Method for rapidly screening amorphous alloy with high elasticity, energy storage and low elasticity loss

Abstract

The invention discloses a method for rapidly screening amorphous alloy with high elasticity, energy storage and low elasticity loss, and belongs to the field of mechanical property test analysis, the method comprises the following steps: adopting physical vapor deposition co-sputtering to obtain amorphous alloy with metal element content in gradient distribution along with the surface position of a substrate, and constructing a sample library; and testing the hardness and the equivalent modulus of each sub-region in the sample library, recording the ratio of the hardness to the equivalent modulus of each test point, and screening out the amorphous alloy composition in the region where the ratio of the hardness to the equivalent modulus is maximum, namely the amorphous alloy composition with low loss and high energy storage. Screening is carried out based on quantitative correlation between intrinsic performance parameters of materials and elastic performance, the method is no longer limited to the size and shape of a test sample and no longer depends on manual trial and error development, a large number of target performance components can be rapidly screened in combination with high-throughput preparation and characterization equipment, and the method has the advantages of being high in efficiency and low in cost.

Description

Technical Field

[0001] The present invention relates to the field of mechanical property test and analysis, and particularly to a method for rapidly screening high-elasticity energy-storing and low-elasticity-loss amorphous alloys. Background Art

[0002] Elastic materials such as spring steel, titanium alloy, rubber, shape memory alloy, etc. have crucial applications in many fields. For example, in the fields of engineering and transportation, musical instruments and acoustics, clock timing or foldable electronic devices. With the rapid development of micro-nano processing technology, the miniaturization of electronic devices requires alloy materials with high-elasticity energy storage and low loss. Therefore, a new generation of advanced elastic alloys needs to be developed.

[0003] The elastic properties of materials include static and dynamic elastic properties. The former is mainly manifested as a high elastic strain limit, which affects the elastic strength, anti-deformation ability and service life of the material. The latter is mainly manifested as low loss, which affects the sensitivity and stability of the device.

[0004] Amorphous alloy is a material with three-dimensional disorder of atoms, showing many excellent mechanical properties. For example, high elastic strain, high specific strength, high wear resistance and high fracture toughness. It has a larger elastic limit compared with traditional crystalline materials, up to two percent. In addition, its elastic loss is also lower than that of spring steel and titanium alloy, making it suitable for the composition development of a new generation of elastic alloy materials. Common elastic amorphous alloys often use zirconium-based amorphous alloys or iron-based amorphous alloys, both of which have low cost and good mechanical properties. The composition of zirconium-based amorphous alloys is mainly based on Zr and Cu, adding elements such as Ni, Al or Ti, Ni to regulate the forming ability and elastic properties. The composition of iron-based amorphous alloys is mainly based on Fe-Si and Fe-Co, adding components such as B, P to improve the amorphous forming ability.

[0005] At present, the elastic loss of amorphous alloys is mainly measured by the vibration method, based on the three-point bending mode or tensile mode of the cantilever beam model to measure the loss tangent value of the ratio of the loss modulus to the storage modulus, or characterized by the damping ratio loss measured by the vibrating cantilever beam model. For example, the invention application with the publication number CN118056864A discloses a rubber-based high-loss modulus damping material and its preparation method and application, which characterizes the loss performance of the rubber-based material through the loss tangent value, and additionally combines the damping ratio loss of collision and vibration to establish a quantitative relationship.

[0006] The elastic energy storage of amorphous alloys is mainly measured by using a nanoindentation instrument to measure the load-displacement curve, and the elastic energy storage is calculated through the unloading curve in the elastic recovery stage, or by using a uniaxial tensile or compression testing machine to measure the stress-strain curve and calculating the integral area in the elastic stage (linear segment). However, these methods for testing elastic loss and elastic energy storage are all based on the idea of trial and error. The elastic property testing is related to the size and shape of the device samples, and it is necessary to prepare samples of the same size for testing and comparison. Moreover, only the elastic properties of one composition can be obtained in one test. For materials with different compositions, it is necessary to prepare samples multiple times and measure the elastic properties multiple times, which not only requires a large amount of manpower and financial resources, but also has the problems of long test cycle and low experimental efficiency.

