CN114672745B - Titanium-based amorphous composite material and preparation method and application thereof - Google Patents
Titanium-based amorphous composite material and preparation method and application thereof Download PDFInfo
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Abstract
The application relates to the technical field of amorphous composite materials, in particular to a titanium-based amorphous composite material and a preparation method and application thereof. The preparation method of the titanium-based amorphous composite material comprises the following steps: preparing materials according to the atomic percentage expression general formula of the titanium-based amorphous composite material, and then performing casting molding treatment; wherein, the atomic percent expression general formula of the titanium-based amorphous composite material is Ti a Zr b (V 12/ 17 Cu 5/17 ) 100‑a‑b‑c Be c (ii) a In the expression general formula of atomic percentage, a is more than or equal to 40 and less than or equal to 55, b is more than or equal to 10 and less than or equal to 25, a + b is more than or equal to 50 and less than or equal to 75, and c is more than or equal to 10 and less than or equal to 14. According to the preparation method, the atomic percentage ratio in the titanium-based amorphous composite material is regulated, so that the amorphous composite material is not easy to oxidize in preparation, the required vacuum degree in the preparation process of the amorphous composite material is effectively reduced, the tissue uniformity, the strength and the toughness of the titanium-based amorphous composite material are remarkably improved, and the melting point of the titanium-based amorphous composite material is reduced.
Description
Technical Field
The application relates to the technical field of amorphous composite materials, in particular to a titanium-based amorphous composite material and a preparation method and application thereof.
Background
The amorphous alloy material has good application prospect in the field of structural and functional materials because the defects such as dislocation, grain boundary and the like do not exist in the system. However, amorphous alloys and amorphous composite materials are easy to break and have poor mechanical properties due to low toughness, and are difficult to process due to high melting points; and the amorphous alloy and the amorphous composite material are easy to oxidize in the casting forming process, the amorphous forming capability is poor, and the large-scale application of the amorphous material is greatly limited.
In order to ensure that the amorphous composite material is not easy to oxidize, the amorphous forming capability is improved, the forming processing is easy, and the strength and the toughness are improved in the preparation process, the current means is to introduce inert protective gas or improve the vacuum degree to high vacuum in the casting forming treatment, but the above way causes the casting forming treatment conditions to be harsh, and is not beneficial to industrialized mass production.
Disclosure of Invention
The application aims to provide a titanium-based amorphous composite material, a preparation method and application thereof, and aims to solve the technical problem that harsh casting molding treatment conditions are required for preventing oxidation and improving amorphous forming capability in the preparation process of the conventional titanium-based amorphous composite material.
The first aspect of the application provides a preparation method of a titanium-based amorphous composite material, which comprises the following steps: performing casting molding treatment after preparing materials according to the atomic percentage expression general formula of the titanium-based amorphous composite material; wherein, the atomic percentage expression general formula of the titanium-based amorphous composite material is Ti a Zr b (V 12/17 Cu 5/17 ) 100-a-b-c Be c (ii) a In the expression general formula of atomic percent, a is more than or equal to 40 and less than or equal to 55, b is more than or equal to 10 and less than or equal to 25, a + b is more than or equal to 50 and less than or equal to 75, and c is more than or equal to 10 and less than or equal to 14.
According to the method, the atomic percentage ratio of the Ti-based amorphous composite material is regulated, so that the proportion of Ti atoms, zr atoms and Be atoms is (40-55): (10-25): (10-14) the number of Be atoms accounts for 10% -14% of the total number of atoms in the titanium-based amorphous composite material, so that the amorphous composite material is not easy to oxidize in the preparation process, and inert gas is not required to Be introduced; also hasCan reduce the vacuum degree required by the amorphous composite material in the preparation process, remarkably improve the amorphous forming capability of the titanium-based amorphous composite material, and ensure that the titanium-based amorphous composite material does not need to regulate and control a system to 10 degrees in the casting and forming process -3 To 10 -2 But at a vacuum of 10 0 The good amorphous composite structure can be formed by casting under the low vacuum environment condition of Pa or above, the preparation condition of the titanium-based amorphous composite material can be met by industrial-grade casting and forming equipment, the cost is low, the process is simple, and the industrial large-scale production is easy to realize; meanwhile, the titanium-based amorphous composite material prepared by the preparation method of the titanium-based amorphous composite material has the advantages of high tissue uniformity, low melting point, excellent strength and toughness and the like, and has good application prospect in the fields of structural and functional materials.
