to obtain ultra-stable metallic glass I.

[0082] Differential scanning calorimetry curves of cast metallic glass I and ultrastable metallic glass I are shown below. Figure 1 .

[0083] Example 2: The chemical composition formula is Ti 21 Zr 21 Cu 21 Ni 21 Be 16 Preparation of ultrastable metallic glasses

[0084] The chemical composition formula is Ti 21 Zr 21 Cu 21 Ni 21 Be 16 The preparation method of ultrastable metallic glass (ultrastable metallic glass II), referring to the chemical composition formula of Ti in Example 1. 20 Zr 20 Cu 20 Ni 20 Be 20 The preparation method of the ultrastable metallic glass (ultrastable metallic glass I) differs from that of Example 1 in that the alloy preparation in step 1 is the same, while the other steps remain the same. The specific differences are as follows:

[0085] Titanium, zirconium, copper, nickel and beryllium blocks with a purity higher than 99.9 wt% were selected for alloy preparation, and were weighed using a high-precision electronic balance with an accuracy of 0.0001 g according to the atomic percentage Ti:Zr:Cu:Ni:Be=21:21:21:21:16.

[0086] The differential scanning calorimetry curve of the cast metallic glass II is visible. Figure 2 .

[0087] (1) Preparation method of ultrastable metallic glass 1

[0088] Based on the temperature conditions obtained in step 4 of Reference Example 1, several more of the above-mentioned metallic glass strips were taken and heated to 769K using a differential scanning calorimeter (DSC) at a heating rate of 10K / min, and then cooled to room temperature at a cooling rate of 50K / min to obtain ultra-stable metallic glass II.

[0089] (2) Preparation method of ultrastable metallic glass

[0090] Based on the temperature conditions obtained by the method in step 4 of Reference Example 1, several more of the above-mentioned metallic glass strips are taken and placed in a quartz tube protected by Ar gas. Then, the quartz tube is placed together in a heat treatment annealing furnace and heated to 759K at a heating rate of 10K / min. The temperature is then held at 759K for 20 minutes. The quartz tube is then removed and cooled to room temperature by air or water to obtain ultra-stable metallic glass II.

[0091] Differential scanning calorimetry (DSC) curves of cast metallic glass II and ultrastable metallic glass II are shown below. Figure 2 .

[0092] Example 3: The chemical composition formula is Ti 19 Zr 19 Cu 19 Ni 19 Be 24 Preparation of ultrastable metallic glasses

[0093] The chemical composition formula is Ti 19 Zr 19 Cu 19 Ni 19 Be 24 The preparation method of ultrastable metallic glass (ultrastable metallic glass III), referring to the chemical composition formula of Ti in Example 1. 20 Zr 20 Cu 20 Ni 20 Be 20 The preparation method of the ultrastable metallic glass (ultrastable metallic glass I) differs from that of Example 1 in that the alloy preparation in step 1 is the same, while the other steps remain the same. The specific differences are as follows:

[0094] Titanium, zirconium, copper, nickel and beryllium blocks with a purity higher than 99.9 wt% were selected for alloy preparation, and were weighed using a high-precision electronic balance with an accuracy of 0.0001 g according to the atomic percentage Ti:Zr:Cu:Ni:Be=19:19:19:19:24.

[0095] The differential scanning calorimetry curve of the cast metallic glass III is visible. Figure 3 .

[0096] (1) Preparation method of ultrastable metallic glass 1

[0097] According to the temperature conditions obtained by the method in step 4 of Reference Example 1, several more of the above-mentioned metallic glass strips were taken and heated to 825K using a differential scanning calorimeter (DSC) at a heating rate of 10K / min, and then cooled to room temperature at a cooling rate of 50K / min to obtain ultra-stable metallic glass III.

[0098] (2) Preparation method of ultrastable metallic glass

[0099] Based on the temperature conditions obtained by the method in step 4 of Reference Example 1, several more of the above-mentioned metallic glass strips are taken and placed in a quartz tube protected by Ar gas. Then, the quartz tube is placed together in a heat treatment annealing furnace and heated to 820K at a heating rate of 10K / min. The temperature is then held at 820K for 20 minutes. The quartz tube is then removed and cooled to room temperature by air or water to obtain ultra-stable metallic glass III.

