Doped transition metal gallium-based liquid metal and preparation method and application thereof

Abstract

The application provides a doped transition metal gallium-based liquid metal and a preparation method and application thereof, and relates to the technical field of liquid metal lubricants. A small amount of zinc element (in a liquid state) is doped in the gallium-based liquid metal, which can obviously promote the adsorption of gallium element on a friction interface, and in turn effectively improve the lubricating performance; by doping copper element, a micron-level, solid CuGa2 lubricating phase can be generated in situ in the gallium-based liquid metal, the in-situ generated CuGa2 lubricating phase can be more uniformly dispersed compared with an externally added lubricating phase, the lubricating phase particles do not produce agglomeration, and meanwhile the lubricating performance is improved; and the gallium-based liquid metal doped with zinc and copper elements has better lubricating performance. The doped zinc alloyed gallium-based liquid metal, the doped copper in-situ self-generated lubricating phase gallium-based liquid metal and the doped zinc and copper composite gallium-based liquid metal provided by the application all have excellent lubricating and wear-resistant performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of liquid metal lubricant, in particular to an alloyed gallium-based liquid metal and a preparation method and application thereof, a gallium-based liquid metal containing in-situ self-lubricating phase and a preparation method and application thereof, and a composite gallium-based liquid metal and a preparation method and application thereof. BACKGROUND

[0002] According to scientific statistics, friction consumes nearly one-third of the world's primary energy, and nearly half of equipment accidents are caused by lubrication failure and excessive wear. Lubrication is an effective means to reduce friction and wear. With the continuous innovation and rapid development of China in the fields of aerospace technology, national defense and military industry, etc., these high-end equipment put forward more and more stringent requirements on the service performance of liquid lubricant. For example, the fifth-generation fighter requires the service temperature and load capacity of lubricating grease to be more than 350℃ and 2GPa respectively, but due to the inherent properties of organic matter, the performance of lubricating grease is difficult to break through this technical index. Therefore, it is imperative to carry out research and development of new liquid lubricants with unique physicochemical properties and lubrication performance.

[0003] Gallium-based liquid metal is a kind of alloy with gallium (Ga) as the main component and indium (In), tin (Sn), lead (Pb), bismuth (Bi) and other low-melting point metals as the auxiliary component, which is in liquid state at room temperature. The typical components are gallium-indium eutectic EGaIn (Ga 75.5 In 24.5 , wt%) and gallium-indium-tin eutectic Galinstan (Ga 68.5 In 21.5 Sn 10 , wt%), which has both metallic properties and fluidity. From the perspective of liquid lubricant, gallium-based liquid metal has extremely low saturated vapor pressure, high service temperature (600℃ without obvious volatilization and good lubrication), good electrical conductivity and thermal conductivity, extremely high load capacity, green and non-toxic environmental protection, etc. It is a new type of liquid lubricant. At present, gallium-based liquid metal has been applied in the X-ray tube bearing of imported medical CT equipment.

[0004] Although gallium-based liquid metal can break through the service performance bottleneck of lubricating grease, there is still a certain gap in its lubrication performance compared with lubricating grease. When using gallium-based liquid metal for lubrication, the friction pair is usually in a boundary or mixed lubrication state, and the friction coefficient is relatively high (about 0.1-0.6, Langmuir 2019, 35:6905-6915).

[0005] Currently, there are two main methods to improve the lubricating performance of gallium-based liquid metal. One is to regulate the type and content of liquid alloy components, such as doping aluminum, silver and bismuth elements (in liquid form in gallium-based liquid metal). For example, Chinese patent CN109852453A discloses that the friction coefficient is reduced by about 20% after doping aluminum and silver elements, the wear rate is reduced by about 50% after doping aluminum, but the wear rate is increased after doping silver. Chinese patent CN114621809A discloses that the friction coefficient is reduced by about 25% after doping bismuth and solid lubricating phase in gallium-based liquid metal, and the change of wear rate is not mentioned. As can be seen from the above, the degree of improvement of the lubricating performance of the currently found doping elements is limited. The other is to add a solid lubricating phase (in solid form in gallium-based liquid metal), such as adding boron nitride and tungsten disulfide (Chinese patents CN114621809A and CN109022100A). However, this method has two obvious shortcomings: the addition of solid lubricating phase must be operated in an atmospheric environment (because non-oxidized gallium does not wet many lubricating phases, and the oxidation of gallium must be used to realize the wrapping and uniform mixing of the solid lubricating phase), but the degree of oxidation of gallium-based liquid metal is difficult to accurately control, and the viscosity increases and the flowability deteriorates after oxidation, which reduces its lubricating performance; the added solid lubricating phase is difficult to disperse uniformly in the gallium-based liquid metal, which is not conducive to the full play of the lubricating performance of the solid lubricating phase, such as shown in the figure. Figure 1 Therefore, it is of great significance to provide a gallium-based liquid metal with excellent lubricating and wear-resistant performance. SUMMARY

[0006] Therefore, the purpose of the present application is to provide an alloyed gallium-based liquid metal and its preparation method and application, a gallium-based liquid metal containing in-situ self-generated lubricating phase and its preparation method and application, and a composite gallium-based liquid metal and its preparation method and application. The three gallium-based liquid metals provided by the present application have excellent lubricating and wear-resistant performance.

[0007] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0008] The present application provides an alloyed gallium-based liquid metal, the chemical composition of which is (Ga-In-Sn base gallium-based liquid metal) (100-x)wt％ Zn xwt％ , 5 > x > 1.

[0009] Preferably, the chemical composition of the Ga-In-Sn base gallium-based liquid metal is Ga 68.5 In 21.5 Sn 10 .

[0010] The application provides a preparation method of the alloyed gallium-based liquid metal, and comprises the following steps: under a protective atmosphere, Ga-In-Sn base gallium-based liquid metal and Zn are mixed according to a chemical composition and then first smelted to obtain the alloyed gallium-based liquid metal.