In a second aspect of the present application, there is provided a titanium-based amorphous composite material, wherein the atomic percent of the titanium-based amorphous composite material is expressed by the general formula Ti a Zr b (V 12/17 Cu 5/17 ) 100-a-b-c Be c (ii) a In the expression general formula of atomic percentage, a is more than or equal to 40 and less than or equal to 55, b is more than or equal to 10 and less than or equal to 25, a + b is more than or equal to 50 and less than or equal to 75, and c is more than or equal to 10 and less than or equal to 14.
According to the method, the atomic percentage ratio of the Ti-based amorphous composite material is regulated, so that the proportion of Ti atoms, zr atoms and Be atoms is (40-55): (10-25): (10-14) and the number of Be atoms accounts for 10-14% of the total number of atoms in the titanium-based amorphous composite material, so that the method is favorable for improving the tissue uniformity, the strength and the toughness of the titanium-based amorphous composite material and reducing the melting point of the titanium-based amorphous composite material, and has good application prospect in the fields of structures and functional materials.
In a third aspect of the present application, an application of the titanium-based amorphous composite material provided in the second aspect above in the preparation of a thin-walled part is provided.
Optionally, the thin-walled member comprises a flexspline, a cell phone shaft, or a watch case.
Optionally, the thin-walled member has a thickness of 0.2-5mm.
The titanium-based amorphous composite material provided by the application has excellent strength and toughness, and can be applied to manufacturing thin-walled parts with high requirements on strength and toughness.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 shows the tensile curves of the titanium-based amorphous composites obtained in examples 1 to 2 and comparative examples 1 to 3 of the present application.
FIG. 2 shows the high temperature DSC curve of the Ti-based amorphous composite material obtained in examples 1-2 of the present application.
FIG. 3 shows the X-ray diffraction pattern of the titanium-based amorphous composite material obtained in example 1-2 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following provides a titanium-based amorphous composite material, and a preparation method and an application thereof.
The application provides a preparation method of a titanium-based amorphous composite material, which comprises the following steps: performing casting molding treatment after preparing materials according to the atomic percentage expression general formula of the titanium-based amorphous composite material; wherein, the atomic percentage expression general formula of the titanium-based amorphous composite material is Ti a Zr b (V 12/17 Cu 5/17 ) 100-a-b-c Be c (ii) a In the expression general formula of atomic percent, a is more than or equal to 40 and less than or equal to 55, b is more than or equal to 10 and less than or equal to 25, a + b is more than or equal to 50 and less than or equal to 75, and c is more than or equal to 10 and less than or equal to 14.
The application is realized by adding titanium-based amorphous composite material intoThe atomic percentage ratio of the Ti atoms, the Zr atoms and the Be atoms is regulated and controlled, so that the ratio of the Ti atoms, the Zr atoms and the Be atoms is (40-55): (10-25): (10-14), wherein the number of Be atoms accounts for 10% -14% of the total number of atoms in the titanium-based amorphous composite material, so that the oxidation of the titanium-based amorphous composite material in the casting and forming process can Be remarkably improved, and inert gas does not need to Be introduced into the titanium-based amorphous composite material in the casting and forming process; the vacuum degree required by the titanium-based amorphous composite material in the casting forming process can be effectively reduced, the amorphous forming capability of the titanium-based amorphous composite material is remarkably improved, and the titanium-based amorphous composite material does not need to be regulated to 10 degrees in the casting forming process -3 To 10 -2 But at a vacuum of 10 0 Pa or above can be cast and molded under the low vacuum environment condition to form a good amorphous composite structure, so that industrial-grade casting and molding equipment can meet the preparation condition of the titanium-based amorphous composite material, and the method has the advantages of low cost, simple process and easy industrial large-scale production.
In this application, "in a vacuum of 10 0 Pa or above under low vacuum environment condition means that the vacuum degree is as low as 10 0 Pa, the titanium-based amorphous composite material can form a good amorphous composite structure, and the required vacuum degree for casting and molding the titanium-based amorphous composite material can be 1Pa, 2Pa, 10MPa or higher.
The atomic percentage ratio of Ti atoms, zr atoms and Be atoms in the titanium-based amorphous composite material is regulated and controlled to Be (40-55): (10-25): (10-14), the number of Be atoms accounts for 10% -14% of the total number of atoms in the titanium-based amorphous composite material, the crystal phase can Be precipitated from the titanium-based amorphous composite material in the cooling process of the cast molding treatment, the residual solution component is converted into an amorphous phase due to higher glass forming capacity, and finally the titanium-based amorphous composite material with second phase toughening is formed, so that the effect of refining crystal grains is realized, and the tissue homogenization in the titanium-based amorphous composite material is improved; the titanium-based amorphous composite material can induce the generation of multiple shear zones in the plastic deformation process, inhibit the rapid propagation of the shear zones and further remarkably improve the toughness and the fracture strength of the titanium-based amorphous composite material.