[0007] Compared with the trial-and-error method, high-throughput experiment, as an important part of the new material R & D plan of the Materials Genome, changes the traditional sequential iteration process into parallel experiments. By means of rapid high-throughput characterization of multi-component material preparation, properties and structures, the phase diagram is drawn, the material properties are optimized, and new materials are rapidly screened. It is a new type of new material development strategy. Therefore, based on the intrinsic physical properties of materials, quickly establishing the quantitative relationship between composition, processing technology and properties, and combining high-throughput preparation and characterization equipment to develop new amorphous alloys is an urgent problem to be solved at present. Summary of the Invention

[0008] To solve the above technical problems, the present invention provides a method for quickly screening amorphous alloys with high elastic energy storage and low elastic loss, based on the quantitative correlation between the ratio of the material-intrinsic physical parameters hardness and equivalent modulus and elastic loss and elastic energy storage, to achieve high-throughput screening and design of the elastic properties of materials.

[0009] To achieve the above invention object, an embodiment provides a method for quickly screening amorphous alloys with high elastic energy storage and low elastic loss, including the following steps:

[0010] Adopt physical vapor deposition co-sputtering, and deposit on the substrate at one time based on different metal element targets to obtain an amorphous alloy with a gradient distribution of metal element content along the surface position of the substrate. Divide the surface of the amorphous alloy into multiple sub-regions to construct a sample library;

[0011] Test the hardness and equivalent modulus of each sub-region in the sample library, record the ratio of the hardness and equivalent modulus of each test point, and screen out the composition of the amorphous alloy in the region with the largest ratio of hardness and equivalent modulus, which is the composition of the amorphous alloy with low loss and high energy storage.

[0012] The present invention prepares a multi-element gradient amorphous alloy by physical vapor deposition multi-target co-sputtering, obtains an amorphous alloy gene library with a large composition range and multiple elements, and screens out the composition of the amorphous alloy with low loss and high energy storage based on the quantitative relationship between the material-intrinsic performance parameters and the elastic properties.

[0013] Preferably, the physical vapor deposition co-sputtering is any one of DC magnetron sputtering, evaporation coating, ink printing, 3D printing, and is not limited thereto.

[0014] More preferably, for the DC magnetron sputtering, the basic air pressure in the sputtering chamber is lower than 10-5 Pa, the working air pressure is 0.5 Pa, the argon gas flow rate is 50 standard cubic centimeters per minute, and the deposition time is 90 minutes.

[0015] Preferably, the substrate is a silicon substrate or a quartz substrate; the diameter of the substrate is 5 cm - 20 cm.

[0016] The purpose of selecting the substrate of the above materials is to ensure that the prepared alloy has smooth and flat properties and meets the mechanical property test conditions.

[0017] Preferably, the amorphous alloy with a gradient distribution of metal element content along the substrate surface position is obtained by regulating the position distance between the target and the substrate or regulating the current power.

[0018] By adjusting the two dynamic parameters of the target distance and the current power in real time, the migration rate of metal atoms and the deposition energy distribution during the sputtering process are controlled. The change in the distance between the target and the substrate directly affects the electric field strength of the plasma sheath layer (the electric field increases when the distance is shortened), while the regulation of the current power changes the plasma density (the ionization rate increases when the power increases). This combination of dynamic parameters enables atoms deposited at different positions to obtain different kinetic energies, thereby achieving a spatial gradient distribution of element content.

[0019] More preferably, the center of the target plane is 10 cm away from the substrate plane, and the target and the substrate form an angle of 60 degrees.

[0020] More preferably, the current power is 50 W - 100 W.

[0021] Preferably, the surface roughness of the amorphous alloy is confirmed by an atomic force microscope or a laser confocal microscope.

[0022] More preferably, the surface roughness of the amorphous alloy is less than 1 nm.

[0023] The surface roughness of the amorphous alloy being less than 1 nm is beneficial to reducing errors during nanoindentation testing and making the obtained results accurate and reliable.

[0024] More preferably, the surface of the amorphous alloy is divided into multiple sub-regions according to a grid, and the shapes and areas of each sub-region are exactly the same, and the deposition thickness is the same.

