CN112877617B - High-temperature block amorphous alloy with excellent amorphous forming ability and preparation method and application thereof - Google Patents
High-temperature block amorphous alloy with excellent amorphous forming ability and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature block amorphous alloy with excellent amorphous forming ability and a preparation method and application thereof, which are characterized in that by researching the composition of a crystalline phase precipitated when Ir-Ta-Ni is rapidly solidified, starting from inhibiting the crystalline phase generated when an alloy melt is solidified, based on a similar competition mechanism, aiming at the composition elements of the crystalline phase, similar elements are selectively added, the strong action among the elements in the crystalline phase is weakened, and the precipitation of the crystalline phase is inhibited, so that the amorphous forming ability of the alloy is improved, a Ta-Ir-Ni-SE alloy system with larger critical amorphous forming size is developed, the problem of small critical size of the amorphous alloy is effectively solved, and the raw material cost of the alloy is also effectively reduced Micro/nano machinery, precise optical devices, medical devices and the like.
Description
Technical Field
The invention relates to the technical field of amorphous alloys, in particular to a high-temperature block amorphous alloy with excellent amorphous forming capability and a preparation method and application thereof.
Background
Amorphous alloy is generally prepared by rapidly cooling alloy melt, and atoms are not easy to be arranged in a three-dimensional periodic manner and are frozen under the condition of rapid cooling, so that a long-range disorder and short-range ordered unique arrangement mode is formed. Atoms in the crystalline alloy are orderly arranged in a long period in a three-dimensional space, and in contrast, the internal atomic arrangement of the amorphous alloy has the characteristics of long-range disorder and short-range order, so that the amorphous alloy is determined to have a series of unique properties, such as good corrosion resistance, elastic limit up to 2%, high strength (GPa magnitude), good wear resistance, near-net-shape forming ability and the like.
Since the discovery of a flaky Au-Si amorphous alloy by Duwez professor Caltech, the form of an amorphous alloy sample is limited to a one-dimensional wire and a two-dimensional strip in a period of time, until a millimeter-sized Pd-based bulk amorphous alloy is prepared for the first time by Chen in Bell laboratory in 1974, the amorphous alloy sample is broken through from two dimensions to three dimensions, but the limited amorphous forming size (1-2 mm) of the alloy is still the primary problem restricting the bulk amorphous alloy from being applied. Through decades of efforts, alloy systems with amorphous critical dimension reaching the centimeter level, namely La-based, Zr-based, Ti-based, Mg-based, Cu-based, Fe-based, Pd-based, Ni-based and the like, have been developed at present, wherein Zr-based bulk amorphous alloys have been applied in military industry and civil industry. At the end of the last century, the Nokia company applies Zr-based amorphous alloy to Virtue mobile phones produced by the Nokia company, and opens the door of application of amorphous alloy devices serving as mobile phone parts in the civil field; in order to thoroughly solve the influence of residual radiation of the depleted uranium armor-piercing bomb, the U.S. military is dedicated to developing research on the amorphous alloy composite armor-piercing bomb by the Johnson group of Caltech.
First, the excellent performances of high strength, high elastic modulus and the like of amorphous alloy and the near-net forming ability of the amorphous alloy during the preparation of devices are favored by commodity manufacturers such as mobile phones, high-grade wristwatches and the like, most mobile phone parts such as camera frames, card taking needles, alloy hinges for folding screens and the like are prepared from amorphous alloy, and meanwhile, the amorphous alloy is concerned by medical equipment manufacturers, and medical devices such as surgical suture needles, scalpels and the like are developed; in addition, the method can also be used for preparing precise optical devices; secondly, with the development of science and technology, micro/nano machinery has attracted people's attention day by day, and is expected to become one of the future economic growth points, the atom arrangement of the traditional crystalline alloy is arranged in a long period on a three-dimensional space, the mechanical properties of the micro/nano device prepared by the crystalline alloy show various anisotropy due to the problem of crystal orientation, the service life of the device is seriously influenced, the atom arrangement of the amorphous alloy is disordered in a long range and ordered in a short range on the three-dimensional space, and the atom arrangement of the amorphous alloy still has various isotropy on the micrometer and nanometer scales, so the amorphous alloy is an ideal material for preparing the micro/nano device. Thirdly, the bulk amorphous alloy is also the preferred material for developing the novel armor piercing bullet without radiation pollution and with excellent performance, because the bulk amorphous alloy has the strength of GPa grade on the one hand when being compressed, and on the other hand, the fracture mode shows that the fracture mode is nearly 45 degrees shear fracture, and has self-sharpening performance, at present, the novel armor piercing bullet of Zr-based amorphous alloy composite tungsten capable of replacing the depleted uranium armor piercing bullet is developed, and the problem of residual radiation of the depleted uranium bullet is thoroughly solved.
