CN117051298A - Transition metal doped gallium-based liquid metal and preparation method and application thereof - Google Patents
Transition metal doped gallium-based liquid metal and preparation method and application thereof Download PDFInfo
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 265
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 227
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052723 transition metal Inorganic materials 0.000 title abstract description 4
- 150000003624 transition metals Chemical class 0.000 title abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 58
- 238000005461 lubrication Methods 0.000 claims abstract description 46
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 36
- 238000003723 Smelting Methods 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 20
- 230000001681 protective effect Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001050 lubricating effect Effects 0.000 abstract description 56
- 239000010949 copper Substances 0.000 abstract description 45
- 239000011701 zinc Substances 0.000 abstract description 45
- 239000002245 particle Substances 0.000 abstract description 17
- 239000000314 lubricant Substances 0.000 abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 42
- 238000001816 cooling Methods 0.000 description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 229910052797 bismuth Inorganic materials 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 15
- 229910052582 BN Inorganic materials 0.000 description 14
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- 229910052718 tin Inorganic materials 0.000 description 11
- 238000005275 alloying Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 229910052738 indium Inorganic materials 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000013590 bulk material Substances 0.000 description 3
- 238000004320 controlled atmosphere Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000012856 weighed raw material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910001213 440C Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004356 Ti Raw Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SPAHBIMNXMGCMI-UHFFFAOYSA-N [Ga].[In] Chemical group [Ga].[In] SPAHBIMNXMGCMI-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910001084 galinstan Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- -1 indium (In) Chemical class 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention provides a transition metal doped gallium-based liquid metal, a preparation method and application thereof, and relates to the technical field of liquid metal lubricants. According to the invention, a small amount of zinc element (existing in a liquid form) is doped in the gallium-based liquid metal, so that the adsorption of the gallium element on a friction interface can be obviously promoted, and the lubricating performance of the gallium-based liquid metal is effectively improved; by doping copper element, micron-sized and solid CuGa can be generated in situ in gallium-based liquid metal 2 Lubricating phase, in situ generated CuGa 2 The lubricating phase and the additional lubricating phase can be dispersed more uniformly, agglomeration among lubricating phase particles is avoided, and meanwhile, the lubricating performance is improved; meanwhile, the gallium-based liquid metal doped with zinc and copper has better lubricating performance. The zinc-doped alloyed gallium-based liquid metal, the copper-doped in-situ self-generated lubrication Xiang Jiaji-containing liquid metal and the zinc-and copper-doped composite gallium-based liquid metal provided by the invention have excellent lubrication and wear resistance.
Description
Technical Field
The invention relates to the technical field of liquid metal lubricants, in particular to an alloyed gallium-based liquid metal, a preparation method and application thereof, an in-situ self-lubricating Xiang Jiaji-containing liquid metal, a preparation method and application thereof, a composite gallium-based liquid metal, and a preparation method and application thereof.
Background
Scientifically, 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 of reducing friction and wear. With the continuous innovation and rapid development of China in the fields of aerospace technology, national defense and military industry and the like, the high-end equipment puts forward more and more stringent requirements on the service performance of the liquid lubricant. For example, five generations of fighter plane require that the service temperature and bearing capacity of the lubricating grease exceed 350 ℃ and 2GPa, respectively, but are limited by the inherent properties of organic matters, and the performance of the lubricating grease is difficult to break through the technical index. Therefore, development work of novel liquid lubricants with unique physicochemical properties and lubricating properties is imperative.
Gallium-based liquid metal is an alloy which takes gallium (Ga) as a main material, takes low-melting-point metals such as indium (In), tin (Sn), lead (Pb), bismuth (Bi) and the like as auxiliary materials, and is liquid at room temperature, and the typical component is 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%) has both metallic and fluidity. From the viewpoint of liquid lubricants, gallium-based liquid metals have extremely low saturated vapor pressure, higher service temperature (no obvious volatilization at 600 ℃ and good lubrication), good electrical conductivity and thermal conductivity, extremely high bearing capacity, greenness and no toxicityEnvironmental protection, etc., is a novel liquid lubricant. Currently, gallium-based liquid metals are used in X-ray tube bearings of imported medical CT devices.
Although gallium-based liquid metal can break through the service performance bottleneck faced by lubricating grease, certain gap exists between the lubricating performance of the gallium-based liquid metal and the lubricating grease. When using gallium-based liquid metal lubrication, the friction pair is typically in a boundary or mixed lubrication state with a high coefficient of friction (about 0.1-0.6, langmuir2019, 35:6905-6915).
Currently, there are two main types of methods for improving the lubricating performance of gallium-based liquid metals. One is to regulate the type and content of the liquid alloy components, such as doped aluminum, silver and bismuth elements (present in liquid form in gallium-based liquid metals). For example, chinese patent CN109852453a discloses that the friction coefficient is reduced by about 20% after doping with aluminum and silver, the wear rate is reduced by about 50% after doping with aluminum, but the wear rate is rather improved after doping with silver. Chinese patent CN114621809a discloses that after doping bismuth and solid lubricating phase with gallium-based liquid metal, the friction coefficient is reduced by about 25%, and no change in wear rate is mentioned. From the above, the doping elements found at present have a limited degree of improvement of the lubricating property. Secondly, a solid lubricating phase (in solid form in gallium-based liquid metals) is added, for example boron nitride, tungsten disulfide, etc. (chinese patents CN114621809a and CN109022100 a). However, this approach suffers from two relatively significant drawbacks: the addition of the solid lubricating phase must be operated in an atmospheric environment (because the non-oxidized gallium is non-wetting to a plurality of lubricating phases, the encapsulation and uniform mixing of the solid lubricating phase must be realized by the oxidation of gallium), but the oxidation degree of the gallium-based liquid metal is difficult to accurately control, the viscosity is increased after oxidation, the fluidity is poor, and the lubricating performance is reduced; the added solid lubricating phase is difficult to uniformly disperse in the gallium-based liquid metal, which is disadvantageous in fully exerting the lubricating property of the solid lubricating phase, as shown in fig. 1. Therefore, it is of great importance to provide a gallium-based liquid metal with excellent lubrication and wear resistance.