In addition, the atom percentage ratio in the titanium-based amorphous composite material is regulated and controlled, so that the ratio of Ti atoms, zr atoms and Be atoms is (40-55): (10-25): (10-14) and the number of Be atoms accounts for 10% -14% of the total number of atoms in the titanium-based amorphous composite material, which is also beneficial to improving the fluidity of the titanium-based amorphous composite material in the casting forming process and obviously reducing the melting point of the titanium-based amorphous composite material, so that the titanium-based amorphous composite material is easy to process and form, a mould used in the casting forming process can Be protected, and the service life of the mould is prolonged.
It should be noted that a, b and c in the expression formula of atomic percent of the titanium-based amorphous composite material can be natural numbers or decimal numbers.
Illustratively, the atomic percentage of the titanium-based amorphous composite material expressed by the general formula a can be 40, 43, 45, 48, 50 or 55, etc.; b can be 10, 12, 15, 17, 20, 22 or 25, etc.; a + b can take on values of 50, 55, 58, 62, 65, 70 or 75, etc.; c may be 10, 11, 12, 13 or 14, etc.
Furthermore, in the expression general formula of atomic percent, a is more than or equal to 45 and less than or equal to 50, b is more than or equal to 18 and less than or equal to 22, a + b is more than or equal to 65 and less than or equal to 72, and c is more than or equal to 11 and less than or equal to 13, which is favorable for further improving the toughness and the breaking strength of the titanium-based amorphous composite material.
Illustratively, the atomic percent expression of the titanium-based amorphous composite material is Ti 48 Zr 20 V 13.4 Cu 5.6 Be 13 Or Ti 48 Zr 20 V 14.8 Cu 6.2 Be 11 The two titanium-based amorphous composite materials can still have excellent yield strength, fracture strength and toughness after being cast and molded under the condition that the vacuum degree is as low as 2Pa and under the condition that inert gas is not introduced.
Because the atomic percentage expression of the titanium-based amorphous composite material is regulated and controlled, the titanium-based amorphous composite material can be enabled to have the vacuum degree of 10 0 Casting under low vacuum condition of Pa or aboveForming to form a good amorphous composite structure; in the application, the vacuum degree of the titanium-based amorphous composite material for casting and forming is selected to be 1-8Pa. Illustratively, the degree of vacuum required to prepare the titanium-based amorphous composite material according to the above-described atomic percentage expression formula may be 1Pa, 2Pa, 4Pa, 5Pa, 7Pa, or 8Pa, or the like.
The method of the cast molding process may be any one selected from the group consisting of vacuum die casting molding, semi-solid die casting molding, low-pressure die casting molding, high-pressure die casting molding, extrusion die casting molding, roll molding, and injection molding.
In the present application, the method of the cast molding process is selected from a vacuum die casting process. The vacuum die-casting forming process is favorable for reducing the porosity of the casting, further improving the mechanical property of the casting, increasing the heat treatability and weldability of the casting, and also is favorable for improving the surface quality (higher density of the surface layer) and the dimensional precision of the casting.
In the application, the vacuum die-casting molding treatment step comprises the steps of smelting the raw materials, preserving heat, pouring the alloy liquid after heat preservation into a mold, and cooling.
Because the limit value of the melting temperature of the vacuum die-casting machine is 1400 ℃, but the melting temperature is above 1200 ℃, the die can be damaged to a great extent, and the melting points of the metal simple substances in the titanium-based amorphous composite material are higher, the metal simple substances are required to be formed into a master alloy ingot, and then the master alloy ingot is used as a raw material for vacuum die-casting molding treatment.
Specifically, the preparation of the titanium-based amorphous composite material by adopting vacuum die-casting molding treatment comprises the following steps:
and S10, preparing a master alloy ingot.
Because the simple substance of beryllium is extremely toxic, the beryllium raw material adopts industrial grade alloy ingot Zr from the perspective of safety 35 Ti 30 Cu 8.25 Be 26.75 And smelting a zirconium (Zr) simple substance, a titanium (Ti) simple substance, a vanadium (V) simple substance, a copper (Cu) simple substance and the GHDT alloy ingot into a master alloy ingot.
In the application, the metal raw materials Ti, zr, V and Cu are high-purity simple substances, and the purities of the Ti, the Zr, the V and the Cu are respectively 99.995%, 99.5%, 99.95% and 99.99%.
In the embodiment of the application, before the Ti, zr, V, cu and GHDT alloy ingots are smelted into the master alloy ingot, fine sand paper is needed to remove oxide layers and oil stains on the surfaces of Ti simple substances, zr simple substances, V simple substances and Cu simple substances, and the titanium simple substances, the Zr simple substances, the V simple substances and the Cu simple substances are ultrasonically cleaned for 10-30min and then dried for standby, so that the influence on the tissue uniformity of the titanium-based amorphous composite material due to impurities in the master alloy ingot is avoided.