Amorphous alloyAs a metastable material, it will be unstable under certain conditions, such as when it reaches or exceeds a certain temperature, it will crystallize, its atoms will be periodically arranged in three-dimensional space, and its excellent properties will be seriously weakened or lost all over. Taking the example of a Zr-Cu-Ni-Al-Ag alloy with good amorphous forming ability, the typical composition of the alloy will crystallize around 510 ℃ and lose its excellent properties. Therefore, development of a glass transition temperature (T) having a high value g ) The bulk amorphous alloy system is a fundamental way for widening the application range of the bulk amorphous alloy. Recently Wang et al (Wang etc. high-temperature bulk metallic graded by composite methods. Nature,2019,569.) reported a T-shaped glass substrate g The article indicates that the strength of the alloy is still as high as 3.7GPa even at 767 ℃, the discovery of the alloy system greatly widens the application field of the bulk amorphous alloy and solves the problem that the bulk amorphous alloy cannot be used due to crystallization at higher temperature. However, the size of the Ir-Ni-Ta- (B) bulk amorphous alloy is only up to
The limited amorphous forming ability and the lower critical amorphous size are the first problems restricting the application of the bulk amorphous alloy, and the key for promoting the application of the high-temperature amorphous alloy is to try to further improve the amorphous forming ability and obtain a large-size full amorphous sample. Therefore, it is highly desirable to develop a large-sized high-temperature bulk amorphous alloy that does not crystallize at a higher temperature (above 700 ℃) and has a high amorphous forming ability.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of poor amorphous forming capability and small size of the conventional high-temperature amorphous alloy, and provides a high-temperature bulk amorphous alloy with excellent amorphous forming capability and large size.
It is still another object of the present invention to provide a method for preparing a high-temperature bulk amorphous alloy having excellent amorphous forming ability.
It is another object of the present invention to provide a use of a high temperature bulk amorphous alloy having an excellent amorphous forming ability.
The above purpose of the invention is realized by the following technical scheme:
the high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir a Ta b Ni c SE d Wherein SE is similar elements, and the similar elements are one or more of Ru, Os, Rh, Pd, Pt, Nb, Fe and Co; a. b, c and d represent atomic composition percentage, wherein a is 12-47, b is 18-48, c is 15-38, d is 0.3-40, and a + b + c + d is 100.
The strong interaction between elements constituting the crystalline phase is the root cause of the precipitation of the crystalline phase during solidification, and thus weakening the interaction between elements in the crystalline phase will contribute to improving the amorphous-forming ability of the alloy. On one hand, elements with similar physical and chemical properties have weaker interaction; on the other hand, Similar Elements (SE) function similarly to other Elements. These two points determine that when A, B two similar elements are present in the alloy system, A, B will compete with other elements in the alloy system, which we call similar competition, which weakens the interaction of element a with other elements, and also with element B. Therefore, based on a similar competition mechanism, similar elements are screened for the constituent elements of the crystalline precipitated phase and added into the alloy system, and for the Ir-Ta-Ni-SE alloy system, the elements with similar physical and chemical properties to Ir are Ru, Os, Pd, Rh and Pt, Ta and Nb belong to VB group and have extremely similar physical and chemical properties, and the elements with similar physical and chemical properties to Ni are Fe and Co and also are Pd belonging to the same group. Based on a similar competition mechanism, the addition of the similar elements helps to inhibit the precipitation of a crystalline phase in an Ir-Ta-Ni alloy system and weaken the interaction between the constituent elements of the crystalline phase. The precipitation of crystalline phase is inhibited in the process of solidifying the alloy liquid, so that the amorphous forming capability of the alloy is improved, and the amorphous alloy with larger size is obtained.
Preferably, the similar elements are one or more of Ru, Rh, Pd, Pt, Nb, Fe and Co.
More preferably, the similar element is one or more of Rh, Pd, Pt, Nb, Co and Fe.
Preferably, a is 18-45, b is 20-46, c is 18-32, and d is 1.5-38.
The invention also provides a preparation method of the high-temperature bulk amorphous alloy, which comprises the following steps:
weighing metal simple substances according to the atomic composition of the amorphous alloy, smelting in an inert atmosphere or high vacuum to obtain a metal ingot, then melting the metal ingot to obtain an alloy melt, injecting the alloy melt into a mold, and quickly solidifying the alloy melt to obtain the high-temperature bulk amorphous alloy.
Preferably, the melting is one of arc melting, electron beam melting or induction melting.