Disclosure of Invention
In view of the above, the invention aims to provide an alloyed gallium-based liquid metal, a preparation method and application thereof, an in-situ self-generated lubrication Xiang Jiaji-containing liquid metal, a preparation method and application thereof, a composite gallium-based liquid metal, a preparation method and application thereof, and the three gallium-based liquid metals provided by the invention have excellent lubrication and wear resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an alloyed gallium-based liquid metal, which has the chemical composition of (Ga-In-Sn basic gallium-based liquid metal) (100-x)wt％ Zn xwt％ ，5≥x≥1。
Preferably, the chemical composition of the Ga-In-Sn based gallium-based liquid metal is Ga 68.5 In 21.5 Sn 10 。
The invention provides a preparation method of the gallium-based liquid metal alloy, which comprises the following steps: and mixing the Ga-In-Sn basic gallium-based liquid metal and Zn according to chemical composition In a protective atmosphere, and then carrying out first smelting to obtain the alloyed gallium-based liquid metal.
The invention provides a liquid metal containing In-situ self-generated lubrication Xiang Jiaji, which comprises the following chemical components (Ga-In-Sn basic gallium-based liquid metal) (100-y)wt％ Cu ywt％ ，3≥y≥1。
Preferably, the chemical composition of the Ga-In-Sn based gallium-based liquid metal is Ga 68.5 In 21.5 Sn 10 。
The invention provides a preparation method of the in-situ self-lubricating Xiang Jiaji-containing liquid metal, which comprises the following steps: and mixing the Ga-In-Sn basic gallium-based liquid metal and Cu according to chemical composition under a protective atmosphere, and then smelting for the second time to obtain the In-situ self-lubricating Xiang Jiaji-containing liquid metal.
The invention provides a composite gallium-based liquid metal, which comprises the following chemical components (alloyed gallium-based liquid metal) (100-z)wt％ - (containing in situ self-lubricating Xiang Jiaji liquid metal) zwt％ Z is more than or equal to 100 and is more than 0; the gallium-based liquid metal alloy is the gallium-based liquid metal alloy or the technical methodThe alloyed gallium-based liquid metal prepared by the preparation method; the in-situ self-lubricating Xiang Jiaji-containing liquid metal is the in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the technical scheme or the in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the preparation method.
The invention provides a preparation method of the composite gallium-based liquid metal, which comprises the following steps: and mixing the alloyed gallium-based liquid metal and the in-situ self-generated lubrication Xiang Jiaji-containing liquid metal according to chemical compositions in a protective atmosphere to obtain the composite gallium-based liquid metal.
Preferably, the temperature of the mixing is 100-300 ℃ and the time is 1-3 h.
The invention provides an alloyed gallium-based liquid metal prepared by the technical scheme or the preparation method, an in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the technical scheme or an in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the preparation method, a composite gallium-based liquid metal prepared by the technical scheme or an application of the composite gallium-based liquid metal prepared by the preparation method in lubrication and wear resistance.
The invention provides an alloyed gallium-based liquid metal, which has the chemical composition of (Ga-In-Sn basic gallium-based liquid metal) (100-x)wt％ Zn xwt％ X is more than or equal to 5 and more than or equal to 1. According to the invention, a small amount of zinc element is doped in the gallium-based liquid metal (in a liquid form), so that adsorption of the gallium element on a friction interface can be obviously promoted, a gallium-rich film becomes uneven, gaps between the friction interfaces are increased, more gallium-based liquid metal can be filled in the gaps, namely, the thickness of a fluid lubrication film is increased, the action of fluid dynamic pressure effect is more obvious, the lubrication performance of the gallium-based liquid metal is improved under the synergistic lubrication action with the gallium-rich film, and compared with the gallium-based liquid metal without doped zinc element, the friction coefficient and the wear rate are obviously reduced. As shown in the test results of the examples, with Ga 68.5 In 21.5 Sn 10 In contrast, (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Zn 1wt％ The friction coefficient of (2) is reduced by 9.4%, and the wear rate is reduced by 55.1%.
The invention provides a preparation method of the gallium-based liquid metal alloy. According to the invention, smelting is carried out in a protective atmosphere, zinc element is dissolved in gallium-based liquid metal in a liquid state, and zinc doping can promote adsorption of gallium on a friction interface, so that the lubricating performance of the gallium is improved. In addition, the preparation method provided by the invention is simple to operate, environment-friendly, low in cost and suitable for industrial production.
The invention provides a liquid metal containing In-situ self-generated lubrication Xiang Jiaji, which comprises the following chemical components (Ga-In-Sn basic gallium-based liquid metal) (100-y)wt％ Cu ywt％ Y is more than or equal to 3 and more than or equal to 1. The invention can generate micron-sized CuGa in situ in gallium-based liquid metal by adding a small amount of copper element 2 Lubricating phase (in the form of solid particles), on the one hand, cuGa 2 The particles themselves have a certain lubrication effect, and during the sliding process, cuGa is used as a lubricant 2 The grains are easy to be compressed smoothly, and can form a glaze with lower shearing resistance, so that the glaze has a certain lubrication effect; on the other hand, during the rubbing process, due to CuGa 2 The particles are intermetallic compounds with lower hardness, are subjected to plastic deformation under the action of contact load, and are attached to the surface of the gallium-rich film, so that the roughness of a friction interface is increased, and gaps between the friction interfaces are further increased, and therefore more gallium-based liquid metal can be filled between the friction interfaces, namely the thickness of a fluid film is increased, the bearing capacity is improved, and the lubricating performance of the gallium-based liquid metal is further improved; in yet another aspect, the liquid metal is capable of fully wetting the CuGa 2 Particles, so CuGa 2 The adsorption of the liquid metal on the surface of the gallium-rich film is improved. Compared with an externally added lubricating phase, the in-situ self-generated lubricating Xiang Jiaji-containing liquid metal provided by the invention not only avoids oxidation of gallium-based liquid metal, but also avoids reduction of lubricating performance caused by oxidation without changing viscosity and fluidity of the liquid metal; in addition, the in-situ self-generated lubricating phase is more uniformly dispersed in the gallium-based liquid metal, and agglomeration among lubricating phase particles is avoided, so that full play can be realizedThe lubrication effect of the lubrication phase greatly improves the lubrication and wear resistance. As shown in the test results of the examples, with Ga 68.5 In 21.5 Sn 10 In contrast, (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ The friction coefficient of (2) is reduced by 3.8%, and the wear rate is reduced by 49.1%.