Further, the solution for ultrasonic cleaning may be absolute ethanol.
According to the atomic percentage expression general formula of the titanium-based amorphous composite material, the mass of the needed GHDT alloy ingot and the mass of the needed Zr, ti, cu and V simple substances are calculated, an electronic balance with the precision of 0.001g is used for weighing, and the weighing error is controlled within +/-0.001 g.
In the present application, the preparation of the master alloy ingot comprises: smelting the weighed Zr, ti, cu and V metal simple substances and the GHDT alloy ingot according to the sequence of melting points from high to low.
The elemental metals of Zr, ti, cu and V and the GHDT alloy ingot are smelted in sequence from high to low in melting point, so that the situation that the metal with high melting point is not fully melted due to the fact that the metal with low melting point is firstly smelted and then wrapped on the surface of the metal with high melting point can be avoided, the uniformity of mixing among metal raw materials is improved, the melting point of the titanium-based amorphous composite material is reduced, and the tissue uniformity of the titanium-based amorphous composite material is improved.
Further, the elemental metals of Zr, ti, cu and V and the alloy ingot containing Be of GHDT can Be smelted to form a master alloy ingot by adopting an arc smelting mode. Specifically, a GHDT alloy ingot with a low melting point and a metal simple substance are placed at the lowest layer in an electric arc furnace crucible, the metal simple substance with a high melting point is placed at the uppermost layer in the electric arc furnace crucible, and a titanium ingot for arc striking and oxygen absorption is placed in another crucible; adjusting the vacuum degree in the arc furnace to 3 x 10 -3 Introducing high-purity argon after the pressure is lower than Pa to enable the pressure in the electric arc furnace to reach 0.04MPa, and carrying out arc striking; firstly smelting a titanium ingot for arc striking and oxygen absorption after arc striking, and if the titanium ingot is smelted and cooled, the surface of the titanium ingot isAfter the color of the alloy ingot is not obviously changed, smelting the V, zr, ti, cu simple substances and the GHDT alloy ingot in sequence, keeping the current at 180-240A, repeatedly smelting for 4-6 times, wherein the time for each smelting is 10-30s, and the cooling time after the smelting is 2-8min, thereby finally obtaining the required master alloy ingot.
And S20, smelting the master alloy ingot into alloy liquid.
Smelting a master alloy ingot into an alloy liquid for pouring into a mold; in the application, the vacuum degree of the master alloy ingot in the heat preservation process after smelting and mixing is selected to be 1-8Pa.
Wherein the smelting temperature of the master alloy ingot is 800-1000 ℃; because the proportion of atoms and interatomic atoms in the titanium-based amorphous composite material is regulated and controlled, the master alloy ingot can be fully melted at the temperature of 800-1000 ℃, the energy conservation is facilitated, the melting temperature which can be reached by a vacuum die casting machine can be met, and the fluidity of the alloy liquid can be improved. As an example, the melting temperature of the master alloy ingot may be 800 ℃, 850 ℃, 880 ℃, 930 ℃, 980 ℃, or 1000 ℃, or the like.
The smelting time of the master alloy ingot is 80-120s, so that metal atoms can be mixed more sufficiently, and the structural uniformity of the titanium-based amorphous composite material is improved. Illustratively, the time for melting the master alloy ingot may be 80s, 95s, 100s, 105s, 110s, or 120s, and so on.
In the application, the heat preservation time is 10-50s, so that the mother alloy ingot can be further fully melted, the fluidity of the alloy liquid can be improved, and the alloy liquid can be conveniently and smoothly poured into a mold in the follow-up process. The incubation time may be, for example, 10s, 20s, 30s, 35s, 42s, or 50s, etc.
And S30, pouring the alloy liquid into a die, carrying out die casting and die assembly, and then opening the die.
And pouring the smelted alloy liquid into a die under the condition that the vacuum degree is 1-8Pa, performing die casting and die closing, and then opening the die.
The temperature of the alloy liquid is 780-980 ℃ during pouring, the relatively low temperature is beneficial to protecting the die and further prolonging the service life of the die, and the alloy liquid has good fluidity during pouring, so that the alloy liquid can be poured into the die more smoothly; illustratively, the temperature of the alloy liquid at the time of pouring may be 780 ℃, 800 ℃, 830 ℃, 900 ℃, 950 ℃, 980 ℃ or the like.