When vacuum non-consumable arc melting or electron beam melting is adopted, the metal cast ingot is repeatedly melted by the arc or the electron beam for at least four times, and the metal cast ingot is required to be turned over after each melting for ensuring the uniformity of the composition of the metal cast ingot.
Preferably, the temperature of the electric arc or electron beam melting is 1200-1650 ℃, and the melting time is 3-15 min.
Preferably, the smelting times are 4-6 times.
When the induction melting is adopted, the melting is carried out at least twice, and after the first melting is finished, the metal ingot is turned over to ensure the uniformity of the alloy ingot.
Preferably, the temperature of the induction melting is 1200-1650 ℃, and the melting time is 9-30 min.
Preferably, the melting temperature is 1200-1650 ℃, and the melting time is 9-30 min.
Preferably, the melting is performed by heating with one of an arc, an electron beam or an induction coil.
The inert atmosphere of the present invention includes, but is not limited to, one or more of high purity argon, high purity helium and high purity nitrogen.
The simple metal substance is pure metal or intermediate alloy meeting the composition proportion requirement, wherein the purity of the pure metal is 97.5-99.99%.
The invention also protects the application of the high-temperature block amorphous alloy in preparing parts of mobile phones or high-grade wristwatches, micro/nano machines, precise optical devices or medical appliances.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, by researching the composition of the crystalline phase precipitated when the Ir-Ta-Ni system is rapidly solidified, starting from inhibiting the crystalline phase generated when the alloy melt is solidified aiming at the composition elements of the crystalline phase, similar elements are selectively added based on a similar competition mechanism, so that the strong action among the elements in the crystalline phase is weakened, and the precipitation of the crystalline phase is inhibited, thereby the amorphous forming capability of the alloy is improved, and the maximum critical amorphous forming size at least is developed
The Ta-Ir-Ni-SE alloy system effectively solves the problem of small critical dimension of amorphous alloy, and simultaneously effectively reduces the cost of the alloy raw materials.
Drawings
FIG. 1 is Ir 30 Ta 40 Ni 30 Made of alloys
XRD results of the samples.
FIG. 2 is Ir 30 Ta 40 Ni 30 Made of alloys
XRD results of the samples.
FIG. 3 is a drawing of suction-cast Ir 30 Ta 40 Ni 30 
Back scattering scanning picture of sample cross section and point selection position of energy spectrum analysis.
FIG. 4 is Ir 30 Ta 38 Ni 27.5 Nb 2 Co 2.5 Alloy suction casting
XRD results of the samples.
FIG. 5 is Ir 16 Ta 34 Ni 22 Rh 14 Co 4 Alloy suction casting
XRD results of the samples.
FIG. 6 is Ir 16 Ta 34 Ni 32 Rh 14 Co 4 Alloy suction casting
Compression properties of the samples.
FIG. 7 is Ir 38 Ta 22 Ni 18 Nb 8 Rh 4 Co 6 Pd 3.5 Fe 0.5 Alloy spray casting
XRD results of the samples.
FIG. 8Ir 38 Ta 21 Ni 18 Nb 8 Rh 4 Co 6 Pd 3.5 Fe 0.5 Mo 1 Alloy spray casting
XRD results of the samples.
FIG. 9 is Ir 38 Ta 22 Ni 14 Nb 12 Rh 4 Co 6 Pd 3.5 Fe 0.5 Alloy spray casting
DSC results for the samples.
FIG. 10 shows the addition of trace Rh pairs
Alloy sample Ir 25 Ta 47 Ni 28 Rh 0.3 And Ir 25 Ta 47 Ni 28 Comparative XRD patterns of amorphous formation ability.
FIG. 11 is Ir 12 Ta 48 Ni 15 Nb 8 Pd 17 Alloy suction casting
XRD results of the samples.
FIG. 12 is Ir 27 Ta 18 Ni 15 Nb 38 Co 2 Alloy suction casting
XRD results of the samples.
FIG. 13 is Ir 47 Ta 23 Ni 18 Pd 1.5 Pt 2.5 Alloy suction casting
XRD results of the samples.
FIG. 14 is Ir 12 Ta 18 Ni 15 Nb 24 Rh 2 Pt 14 Alloy suction casting
XRD results of the samples.