The invention provides a preparation method of the liquid metal containing in-situ self-generated lubrication Xiang Jiaji. The invention carries out smelting in protective atmosphere, copper element is dissolved in gallium-based liquid metal in liquid form, the solubility of copper in the gallium-based liquid metal is reduced along with the reduction of temperature in the cooling process, and excessive copper element reacts with gallium to generate micron-sized CuGa 2 The particles form gallium-based liquid metal with evenly distributed solid-liquid two phases coexisting, thereby realizing the effect of reducing friction and abrasion and further improving the lubrication and wear resistance of the gallium-based liquid metal. In addition, the preparation method provided by the invention is simple to operate, environment-friendly, low in cost and suitable for industrial production.
The invention provides a composite gallium-based liquid metal, which comprises the following chemical components (alloyed gallium-based liquid metal) (100-z)wt％ - (containing in situ self-lubricating Xiang Jiaji liquid metal) zwt％ Z is more than or equal to 100 and is more than 0; the alloyed gallium-based liquid metal is the alloyed gallium-based liquid metal prepared by the technical scheme or the preparation method; the in-situ self-lubricating Xiang Jiaji-containing liquid metal is the in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the technical scheme or the in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the preparation method. The composite gallium-based liquid metal provided by the invention is doped with zinc and copper elements simultaneously, contains an in-situ self-generated lubricating phase, has large adsorption quantity of gallium elements on a friction interface, has the advantages of alloying gallium-based liquid metal and in-situ self-generated lubricating Xiang Jiaji liquid metal, and further improves the lubricating and wear-resisting properties of the gallium-based liquid metal under the combined action of the two.
As shown in the test results of the examples, ga is doped with zinc and copper elements 68.5 In 21.5 Sn 10 Comparison with each other，[(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 of (2) is reduced by 26.5%, and the abrasion rate is reduced by 69.4%.
The invention provides a preparation method of the composite gallium-based liquid metal. The invention mixes under the protective atmosphere, and further improves the lubrication and wear resistance of the gallium-based liquid metal. In addition, the preparation method provided by the invention is simple to operate, environment-friendly, low in cost and suitable for industrial production.
Drawings
FIG. 1 shows [ (Ga) prepared in comparative example 7 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ Alloying liquid metal] 98.5wt％ -Ag 1.5wt％ SEM and EDS pictures of an Ag lubrication phase added in the liquid metal;
FIG. 2 is Ga prepared in comparative example 1 68.5 In 21.5 Sn 10 Liquid Metal, prepared in example 2 (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ Liquid metal and comparative example 5 preparation (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ Forming surface morphology and element composition diagrams of the abrasive spots by the liquid metal under the same friction test condition;
FIG. 3 shows the composition of example 3 (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ And Ga prepared in comparative example 1 68.5 In 21.5 Sn 10 XRD patterns of two liquid metals;
FIG. 4 shows the composition of example 3 (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ Medium CuGa 2 Dispersion of the phases in the gallium-based liquid metal (left) and elemental plane distribution patterns (middle, right);
FIG. 5 shows Ga prepared in comparative example 1 68.5 In 21.5 Sn 10 Liquid metal and [ (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％ Friction coefficient and disc wear rate of friction pair under the same friction test conditions for liquid metal.
Detailed Description
The invention provides an alloyed gallium-based liquid metal, which has the chemical composition of (Ga-In-Sn basic gallium-based liquid metal) (100-x)wt％ Zn xwt％ X is more than or equal to 5 and more than or equal to 1. In the present invention, the x is particularly preferably 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5. In the present invention, the chemical composition of the Ga-In-Sn based gallium-based liquid metal is preferably Ga In terms of mass percent 68.5 In 21.5 Sn 10 。
In the present invention, the preparation method of the Ga-In-Sn based gallium-based liquid metal preferably comprises the following steps: and mixing Ga, in and Sn according to chemical compositions and smelting (marked as third smelting) In a protective atmosphere to obtain the Ga-In-Sn basic gallium-based liquid metal.
The raw materials adopted by the invention are all commercial products unless specified.
In the present invention, the Ga, in, and Sn are preferably In the shape of a wire or a block, the Ga is more preferably In the shape of a block, and the In and Sn are more preferably In the shape of a wire; the invention is not particularly limited to the size of the bulk material and the wire material, and the size well known to the person skilled in the art can be adopted; the purity of Ga, in and Sn is 99.99%.
In the present invention, the mixing is preferably performed by placing the raw materials in a crucible and mixing them in a glove box; the crucible is preferably made of boron nitride; in the invention, the protective atmosphere is preferably argon or helium, the oxygen content of the protective atmosphere is preferably less than or equal to 10ppm, and the water content is preferably less than or equal to 10ppm.
In the invention, the temperature of the third smelting is preferably 100-300 ℃, more preferably 200 ℃, and the heat preservation time of the third smelting is preferably 1-3 h, more preferably 2h; the third smelting is preferably carried out in a controlled atmosphere sintering furnace, preferably a tube furnace or a box furnace.
After the third smelting, the invention preferably further comprises cooling to room temperature to obtain the Ga-In-Sn basic gallium-based liquid metal. The cooling method is not particularly limited, and a cooling method well known to those skilled in the art, such as natural cooling with a furnace, may be adopted.
The invention provides a preparation method of the gallium-based liquid metal alloy, which comprises the following steps: and mixing the Ga-In-Sn basic gallium-based liquid metal and Zn according to chemical composition In a protective atmosphere, and then carrying out first smelting to obtain the alloyed gallium-based liquid metal.
In the present invention, the Zn is preferably in the shape of a wire or a block, more preferably a wire; the invention is not particularly limited to the size of the bulk material and the wire material, and the size well known to the person skilled in the art can be adopted; the purity of Zn is 99.99%.