[0025] More preferably, the size of each sub-region is 100 μm × 100 μm.

[0026] Further preferably, the deposition thickness of each sub-region is 0.5 μm - 1.5 μm.

[0027] Preferably, the hardness and equivalent modulus are tested by a nanoindentation instrument or a Vickers hardness tester.

[0028] When a nanoindentation instrument is selected for testing, automatic and rapid measurement can be performed based on a micro-region, improving the acquisition efficiency; when a Vickers hardness tester is selected for testing, the testing steps are simple and easy to operate.

[0029] Further preferably, the indentation depth tested by the nanoindentation instrument does not exceed 1 / 10 of the deposition thickness of the sub-region.

[0030] Selecting the indentation depth within the above range can truly reflect the mechanical properties of the amorphous alloy.

[0031] Preferably, energy dispersive spectroscopy analysis is used to measure the elemental composition and concentration of the amorphous alloy in each sub-region.

[0032] Preferably, the nanoindentation test is carried out by the displacement control method to obtain the unloading curve p-h, and the equivalent modulus corresponding to each test point is obtained by fitting the unloading curve with a formula.

[0033] Further preferably, the formula for fitting the unloading curve is as follows:

[0034]

[0035] Among them, S is the initial slope of the unloading curve, E r is the equivalent modulus of the test point, and A is the contact projection area of the indentation.

[0036] In one embodiment, the amorphous alloy in the sample library is a Zr-Ti-Cu-Ni-Be amorphous alloy or a Zr-Cu-Ni-Al amorphous alloy.

[0037] Further preferably, in the Zr-Ti-Cu-Ni-Be amorphous alloy, the Zr content is 30 wt% - 52 wt%, the Ti content is 26 wt% - 46 wt%, the Cu content is 5 wt% - 15 wt%, the Ni content is 5 wt% - 15 wt%, and the Be content is 2.5 wt% - 5 wt%;

[0038] In the Zr-Cu-Ni-Al amorphous alloy, the Zr content is 42 wt% - 70 wt%, the Cu content is 20 wt% - 30 wt%, the Ni content is 5 wt% - 10 wt%, and the Al content is 3 wt% - 4 wt%.

[0039] Compared with the prior art, the beneficial effects of the present invention at least include:

[0040] (1) Samples with a large composition space are rapidly prepared by physical vapor deposition co-sputtering. Based on microscopic mechanical property characterization equipment, the relationship between hardness and equivalent modulus in different composition spaces is rapidly obtained, improving the prediction efficiency of material mechanical properties.

[0041] (2) Based on the amorphous alloy samples in the sample library, a quantitative relationship is established between elastic loss, elastic energy storage performance and the ratio of the intrinsic hardness and equivalent modulus of the material. Furthermore, elastic loss and elastic energy storage performance are screened through the intrinsic parameters of the material, improving the screening efficiency and reducing the cost. Description of the Drawings

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for description in the embodiments or the prior art.

[0043] Figure 1 Schematic diagram of the device for physical vapor deposition co-sputtering deposition high-throughput sample library provided in Embodiment 1;

[0044] Figure 2 Schematic diagram of the analysis for obtaining the equivalent elastic modulus by indentation test and load-displacement curve provided in Embodiment 1;

[0045] Figure 3 Distribution diagram of the ratio of hardness to equivalent modulus of the high-throughput sample library prepared in Embodiment 1 with respect to element composition;

[0046] Figure 4 Elastic loss is characterized by the damping ratio of vibration or collision provided by the present invention;

[0047] Figure 5 Schematic diagram of the relationship between elastic loss and the ratio of hardness and equivalent modulus provided by the present invention;

[0048] Figure 6 Schematic diagram of the relationship between elastic loss and elastic energy storage provided by the present invention. Detailed Embodiments

[0049] To make the objectives, technical solutions and advantages of the present invention more clearly understood, the following further details the present invention with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and do not limit the protection scope of the present invention.