FIG. 15 is Ir 27 Ta 18 Ni 15 Nb 38 Co 2 Alloy suction casting
DSC results for the samples.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
The high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 30 Ta 38 Ni 27.5 Nb 2 Co 2.5 。
The preparation method of the high-temperature bulk amorphous alloy comprises the following steps:
according to Ir 30 Ta 38 Ni 27.5 Nb 2 Co 2.5 Preparing 10g of material, smelting by vacuum non-consumable arc, putting the material in a water-cooled copper crucible, closing a furnace cover and an air inlet valve, opening a mechanical pump to pump the vacuum degree of a furnace chamber to 3 multiplied by 10 0 Pa, opening the electromagnetic valve until the vacuum degree is stabilized at 3 multiplied by 10 0 When the pressure is lower than Pa, closing the mechanical pump exhaust valve, opening the molecular pump and a gate valve of the molecular pump, pumping the vacuum of the cavity by adopting the molecular pump, and reducing the vacuum degree to 3 multiplied by 10 -3 When Pa, closing the gate valve, filling high-purity argon gas of 0.2atm into the chamber, opening the mechanical pump extraction valve, repeating the above process for 5 times until the molecular pump pumps the vacuum degree of the chamber to 3 × 10 -3 When Pa, closing the gate valve, filling high-purity argon of 0.3atm into the chamber, firstly smelting the Ti ingot for 3min by using an electric arc according to related operation requirements, reducing the current intensity of the electric arc, and beginning to smelt 10g of materials, wherein each material is smelted for 3min at least for 4 times, so as to obtain alloy ingots with uniform compositions; transferring the melted alloy ingot from the melting crucible to a suction casting crucible by a manipulator, in order to reduce the oxygen content in the chamber as much as possible, melting Zr ingot for 3min by electric arc, and then melting Ir by electric arc 30 Ta 38 Ni 30 Nb 2 And after the alloy ingot is completely melted, clicking a key to switch on a mechanical pump, and completely sucking alloy liquid to a copper mold through air pressure difference so as to obtain an alloy rod with the diameter of 4 mm.
Example 2
Has excellent amorphousThe high-temperature bulk amorphous alloy with the forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 16 Ta 34 Ni 32 Rh 14 Co 4 。
The preparation method of the high-temperature bulk amorphous alloy comprises the following steps:
preparing 12g of materials according to the components, and before smelting, sequentially pumping the vacuum degree in a smelting furnace chamber to 5 multiplied by 10 by adopting a mechanical pump and a molecular pump -3 Pa, closing the air extraction pipeline, filling high-purity argon into the chamber, and then sequentially pumping the vacuum degree in the chamber to 5 multiplied by 10 by using a mechanical pump and a molecular pump -3 Pa, repeating the steps for 3 times, and repeatedly smelting the materials for 6 times by adopting an electron beam to ensure the uniformity of the alloy ingot; placing the smelted alloy ingot in a crucible of a non-consumable electric arc furnace capable of sucking and casting, closing a cavity, and pumping the vacuum degree in the cavity to 2 multiplied by 10 by adopting a mechanical pump and a molecular pump in sequence -3 Pa, closing the air extraction pipeline, filling high-purity argon into the chamber, and then sequentially pumping the vacuum degree in the chamber to 2 multiplied by 10 by using a mechanical pump and a molecular pump -3 Pa, repeating the above steps for 3 times, charging high-purity Ar gas of 0.3atm into the chamber, starting electric arc to melt Zr ingot for 5min to eliminate residual oxygen molecules in the chamber to the maximum extent, melting the mother alloy ingot with electric arc, clicking suction casting button, suction casting the alloy melt to the die hole
In a copper mold to obtain
The rod-shaped sample of (1).
Example 3
The high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system which sequentially comprises Ir 40 Ta 30 Ni 19 Rh 11 、Ir 16 Ta 20 Ni 22 Nb 26 Co 10 Pd 4 And Ir 26 Ta 30 Ni 19 Pt 8 Nb 6 Co 11 。
The preparation method of the bulk amorphous alloy except that the weight of the material is changed from 12g to 6g
The copper mould is replaced by
Except for the copper mold, the other preparation process parameters were exactly the same as in example 2.