In the present invention, the raw materials are preferably mixed in a glove box by placing them in a crucible, and the material of the crucible is preferably boron nitride. In the invention, the protective atmosphere is preferably argon or helium, the oxygen content of the protective atmosphere is preferably less than or equal to 10ppm, and the water content is preferably less than or equal to 10ppm.
In the invention, the temperature of the first smelting is preferably 500-650 ℃, more preferably 550-600 ℃, and the heat preservation time of the first smelting is preferably 1-3 h, more preferably 2h; the first smelting is preferably carried out in a controlled atmosphere sintering furnace, preferably a tube furnace or a box furnace.
After the first smelting, the invention preferably further comprises cooling to room temperature to obtain the gallium-based liquid metal alloy. The cooling method is not particularly limited, and a cooling method well known to those skilled in the art, such as natural cooling with a furnace, may be adopted.
The invention provides a liquid metal containing In-situ self-generated lubrication Xiang Jiaji, which comprises the following chemical components (Ga-In-Sn basic gallium-based liquid metal) (100-y)wt％ Cu ywt％ Y is more than or equal to 3 and more than or equal to 1. In the present invention, y is particularly preferably 1, 1.5, 2, 2.5 or 3. In the invention, the weight percentage of the components isThe chemical composition of the Ga-In-Sn based gallium-based liquid metal is preferably Ga 68.5 In 21.5 Sn 10 。
The invention provides a preparation method of the in-situ self-lubricating Xiang Jiaji-containing liquid metal, which comprises the following steps: and mixing the Ga-In-Sn basic gallium-based liquid metal and Cu according to chemical composition under a protective atmosphere, and then smelting for the second time to obtain the In-situ self-lubricating Xiang Jiaji-containing liquid metal.
In the present invention, the Cu is preferably in the shape of a wire or a block, more preferably a wire; the invention is not particularly limited to the size of the bulk material and the wire material, and the size well known to the person skilled in the art can be adopted; the purity of the Cu is 99.99%.
In the present invention, the mixing is preferably performed in a crucible, and the material of the crucible is preferably boron nitride. In the invention, the protective atmosphere is preferably argon or helium, the oxygen content of the protective atmosphere is preferably less than or equal to 10ppm, and the water content is preferably less than or equal to 10ppm.
In the invention, the temperature of the second smelting is preferably 1200-1350 ℃, more preferably 1250 ℃, and the heat preservation time of the second smelting is preferably 1-3 h, more preferably 2h; the second smelting is preferably carried out in a controlled atmosphere sintering furnace, preferably a tube furnace or a box furnace.
After the second smelting, the invention preferably further comprises cooling to room temperature to obtain the liquid metal containing the in-situ self-generated lubrication Xiang Jiaji. The cooling method is not particularly limited, and a cooling method well known to those skilled in the art, such as natural cooling with a furnace, may be adopted.
The invention provides a composite gallium-based liquid metal, which comprises the following chemical components (alloyed gallium-based liquid metal) (100-z)wt％ - (containing in situ self-lubricating Xiang Jiaji liquid metal) zwt％ Z is more than or equal to 100 and is more than 0; the alloyed gallium-based liquid metal is the alloyed gallium-based liquid metal prepared by the technical scheme or the preparation method; the in-situ self-generated lubrication Xiang Jiaji-containing liquid metal is the original-contained liquid metal according to the technical schemeIn-situ self-lubricating Xiang Jiaji liquid metal or Xiang Jiaji liquid metal containing in-situ self-lubricating prepared by the preparation method according to the technical scheme. In the present invention, z is preferably 10 to 90, particularly preferably 10, 20, 30, 40, 50, 60, 70, 80 or 90.
The invention provides a preparation method of the composite gallium-based liquid metal, which comprises the following steps: and mixing the alloyed gallium-based liquid metal and the in-situ self-generated lubrication Xiang Jiaji-containing liquid metal according to chemical compositions in a protective atmosphere to obtain the composite gallium-based liquid metal.
In the present invention, the temperature of the mixing is preferably 100 to 300 ℃, more preferably 150 to 250 ℃, still more preferably 200 ℃; the mixing time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, still more preferably 2 hours; the mixing is preferably stirring mixing.
After the mixing, the invention preferably further comprises cooling to room temperature to obtain the composite gallium-based liquid metal. The cooling method is not particularly limited, and a cooling method well known to those skilled in the art, such as natural cooling, may be used.
The invention provides an alloyed gallium-based liquid metal prepared by the technical scheme or the preparation method, an in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the technical scheme or an in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the preparation method, a composite gallium-based liquid metal prepared by the technical scheme or an application of the composite gallium-based liquid metal prepared by the preparation method in lubrication and wear resistance.
The alloyed gallium-based liquid metal, the preparation method and the application thereof, the in-situ self-lubricating Xiang Jiaji-containing liquid metal, the preparation method and the application thereof and the composite gallium-based liquid metal are provided in the following detailed description with reference to examples, but are not to be construed as limiting the scope of the invention.
In the following examples and comparative examples, ga raw material (simple substance) was In the form of a block, in raw material (simple substance), sn raw material (simple substance), zn raw material (simple substance) and Cu raw material (simple substance) were wires having a diameter of 1mm, and the purity of each raw material was 99.99%. The Sc raw material (simple substance) and the Mg raw material (simple substance) are wires with the diameter of 1mm, the Ti raw material (simple substance) is powder with the diameter of 10-50 mu m, and the purity of each raw material is 99.9 percent. The Ag raw material (simple substance) is 100-500 nm powder, and the purity is 99.99%. Bi raw materials (simple substances) are two: wherein Bi raw material (simple substance) used in comparative example 5 is spherical-like particles with diameter of 1-3 mm, and purity is 99.95%; the Bi raw material (simple substance) used in comparative example 6 was 100 to 500nm powder with a purity of 99.99%.