[0050] Embodiment 1

[0051] Taking the Zr-Ti-Cu-Ni-Be bulk amorphous alloy system as an example, Zr-Ti-Cu-Ni-Be amorphous alloys can be fabricated into rods with a diameter of over 8 cm, having an elastic limit of over 2% and a yield strength of over 1.4 GPa, and are suitable as a material system for elastic devices. Based on a multi-target physical vapor deposition apparatus, the targets selected are zirconium target, titanium target, beryllium copper target (the mass ratio of copper to beryllium in the composite target is 2:1), and nickel target; the substrates used are silicon substrates or quartz substrates with a diameter between 5 and 20 cm; the position distance between the targets and the substrates and the current power of the targets are adjusted to form a composition gradient. The center of the target plane is 10 cm away from the substrate plane, and the targets and the substrates form an angle of 60 degrees.

[0052] As Figure 1 shown, the base pressure in the sputtering chamber is below 10 -5 Pa, the working pressure is 0.5 Pa, the argon gas flow rate is 50 standard cubic centimeters per minute, and the deposition time is 90 minutes. The composition is deposited onto the substrate by DC magnetron sputtering with a power range between 50 W and 100 W to obtain a sample with a gradient composition, where the Zr content is 30 wt% - 52 wt%, the Ti content is 26 wt% - 46 wt%, the Cu content is 5 wt% - 15 wt%, the Ni content is 5 wt% - 15 wt%, and the Be content is 2.5 wt% - 5 wt%.

[0053] The surface roughness of the composition sample is confirmed to be below 1 nm by atomic force microscopy or laser confocal microscopy to avoid affecting the later measurement results. The sample is divided into regions according to a grid, with each grid unit size of 100 μm × 100 μm. Energy dispersive spectroscopy analysis based on an energy dispersive spectrometer is used to characterize the composition concentration gradient of different grids, and a large composition space sample library is constructed.

[0054] Based on the amorphous alloy composition regions of different grids, a nanoindentation tester is used to test amorphous alloys with different compositions. The test parameters are adjusted according to the sample thickness. The deposited thickness of the sample is generally about 1 μm, so the effective indentation depth should be less than 100 nm. The approaching speed of the nano-probe surface is 10 nm / s, the holding time is 1 s, the Poisson's ratio is 0.367, the load size is set to 2.5 mN, and the loading rate is 1 mN / s. The load-displacement curve is measured for each composition grid. According to the load size P max and the indentation area A, the hardness H is calculated by the formula H = P max / A, and the hardness of the zirconium-based amorphous alloy is around 7 GPa.

[0055] As Figure 2 shown, the unloading curve p-h is obtained by the displacement control method. According to the slope of the unloading region curve and the indentation area size of the load-displacement curve, the equivalent modulus corresponding to each test point is obtained by fitting the unloading curve with the formula:

[0056]

[0057] Among them, S is the initial slope of the unloading curve, E r is the equivalent modulus of the test point, and A is the contact projection area of the indentation. Each component grid is measured three times and the average value is taken. The equivalent modulus of the zirconium-based amorphous alloy in this embodiment is around 100 GPa.

[0058] As Figure 3 shown, the hardness and equivalent modulus of different component regions are collected, the ratio of the equivalent modulus to the hardness of each test point is recorded, and a composition-property map is plotted.

[0059] The elastic loss and elastic energy storage are tested to verify the relationship between the ratio of the equivalent modulus to the hardness and the elastic loss and elastic energy storage. The specific tests for elastic loss and elastic energy storage are as follows:

[0060] Elastic energy storage test: According to the composition ratio in the first part above, for example (Zr 41.6 Ti 36.3 Cu 8.9 Ni 8.8 Be 4.4 ) rod-shaped materials with a diameter of 2 mm are prepared by suction casting. It is determined by X-ray diffractometer that the rod is completely amorphous, and then it is cut into cylinders with a length of 4 mm. A universal testing machine is used to measure the elastic energy storage. A quasi-static compressive stress-strain curve is carried out on the sample, and the strain rate is 0.1% / s. The general elastic strain of the zirconium-based amorphous alloy is about 2%. According to the slope of the stress-strain curve, the Young's modulus E can be obtained, and then the area E elastic = σ y ε e / 2 of the elastic deformation region is calculated. This area is the magnitude of the elastic energy storage, which is defined as the elastic energy stored per unit volume.