[0011] The application provides a gallium-based liquid metal containing an in-situ self-grown lubricating phase, and the chemical composition is (Ga-In-Sn base gallium-based liquid metal) (100-y)wt％ Cu ywt％ , 3 >= y >= 1.

[0012] Preferably, the Ga-In-Sn base gallium-based liquid metal has a chemical composition of Ga 68.5 In 21.5 Sn 10 .

[0013] The application provides a preparation method of the gallium-based liquid metal containing an in-situ self-grown lubricating phase, and the preparation method comprises the following steps: under a protective atmosphere, Ga-In-Sn base gallium-based liquid metal and Cu are mixed according to a chemical composition and then second smelted to obtain the gallium-based liquid metal containing an in-situ self-grown lubricating phase.

[0014] The application provides a composite gallium-based liquid metal, and the chemical composition is (alloyed gallium-based liquid metal) (100-z)wt％ -(gallium-based liquid metal containing an in-situ self-grown lubricating phase) zwt％ , 100 >= z > 0; the alloyed gallium-based liquid metal is the alloyed gallium-based liquid metal in the above technical solution or the alloyed gallium-based liquid metal prepared by the preparation method in the above technical solution; the gallium-based liquid metal containing an in-situ self-grown lubricating phase is the gallium-based liquid metal containing an in-situ self-grown lubricating phase in the above technical solution or the gallium-based liquid metal containing an in-situ self-grown lubricating phase prepared by the preparation method in the above technical solution.

[0015] The application provides a preparation method of the composite gallium-based liquid metal, and the preparation method comprises the following steps: under a protective atmosphere, alloyed gallium-based liquid metal and gallium-based liquid metal containing an in-situ self-grown lubricating phase are mixed according to a chemical composition to obtain the composite gallium-based liquid metal.

[0016] Preferably, the temperature of the mixing is 100-300 DEG C, and the time is 1-3 h.

[0017] The application provides application of the alloyed gallium-based liquid metal, the gallium-based liquid metal prepared by the preparation method, the gallium-based liquid metal containing in-situ self-lubricating phase, the composite gallium-based liquid metal or the composite gallium-based liquid metal prepared by the preparation method in lubricating wear resistance.

[0018] The application provides an alloyed gallium-based liquid metal, which has a chemical composition of (Ga-In-Sn base gallium-based liquid metal) (100-x)wt％ Zn xwt％ , 5 >= x >= 1. A small amount of zinc element (in a liquid state) is doped in the gallium-based liquid metal, so that the adsorption of gallium on a friction interface can be obviously promoted, the gallium-rich film becomes uneven, the gap between the friction interfaces is increased, and then more gallium-based liquid metal can be filled in the gap, that is, the thickness of the fluid lubricating film is increased, the fluid dynamic pressure effect is more significant, and the lubricating performance is improved under the synergistic lubricating effect of the gallium-rich film, compared with the gallium-based liquid metal without the doped zinc element, the friction coefficient and the wear rate are significantly reduced. As shown in the test results of the embodiment, compared with Ga 68.5 In 21.5 Sn 10 , the friction coefficient of (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Zn 1wt％ is reduced by 9.4%, and the wear rate is reduced by 55.1%.

[0019] The application provides a preparation method of the alloyed gallium-based liquid metal. The melting is carried out under a protective atmosphere, the zinc element is dissolved in the gallium-based liquid metal in a liquid state, and the doping of zinc can promote the adsorption of gallium on the friction interface, and then the lubricating performance is improved. Moreover, the preparation method provided by the application is simple in operation, green and environmentally friendly, low in cost and suitable for industrialized production.

[0020] The application provides a gallium-based liquid metal containing in-situ self-lubricating phase, which has a chemical composition of (Ga-In-Sn base gallium-based liquid metal) (100-y)wt％ Cu ywt％, 3≥y≥1.The present application can generate micron CuGa2 lubricating phase (in the form of solid particles) in-situ in gallium-based liquid metal by adding a small amount of copper element, which has a certain lubricating effect on one hand, because CuGa2 particles have a certain lubricating effect, and on the other hand, because CuGa2 particles are a kind of low-hardness intermetallic compound, plastic deformation occurs under the action of contact load, which makes the roughness of the friction interface increase, and thus the gap between the friction interfaces increases, so more gallium-based liquid metal can fill the gap between the friction interfaces, i.e., the thickness of the fluid film is increased, the load-carrying capacity is improved, and thus the lubricating performance of the gallium-based liquid metal is improved; on the other hand, the liquid metal can completely wet the CuGa2 particles, so the adsorption of CuGa2 improves the wetting performance of the liquid metal on the surface of the gallium-rich film. Compared with the externally added lubricating phase, the gallium-based liquid metal containing in-situ self-generated lubricating phase provided by the present application not only avoids the oxidation of the gallium-based liquid metal, does not change the viscosity and flowability of the gallium-based liquid metal, and avoids the decrease in lubricating performance caused by oxidation; moreover, the in-situ self-generated lubricating phase is more uniformly dispersed in the gallium-based liquid metal, and the lubricating phase particles do not agglomerate, so the lubricating effect of the lubricating phase can be fully played, and the lubricating and anti-wear performance is greatly improved. As shown in the test results of the examples, compared with Ga 68.5 In 21.5 Sn 10 , the friction coefficient of (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ is reduced by 3.8%, and the wear rate is reduced by 49.1%.

[0021] The present application provides a preparation method of the gallium-based liquid metal containing in-situ self-generated lubricating phase as described in the above technical solution. The present application is melted in a protective atmosphere, and the copper element is dissolved in the gallium-based liquid metal in a liquid state, and during the cooling process, the solubility of copper in the gallium-based liquid metal decreases as the temperature decreases, and the excess copper element reacts with gallium to generate micron CuGa2 particles, forming a gallium-based liquid metal with uniformly distributed solid-liquid two-phase coexistence, achieving the effect of reducing friction and wear, and thus improving the lubricating and anti-wear performance. Moreover, the preparation method provided by the present application is simple, green and environmentally friendly, low in cost, and suitable for industrial production.