Example 1
(Ga 68.5 In 21.5 Sn 10 ) 99.wt％ Zn 1wt％ Is prepared from
1) Weighing gallium blocks, indium wires and tin wires according to the mass ratio of 68.5:21.5:10, mixing and placing the gallium blocks, the indium wires and the tin wires in a boron nitride crucible, then placing the crucible in a tubular furnace, heating to 200 ℃ under the protection of argon, preserving heat for 2 hours, cooling to room temperature, and obtaining basic gallium-based liquid metal Ga 68.5 In 21.5 Sn 10 ；
2) In a glove box in an argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the gallium-based liquid metal Ga is weighed according to the mass ratio of 99:1 68.5 In 21.5 Sn 10 And zinc wires, mixing and placing the zinc wires in a boron nitride crucible, then placing the crucible in a tube furnace, heating to 550 ℃ under the protection of argon, preserving heat for 2 hours, and cooling to room temperature to obtain alloyed gallium-based liquid metal (Ga) 68.5 In 21.5 Sn 10 ) 99wt％ Zn 1wt％ 。
Example 2
(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ Is prepared from
In a glove box in argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the basic gallium-based liquid metal Ga prepared in the example 1 is weighed according to the mass ratio of 97:3 68.5 In 21.5 Sn 10 Mixing with zinc wire, placing into boron nitride crucible, placing the crucible into tubular furnace, heating to 550 deg.C under the protection of argon gasPreserving heat at the temperature of 2 hours, cooling to the room temperature to obtain the gallium-based liquid metal (Ga) 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ 。
In FIG. 2, (a) is Ga prepared in comparative example 1 68.5 In 21.5 Sn 10 Surface morphology and elemental composition to form plaque under lubricating conditions, (b) the composition of (Ga) prepared in example 2 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ Surface morphology and elemental composition that formed plaque under the same rub test conditions. As can be seen from FIGS. 2 (a) and (b), when Ga is used 68.5 In 21.5 Sn 10 When the steel friction pair is lubricated, a gallium-rich film formed on the surface of the mill marks is incomplete, part of steel matrixes are exposed, the gallium-rich film is relatively smooth and flat, and the gallium content adsorbed on the surface of the mill marks is 12.73wt%; when using (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ When the steel friction pair is lubricated, the steel substrate on the surface of the grinding spot is completely covered by the gallium-rich film, the gallium-rich film is piled up into a strip shape along the sliding direction, the gallium-rich film becomes uneven, and the gallium content adsorbed on the surface of the grinding spot is 16.34wt%. The doping of zinc element can obviously promote the adsorption of gallium element on the friction interface in gallium-based liquid metal, the gallium-rich film becomes uneven, the gap between the friction interfaces is increased, more gallium-based liquid metal can be filled in the gap, namely, the thickness of the fluid lubrication film is increased, the action of the fluid dynamic pressure effect is more obvious, and the lubrication performance of the gallium-rich film is improved under the cooperative lubrication action with the gallium-rich film.
Example 3
(Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ Is prepared from
In a glove box in argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the basic gallium-based liquid metal Ga prepared in the example 1 is weighed according to the mass ratio of 99:1 68.5 In 21.5 Sn 10 Mixing with copper wire, placing in boron nitride crucible, placing the crucible in tubular furnace, heating to 1250 deg.C under the protection of argon gas, holding temperature for 2 hr, cooling to room temperature to obtain the invented product containing in-situ self-grown lubricationPhase gallium based liquid metal (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ 。
FIG. 3 shows the composition of example 3 (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ And Ga prepared in comparative example 1 68.5 In 21.5 Sn 10 XRD patterns of the two liquid metals. As can be seen from fig. 3, in addition to the amorphous peaks of the gallium-based liquid metal, the phase difference between (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ Is of CuGa 2 Phase peaks, which indicate in-situ formation of CuGa in liquid metal 2 And (3) phase (C).
The sample (Ga) prepared in example 3 was subjected to Scanning Electron Microscopy (SEM) 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ When observed, FIG. 4 shows (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Cu 1wt％ Medium CuGa 2 The dispersion of the phases in the gallium-based liquid metal (left) and the elemental plane distribution diagram (middle, right), as can be seen from fig. 4, cuGa 2 The phase exists in the form of particles with the size of 5-10 um and CuGa 2 The particles are present alone in the liquid metal, in the absence of CuGa 2 Agglomeration of particles.
Example 4
(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ Is prepared from
In a glove box in argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the basic gallium-based liquid metal Ga prepared in the example 1 is weighed according to the mass ratio of 97:3 68.5 In 21.5 Sn 10 Mixing with copper wire, placing in boron nitride crucible, placing the crucible in tubular furnace, heating to 1250 deg.C under the protection of argon gas, holding for 2 hr, cooling to room temperature to obtain liquid metal (Ga) containing in-situ self-lubricating Xiang Jiaji 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ 。
Example 5
[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 50wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ Is prepared from
In a glove box under argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the alloyed liquid metal (Ga) prepared in example 2 is weighed according to the mass ratio of 1:1 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ And the liquid metal containing in-situ self-lubricating Xiang Jiaji (Ga) prepared in example 4 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ Mixing and placing the materials in a conical flask, placing the conical flask in an oil bath pot at 150 ℃, stirring the materials for 2 hours by using a magnet, and cooling the materials to room temperature to obtain the gallium-based liquid metal lubricant with the advantages of antifriction and wear resistance and efficient lubrication.
Example 6
[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ ] 70wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 30wt％ Is prepared from
In a glove box under argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the alloyed liquid metal (Ga) prepared in example 2 is weighed according to a mass ratio of 7:3 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ And the liquid metal containing in-situ self-lubricating Xiang Jiaji (Ga) prepared in example 4 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ Mixing and placing the materials in a conical flask, placing the conical flask in an oil bath pot at 150 ℃, stirring the materials for 2 hours by using a magnet, and cooling the materials to room temperature to obtain the gallium-based liquid metal lubricant with the advantages of antifriction and wear resistance and efficient lubrication.