Example 4
The high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 38 Ta 22 Ni 18 Nb 8 Rh 4 Co 6 Pd 3.5 Fe 0.5 。
The preparation method of the high-temperature bulk amorphous alloy comprises the following steps:
preparing 26g of material according to the above components, placing the prepared 26g of material in a water-cooled copper crucible in a vacuum non-consumable arc furnace, closing a furnace cover and an air inlet valve, and opening a mechanical pump to pump the vacuum degree of a furnace chamber to 3 × 10 0 Pa, opening the electromagnetic valve until the vacuum degree is stabilized at 5 multiplied by 10 0 When the pressure is lower than Pa, closing the mechanical pump exhaust valve, opening the molecular pump and a gate valve of the molecular pump, pumping the vacuum of the cavity by adopting the molecular pump, and reducing the vacuum degree to 5 multiplied by 10 -3 When Pa, closing the gate valve, filling high-purity argon gas of 0.2atm into the chamber, opening the mechanical pump extraction valve, repeating the above process for 4 times until the molecular pump pumps the vacuum degree of the chamber to 3 × 10 -3 When Pa, closing the gate valve, filling high-purity argon of 0.5atm into the chamber, firstly smelting Zr ingots for 5min by using an electric arc according to related operation requirements, reducing the current intensity of the electrodes, moving the tungsten electrodes to the position of materials to be smelted, gradually increasing the current intensity of the electrodes, and beginning to smelt 26g of materials, wherein each material is smelted for 5 times, and each time is smelted for 4min to obtain alloy ingots with uniform compositions; the amorphous round bar is prepared by adopting suspension smelting and spray casting integrated equipment, and the method specifically comprises the following steps: firstly, the smelted alloy ingot is loaded into a furnace with a small hole on the bottomIn the test tube, a die hole is arranged below the test tube
The copper mould regulates and controls the lifting of the test tube through a mechanical device, and the small hole of the test tube is aligned to the opening of the mould; the vacuum degree of the equipment chamber is pumped to 2 multiplied by 10 by adopting a mechanical pump and a molecular pump in sequence -3 Pa, closing a gate valve of the molecular pump and filling high-purity argon into the cavity to serve as protective atmosphere; and starting an induction melting power supply, and immediately spraying molten alloy liquid into a copper mould through a small hole at the bottom by using high-purity argon gas flow after the mother alloy ingot is melted, so as to obtain the alloy round bar with the diameter of 8 mm.
Example 5
The high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 24.7 Ta 47 Ni 28 Rh 0.3 . The preparation method is the same as that of example 1.
Example 6
The high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 12 Ta 48 Ni 15 Nb 8 Pd 17 . The preparation method is the same as that of example 1.
Example 7
The high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 27 Ta 18 Ni 15 Nb 38 Co 2 . The preparation method is the same as that of example 1.
Example 8
The high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 47 Ta 23 Ni 18 Pd 1.5 Pt 2.5 . The preparation method is the same as that of example 1.
Example 9
High amorphous forming abilityThe high-temperature bulk amorphous alloy is Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 12 Ta 18 Ni 15 Nb 24 Rh 2 Pt 14 . The preparation method is the same as that of example 1.
Example 10
The high-temperature bulk amorphous alloy with excellent amorphous forming capability is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir 28 Ta 46.5 Ni 18 Rh 7.5 、Ir 18 Ta 22 Ni 33 Nb 9 Co 12 Fe 2 Pd 4 And Ir 26 Ta 35 Ni 28 Nb 6.5 Rh 4.5 。
Comparative example 1
Ir of this comparative example 30 Ta 40 Ni 30 Amorphous alloy of 3mm prepared by suction casting at the composition point
A round bar.
Comparative example 2
In Ir 38 Ta 22 Ni 18 Nb 8 Rh 4 Co 6 Pd 3.5 Fe 0.5 On the basis of the components of the alloy, a very small amount of non-similar element Mo is added, and the influence of Mo on the amorphous forming capability of the alloy is researched. In particular, the above-mentioned and
same preparation Process for preparing Ir 38 Ta 21 Ni 18 Nb 8 Rh 4 Co 6 Pd 3.5 Fe 0.5 Mo 1 Is/are as follows
A round bar.
Performance testing
1. XRD test
The XRD results for the 3mm round bar obtained in comparative example 1 are shown in fig. 1, and show that the sample is not an all-amorphous sample and has a distinct crystalline phase. In order to study the composition of precipitated phases, further suction casting is adopted to prepare
The sample is confirmed to be free of amorphous phase and crystalline phase by adopting XRD, SEM, energy spectrum analysis and other testing means, and the test results of XRD and SEM are respectively shown in figures 2 and 3. From the results of XRD, it was found that a plurality of crystalline phases were precipitated in the sample, and Ir was suspected 3 Ta、Ir 1.25 Ni 1.65 Ta 2.1 Precipitation of crystalline phases and other unknown crystalline phases. The results of the back-scattering scan and the energy spectrum analysis further showed the complexity of the crystalline precipitated phases in the sample, although the back-scattering scan results showed that the crystalline phases in the sample appeared to have blocky white crystalline phases and black crystalline phases, and further the energy spectrum analysis from table 1 showed that the composition of the white crystalline phases at different locations differed significantly, indicating that the white crystalline phases may be composed of different crystalline phases, as was the case with the blocky black crystalline phases.