[0022] The present application provides a composite gallium-based liquid metal, which has a chemical composition of (alloyed gallium-based liquid metal) (100-z)wt％ -(gallium-based liquid metal containing in-situ self-generated lubricating phase) zwt％100≥z>0; the alloyed gallium-based liquid metal is the alloyed gallium-based liquid metal described in the above technical solution or the alloyed gallium-based liquid metal prepared by the preparation method described in the above technical solution; the gallium-based liquid metal containing the in-situ self-generated lubricating phase is the gallium-based liquid metal containing the in-situ self-generated lubricating phase described in the above technical solution or the gallium-based liquid metal containing the in-situ self-generated lubricating phase prepared by the preparation method described in the above technical solution. The composite gallium-based liquid metal provided by the present invention is simultaneously doped with zinc and copper elements, contains an in-situ self-generated lubricating phase, and has a large adsorption amount of gallium elements on the friction interface. It has the above-mentioned advantages of alloyed gallium-based liquid metal and gallium-based liquid metal containing the in-situ self-generated lubricating phase. Moreover, the combined effect of the two further improves the lubrication and anti-wear performance of the gallium-based liquid metal.

[0023] As shown in the test results of the examples, compared with Ga undoped of zinc and copper elements... 68.5 In 21.5 Sn 10 In comparison, [(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 50wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ The coefficient of friction decreased by 26.5%, and the wear rate decreased by 69.4%.

[0024] This invention provides a method for preparing the composite gallium-based liquid metal described in the above-mentioned technical solution. The present invention involves mixing under a protective atmosphere, which further improves the lubrication and anti-wear properties of the gallium-based liquid metal. Moreover, the preparation method provided by this invention is simple to operate, environmentally friendly, low in cost, and suitable for industrial production. Attached Figure Description

[0025] Figure 1 [(Ga] prepared for Comparative Example 7 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ Alloyed liquid metal 98.5wt％ -Ag 1.5wt％ SEM and EDS images of an externally added Ag lubricating phase in liquid metal;

[0026] Figure 2 Ga prepared for Comparative Example 1 68.5 In 21.5 Sn 10 Liquid metal, (Ga) prepared in Example 2 68.5 In21.5 Sn 10 ) 97wt％ Zn 3wt％ Liquid metal and Comparative Example 5 preparation (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ Surface morphology and elemental composition map of the wear scar formed by the liquid metal under the same friction test conditions;

[0027] Figure 3 (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ Ga 68.5 In 21.5 Sn 10 XRD spectra of the two liquid metals;

[0028] Figure 4 (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ Dispersion of CuGa2 phase in gallium-based liquid metal (left) and elemental mapping (middle, right) of Cu;

[0029] Figure 5 Ga 68.5 In 21.5 Sn 10 Liquid metal and Example 5 preparation [(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 50wt％ - [(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ Friction coefficient of the friction pair and disc wear rate of the liquid metal under the same friction test conditions. DETAILED DESCRIPTION

[0030] The present application provides a gallium-based liquid metal alloy, the chemical composition is (Ga-In-Sn base gallium-based liquid metal) (100-x)wt％ Zn xwt％, 5≥x≥1. In the present application, x is particularly preferably 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5. In the present application, the chemical composition of the Ga-In-Sn base gallium-based liquid metal is preferably Ga 68.5 In 21.5 Sn 10 .

[0031] In the present application, the preparation method of the Ga-In-Sn base gallium-based liquid metal preferably comprises the following steps: under a protective atmosphere, Ga, In and Sn are mixed according to the chemical composition and then melted (denoted as third melting) to obtain a Ga-In-Sn base gallium-based liquid metal.

[0032] Unless otherwise specified, the raw materials used in the present application are all commercially available.

[0033] In the present application, the shapes of Ga, In and Sn are preferably wire or block, the shape of Ga is more preferably block, and the shapes of In and Sn are more preferably wire; the present application does not have special limitations on the size of the block and wire, and the size known to those skilled in the art can be used; the purity of Ga, In and Sn is all 99.99%.

[0034] In the present application, the mixing is preferably carried out in a glove box by placing the raw materials in a crucible; the material of the crucible is preferably boron nitride; in the present application, the protective atmosphere is preferably argon or helium, and the oxygen content of the protective atmosphere is preferably ≤10 ppm, and the water content is preferably ≤10 ppm.

[0035] In the present application, the temperature of the third melting is preferably 100-300℃, more preferably 200℃, and the holding time of the third melting is preferably 1-3h, more preferably 2h; the third melting is preferably carried out in a controllable atmosphere sintering furnace, and the melting furnace is preferably a tube furnace or a box furnace.

[0036] After the third melting, the present application preferably further comprises cooling to room temperature to obtain a Ga-In-Sn base gallium-based liquid metal. The present application does not have special limitations on the cooling, and the cooling method known to those skilled in the art can be used, such as natural cooling in the furnace.

[0037] The present application provides a preparation method of the alloyed gallium-based liquid metal described in the above technical solution, comprising the following steps: under a protective atmosphere, Ga-In-Sn base gallium-based liquid metal and Zn are mixed according to the chemical composition and then first melted to obtain an alloyed gallium-based liquid metal.

[0038] In the present application, the shape of the Zn is preferably wire or block, more preferably wire; the present application does not have special limitations on the size of the block and wire, and the size known to those skilled in the art can be used; the purity of the Zn is all 99.99%.

[0039] In the present application, the mixing is preferably mixing the raw materials in a crucible in a glove box, and the material of the crucible is preferably boron nitride. In the present application, the protective atmosphere is preferably argon or helium, and the oxygen content of the protective atmosphere is preferably ≤10 ppm, and the water content is preferably ≤10 ppm.

[0040] In the present application, the temperature of the first melting is preferably 500-650℃, more preferably 550-600℃, and the holding time of the first melting is preferably 1-3h, more preferably 2h; the first melting is preferably carried out in a controllable atmosphere sintering furnace, and the melting furnace is preferably a tube furnace or a box furnace.