Example 7
[(Ga 68.5 In 21.5 Sn 10 ) 99wt％ Zn 1wt％ ] 50wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ Is prepared from
In an argon atmosphereIn a glove box, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the alloying liquid metal (Ga) prepared in example 1 is weighed according to the mass ratio of 1:1 68.5 In 21.5 Sn 10 ) 99wt％ Zn 1wt％ And the liquid metal containing in-situ self-lubricating Xiang Jiaji (Ga) prepared in example 4 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ Mixing and placing the materials in a conical flask, placing the conical flask in an oil bath pot at 150 ℃, stirring the materials for 2 hours by using a magnet, and cooling the materials to room temperature to obtain the gallium-based liquid metal lubricant with the advantages of antifriction and wear resistance and efficient lubrication.
Example 8
(Ga 68.5 In 21.5 Sn 10 ) 95wt％ Zn 5wt％ Is prepared from
In a glove box in argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the basic gallium-based liquid metal Ga prepared in the example 1 is weighed according to the mass ratio of 95:5 68.5 In 21.5 Sn 10 Mixing with zinc wire, placing into boron nitride crucible, placing the crucible into tubular furnace, heating to 550deg.C under argon protection, maintaining for 2 hr, cooling to room temperature to obtain alloyed gallium-based liquid metal (Ga) 68.5 In 21.5 Sn 10 ) 95wt％ Zn 5wt％ 。
Example 9
[(Ga 68.5 In 21.5 Sn 10 ) 95wt％ Zn 5wt％ ] 50wt％ -[(Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ ] 50wt％ Is prepared from
In a glove box under argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the alloyed liquid metal (Ga) prepared in example 8 is weighed according to the mass ratio of 1:1 68.5 In 21.5 Sn 10 ) 95wt％ Zn 5wt％ And the liquid metal containing in-situ self-lubricating Xiang Jiaji (Ga) prepared in example 4 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ Mixing and placing in a conical flask, and placing the conical flask in an oil bath at 150deg.CStirring for 2 hours by using a magnet in a pot, and cooling to room temperature to obtain the gallium-based liquid metal lubricant with the advantages of antifriction and high-efficiency lubrication.
Comparative example 1
Basic gallium-based liquid metal Ga prepared by the method of example 1 step 1) 68.5 In 21.5 Sn 10 。
Comparative example 2
(Ga 68.5 In 21.5 Sn 10 ) 99wt％ Ti 1wt％ Is prepared from
In a glove box in argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the basic gallium-based liquid metal Ga prepared in the comparative example 1 is weighed according to the mass ratio of 99:1 68.5 In 21.5 Sn 10 Mixing with titanium powder, placing in a boron nitride crucible, placing the crucible in a tube furnace, heating to 1700 deg.C under the protection of argon gas, maintaining for 2 hr, cooling to room temperature to obtain gallium-based liquid metal lubricant (Ga) 68.5 In 21.5 Sn 10 ) 99wt％ Ti 1wt％ 。
Comparative example 3
(Ga 68.5 In 21.5 Sn 10 ) 99wt％ Sc 1wt％ Is prepared from
In a glove box in argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the basic gallium-based liquid metal Ga prepared in the comparative example 1 is weighed according to the mass ratio of 99:1 68.5 In 21.5 Sn 10 And scandium wire, mixing and placing the mixture in a boron nitride crucible, then placing the crucible in a tube furnace, heating to 1700 ℃ under the protection of argon, preserving heat for 2 hours, and cooling to room temperature to obtain a gallium-based liquid metal lubricant (Ga) 68.5 In 21.5 Sn 10 ) 99wt％ Sc 1wt％ 。
Comparative example 4
(Ga 68.5 In 21.5 Sn 10 ) 99wt％ Mg 1wt％ Is prepared from
In a glove box in an argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and comparative example 1 is weighed according to the mass ratio of 99:1Prepared basic gallium-based liquid metal Ga 68.5 In 21.5 Sn 10 And magnesium wire, mixing and placing the mixture into a boron nitride crucible, then placing the crucible into a tube furnace, heating to 800 ℃ under the protection of argon, preserving heat for 2 hours, and cooling to room temperature to obtain a gallium-based liquid metal lubricant (Ga) 68.5 In 21.5 Sn 10 ) 99wt％ Mg 1wt％ 。
Comparative example 5
(Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ Is prepared from
In a glove box in argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the basic gallium-based liquid metal Ga prepared in the comparative example 1 is weighed according to the mass ratio of 99:1 68.5 In 21.5 Sn 10 And bismuth particles, mixing and placing the bismuth particles in a boron nitride crucible, then placing the crucible in a tube furnace, heating to 350 ℃ under the protection of argon, preserving heat for 2 hours, and cooling to room temperature to obtain a gallium-based liquid metal lubricant (Ga) 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ 。
FIG. 2 (c) shows the composition of (Ga) prepared in comparative example 5 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ Surface morphology and elemental composition that formed plaque under the same rub test conditions. As can be seen from FIG. 2 (c), compared to Ga 68.5 In 21.5 Sn 10 The lubricated, pitted surface gallium content (12.65 wt.%) was determined by the method of (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ The gallium adsorbed on the surface of the lubricated abrasive spots is obviously reduced, and the gallium content is 8.65 weight percent. In addition, the gallium-rich film formed on the surface of the abrasive spots is incomplete, and part of the steel matrix is exposed. The doping of the bismuth element obviously reduces the adsorption of the gallium element on the friction interface, the gallium-rich film is relatively smooth and flat, and the gap between the friction interfaces is smaller, so that less gallium-based liquid metal can be filled in the gap, namely, the thickness of the fluid lubrication film is reduced, the action of the fluid dynamic pressure effect is weakened, and the lubrication performance is reduced.