[0100] Differential scanning calorimetry (DSC) curves of cast metallic glass III and ultrastable metallic glass III are shown below. Figure 3 .

[0101] Example 4: The chemical composition formula is Ti 20 Hf 20 Cu 20 Ni 20 Be 20 Preparation of ultrastable metallic glasses

[0102] The chemical composition formula is Ti 20 Hf 20 Cu 20 Ni 20 Be 20 The preparation method of ultrastable metallic glass (ultrastable metallic glass IV) refers to the chemical composition formula of Ti in Example 1. 20 Zr 20 Cu 20 Ni 20 Be 20The preparation method of the ultrastable metallic glass (ultrastable metallic glass I) differs from that of Example 1 in that the alloy preparation in step 1 is the same, while the other steps remain the same. The specific differences are as follows:

[0103] Titanium, hafnium, copper, nickel and beryllium blocks with a purity higher than 99.9 wt% were selected for alloy preparation, and weighed using a high-precision electronic balance with an accuracy of 0.0001 g according to the atomic percentage Ti:Hf:Cu:Ni:Be=19:19:19:19:24.

[0104] Differential scanning calorimetry (DSC) curves of the cast metallic glass IV are visible. Figure 4 .

[0105] (1) Preparation method of ultrastable metallic glass 1

[0106] Based on the temperature conditions obtained in step 4 of Reference Example 1, several more of the above-mentioned metallic glass strips were taken and heated to 823K using a differential scanning calorimeter (DSC) at a heating rate of 10K / min, and then cooled to room temperature at a cooling rate of 50K / min to obtain ultrastable metallic glass IV.

[0107] (2) Preparation method of ultrastable metallic glass

[0108] Based on the temperature conditions obtained in step 4 of Reference Example 1, several more metallic glass strips were taken and placed in a quartz tube protected by Ar gas. Then, the strips were placed together with the quartz tube in a heat treatment annealing furnace and heated to 813 K at a heating rate of 10 K / min. The temperature was then maintained at 813 K for 20 min. The quartz tube was then removed and cooled to room temperature by air or water to obtain ultrastable metallic glass IV.

[0109] Differential scanning calorimetry (DSC) curves of cast metallic glass IV and ultrastable metallic glass IV are shown below. Figure 4 .

[0110] Example 5: Chemical composition formula is (TiZrHf) 40 Cu 20 Ni 20 Be 20 Preparation of ultrastable metallic glasses

[0111] The chemical composition formula is (TiZrHf). 40 Cu 20 Ni 20 Be 20 The preparation method of ultrastable metallic glass (ultrastable metallic glass V) refers to the chemical composition formula of Ti in Example 1. 20 Zr 20 Cu 20 Ni20 Be 20 The preparation method of the ultrastable metallic glass differs from that of Example 1 in that the alloy preparation in step 1 is the same, while the other steps remain the same. The specific differences are as follows:

[0112] Titanium, zirconium, hafnium, copper, nickel, and beryllium blocks with a purity higher than 99.9 wt% were selected for alloy preparation. The alloy was weighed using a high-precision electronic balance with an accuracy of 0.0001 g according to the atomic percentage Ti:Zr:Hf:Cu:Ni:Be = 13.3:13.3:13.3:20:20:20.

[0113] (1) Preparation method of ultrastable metallic glass 1

[0114] The differential scanning calorimetry curve of the cast metallic glass V is visible. Figure 5 .

[0115] Based on the temperature conditions obtained in step 4 of Reference Example 1, several more of the above-mentioned metallic glass strips were taken and heated to 790K using a differential scanning calorimeter (DSC) at a heating rate of 10K / min, and then cooled to room temperature at a cooling rate of 50K / min to obtain ultrastable metallic glass V.

[0116] (2) Preparation method of ultrastable metallic glass

[0117] Based on the temperature conditions obtained by the method in step 4 of Reference Example 1, several more of the above-mentioned metallic glass strips are taken and placed in a quartz tube protected by Ar gas. Then, the quartz tube is placed together in a heat treatment annealing furnace and heated to 780K at a heating rate of 10K / min. The temperature is then held at 780K for 20 minutes. The quartz tube is then removed and cooled to room temperature by air or water to obtain the ultra-stable metallic glass V.