At this stage, the temperature of the mold is maintained at 150-240 ℃; because the temperature of the alloy liquid is higher during pouring and the temperature of the die is controlled to be 150-240 ℃, metal atoms can form a long-range disordered non-crystalline state in the solidification process rather than being arranged according to a period, and the amorphous granularity can be effectively improved so as to improve the tissue uniformity of the titanium-based amorphous composite material; more importantly, the method is beneficial to forming an endogenous second phase reinforced amorphous composite material so as to improve the toughness and the breaking strength of the titanium-based amorphous composite material. Illustratively, the temperature of the mold may be 150 ℃, 180 ℃, 200 ℃, 220 ℃, or 240 ℃, and so on.
In the application, the die-casting and die-closing time is 4-6s, and the pressure of die-casting and die-closing is 125-130MPa, so that the internal crystalline phase of the titanium-based amorphous composite material can be uniformly refined, and the plasticity of the titanium-based amorphous composite material is improved.
As an example, the time for mold clamping may be 4s, 4.5s, 5s, 5.2s, or 6s, etc.; the mold clamping pressure is 125MPa, 127MPa, 128MPa or 130MPa, and the like.
And S40, cooling the alloy liquid in the die.
After the die is opened for 2-3min, the die is naturally cooled to room temperature, so that the volume fraction and the distribution uniformity of a crystalline phase in the amorphous composite material can be further improved.
By way of example, the time between opening the mold and the start of the mold to cool down naturally may be 2min, 2.5min, 3min, or the like.
The titanium-based amorphous composite material prepared after cooling can be used as a flexible gear blank, and the flexible gear blank is subjected to surface treatment to obtain the flexible gear.
The preparation method of the titanium-based amorphous composite material provided by the application at least has the following advantages:
the atomic percentage ratio of Ti atoms and Zr atoms in the titanium-based amorphous composite material is regulated and controlled to ensure that the Ti atoms and the Zr atomsAnd the proportion of Be atoms is (40-55): (10-25): (10-14), and the number of Be atoms accounts for 10% -14% of the total number of atoms in the titanium-based amorphous composite material, so that the amorphous composite material is not easy to oxidize in the preparation process, the amorphous forming capability of the titanium-based amorphous composite material is remarkably improved, and the titanium-based amorphous composite material is enabled to have the vacuum degree as low as 10 under the condition that inert protective gas is not required to Be introduced into the titanium-based amorphous composite material and the vacuum degree of a system 0 The casting forming can still be carried out under the condition of low vacuum degree of Pa, the preparation condition of the titanium-based amorphous composite material can be met by industrial-grade casting forming equipment, the cost is low, the process is simple, and the industrial large-scale production is easy to realize; meanwhile, the titanium-based amorphous composite material prepared by the preparation method of the titanium-based amorphous composite material has the advantages of high tissue uniformity, low melting point, excellent strength and toughness and the like, and has good application prospect in the fields of structural and functional materials.
The application also provides a titanium-based amorphous composite material, and the atomic percent expression general formula of the titanium-based amorphous composite material is Ti a Zr b (V 12/17 Cu 5/17 ) 100-a-b-c Be c (ii) a In the expression general formula of atomic percentage, a is more than or equal to 40 and less than or equal to 55, b is more than or equal to 10 and less than or equal to 25, a + b is more than or equal to 50 and less than or equal to 75, and c is more than or equal to 10 and less than or equal to 14.
The atomic percentage ratio of Ti atoms, zr atoms and Be atoms in the titanium-based amorphous composite material is regulated and controlled to Be (40-55): (10-25): (10-14), and the number of Be atoms accounts for 10% -14% of the total number of atoms in the titanium-based amorphous composite material, thereby being beneficial to improving the tissue uniformity, the strength and the toughness of the titanium-based amorphous composite material and reducing the melting point of the titanium-based amorphous composite material.
Furthermore, in the expression general formula of atomic percent, a is more than or equal to 45 and less than or equal to 50, b is more than or equal to 18 and less than or equal to 22, a + b is more than or equal to 65 and less than or equal to 72, and c is more than or equal to 11 and less than or equal to 13, which is beneficial to further improving the toughness and the breaking strength of the titanium-based amorphous composite material.
Illustratively, the atomic percent expression of the titanium-based amorphous composite material is Ti 48 Zr 20 V 13.4 Cu 5.6 Be 13 Or Ti 48 Zr 20 V 14.8 Cu 6.2 Be 11 The two titanium-based amorphous composite materials have excellent yield strength, fracture strength and toughness.