Comparative example 6
[ (Ga) prepared in example 4 of Chinese patent CN114621802A 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ Alloying liquid metal]-[Ga 65 In 22 Sn 13 Oxide compound] 2wt％ 。
1) In a glove box under argon atmosphere, the oxygen content was 10ppm or less, the water content was 10ppm or less, and the composition was prepared according to (Ga 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ Weighing gallium blocks, indium wires, tin wires and bismuth powder according to the proportion; placing the weighed raw materials into a conical flask, then placing the conical flask into an oil bath pot at 200 ℃, stirring the mixture for 1h by using a magnet, and cooling to obtain an alloyed gallium-based liquid metal;
2) Weighing gallium blocks, indium wires and tin wires according to the mass percentage of 65:22:13, placing the gallium blocks, the indium wires and the tin wires in a conical flask, stirring the mixture for 1h in an oil bath pot at 180 ℃, and cooling the mixture to obtain basic gallium-based liquid metal Ga 65 In 22 Sn 13 Placing basic gallium-based liquid metal in a beaker, placing the beaker in a muffle furnace, and preserving the temperature of the atmosphere at 300 ℃ for 2 hours to realize preliminary oxidation; then placing the beaker into an oil bath pot at 200 ℃, stirring the magnet for 1h in the atmospheric environment, fully oxidizing, and cooling to obtain liquid metal oxide;
3) According to (alloying liquid metal) 98wt％ - (liquid metal oxide) 2w％ Weighing alloyed liquid metal and liquid metal oxide according to the proportion, placing the alloyed liquid metal and the liquid metal oxide in a conical flask, stirring the conical flask for 1.2 hours by a magnet, then placing the conical flask in an ultrasonic cleaner, and performing ultrasonic dispersion for 0.8 hour to obtain the gallium-based liquid metal high-temperature lubricant [ (Ga) 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ Alloying liquid metal]-[Ga 65 In 22 Sn 13 Oxide compound] 2wt％ 。
The existing method is to stir gallium-based liquid metal in air, so that the original gallium-based liquid metal reacts with the air to generate gallium oxide, the viscosity of the gallium-based liquid metal is increased, the wettability between the liquid metal and a friction pair is improved, but the fluidity and lubricity of the gallium-based liquid metal are damaged by the action of oxidization, and the gallium-based liquid metal is cooled by doping copper elementsIn the process of (2), since Cu has low solubility in Ga, according to Ga-Cu phase diagram, micron-sized GuGa is precipitated in liquid metal 2 Granule, guGa 2 The particles themselves are a lubricating phase, as compared to other means of incorporation of GuGa 2 Particles or other lubricating phases, the preparation method provided by the invention can generate GuGa in situ 2 Lubricating phase, guGa 2 The lubricating phase is not agglomerated and uniformly dispersed, and the lubricating and wear-resisting properties are better.
Comparative example 7
Chinese patent CN114634835A [ (Ga) prepared in example 1 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ Alloying liquid metal] 98.5wt％ -Ag 1.5wt％ 。
1) In a glove box in an argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and the gallium block, the indium wire and the tin wire are weighed according to the mass ratio of 65:22:13; placing the weighed raw materials into a conical flask, then placing the conical flask into an oil bath pot at 200 ℃, stirring with a magnet for 1h, and cooling to obtain basic gallium-based liquid metal Ga 65 In 22 Sn 13 ；
2) In a glove box in an argon atmosphere, the oxygen content is less than or equal to 10ppm, the water content is less than or equal to 10ppm, and Ga is weighed according to the mass ratio of 98:2 65 In 22 Sn 13 Liquid metal and bismuth powder; placing the weighed raw materials into a conical flask, placing the conical flask into an oil bath at 210 ℃, stirring with a magnet for 0.8h, and cooling to obtain alloyed gallium-based liquid metal (Ga) 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ ；
3) In air, according to (alloyed gallium-based liquid metal) 98.5wt％ -Ag 1.5wt％ Weighing the gallium-based liquid metal alloy and silver powder, grinding for 1h in an air environment in a mortar, and then performing ultrasonic dispersion for 0.5h to obtain the gallium-based liquid metal lubricant with high conductivity and strong lubrication.
FIG. 1 shows [ (Ga) 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ Alloying liquid metal] 98.5wt％ -Ag 1.5wt％ In addition to the Ag lubricating phaseSEM and EDS images. As can be seen from FIG. 1, agglomeration occurs between the added Ag lubricating phase particles, which is unfavorable for fully playing the lubricating role of the lubricating phase.
Test example 1
The gallium-based liquid metal prepared in the examples and the comparative examples were tested for lubricating properties as follows:
friction test conditions: all friction tests were performed on an MCR302e rheometer equipped with ball/three plate tribological test attachments, which were rubbed by pressing an upper rotating ball (12.7 mm diameter) into the lower three fixed plates (15 x 6 x 3mm in size). The contact is in the form of a point contact, with a circular pit of the abrasive spot on each disc. AISI 440C steel was chosen as the material for the balls and disks because it is a commonly used wear resistant martensitic stainless steel. The friction tests were carried out under a load of 5N (Hertz contact stress of 0.66 GPa) and a sliding speed of 0.5m/s, the sliding distance was 300m, and the test temperature was 40 ℃.
Coefficient of friction: in order to ensure the reliability of the experimental results, each group of experiments is repeated three times under the same condition, after each friction coefficient curve is stable, the average value of the friction coefficient of a single experiment is taken, and then the average value of the three experiments is calculated.
Wear rate: and (5) placing the abrasive spots under a white light interference three-dimensional profiler to measure the abrasion volume, and calculating the abrasion rate. To ensure the reliability of the experimental results, each group of experiments was repeated three times under the same conditions, and the wear rate data of the three experiments were averaged.
The test results are shown in Table 1.
Table 1 results of lubricating property test of gallium-based liquid metal lubricants prepared in examples and comparative examples
As can be seen from Table 1, at the same frictionUnder test conditions, with Ga prepared in comparative example 1 68.5 In 21.5 Sn 10 The friction coefficient of the lubricated friction pairs was reduced to a different extent from that of the gallium-based liquid metal lubricated friction pairs prepared in examples 1 to 9. Wherein [ (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 friction pair had the lowest coefficient of friction, which was reduced by 26.5% for example 5 compared to the friction pair of comparative example 1.
Under the same friction test conditions, the Ga prepared in comparative example 1 68.5 In 21.5 Sn 10 The wear rate of the lubrication was reduced to a different extent from that of the gallium-based liquid metal lubrication prepared in examples 1 to 9. Wherein [ (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 wear rate of lubrication was the lowest, and the wear rate of example 5 was reduced by 69.4% compared to that of comparative example 1.