[0041] After the first melting, the present application preferably further comprises cooling to room temperature to obtain an alloyed gallium-based liquid metal. The present application does not have special limitations on the cooling, and the cooling method known to those skilled in the art can be used, such as natural cooling in the furnace.

[0042] The present application provides a gallium-based liquid metal containing in-situ self-grown lubricating phase, and the chemical composition is (Ga-In-Sn basic gallium-based liquid metal) (100-y)wt％ Cu ywt％ , 3≥y≥1. In the present application, y is particularly preferably 1, 1.5, 2, 2.5 or 3. In the present application, the chemical composition of the Ga-In-Sn basic gallium-based liquid metal is preferably Ga 68.5 In 21.5 Sn 10 .

[0043] The present application provides a preparation method of the gallium-based liquid metal containing in-situ self-grown lubricating phase as described in the above technical solution, comprising the following steps: under a protective atmosphere, the Ga-In-Sn basic gallium-based liquid metal and Cu are mixed according to the chemical composition and then secondly melted to obtain a gallium-based liquid metal containing in-situ self-grown lubricating phase.

[0044] In the present application, the shape of the Cu is preferably wire or block, more preferably wire; the present application does not have special limitations on the size of the block and wire, and the size known to those skilled in the art can be used; the purity of the Cu is all 99.99%.

[0045] In the present application, the mixing is preferably carried out in a crucible, and the material of the crucible is preferably boron nitride. In the present application, the protective atmosphere is preferably argon or helium, and the oxygen content of the protective atmosphere is preferably ≤10 ppm, and the water content is preferably ≤10 ppm.

[0046] In the present application, the temperature of the second melting is preferably 1200-1350℃, more preferably 1250℃, and the holding time of the second melting is preferably 1-3h, more preferably 2h; the second melting is preferably carried out in a controllable atmosphere sintering furnace, and the melting furnace is preferably a tube furnace or a box furnace.

[0047] After the second melting, the present application preferably further comprises cooling to room temperature to obtain a gallium-based liquid metal containing in-situ self-generated lubricating phase. The present application does not have special limitations on the cooling, and any cooling method known to those skilled in the art can be used, such as natural cooling in the furnace.

[0048] The present application provides a composite gallium-based liquid metal, which has a chemical composition of (alloyed gallium-based liquid metal) (100-z)wt％ -(gallium-based liquid metal containing in-situ self-generated lubricating phase) zwt％ , 100≥z>0; the alloyed gallium-based liquid metal is the alloyed gallium-based liquid metal described in the above technical solution or prepared by the preparation method described in the above technical solution; the gallium-based liquid metal containing in-situ self-generated lubricating phase is the gallium-based liquid metal containing in-situ self-generated lubricating phase described in the above technical solution or prepared by the preparation method described in the above technical solution. In the present application, z is preferably 10-90, and more preferably 10, 20, 30, 40, 50, 60, 70, 80 or 90.

[0049] The present application provides a preparation method of the composite gallium-based liquid metal described in the above technical solution, which comprises the following steps: mixing an alloyed gallium-based liquid metal and a gallium-based liquid metal containing in-situ self-generated lubricating phase according to the chemical composition under a protective atmosphere to obtain a composite gallium-based liquid metal.

[0050] In the present application, the temperature of the mixing is preferably 100-300℃, more preferably 150-250℃, and further preferably 200℃; the time of the mixing is preferably 1-3h, more preferably 1.5-2.5h, and further preferably 2h; and the mixing is preferably stirring mixing.

[0051] After the mixing, the present application preferably further comprises cooling to room temperature to obtain a composite gallium-based liquid metal. The present application does not have special limitations on the cooling, and any cooling method known to those skilled in the art can be used, such as natural cooling.

[0052] The present invention provides the application of the alloyed gallium-based liquid metal described in the above-mentioned technical solutions or the alloyed gallium-based liquid metal prepared by the preparation method described in the above-mentioned technical solutions, the gallium-based liquid metal containing an in-situ self-generated lubricating phase described in the above-mentioned technical solutions or the gallium-based liquid metal containing an in-situ self-generated lubricating phase prepared by the preparation method described in the above-mentioned technical solutions, the composite gallium-based liquid metal described in the above-mentioned technical solutions or the composite gallium-based liquid metal prepared by the preparation method described in the above-mentioned technical solutions in lubrication and anti-wear.

[0053] The following detailed descriptions, in conjunction with embodiments, illustrate the alloyed gallium-based liquid metals and their preparation methods and applications, gallium-based liquid metals containing in-situ self-generated lubricating phases and their preparation methods and applications, and composite gallium-based liquid metals and their preparation methods and applications provided by the present invention. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0054] In the following examples and comparative examples, Ga raw material (elemental) was in block form; In raw material (elemental), Sn raw material (elemental), Zn raw material (elemental), and Cu raw material (elemental) were filaments with a diameter of 1 mm, and the purity of each raw material was 99.99%. Sc raw material (elemental) and Mg raw material (elemental) were filaments with a diameter of 1 mm; Ti raw material (elemental) was powder with a diameter of 10-50 μm, and the purity of each raw material was 99.9%. Ag raw material (elemental) was powder with a diameter of 100-500 nm and a purity of 99.99%. There were two types of Bi raw material (elemental): the Bi raw material (elemental) used in Comparative Example 5 was spherical particles with a diameter of 1-3 mm and a purity of 99.95%; the Bi raw material (elemental) used in Comparative Example 6 was powder with a diameter of 100-500 nm and a purity of 99.99%.