In the application, the titanium-based amorphous composite material is prepared according to the general expression of atomic percent of the titanium-based amorphous composite material, and then the vacuum degree is reduced to 10 0 Pa and the titanium-based amorphous composite material prepared by casting and molding under the condition of not introducing inert gas still has excellent mechanical properties, the tensile breaking strength of the composite material is 1000-1600MPa, the tensile breaking elongation of the composite material is 8-18 percent, and the composite material has good application prospect in the fields of structural and functional materials.
Furthermore, the titanium-based amorphous composite material provided by the application has excellent thermodynamic properties such as low melting point, low glass transition temperature and wide supercooling liquid phase region width, wherein the melting temperature is 600-750 ℃, the glass transition temperature (Tg) is 320-360 ℃, and the supercooling liquid phase region width (Delta T) is 30-80 ℃.
The titanium-based amorphous composite material provided by the application has at least the following advantages:
the atomic percentage ratio of Ti atoms, zr atoms and Be atoms in the titanium-based amorphous composite material is regulated and controlled to Be (40-55): (10-25): (10-14), and the number of Be atoms accounts for 10% -14% of the total number of atoms in the titanium-based amorphous composite material, thereby being beneficial to improving the tissue uniformity, the strength and the toughness of the titanium-based amorphous composite material and reducing the melting point of the titanium-based amorphous composite material, and having good application prospect in the fields of structures and functional materials.
The application also provides an application of the titanium-based amorphous composite material in preparation of a thin-wall part.
Optionally, the thin walled member comprises a flexspline, a cell phone shaft, or a watch case.
Optionally, the thin-walled member has a thickness of 0.2-5mm.
The atomic percentage ratio of the titanium-based amorphous composite material is regulated, so that the ratio of Ti atoms to Zr atoms to Be atoms is (40-55): (10-25): (10-14), and the number of Be atoms accounts for 10% -14% of the total number of atoms in the titanium-based amorphous composite material, so that the titanium-based amorphous composite material has good strength and toughness, and can Be applied to manufacturing thin-walled parts with high requirements on strength and toughness, such as flexible gears or mobile phone rotating shafts and other thin-walled parts.
The thin-walled material is not limited to the above-described components, and may include other precision components.
The characteristics and properties of the titanium-based amorphous composite material and the preparation method thereof are further described in detail with reference to the following examples.
Example 1
This example provides a Ti-based amorphous composite material and a method for preparing the same, wherein the atomic percentage expression of the Ti-based amorphous composite material is Ti 48 Zr 20 V 13.4 Cu 5.6 Be 13 (denoted as TL 1) prepared using the following procedure:
(1) Preparation of raw materials:
removing oxide layers and oil stains on the surfaces of the metal raw materials Zr, ti, V and Cu simple substances by using fine sand paper, putting the metal raw materials into a beaker, adding absolute ethyl alcohol until the absolute ethyl alcohol submerges the metal raw materials, carrying out ultrasonic treatment for 15min, and drying for later use.
(2) Preparing a master alloy ingot:
wiping a water-cooled copper crucible of an electric arc furnace clean by using polishing paste, and sequentially stacking 14.903g of a GHDT alloy ingot, 0.570g of a Cu simple substance, 9.095g of a Ti simple substance, 1.549g of a Zr simple substance and 3.884g of a V simple substance in the water-cooled copper crucible, wherein the GHDT alloy ingot is positioned at the lowermost layer, the V simple substance is positioned at the uppermost layer, and the raw materials are also put into the other 3 water-cooled copper crucibles according to the method; putting a titanium ingot into the middle water-cooled copper crucible, and closing a cabin door of the electric arc furnace; opening the mechanical pump, closing the mechanical pump when the pressure in the electric arc furnace reaches below 10Pa, then opening the molecular pump to reduce the vacuum degree in the electric arc furnace to 3 × 10 -3 In a high vacuum state below Pa, the molecular pump is closed, and high-purity argon is filled into the furnace to ensure that the pressure in the furnace reaches 0.04MPa; after arc striking, firstly smelting a titanium ingot, if the color of the surface of the titanium ingot does not obviously change after the titanium ingot is smelted and cooled, then smelting alloy ingots of a V simple substance, a Zr simple substance, a Ti simple substance, a Cu simple substance and GHDT (gallium-zinc-antimony) from top to bottom in sequence to keep the current at 160A, and repeatedly turning over each alloy ingotAnd (4) performing rotary smelting for 6 times, wherein the smelting time is 20s each time, and cooling for 5min after smelting to obtain a master alloy ingot.