[0118] Differential scanning calorimetry curves of cast metallic glass V and ultrastable metallic glass V are shown below. Figure 5 .

[0119] Example 6: Comparative Test of Structural Properties of Cast Metallic Glasses I-IV and Ultrastable Metallic Glasses I-IV

[0120] The structural performance of the cast metallic glasses I-IV and ultrastable metallic glasses I-IV prepared in Examples 1-5 was tested, and the specific steps are as follows:

[0121] (1) X-ray diffraction

[0122] X-ray diffraction (XRD) was used to confirm whether the ultrastable metallic glass I and the cast metallic glass I were amorphous structures. Specific parameters were: Cu Kα rays were used, and the scan rate was 2° / min.

[0123] The XRD results of cast metallic glass I and ultrastable metallic glass I are shown in the figure. Figure 6 .

[0124] The XRD results of the cast metallic glass II and the ultrastable metallic glass II are shown in the figure. Figure 7 .

[0125] The XRD results of the cast metallic glass III and the ultrastable metallic glass III are shown in the figure. Figure 8 .

[0126] The XRD results of the cast metallic glass IV and the ultrastable metallic glass IV are shown in the figure. Figure 9 .

[0127] The XRD results of the cast metallic glass V and the ultrastable metallic glass V are shown in the figure. Figure 10 .

[0128] Combination Figures 1-10 The results showed that the XRD spectra of both the cast metallic glass I-V and the ultrastable glass I-V were typical "bun peaks" and no sharp Bragg diffraction peaks were observed, indicating that they were all amorphous structures within the XRD detection accuracy range.

[0129] (2) Transmission electron microscopy

[0130] Transmission electron microscopy (TEM) was used to examine cast metallic glass I and ultrastable metallic glass I. The presence of lattice fringes was confirmed based on the image results, thereby determining whether the sample was an amorphous structure.

[0131] TEM results for cast metallic glass I and ultrastable metallic glass I are shown in Figure 11 .

[0132] The results show that the HRTEM images of both the cast metallic glass I and the ultrastable glass I exhibit typical labyrinthine patterns with no lattice fringes, indicating that both are completely amorphous at the nanoscale with no nanocrystalline precipitation. The SAED of both glasses shows diffused diffraction rings without sharp diffraction spots. No significant contrast was observed in the HADDF of either glass, indicating that the two glasses are homogeneous in composition and have not undergone phase separation or nanocrystallization. In conclusion, the TEM structures fully demonstrate that the heat-treated ultrastable glass is a completely amorphous structure.

[0133] (3) Synchrotron radiation

[0134] Data on the distribution function G(r) were obtained using synchrotron radiation. By fitting the G(r) curve, the structural order of ultrastable metallic glass I and cast metallic glass I was quantified.

[0135] The distribution function G(r) of cast metallic glass I and ultrastable metallic glass I is shown in [reference]. Figure 12 .

[0136] The results show that the distribution function curve G(r) reveals structural differences between the two types of glass, especially significant differences in the mid-range scale. Intuitively, the G(r) curve of the ultrastable glass decays more slowly, indicating a more ordered structure. The peak height h(r) and r of the G(r) curve were fitted using an exponential decay function: h(r) = A·exp(-r / ξ), where A is the amplitude and ξ is the cutoff distance. ξ quantitatively measures the rate of decay of the G(r) curve; the larger the ξ, the slower the decay, indicating an increased degree of order in the alloy structure. (The cutoff distance of the ultrastable metallic glass is also shown.) Compared to as-cast The increase of 62.3% reflects the significant orderliness of its structure.

[0137] (4) Thermodynamic performance testing

[0138] Flash differential scanning calorimetry (flash DSC) was used to obtain flash DSC results by heating and detecting at a heating rate of 1000 K / s.

[0139] Flash DSC results for cast metallic glass I and ultrastable metallic glass I are shown below. Figure 13 .