[0055] Example 1

[0056] (Ga 68.5 In 21.5 Sn 10 ) 99.wt％ Zn 1wt％ Preparation

[0057] 1) Weigh gallium blocks, indium wire, and tin wire according to a mass ratio of 68.5:21.5:10, mix them, and place them in a boron nitride crucible. Then, place the crucible in a tube furnace and heat it to 200°C for 2 hours under argon protection. After cooling to room temperature, basic gallium-based liquid metal Ga is obtained. 68.5 In 21.5 Sn 10 ;

[0058] 2) In an argon-atmosphere glove box with an oxygen content ≤10ppm and a water content ≤10ppm, weigh basic gallium-based liquid metal Ga at a mass ratio of 99:1. 68.5 In 21.5 Sn10 and zinc wire, mixed and placed in a boron nitride crucible, and then the crucible was placed in a tube furnace, heated to 550°C under argon protection for 2h, cooled to room temperature, to obtain the alloyed gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Zn 1wt％ .

[0059] Example 2

[0060] (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ Preparation

[0061] In an argon atmosphere glove box, the oxygen content was ≤10ppm, the water content was ≤10ppm, the base gallium-based liquid metal Ga 68.5 In 21.5 Sn 10 and zinc wire, mixed and placed in a boron nitride crucible, and then the crucible was placed in a tube furnace, heated to 550°C under argon protection for 2h, cooled to room temperature, to obtain the alloyed gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ .

[0062] Figure 2 In (a) is Ga 68.5 In 21.5 Sn 10 The surface morphology and elemental composition of the wear scar formed under lubricated conditions, (b) is (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ The surface morphology and elemental composition of the wear scar formed under the same friction test conditions. From Figure 2 In (a) and (b), when Ga 68.5 In 21.5 Sn 10 lubricates the steel friction pair, the gallium-rich film formed on the wear scar surface is not complete, with some steel substrate exposed, the gallium-rich film is relatively smooth and flat, and the gallium content adsorbed on the wear scar surface is 12.73wt%; when (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn3wt％ When the steel friction pair is lubricated, the steel substrate of the wear scar surface is completely covered by the gallium-rich film, and the gallium-rich film is accumulated in a strip shape along the sliding direction, the gallium-rich film becomes uneven, and the content of adsorbed gallium on the wear scar surface is 16.34wt%. The doping of zinc element can obviously promote the adsorption of gallium element on the friction interface in the gallium-based liquid metal, the gallium-rich film becomes no longer flat, increases the gap between the friction interface, so that more gallium-based liquid metal can be filled in the gap, that is, the thickness of the fluid lubrication film is increased, the effect of fluid dynamic pressure is more significant, and under the synergistic lubrication of the gallium-rich film, the lubrication performance is improved.

[0063] Example 3

[0064] (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ Preparation

[0065] In an argon atmosphere glove box, the oxygen content is ≤10ppm, the water content is ≤10ppm, and the base gallium-based liquid metal Ga 68.5 In 21.5 Sn 10 prepared in Example 1 is weighed according to a mass ratio of 99:1, mixed and placed in a boron nitride crucible, and then the crucible is placed in a tube furnace, and heated to 1250℃ under the condition of argon protection for 2h, and cooled to room temperature to obtain a gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ .

[0066] Figure 3 (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ prepared in Example 3 and Ga 68.5 In 21.5 Sn 10 prepared in Comparative Example 1. The XRD spectra of the two liquid metals are shown in Figure 3 It can be seen that, in addition to the amorphous peak of the gallium-based liquid metal, the peak of CuGa2 phase appears in (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ , which indicates that the CuGa2 phase is generated in situ in the liquid metal.

[0067] The (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ The observation, Figure 4 The (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ The dispersion of CuGa2 phase in the gallium-based liquid metal (left) and the element surface distribution map (middle, right) of the gallium-based liquid metal prepared in Example 3 were observed by SEM. Figure 4 It can be seen that the CuGa2 phase exists in the form of particles with a size of 5-10 um, and the CuGa2 particles exist alone in the liquid metal without agglomeration of CuGa2 particles.

[0068] Example 4

[0069] The (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ Preparation

[0070] In an argon atmosphere glove box with oxygen content ≤10 ppm and water content ≤10 ppm, the base gallium-based liquid metal Ga 68.5 In 21.5 Sn 10 and copper wire were weighed according to a mass ratio of 97:3, mixed and placed in a boron nitride crucible, and then the crucible was placed in a tube furnace, and under the condition of argon protection, the temperature was raised to 1250℃ and kept for 2h, and then cooled to room temperature to obtain a gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ .

[0071] Example 5

[0072] The (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 50wt％ The (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ Preparation

[0073] In an argon atmosphere glove box with oxygen content <10 ppm, water content <10 ppm, the alloyed liquid metal (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ and the in-situ self-generated lubricating phase containing gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ , mixed and placed in a conical flask, the conical flask was placed in an oil bath at 150°C and stirred with a magnetic stirrer for 2h, cooled to room temperature to obtain the gallium-based liquid metal lubricant with reduced wear, wear-resistant and efficient lubrication.

[0074] Example 6

[0075] [(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 70wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 30wt％ Preparation of

[0076] In an argon atmosphere glove box with oxygen content <10 ppm, water content <10 ppm, the alloyed liquid metal (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ and the in-situ self-generated lubricating phase containing gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ , mixed and placed in a conical flask, the conical flask was placed in an oil bath at 150°C and stirred with a magnetic stirrer for 2h, cooled to room temperature to obtain the gallium-based liquid metal lubricant with reduced wear, wear-resistant and efficient lubrication.

[0077] Example 7

[0078] [(Ga 68.5 In 21.5 Sn 10 ) 99wt％ Zn 1wt％ ] 50wt％- [(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ Preparation of

[0079] In an argon atmosphere glove box with oxygen content ≤10 ppm, water content ≤10 ppm, the alloying liquid metal (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Zn 1wt％ and the gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ containing in-situ self-lubricating phase prepared in Example 4 were weighed according to the mass ratio of 1:1, mixed and placed in a conical flask, the conical flask was placed in an oil bath at 150℃ and stirred with a magnetic stirrer for 2h, cooled to room temperature to obtain the gallium-based liquid metal lubricant with wear reduction, wear resistance and high efficiency lubrication.