Table 1 corresponds to the results of the energy spectrum analysis (Atomic%)
| Position of | Ir | | Ni |
| Spectrum | |||
| 1 | 36.95 | 45.44 | 17.61 |
| Spectrum2 | 20.79 | 43.79 | 35.42 |
| Spectrum3 | 46.33 | 36.74 | 16.93 |
| Spectrum4 | 33.63 | 44.85 | 21.52 |
For further analysis, the crystalline phases at the spectra 1, spectra 3, and spectra 4 positions in FIG. 3 can be simply classified as (Ir, Ta) rich crystalline phases, while the crystalline phase in spectra 2 is considered as (Ta, Ni) rich crystalline phase. No matter how the composition of Ir-Ta-Ni changes, according to the combination rule of elements, the crystalline precipitated phase influencing the amorphous forming capability of the alloy system is not one or more of (Ir, Ta) -rich crystalline phase, (Ta, Ni) -rich crystalline phase and (Ir, Ni) -rich crystalline phase. The precipitation of the above-mentioned crystalline phase during rapid solidification is the root cause of the limited ability of the Ir-Ta-Ni alloy of comparative example 1 to form amorphous material.
In example 1 of the present invention, 2 at% of Nb and 2.5 at% of Co were added in place of Ta and Ni in equal amounts, respectively, and suction casting was performed
The sample is obtained by cutting the alloy rod from the position of 6mm above the bottom of the prepared alloy rod, and performing XRD test on the section of the alloy rod, wherein the scanning range is 20-80 degrees, and the scanning rate is 4 degreesAnd/min. The XRD test result is shown in figure 4, and the test result is a typical steamed bread peak without the appearance of other miscellaneous peaks, which shows that the sample is in a full amorphous phase, which shows that Nb and Co are respectively added into the alloy as similar elements of Ta and Ni to obtain Ir 30 Ta 38 Ni 27.5 Nb 2 Co 2.5 The quinary alloy effectively inhibits the precipitation of crystalline phases due to the addition of similar elements, and improves the amorphous forming capability of the alloy.
From example 2
The sample is cut at the position of more than 8mm of the bottom of the rod-shaped sample and is used for XRD test, the scanning range is 20-80 degrees, the scanning speed is 5 degrees/min, the specific test result is shown in figure 5, and the figure shows that only a small amount of crystalline precipitated phases exist in the sample, which indicates that the amorphous critical dimension of the alloy is close to that of the alloy
A sample is transversely cut from the position of more than 10mm at the bottom of the 8mm alloy round rod in the example 4 and subjected to XRD test, the scanning range is 20-85 degrees, the scanning speed is 4 degrees/min, the specific test result is shown in figure 7, the result shows that the sample is completely amorphous, and the critical amorphous size of the component is at least as large as
Wherein the fully amorphous sample size of a typical composition in the present invention is
It cannot be said that the amorphous critical dimension of the Ir-Ta-Ni-SE alloy system is
It is considered that the amorphous critical dimension of the typical composition in the alloy system is at least
Comparative example 2 is in Ir 38 Ta 22 Ni 18 Nb 8 Rh 4 Co 6 Pd 3.5 Fe 0.5 On the basis of the alloy, only a small amount of non-similar element Mo is added, namely the composition is Ir 38 Ta 21 Ni 18 Nb 8 Rh 4 Co 6 Pd 3.5 Fe 0.5 Mo 1 Preparation of the alloy
Round bar, and further XRD testing was performed, the results are shown in fig. 8. As can be seen from a comparison of fig. 8 and 7, even a very small amount of Mo, which is a non-similar element, is added to the alloy, which results in a serious deterioration in the amorphous forming ability of the alloy.
Ir prepared in examples 5 to 9 24.7 Ta 47 Ni 28 Rh 0.3 、Ir 12 Ta 48 Ni 15 Nb 8 Pd 17 、Ir 27 Ta 18 Ni 15 Nb 38 Co 2 、Ir 47 Ta 23 Ni 18 Pd 1.5 Pt 2.5 、Ir 12 Ta 18 Ni 15 Nb 24 Rh 2 Pt 14 Alloy ingots with uniform compositions are smelted, alloy round bars with different outer diameters are further prepared by a suction casting method, and the specific round bar diameters corresponding to different alloy compositions are shown in table 2. All round rods are transversely cut and sampled at a position 1 cm away from the bottom end of the round rods, the cross sections of the round rods are ground flat by using No. 800 and No. 1200 water mill sandpaper, and then XRD (X-ray diffraction) tests are carried out, and the test results are respectively shown in figures 10-14.