[0140] The results show that the glass transition temperatures of as-cast and ultrastable metallic glasses were calibrated at an ultrafast heating rate of 1000 K / s (typical curves are shown in Figure 1). Figure 13 As shown in Table 1, the statistical results indicate that a higher glass transition temperature means that more energy is required to excite atoms from the confined glass state to the mobile equilibrium supercooled liquid state. The glass transition temperature of the ultrastable metallic glass is 12.8% higher than that of the as-cast state, indicating that its kinetic stability is significantly improved compared to the as-cast metallic glass.

[0141] (5) Density test

[0142] Density tests were performed to compare the ultrastable metallic glass I and cast metallic glass I obtained by the preparation method of the present invention, the ultrastable metallic glass prepared by physical vapor deposition, and the ultrastable metallic glass prepared by natural aging.

[0143] The densities of ultrastable metallic glass I and cast metallic glass I were tested using a gas displacement method. The test temperature was 35 ± 0.01 °C, and the displacement gas used was helium with a purity of 99.999%. The density data of ultrastable metallic glasses prepared by physical vapor deposition and by natural aging were obtained from existing literature.

[0144] The results of the comparative density test of ultra-stable metallic glass I are shown in the figure. Figure 14 .

[0145] The results show that density is an important indicator reflecting the thermodynamic stability of glass. The lower the energy state of the glass, the higher its density, and the closer it is to the density of the corresponding crystalline state. Compared with cast metallic glass I, the density of ultrastable glass I increased by 2.3%; compared with the crystalline state, the density of ultrastable glass I was only 0.7% lower. The density increases caused by physical vapor deposition, natural aging, and the present method were compared. The density increase of ultrastable glass prepared by physical vapor deposition is generally 1-2% compared with cast metallic glass, while the density increases of amber aged for 110 million years and Ce-Al-Cu metallic glass aged for 17.7 years are 2.05% and 1.19%, respectively. The density increase of ultrastable metallic glass I prepared by the present invention is 2.3%, which is higher than the previously reported value of ultrastable glass.

[0146] (6) Mechanical property testing

[0147] The hardness and reduced modulus of ultrastable metallic glasses I-V and cast metallic glasses I-V were determined using nanoindentation. The loading and unloading rates during the tests were both 1 mN / s. -1 The maximum load is 30mN, and the holding time at the maximum load is 5s.

[0148] The density, modulus, hardness, glass transition temperature (Tg), supercooled liquid phase width (ΔT), and density, modulus, and hardness of the cast metallic glass I and the ultrastable metallic glass I are shown in Table 1.

[0149] Table 1

[0150]

[0151] Among them, the crystalline state is the product of the complete crystallization of cast metallic glass I, T g@1000K / s ΔT is the glass transition temperature at 1000 K / s. @10K / min Width of the supercooled liquid phase region measured at 10 K / min

[0152] The results show that, compared to the cast metallic glass I, the modulus and hardness of the ultrastable glass I increased by 26.9% and 26.0%, respectively. As a structure-sensitive quantity, the significant change in modulus indicates a substantial alteration in the alloy's structure. Generally, the modulus of metallic glasses is about 30% lower than that of the corresponding crystalline state, a phenomenon known as "modulus softening." However, the modulus of the ultrastable glass in this invention is only 5.1% lower than that of the crystalline state, indicating that the energy state of this ultrastable glass is close to that of the crystalline state.

[0153] The changes in modulus and hardness of ultra-stable metallic glasses I-V compared to cast metallic glasses I-V are shown in Table 2.

[0154] Table 2

[0155] Modulus increase (%) Hardness increase (%) Ultra-stable metallic glass I compared to cast metallic glass I 27.0 26.0 Ultra-stable metallic glass II compared to cast metallic glass II 29.0 30.2 Ultra-stable metallic glass III compared to cast metallic glass III 19.8 21.6 Ultra-stable metallic glass IV compared to cast metallic glass IV 20.0 28.1 Ultra-stable metallic glass V compared to cast metallic glass V 17.4 22.5

[0156] The results show that after the glass-glass transition from I to V, the modulus of the ultra-stable metallic glass increases by 17.4% to 29.0%, and the hardness increases by 21.6% to 30.2%. Such a significant increase in modulus and hardness cannot be achieved by simple relaxation annealing, which confirms that the glass obtained after annealing is an ultra-stable metallic glass.