[0080] Example 8

[0081] (Ga 68.5 In 21.5 Sn 10 ) 95wt％ Zn 5wt％ Preparation of

[0082] In an argon atmosphere glove box with oxygen content ≤10 ppm, water content ≤10 ppm, the base gallium-based liquid metal Ga 68.5 In 21.5 Sn 10 and zinc wire prepared in Example 1 were weighed according to the mass ratio of 95:5, mixed and placed in a boron nitride crucible, and then the crucible was placed in a tube furnace, heated to 550℃ under argon protection for 2h, and cooled to room temperature to obtain the alloyed gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 95wt％ Zn 5wt％ .

[0083] Example 9

[0084] [(Ga 68.5 In 21.5 Sn 10 ) 95wt％ Zn 5wt％ ] 50wt％ - [(Ga 68.5 In 21.5Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ Preparation of

[0085] In an argon atmosphere glove box with oxygen content ≤10 ppm, water content ≤10 ppm, the alloying liquid metal (Ga 68.5 In 21.5 Sn 10 ) 95wt％ Zn 5wt％ and the gallium-based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ , and placed in a conical flask, the conical flask was placed in an oil bath at 150℃, and stirred with a magnetic son for 2h, cooled to room temperature, to obtain the gallium-based liquid metal lubricant with reduced friction and wear and high efficiency lubrication.

[0086] Comparative Example 1

[0087] The base gallium-based liquid metal Ga 68.5 In 21.5 Sn 10 prepared according to the method of step 1) of Example 1.

[0088] Comparative Example 2

[0089] (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Ti 1wt％ Preparation of

[0090] In an argon atmosphere glove box with oxygen content ≤10 ppm, water content ≤10 ppm, the base gallium-based liquid metal Ga 68.5 In 21.5 Sn 10 prepared in Comparative Example 1 was weighed according to a mass ratio of 99:1, mixed and placed in a boron nitride crucible, and then the crucible was placed in a tube furnace, heated to 1700℃ under argon protection for 2h, and cooled to room temperature to obtain the gallium-based liquid metal lubricant (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Ti 1wt％ .

[0091] Comparative Example 3

[0092] (Ga 68.5 In21.5 Sn 10 ) 99wt％ Sc 1wt％ Preparation

[0093] In a glove box under an argon atmosphere with oxygen content ≤10ppm and water content ≤10ppm, the basic gallium-based liquid metal Ga prepared in Comparative Example 1 was weighed at a mass ratio of 99:1. 68.5 In 21.5 Sn 10 Scandium wire was mixed with boron nitride and placed in a boron nitride crucible. The crucible was then placed in a tube furnace and heated to 1700℃ for 2 hours under argon protection. After cooling to room temperature, a gallium-based liquid metal lubricant (Ga) was obtained. 68.5 In 21.5 Sn 10 ) 99wt％ Sc 1wt％ .

[0094] Comparative Example 4

[0095] (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Mg 1wt％ Preparation

[0096] In a glove box under an argon atmosphere with oxygen content ≤10ppm and water content ≤10ppm, the basic gallium-based liquid metal Ga prepared in Comparative Example 1 was weighed at a mass ratio of 99:1. 68.5 In 21.5 Sn 10 Magnesium wire was mixed with boron nitride and placed in a boron nitride crucible. The crucible was then placed in a tube furnace and heated to 800°C for 2 hours under argon protection. After cooling to room temperature, a gallium-based liquid metal lubricant (Ga) was obtained. 68.5 In 21.5 Sn 10 ) 99wt％ Mg 1wt％ .

[0097] Comparative Example 5

[0098] (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ Preparation

[0099] In a glove box under an argon atmosphere with oxygen content ≤10ppm and water content ≤10ppm, the basic gallium-based liquid metal Ga prepared in Comparative Example 1 was weighed at a mass ratio of 99:1. 68.5 In 21.5 Sn10 and bismuth particles, mixed and placed in a boron nitride crucible, and then the crucible was placed in a tube furnace, heated to 350°C under the protection of argon for 2h, cooled to room temperature, to obtain a gallium-based liquid metal lubricant (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ .

[0100] Figure 2 In (c) was prepared from Comparative Example 5 (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ The surface morphology and elemental composition of the wear scar formed under the same friction test conditions. From Figure 2 In (c) can be seen, compared with Ga 68.5 In 21.5 Sn 10 lubricated wear scar surface gallium content (12.65wt%) compared with (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ The wear scar surface adsorbed gallium element significantly reduced, gallium content was 8.65wt%. In addition, the wear scar surface formed by the gallium-rich film is not complete, and part of the steel substrate is exposed. The doping of bismuth element significantly reduces the adsorption of gallium element on the friction interface, the gallium-rich film is relatively smooth and flat, and the gap between the friction interface is small, so that less gallium-based liquid metal can be filled in the gap, that is, the thickness of the fluid lubrication film is reduced, the effect of hydrodynamic pressure is weakened, and therefore the lubrication performance is reduced.

[0101] Comparative Example 6

[0102] Chinese patent CN114621802A Example 4 prepared [(Ga 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ alloyed liquid metal]-[Ga 65 In 22 Sn 13 oxide] 2wt％ .