[0061] Elastic loss test: The measurement of elastic loss has different means and methods according to the actual working conditions. For example, for sheet and plate-shaped samples, the spontaneous elastic loss under vibration is measured by the cantilever beam method ( Figure 4 ), for example, zirconium-based amorphous alloy (Zr 41.6 Ti 36.3 Cu 8.9 Ni 8.8 Be 4.4)A zirconium-based amorphous alloy cantilever beam with a length of 20 cm, a width of 1 cm, and a thickness of 0.8 mm is obtained by wire cutting from a 0.8-mm-thick plate. One end is fixed, and a micro-accelerometer is bonded with beeswax. The other end is excited by a hammer, and the characteristic frequency and damping ratio loss at this size can be measured. By changing the cantilever length of the cantilever beam, the relationship between the characteristic frequency and damping ratio loss of the zirconium-based amorphous alloy can be established, and the elastic loss at the frequency required by the working condition can be given. In addition, for thin film samples and small samples, the tangent of the loss angle, also known as the quality factor, is generally used to judge the elastic loss. Small plates of amorphous alloy can also be obtained by wire cutting to form plates with a length of 5 cm, a width of 1 cm, and a thickness of 0.8 cm. They are clamped by a double-cantilever fixture of a dynamic thermomechanical analyzer, and a deformation of five-thousandths is selected to measure the loss modulus and storage modulus in the range of 0.5 Hz - 200 Hz. The tangent of the loss angle is measured by the ratio of the two, and the elastic loss at the frequency required by the working condition is obtained. Amorphous alloy thin film samples can be prepared by the single-roll casting method. The melted alloy ingot is melted in an argon atmosphere and rapidly cooled at a roll speed of 30 m / s - 40 m / s to prepare amorphous ribbons with a thickness between 20 μm - 30 μm and a width between 1 mm - 2 mm. It is confirmed by an X-ray diffractometer that the sample is completely amorphous. Then, a 2-cm-long ribbon sample is intercepted and the loss modulus and storage modulus are measured in the range of 0.5 Hz - 200 Hz by the thin film tensile fixture of a dynamic thermomechanical analyzer with a set deformation of three-thousandths, and thus the tangent of the loss angle is obtained. For samples with a larger thickness or samples under impact working conditions, the elastic collision method is used to measure( Figure 4 )the corresponding elastic collision loss. First, the sample is cut into a cylinder with a height of 3 cm and a diameter of 25 mm by wire cutting or milling. It is bonded to a large-sized cast iron block with beeswax, and generally, a thickness more than ten times that of the cylinder is sufficient. A titanium alloy ball with a diameter of 0.8 mm is selected to freely fall from 30 cm to collide with the test sample, and the collision interval time and rebound height are measured by a sensor bonded to the cast iron block or a high-speed camera, and the ratio between the two heights is calculated Furthermore, the damping ratio loss ζ of the collision is obtained. The elastic impact energy of each collision can be known from the height. According to the evolution relationship between the damping ratio loss and the impact energy, the loss at different working conditions can be obtained. The elastic losses measured by different methods for the same material are positively correlated, so their relative magnitudes can be compared.

[0062] In addition, after annealing to change the hardness and equivalent modulus of the amorphous alloy, its loss will also change and still follow this relationship. Therefore, this method can also be used to screen heat treatment processes that reduce loss and increase energy storage. When the hardness and equivalent modulus are less than 0.38, the loss satisfies ζ = -2010.75H / Er + 76.85; when the hardness and equivalent modulus are greater than 0.38, the loss satisfies ζ = -25.58H / Er + 2.21.

[0063] As Figure 5 shown, there is a quantitative negative correlation between the ratio of hardness to equivalent modulus and elastic loss (damping ratio loss, loss tangent value, impact damping ratio loss), so that elastic alloy materials with low loss can be quickly screened by the ratio of hardness to equivalent modulus.