[0157] (7) Anti-crystallization ability test

[0158] Differential scanning calorimetry (DSC) was used to study the ultrastable metallic glass I at its T... g The alloy was held at +70K for 10 hours, and differential scanning calorimetry, X-ray diffraction (XRD), and nanoindentation were used to test the anti-crystallization ability and mechanical property stability of the prepared alloy.

[0159] Ultrastable metallic glass I in its T g XRD patterns, DSC curves, and nanoindentation load-displacement curves before and after annealing at +70K for 10 hours are shown below. Figure 15 .

[0160] The results showed that after 10 hours of high-temperature annealing, the XRD pattern still maintained a diffuse "bun peak" shape, without any sharp Bragg diffraction peaks, indicating that the ultrastable metallic glass I sample remained amorphous and did not crystallize. Furthermore, a comparison of the DSC curves before and after annealing showed that the crystallization enthalpy did not decrease, confirming the conclusion that no crystallization occurred. Nanoindentation was used to test the modulus and hardness of the ultrastable metallic glass I sample before and after annealing, revealing that the modulus and hardness increased by only 0.9% and 3.5%, respectively, proving that the mechanical properties of the ultrastable metallic glass I sample remained quite stable.

[0161] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing ultrastable metallic glasses, characterized in that, include: S1: The alloy ingredients are smelted to obtain cast metallic glass with glass-glass transition properties; S2: The cast metallic glass is heat-treated to induce a glass-glass transition without crystallization, resulting in an ultrastable metallic glass. The process parameters of the heat treatment are determined by the differential scanning calorimetry (DSC) curve of the cast metallic glass, and the temperature at which the glass-glass transition does not occur, determined by the exothermic peak in the DSC curve, is taken as the final heating temperature of the heat treatment.

2. The method according to claim 1, characterized in that, The alloy composition includes two or more of the following: titanium, zirconium, hafnium, copper, nickel, beryllium, cobalt, aluminum, niobium, lanthanum, cerium, and cobalt.

3. The method according to claim 1, characterized in that, The alloy composition includes titanium, zirconium, copper, nickel, and beryllium.

4. The method according to claim 1, characterized in that, The alloy composition includes titanium, hafnium, copper, nickel, and beryllium.

5. The method according to claim 1, characterized in that, The alloy composition includes titanium, zirconium, hafnium, copper, nickel, and beryllium.

6. The method according to claim 1, characterized in that, The smelting process includes the following steps: a. The alloy ingredients are subjected to electric arc melting to obtain a master alloy ingot; b. After induction melting of the master alloy ingot, cooling and solidification are performed to obtain the cast metallic glass.

7. The method according to claim 1, characterized in that, The heat treatment further includes: The cast metallic glass is heated to the final temperature and then cooled to obtain an ultrastable metallic glass.

8. The method according to claim 1, characterized in that, The heat treatment further includes: The cast metallic glass is heated to a temperature 5-10 K below the final temperature and then held at that temperature. After the holding temperature is followed by a cooling process, an ultra-stable metallic glass is obtained.

9. A superstable metallic glass, characterized in that, The ultrastable metallic glass is prepared by the method according to any one of claims 1 to 8.

10. The ultrastable metallic glass according to claim 9, characterized in that, The alloy composition of the ultrastable metallic glass, expressed as Ti by atomic percentage, is... a Zr b Cu c Ni d Be e Where: 19%≤a≤21%, 19%≤b≤21%, 19%≤c≤21%, 19%≤d≤21%, 16%≤e≤24%, a+b+c+d+e=100%.

11. The ultrastable metallic glass according to claim 9, characterized in that, The alloy composition of the ultrastable metallic glass, expressed as Ti by atomic percentage, is... A Hf B Cu C Ni D Be E Where: 19%≤A≤21%, 19%≤B≤21%, 19%≤C≤21%, 19%≤D≤21%, 16%≤E≤24%, A+B+C+D+E=100%.

12. The ultrastable metallic glass according to claim 9, characterized in that, The alloy composition of the ultrastable metallic glass, expressed as Ti by atomic percentage, is... I Zr II Hf III Cu IV Ni V Be VI , where: I=II=III, 12%≤I≤14%, IV=V=VI, 19%≤IV≤22%, I+II+III+IV+V+VI=100%.

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