[0103] 1) In an argon atmosphere glove box, the oxygen content is ≤10ppm, the water content is ≤10ppm, according to (Ga 65 In 22 Sn 13 ) 98wt％ Bi 2wt％Gallium block, indium wire, tin wire and bismuth powder are weighed according to the proportion; the weighed raw materials are placed in a conical flask, and then the conical flask is placed in a 200 DEG C oil bath, and the magnetic stirring is carried out for 1 h, and the alloyed gallium-based liquid metal is obtained after cooling;

[0104] 2) Gallium block, indium wire and tin wire are weighed according to the mass percentage of 65:22:13, placed in a conical flask, stirred in a 180 DEG C oil bath for 1 h, and the base gallium-based liquid metal Ga is obtained after cooling; 65 In 22 Sn 13 The base gallium-based liquid metal is placed in a beaker, and the beaker is placed in a muffle furnace in an atmospheric environment at 300 DEG C for 2 h to achieve preliminary oxidation; then the beaker is placed in a 200 DEG C oil bath, and the magnetic stirring is carried out for 1 h in an atmospheric environment, and the liquid metal oxide is obtained after sufficient oxidation and cooling;

[0105] 3) The alloyed liquid metal and the liquid metal oxide are weighed according to the proportion of (alloyed liquid metal) 98wt％ -(liquid metal oxide) 2w％ , placed in a conical flask, and stirred with a magnet for 1.2 h, and then the conical flask is placed in an ultrasonic cleaner, and ultrasonic dispersion is carried out for 0.8 h to obtain a gallium-based liquid metal high-temperature lubricant [(Ga 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ alloyed liquid metal]-[Ga 65 In 22 Sn 13 oxide] 2wt％ .

[0106] The existing method is to stir the gallium-based liquid metal in air, so that the original gallium-based liquid metal reacts with air to generate gallium oxide, thereby increasing the viscosity of the gallium-based liquid metal, and improving the wettability between the liquid metal and the friction pair. However, the oxidation process also destroys the flowability and lubricity of the gallium-based liquid metal. By doping copper element, in the cooling process, due to the low solubility of Cu in Ga, according to the Ga-Cu phase diagram, micron-sized GuGa2 particles will be precipitated in the liquid metal. GuGa2 particles are a kind of lubricating phase. Compared with other ways of adding GuGa2 particles or other lubricating phases, the preparation method provided by the present application can in-situ generate GuGa2 lubricating phase. GuGa2 lubricating phase does not agglomerate and is uniformly dispersed, and has better lubrication and wear resistance.

[0107] Comparative Example 7

[0108] Chinese patent CN114634835A embodiment 1 prepared [(Ga 65 In 22 Sn13 ) 98wt％ Bi 2wt％ alloyed liquid metal 98.5wt％ -Ag 1.5wt％ .

[0109] 1) In a glove box with argon atmosphere, the oxygen content is ≤10 ppm, the water content is ≤10 ppm, and gallium blocks, indium wires and tin wires are weighed according to the mass ratio of 65:22:13; the weighed raw materials are placed in an Erlenmeyer flask, and then the Erlenmeyer flask is placed in an oil bath at 200℃, and the magnetic stirrer is stirred for 1h, and the cooled to obtain a basic gallium-based liquid metal Ga 65 In 22 Sn 13 ;

[0110] 2) In a glove box with argon atmosphere, the oxygen content is ≤10 ppm, the water content is ≤10 ppm, and Ga 65 In 22 Sn 13 liquid metal and bismuth powder are weighed according to the mass ratio of 98:2; the weighed raw materials are placed in an Erlenmeyer flask, and then the Erlenmeyer flask is placed in an oil bath at 210℃, and the magnetic stirrer is stirred for 0.8h, and the cooled to obtain an alloyed gallium-based liquid metal (Ga 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ ;

[0111] 3) In the air, the alloyed gallium-based liquid metal and silver powder are weighed according to the mass ratio of (alloyed gallium-based liquid metal) 98.5wt％ -Ag 1.5wt％ , and are placed in a mortar, and are ground in the air for 1h, and then are ultrasonically dispersed for 0.5h, to obtain a high-conductivity and strong-lubrication gallium-based liquid metal lubricant.

[0112] Figure 1 is [(Ga 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ alloyed liquid metal 98.5wt％ -Ag 1.5wt％ The SEM and EDS images of the Ag lubricating phase added in the alloyed liquid metal show that Figure 1 agglomeration will occur between the particles of the added Ag lubricating phase, which is not conducive to fully exerting the lubricating effect of the lubricating phase.

[0113] Test Example 1

[0114] The gallium-based liquid metal prepared in the examples and comparative examples is tested for lubricating performance, and the test method is as follows:

[0115] Friction test condition: All the friction tests were performed on a MCR302e rheometer equipped with a ball / three-plate tribology test accessory, which is a device that allows friction to be achieved by pressing a rotating ball (12.7 mm in diameter) against three stationary plates (15*6*3 mm in size). The contact is point contact, with a circular indentation on each plate. AISI 440C steel was chosen as the material for the ball and the plates, because it is a commonly used wear-resistant martensitic stainless steel. The friction tests were performed at a load of 5 N (Hertz contact stress of 0.66 GPa), a sliding speed of 0.5 m / s, a sliding distance of 300 m, and a test temperature of 40°C.

[0116] Friction coefficient: To ensure the reliability of the experimental results, each group of experiments was repeated three times under the same conditions. After each friction coefficient curve was stable, the average value of the friction coefficient of a single experiment was taken, and then the average value of the three experiments was calculated.

[0117] Wear rate: The wear volume was measured by placing the wear scar under a white light interferometric three-dimensional profilometer, and the wear rate was calculated. To ensure the reliability of the experimental results, each group of experiments was repeated three times under the same conditions, and the average value of the wear rate data of the three experiments was taken.

[0118] The test results are shown in Table 1.

[0119] Table 1 Lubrication performance test results of gallium-based liquid metal lubricants prepared by examples and comparative examples

[0120]

[0121]

[0122] As can be seen from Table 1, under the same friction test conditions, the friction coefficient of the friction pair lubricated by Ga 68.5 In 21.5 Sn 10 lubricated by Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 50wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ lubricated by Ga

[0123] Under the same friction test conditions, compared with Ga prepared from Comparative Example 1 68.5 In 21.5 Sn 10 Compared to other lubricants, the wear rates of gallium-based liquid metal lubricants prepared in Examples 1-9 all showed varying degrees of reduction. Among them, the wear rate of [(Ga...] prepared in Example 5... 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 50wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ The lubricated material exhibited the lowest wear rate; compared to Comparative Example 1, the wear rate in Example 5 was reduced by 69.4%.