TABLE 2 preparation of corresponding relationships for round bars of different diameters using different alloy compositions
As can be seen from FIG. 10, Ir 24.7 Ta 47 Ni 28 Of alloys
Almost all crystalline phases in the sample, in Ir 25 Ta 47 Ni 28 On the basis, the crystalline phase in the alloy can not be completely inhibited but most of the crystalline phase is inhibited only by substituting the same amount of the extremely-micro 0.3 percent Rh for Ir,
most of the samples are amorphous phases and only a small part of crystalline phases, and the addition of trace elements can improve the amorphous forming capability of the alloy.
As can be seen from FIG. 11, the composition Ir is used in the range of 2 θ from 70 to 80 ° 12 Ta 48 Ni 15 Nb 8 Pd 17 The alloy of (a) produced a sample of 5mm in diameter with very little crystalline phase, although the sample was not an all-amorphous sample, indicating that the amorphous critical dimension of the composition is extremely close to that of the composition
As can be seen from FIG. 12, composition Ir is used 27 Ta 18 Ni 15 Nb 38 Co 2 The alloy of (1) is prepared into a sample with the diameter of 4mm, the sample is a full amorphous sample, and the amorphous critical dimension of the alloy is at least
As can be seen from FIG. 13, composition Ir is used 47 Ta 23 Ni 18 Pd 1.5 Pt 2.5 The alloy of (a) produced a sample with a diameter of 7mm containing a small amount of crystalline phase, which indicates that the amorphous critical dimension of the constituent alloy is less than 7 mm.
As can be seen from FIG. 14, the composition Ir 12 Ta 18 Ni 15 Nb 24 Rh 2 Pt 14 The sample with the diameter of 6mm prepared by the alloy is an all-amorphous sample, and shows that the alloy is notThe critical dimension of the crystal is at least 6 mm.
2. Mechanical Property test
The change of the alloy composition influences the performance of amorphous forming ability, thermodynamic stability and the like of the alloy on one hand and influences the mechanical property of the alloy on the other hand. With the change of alloy composition, the mechanical property difference of the amorphous alloy is obvious. Taking the sample prepared in the example 2, breaking a master alloy ingot for preparing the high-temperature amorphous alloy sample, weighing 4-6 g of blocks, putting the blocks into a crucible of a suction-castable non-consumable electric arc furnace, and preparing the sample with the diameter similar to that prepared in the step (2)
A rod-shaped amorphous alloy sample is prepared by cutting a rod into small cylinders with the height-diameter ratio of 2:1 by a precision cutting saw, using the small cylinders as mechanical property test samples, and grinding two ends of each small cylinder by 2000# abrasive paper to ensure that two end surfaces are parallel and the two end surfaces are perpendicular to the axial direction of each small cylinder. The compression strain rate of the sample is 2 multiplied by 10 when the test is carried out on an Instron material mechanical property tester -4 。
The test results are shown in FIG. 6, which shows that when the test is performed using a sample having a diameter of 2mm and a height to diameter ratio of 2:1, the strength of the sample is 5.4GPa, and the compressive strain is about 1%.
A precision cutting saw is adopted to cut the bar into small cylinders with the height-diameter ratio of 2:1, the small cylinders are used as mechanical property test samples, two ends of each small cylinder are ground flat by 2000# abrasive paper, and the two end faces are ensured to be parallel while the axial direction of the two end faces and the small cylinder is ensured to keep vertical relation. The compression strain rate of the sample is 2 multiplied by 10 when the test is carried out on an Instron material mechanical property tester -4 。
The strength and compressive strain of bulk amorphous alloys of different compositions are shown in table 3.
TABLE 3 relationship of amorphous alloy composition to its mechanical properties
| Alloy composition | Compressive strength | Compressive strain |
| Ir 40 Ta 30 Ni 19 Rh 11 | 5.6GPa | 0.2％ |
| Ir 16 Ta 20 Ni 22 Nb 26 Co 10 Pd 4 | 3.5GPa | 15％ |
| Ir 26 Ta 30 Ni 19 Pt 8 Nb 6 Co 11 | 5.2GPa | 3.5％ |
From the comprehensive mechanical properties of the amorphous alloy in the embodiment 3, the high-temperature bulk amorphous alloy prepared by the invention has the compression strength of 3.6-5.4 GPa and the average compression strain of 0.2-15%.
3. High temperature DSC test
Controlling the quality of the alloy ingot prepared in the example 4 to be 3-4 g, and setting the hole of a copper die as
Still adopting the method of preparing the sample by adopting the suspension smelting and spray casting integrated equipment to prepare the amorphous round rod to obtain the amorphous round rod with the diameter of 2mm, cutting a wafer on the amorphous round rod, controlling the quality of the wafer to be 15-20 mg, adopting 2000# abrasive paper to grind two surfaces of the wafer flat, and obtaining the amorphous round rod with the diameter of 2mmSamples for high temperature DSC testing. The characteristic temperature parameter of the alloy is characterized by adopting high-temperature DSC, and the heating procedure is as follows: the temperature is increased from the room temperature to 1400 ℃, the heating rate is 20K/min, the protective atmosphere is high-purity argon, and the gas flow is 50 ml/min. The high temperature DSC data for this sample is shown in figure 9 and shows a glass transition temperature Tg in excess of 800 ℃.