(3) Vacuum die-casting and forming treatment:
putting the master alloy ingot obtained in the step (2) into an induction melting quartz crucible of a vacuum die casting machine, closing a cabin door, and opening a mechanical pump to enable the vacuum degree in a cavity to reach 5Pa; opening an induction melting switch, controlling the melting temperature to be 900 ℃, keeping the temperature for 90s, and preserving the heat for 30s after the alloy ingot in the quartz crucible is completely melted; and when the temperature of the alloy liquid is 850 ℃, turning over the quartz crucible, enabling the alloy to flow into a die with the temperature of 200 ℃, and then closing the die, wherein the die-casting and closing time is 5s, and the die-casting and closing pressure is 130MPa. And opening the die for 2min, and then opening the cabin door of the vacuum die casting machine to naturally cool the die to room temperature.
Example 2
This example provides a Ti-based amorphous composite material and a method for preparing the same, and example 2 differs from example 1 in that the atomic percent expression of the Ti-based amorphous composite material in example 2 is Ti 48 Zr 20 V 14.8 Cu 6.2 Be 11 (marked as TL 2), the mass of the Cu simple substance, the Ti simple substance, the Zr simple substance, the V simple substance and the GHDT alloy ingot used in the preparation process are 0.987g, 9.540g, 2.857g, 4.220g and 12.397g respectively.
Comparative example 1
The comparative example 1 is different from the example 1 in that the atomic percent expression of the titanium-based amorphous composite material in the comparative example 1 is Ti 48 Zr 20 V 16.2 Cu 6.8 Be 9 (marked as TL 3), the mass of the elementary Cu, the elementary Ti, the elementary Zr, the elementary V and the GHDT alloy ingot used in the preparation process are 1.390g, 9.969g, 4.116g, 4.545g and 9.980g respectively.
Comparative example 2
The comparative example 2 is different from the example 1 in that the atomic percent expression of the titanium-based amorphous composite material in the comparative example 2 is Ti 48 Zr 20 V 19.1 Cu 7.9 Be 5 (marked as TL 4), the mass of the Cu simple substance, ti simple substance, zr simple substance, V simple substance and GHDT alloy ingot used in the preparation process are 1.783g, 10386g, 5.342g, 1.857g and 7.631g respectively.
Comparative example 3
The comparative example provides a titanium-based amorphous composite material and a preparation method thereof, and the difference between the comparative example 3 and the example 1 is that the atomic percent expression of the titanium-based amorphous composite material in the comparative example 3 is Ti 50 Zr 21 V 12 Cu 4 Be 13 (marked as TL 5), the mass of the elementary substance Cu, the elementary substance Ti, the elementary substance Zr, the elementary substance V and the GHDT alloy ingot used in the preparation process are respectively 2.161g, 10788g, 6.52g, 5.161g and 5.370g.
Examples of the experiments
The mechanical properties and the thermodynamic properties of the titanium-based amorphous composite materials prepared in the examples 1-2 and the comparative examples 1-3 are characterized, and the characterization results are shown in table 1; FIG. 1 is a tensile graph of the titanium-based amorphous composite materials obtained in examples 1 to 2 and comparative examples 1 to 3, FIG. 2 is a high temperature DSC graph of the titanium-based amorphous composite materials obtained in examples 1 to 2, and FIG. 3 is an X-ray diffraction pattern of the titanium-based amorphous composite materials obtained in examples 1 to 2.
TABLE 1
In Table 1, "/" indicates that no relevant data was measured.
As can be seen from Table 1 and FIG. 1, the comprehensive mechanical properties of the titanium-based amorphous composite material prepared in examples 1-2 are better than those of the titanium-based amorphous composite material prepared in comparative examples 1-3, and particularly, the elongation at break of the titanium-based amorphous composite material prepared in examples 1-2 is significantly higher than that of the titanium-based amorphous composite material prepared in comparative examples 1-3, which indicates that the strength and toughness of the titanium-based amorphous composite material can be effectively improved after the atomic percentage expression of the titanium-based amorphous composite material is adjusted. Meanwhile, the yield strength of the titanium-based amorphous composite material prepared in comparative example 2 could not be measured because of its significantly low fracture strength.
As can be seen from FIG. 2, the casting molding of examples 1-2 of the present application under a vacuum degree as low as 5Pa still allows the titanium-based amorphous composite material to have excellent thermodynamic properties.
As can be seen from FIG. 3, the Ti-based amorphous composite material prepared in the examples 1-2 of the present application shows a beta crystalline phase peak in addition to the typical diffuse scattering diffraction peak, i.e. the Ti-based amorphous composite material prepared in the examples 1-2 of the present application consists of a crystalline phase and an amorphous phase, which shows that the Ti-based amorphous composite material prepared in the present application is not easily oxidized and has good amorphous forming ability under a vacuum degree as low as 5Pa after the atomic percentage expression of the Ti-based amorphous composite material is adjusted.