[0124] By comparing Examples 3-4 and Comparative Examples 1-4, it was found that the Ga prepared in Comparative Example 1... 68.5 In 21.5 Sn 10 In comparison, doping with Ti, Sc, and Mg all reduce the lubrication performance of gallium-based liquid metals, especially Mg doping, which is extremely detrimental to their lubrication properties. However, the gallium-based liquid metals prepared in Examples 3 and 4 exhibit in-situ formation of a micron-sized CuGa2 self-lubricating phase, which effectively reduces the friction coefficient and wear rate of the friction pair. Under the same friction test conditions, the (Ga2) prepared in Example 4... 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ It exhibits good lubrication properties, similar to the Ga prepared from Comparative Example 1. 68.5 In 21.5 Sn 10 Compared with the lubricated friction pair, the coefficient of friction and wear rate were reduced by 3.8% and 49.1%, respectively.

[0125] By comparing the experimental results of Example 2, Comparative Example 1, and Comparative Example 5, and Figure 2 It can be seen that, from (Ga) 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ The gallium content on the lubricated wear scar surface is higher than that of Ga. 68.5 In 21.5 Sn 10 The gallium content on the lubricated wear scar surface, and the gallium content of (Ga) 68.5 In 21.5 Sn 10) 99wt％ Bi 1wt％ The gallium content of the lubricated wear scar surface is lower than that of Ga 68.5 In 21.5 Sn 10 The gallium content of the lubricated wear scar surface. The doping of Zn element promotes the adsorption of gallium and improves the lubricating performance of the gallium-based liquid metal, while the doping of Bi element inhibits the adsorption of gallium and reduces the lubricating performance of the gallium-based liquid metal.

[0126] It can be seen from Comparative Example 3, Example 4, Comparative Example 1 and Comparative Example 6 that although the wettability of the liquid metal is improved by oxidation in Comparative Example 6, the viscosity of the liquid metal is also increased, and the wear rate is also increased.

[0127] The present application improves the lubricating performance of the gallium-based liquid metal by Zn alloying, and in-situ generates uniformly dispersed micron CuGa2 lubricating phase in the gallium-based liquid metal, thereby optimizing the basic gallium-based liquid metal to (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ , and the (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ are mixed in a mass ratio of 1:1 to obtain the composite gallium-based liquid metal of Example 5. Figure 5 The Ga 68.5 In 21.5 Sn 10 prepared from Comparative Example 1 and the [(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 50wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ The friction coefficient and the wear rate of the friction pair under the same friction test conditions. The Ga Figure 5 It can be seen that the lubricating performance of the gallium-based liquid metal lubricant prepared in Example 5 is greatly reduced in terms of friction coefficient and wear rate compared with Comparative Example 1, and the reduction is 26.5% and 69.4% respectively. Compared with the [(Ga 65 In 22 Sn 13 ) 98wt％Bi 2wt％ Alloyed liquid metal 98.5wt％ -Ag 1.5wt％ In comparison, the wear rate of Example 5 is reduced by 70.3%, so the in-situ generated and uniformly dispersed CuGa2 particles can play a good anti-wear role and have a positive effect on reducing the wear rate of the friction pair. It is shown that the prepared transition metal-doped gallium-based liquid metal lubricant has excellent lubricating performance.

[0128] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the protection scope of the present application.

Claims

1. A gallium-based liquid metal containing an in-situ self-generated lubricating phase, having a chemical composition (Ga-In-Sn base gallium-based liquid metal) (100-y)wt％ Cu ywt％ , 3 > y > 1; the in-situ self-generated lubricating phase being a micron-sized CuGa2 phase.

2. The in-situ self-lubricating gallium-based liquid metal containing phase of claim 1, wherein, The Ga-In-Sn base gallium-based liquid metal has a chemical composition of Ga 68.5 In 21.5 Sn 10 .

3. The method for preparing the gallium-based liquid metal containing in-situ self- formed lubricating phase according to claim 1 or 2, comprising the following steps: secondly melting the Ga-In-Sn base gallium-based liquid metal and Cu in chemical composition under a protective atmosphere to obtain the gallium-based liquid metal containing in-situ self-formed lubricating phase.

4. A composite gallium-based liquid metal, having a chemical composition (alloyed gallium-based liquid metal) (100-z)wt％ - (gallium-based liquid metal containing in-situ generated lubricating phase) zwt％ , 100 > z > 0; the alloyed gallium-based liquid metal having a chemical composition (Ga-In-Sn based gallium-based liquid metal) (100-x)wt％ Zn xwt％ , 5 > x > 1; the gallium-based liquid metal containing in-situ generated lubricating phase being the gallium-based liquid metal containing in-situ generated lubricating phase according to any one of claims 1 to 2 or the gallium-based liquid metal containing in-situ generated lubricating phase prepared according to the method of claim 3.

5. The composite gallium-based liquid metal of claim 4, wherein, The chemical composition of the Ga-In-Sn base gallium-based liquid metal in the alloyed gallium-based liquid metal is Ga 68.5 In 21.5 Sn 10 .

6. The composite gallium-based liquid metal of claim 4 or 5, wherein, The method for preparing the alloyed gallium-based liquid metal comprises the following steps: firstly melting the Ga-In-Sn base gallium-based liquid metal and Zn in chemical composition under a protective atmosphere to obtain the alloyed gallium-based liquid metal.

7. The method for preparing the composite gallium-based liquid metal according to any one of claims 4-6, comprising the following steps: mixing the alloyed gallium-based liquid metal and the gallium-based liquid metal containing in-situ self-formed lubricating phase in chemical composition under a protective atmosphere to obtain the composite gallium-based liquid metal.

8. The production method according to claim 7, characterized by, The temperature of the mixing is 100-300℃, and the time is 1-3h.

9. The application of the gallium-based liquid metal containing in-situ self-formed lubricating phase according to any one of claims 1-2 or prepared by the method of claim 3, the composite gallium-based liquid metal according to any one of claims 4-6 or prepared by the method of any one of claims 7-8 in lubricating and anti-wear.

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