Ir prepared as in example 7 27 Ta 18 Ni 15 Nb 38 Co 2 Alloy is the object of study, and is prepared
The rod sample is sampled to test the characteristic thermodynamic parameters of the amorphous alloy, and the test result is shown in figure 15, from which the glass transition temperature T of the alloy is known g Slightly below 800 ℃.
The characteristic temperature parameter of the alloy is characterized by adopting high-temperature DSC, and the heating procedure is as follows: the temperature is increased from the room temperature to 1400 ℃, the heating rate is 20K/min, the protective atmosphere is high-purity argon, and the gas flow is 50 ml/min. Glass transition temperatures T of three compositions of bulk amorphous alloys in example 10 g As shown in table 4.
TABLE 4 alloy composition and glass transition temperature T g In relation to (2)
As can be seen from the measured glass transition temperatures, the high temperature bulk amorphous alloy prepared by the present invention has T g Is 740 to 890 ℃. This indicates that the high temperature bulk amorphous alloy of the present invention cannot be used at higher temperatures due to crystallization.
From the above results, the invention starts with the inhibition of the crystalline phase precipitated in the solidification process of the alloy melt, selectively adds similar elements based on a similar competition mechanism, and develops the Ir-Ta-Ni-SE alloy system by introducing the similar elements into the alloy system to weaken the strong interaction among the elements in the crystalline phase, thereby effectively inhibiting the precipitation of the crystalline phase, achieving the purpose of improving the amorphous forming capability of the alloy system, and obtaining the high-temperature bulk amorphous alloy with excellent amorphous forming capability.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. The high-temperature bulk amorphous alloy with excellent amorphous forming capability is characterized in that the high-temperature bulk amorphous alloy is an Ir-Ta-Ni-SE alloy system, and the atomic composition of the high-temperature bulk amorphous alloy is Ir a Ta b Ni c SE d Wherein SE is a similar element, represented by SE 1 And SE 2 Composition of, wherein, SE 1 Is one or more of Ru, Os, Rh, Pd, Pt and Nb, SE 2 Is one or two of Fe and Co, SE 1 And SE 2 Are all greater than 0 at; a. b, c and d represent atomic composition percentage, wherein a is 12-47, b is 18-48, c is 15-38, d is 0.3-40, and a + b + c + d =100, and the critical amorphous forming size of the amorphous alloy is at least phi 8 mm.
2. A high temperature bulk amorphous alloy according to claim 1, wherein the similar element SE1 is one or more of Ru, Rh, Pd and Pt.
3. A high temperature bulk amorphous alloy according to claim 1, wherein a is 18 to 45, b is 20 to 46, c is 18 to 32, d is 1.5 to 38, and a + b + c + d = 100.
4. A method for preparing a high-temperature bulk amorphous alloy according to any one of claims 1 to 3, comprising the following steps:
weighing metal simple substances according to the atomic composition of the amorphous alloy, smelting in an inert atmosphere or high vacuum to obtain a metal ingot, then melting the metal ingot to obtain an alloy melt, injecting the alloy melt into a mold, and quickly solidifying the alloy melt to obtain the high-temperature bulk amorphous alloy;
wherein the metal simple substance is pure metal or intermediate alloy meeting the atomic composition ratio requirement of amorphous alloy; the smelting adopts one of electric arc smelting, electron beam smelting or induction smelting; the temperature of the electric arc or electron beam smelting is 1200-1650 ℃, and the smelting time is 3-15 min.
5. The preparation method according to claim 4, wherein the temperature of the induction melting is 1200-1650 ℃, and the melting time is 9-30 min.
6. The method of claim 4, wherein the melting is performed by heating with one of an arc, an electron beam, or an induction coil.
7. Use of the high temperature bulk amorphous alloy according to any one of claims 1 to 3 in the preparation of components of mobile phones or high-grade wristwatches, micro/nano machines, precision optical devices or medical devices.
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| US5593514A (en) * | 1994-12-01 | 1997-01-14 | Northeastern University | Amorphous metal alloys rich in noble metals prepared by rapid solidification processing |
| CN104372266A (en) * | 2014-11-17 | 2015-02-25 | 北京航空航天大学 | Platinum-based bulk amorphous alloy and preparation method thereof |
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