[0064] As Figure 6 shown, the loss of amorphous alloy is much lower than that of crystalline alloy, and there is also a negative correlation between elastic loss and elastic energy storage. The lower the loss, the greater the elastic energy storage. Based on the quantitative relationship between the ratio of hardness equivalent modulus and elastic loss and elastic energy storage, it can be used to screen amorphous alloy materials with low loss and high energy storage.

[0065] Example 2

[0066] The experimental process of Example 2 is the same as that of Example 1, except that taking the Zr-Cu-Ni-Al bulk amorphous alloy system as an example, the selected targets are zirconium target, aluminum-copper target (the mass ratio of composite target copper to aluminum is 7.5:1), and nickel target. The gradient composition sample obtained by deposition, in which the Zr content is 42wt%-70wt%, the Cu content is 20wt%-30wt%, the Ni content is 5wt%-10wt%, and the Al content is 3wt%-4wt%.

[0067] It can be seen from the above examples that the present invention screens based on the quantitative correlation between the intrinsic performance parameters of the material and the elastic performance, no longer limited to the size and shape of the test sample, nor relying on manual trial and error development, only related to the intrinsic physical properties of the material. Combining high-throughput preparation and characterization equipment, it can quickly and massively screen target performance components, with the advantages of high efficiency and low cost.

[0068] The above specific embodiments have described in detail the technical solutions and beneficial effects of the present invention. It should be understood that the above is only the most preferred embodiment of the present invention and is not used to limit the present invention. Any modifications, supplements, equivalent substitutions, etc. made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for rapidly screening amorphous alloys with high elastic energy storage and low elastic loss, characterized in that, Including the following steps: Using physical vapor deposition co-sputtering, depositing on a substrate at one time based on different metal element targets to obtain an amorphous alloy with a gradient distribution of metal element content along the surface position of the substrate, dividing the surface of the amorphous alloy into multiple sub-regions, and constructing a sample library; Testing the hardness and equivalent modulus of each sub-region in the sample library, recording the ratio of the hardness and equivalent modulus of each test point, and screening out the composition of the amorphous alloy in the region with the largest ratio of hardness and equivalent modulus, which is the composition of the amorphous alloy with low loss and high energy storage.

2. The method according to claim 1, characterized in that, The substrate is a silicon substrate or a quartz substrate; The diameter of the substrate is 5 cm - 20 cm.

3. The method according to claim 1, wherein The amorphous alloy with a gradient distribution of metal element content along the surface position of the substrate is obtained by adjusting the position distance between the target and the substrate or by adjusting the current power.

4. The method according to claim 3, wherein The current power is 50 W - 100 W.

5. The method according to claim 1, wherein The surface roughness of the amorphous alloy is less than 1 nm.

6. The method according to claim 1, wherein The dividing the surface of the amorphous alloy into multiple sub-regions includes: dividing the surface of the amorphous alloy into multiple sub-regions according to a grid, the shapes and areas of each sub-region are exactly the same, and the deposition thickness is the same.

7. The method according to claim 6, characterized in that, The deposition thickness is 0.5 μm - 1.5 μm.

8. The method according to claim 1, characterized in that, The hardness and equivalent modulus test is carried out by a nano-indentation instrument or a Vickers hardness tester, and the indentation depth tested by the nano-indentation instrument does not exceed 1 / 10 of the deposition thickness of the sub-region.

9. The method according to claim 1, characterized in that The amorphous alloy in the sample library is a Zr-Ti-Cu-Ni-Be amorphous alloy or a Zr-Cu-Ni-A1 amorphous alloy.

10. The method according to claim 9, characterized in that, In the Zr-Ti-Cu-Ni-Be amorphous alloy, the Zr content is 30 wt% - 52 wt%, the Ti content is 26 wt% - 46 wt%, the Cu content is 5 wt% - 15 wt%, the Ni content is 5 wt% - 15 wt%, and the Be content is 2.5 wt% - 5 wt%; In the Zr-Cu-Ni-A1 amorphous alloy, the Zr content is 42 wt% - 70 wt%, the Cu content is 20 wt% - 30 wt%, the Ni content is 5 wt% - 10 wt%, and the A1 content is 3 wt% - 4 wt%.

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