In conclusion, the atomic percentage ratio of the Ti-based amorphous composite material is regulated, so that the ratio of Ti atoms to Zr atoms to Be atoms is (40-55): (10-25): (10-14) and the number of Be atoms accounts for 10-14% of the total number of atoms in the titanium-based amorphous composite material, so that the amorphous composite material is not easy to oxidize in the preparation process, the amorphous forming capability of the titanium-based amorphous composite material is remarkably improved, and the titanium-based amorphous composite material is enabled to Be low in the vacuum degree of a system to 10 degrees under the condition that inert atmosphere is not required to Be introduced 0 The titanium-based amorphous composite material can still be cast and molded under the condition of Pa, the preparation condition of the titanium-based amorphous composite material can be met by industrial-grade casting and molding equipment, the cost is low, the process is simple, and the industrial large-scale production is easy to realize; meanwhile, the titanium-based amorphous composite material prepared by the preparation method of the titanium-based amorphous composite material has the advantages of high tissue uniformity, low melting point, excellent strength and toughness and the like, and has good application prospect in the field of structural and functional materials.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (14)
1. A preparation method of a titanium-based amorphous composite material is characterized by comprising the following steps: performing casting molding treatment after preparing materials according to the atomic percentage expression general formula of the titanium-based amorphous composite material; the casting molding treatment adopts vacuum die-casting molding and is carried out under the condition that inert protective gas is not needed to be introduced and the vacuum degree of a system is 1-8 Pa;
wherein the atomic percent expression general formula of the titanium-based amorphous composite material is Ti a Zr b (V 12/17 Cu 5/17 ) 100-a-b-c Be c (ii) a In the expression general formula of atomic percentage, a is more than or equal to 40 and less than or equal to 55, b is more than or equal to 10 and less than or equal to 25, a + b is more than or equal to 50 and less than or equal to 70, and c is more than or equal to 10 and less than or equal to 14; the tensile breaking strength of the titanium-based amorphous composite material is 1123-1600MPa, and the tensile breaking elongation of the titanium-based amorphous composite material is 8-18%.
2. The method for preparing titanium-based amorphous composite material according to claim 1, wherein the step of the cast molding process comprises: smelting the raw materials at 800-1000 ℃, preserving heat, pouring the alloy liquid after heat preservation into a mold, and cooling.
3. The method for preparing the titanium-based amorphous composite material as claimed in claim 2, wherein the temperature of the alloy liquid during casting is 780-980 ℃, and the temperature of the mold is 150-240 ℃.
4. The method for preparing the titanium-based amorphous composite material as claimed in claim 2, wherein the time for melting is 80-120s, and the time for holding is 10-50s.
5. The method for preparing the titanium-based amorphous composite material as claimed in claim 2, wherein the step of pouring the heat-preserved alloy liquid into a mold and then cooling comprises the steps of: and pouring the smelted alloy liquid into a die, die casting and closing the die for 4-6s, then opening the die, and then cooling.
6. The method of claim 5, wherein the cooling step comprises: opening the die for 2-3min, and naturally cooling the die to room temperature.
7. The method for preparing the titanium-based amorphous composite material as claimed in claim 5, wherein the pressure of the die casting mold is 125-130MPa.
8. A Ti-based amorphous composite material prepared by the method of any one of claims 1 to 7, wherein the Ti-based amorphous composite material has an atomic percent expression of the general formula Ti a Zr b (V 12/17 Cu 5/17 ) 100-a-b-c Be c (ii) a In the expression general formula of atomic percentage, a is more than or equal to 40 and less than or equal to 55, b is more than or equal to 10 and less than or equal to 25, a + b is more than or equal to 50 and less than or equal to 70, and c is more than or equal to 10 and less than or equal to 14.
9. The titanium-based amorphous composite material as claimed in claim 8, wherein the atomic percentage expression formula is 45. Ltoreq. A.ltoreq.50, 18. Ltoreq. B.ltoreq.22, 65. Ltoreq. A + b.ltoreq.70, 11. Ltoreq. C.ltoreq.13.
10. The Ti-based amorphous composite material as claimed in claim 9, wherein the Ti-based amorphous composite material has an atomic percentage expression of Ti 48 Zr 20 V 13.4 Cu 5.6 Be 13 Or Ti 48 Zr 20 V 14.8 Cu 6.2 Be 11 。
11. The titanium-based amorphous composite material according to claim 8, having a melting temperature of 600-750 ℃.
12. Use of the titanium-based amorphous composite material according to any one of claims 8 to 11 for the preparation of thin-walled articles.
13. The use according to claim 12, wherein the thin walled member comprises a flexspline, a cell phone shaft, or a watch case.
14. Use according to claim 12, wherein the thickness of the thin-walled part is 0.2-5mm.
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