As found by comparative examples 3 to 4 and comparative examples 1 to 4, ga prepared in comparative example 1 68.5 In 21.5 Sn 10 Compared with the prior art, the lubricating performance of gallium-based liquid metal is reduced by doping Ti, sc and Mg, and the lubricating performance is extremely unfavorable by doping Mg element. However, the gallium-based liquid metals prepared in examples 3 and 4 generated micron CuGa in situ 2 The self-lubricating phase can effectively reduce the friction coefficient and the wear rate of the friction pair. Under the same friction test conditions, the composition prepared in example 4 (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ Has good lubricating properties, and is comparable to Ga prepared in comparative example 1 68.5 In 21.5 Sn 10 The friction coefficient and wear rate of the lubricated friction pair were reduced by 3.8% and 49.1%, respectively.
From the experimental results of comparative example 2, comparative example 1 and comparative example 5 and fig. 2, it can be seen that (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ The gallium content of the lubricated and spotted surface is higher than that of Ga 68.5 In 21.5 Sn 10 The lubricated, plaque surface gallium content is determined by (Ga 68.5 In 21.5 Sn 10 ) 99wt％ Bi 1wt％ The gallium content of the lubricated and ground surface is lower than that of Ga 68.5 In 21.5 Sn 10 The lubricated mill-spotted surface gallium content. The doping of Zn promotes the adsorption of gallium, improves the lubricating performance of gallium-based liquid metal, and the doping of Bi can inhibit the adsorption of gallium, and reduces the lubricating performance of gallium-based liquid metal.
As is clear from comparative examples 3, 4, 1 and 6, comparative example 6 improves wettability of liquid metal by oxidation, but also increases its viscosity and causes an increase in wear rate. The wear rate of comparative example 6 was increased by 126.1% compared to that of comparative example 1.
The invention improves the lubricating performance of gallium-based liquid metal through Zn alloying, and simultaneously generates micron CuGa which is uniformly dispersed in situ in the gallium-based liquid metal 2 Lubricating phase, optimizing the base gallium-based liquid metal to (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Zn 3wt％ After that, it is combined with (Ga 68.5 In 21.5 Sn 10 ) 97wt％ Cu 3wt％ Mixing according to a mass ratio of 1:1 to obtain the composite gallium-based liquid metal in the embodiment 5. FIG. 5 compares Ga prepared from comparative example 1 68.5 In 21.5 Sn 10 And [ (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％ Friction coefficient and wear rate of friction pair under the same friction test conditions. As can be seen from FIG. 5, the gallium-based liquid metal lubricant prepared in example 5 exhibited lubricating properties in terms of friction coefficient and wear rateCompared with comparative example 1, the reduction is greatly reduced by 26.5% and 69.4%, respectively. [ (Ga) prepared in comparison with comparative example 7 65 In 22 Sn 13 ) 98wt％ Bi 2wt％ Alloying liquid metal] 98.5wt％ -Ag 1.5wt％ Compared with example 5, the abrasion rate is reduced by 70.3%, so the in-situ self-generated and uniformly dispersed CuGa 2 The particles can play a good role in wear resistance and have a positive effect on reducing the wear rate of friction pairs. The doped transition metal gallium-based liquid metal lubricant prepared by the invention has excellent lubricating performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An alloyed gallium-based liquid metal with a chemical composition of (Ga-In-Sn base gallium-based liquid metal) (100-x)wt％ Zn xwt％ ，5≥x≥1。
2. The alloyed gallium-based liquid metal according to claim 1, wherein the chemical composition of the Ga-In-Sn-based gallium-based liquid metal In mass percent is Ga 68.5 In 21.5 Sn 10 。
3. A method of preparing an alloyed gallium-based liquid metal according to claim 1 or 2, comprising the steps of:
and mixing the Ga-In-Sn basic gallium-based liquid metal and Zn according to chemical composition In a protective atmosphere, and then carrying out first smelting to obtain the alloyed gallium-based liquid metal.
4. An In-situ self-lubricating Xiang Jiaji-containing liquid metal with the chemical composition of (Ga-In-Sn basic gallium-based liquid metal) (100-y)wt％ Cu ywt％ ，3≥y≥1。
5. The In-situ self-lubricating Xiang Jiaji liquid metal containing according to claim 4, wherein the Ga-In-Sn based gallium-based liquid metal has a chemical composition of Ga In mass percent 68.5 In 21.5 Sn 10 。
6. A method of preparing a liquid metal containing in-situ self-lubricating Xiang Jiaji as claimed in claim 4 or 5, comprising the steps of:
and mixing the Ga-In-Sn basic gallium-based liquid metal and Cu according to chemical composition under a protective atmosphere, and then smelting for the second time to obtain the In-situ self-lubricating Xiang Jiaji-containing liquid metal.
7. A composite gallium-based liquid metal comprises the following chemical components (alloyed gallium-based liquid metal) (100-z)wt％ - (containing in situ self-lubricating Xiang Jiaji liquid metal) zwt％ Z is more than or equal to 100 and is more than 0; the alloyed gallium-based liquid metal is the alloyed gallium-based liquid metal according to any one of claims 1 to 2 or the alloyed gallium-based liquid metal produced by the production method according to claim 3; the in-situ self-lubricating Xiang Jiaji-containing liquid metal is the in-situ self-lubricating Xiang Jiaji-containing liquid metal according to any one of claims 4 to 5 or the in-situ self-lubricating Xiang Jiaji-containing liquid metal prepared by the preparation method according to claim 6.
8. The method for preparing the composite gallium-based liquid metal according to claim 7, comprising the steps of:
and mixing the alloyed gallium-based liquid metal and the in-situ self-generated lubrication Xiang Jiaji-containing liquid metal according to chemical compositions in a protective atmosphere to obtain the composite gallium-based liquid metal.
9. The method according to claim 8, wherein the temperature of the mixing is 100 to 300 ℃ for 1 to 3 hours.
10. Use of an alloyed gallium-based liquid metal according to any one of claims 1-2 or a gallium-based liquid metal obtainable by a method according to any one of claims 3, an in-situ self-lubricating Xiang Jiaji-containing liquid metal obtainable by a method according to any one of claims 4-5 or an in-situ self-lubricating Xiang Jiaji-containing liquid metal obtainable by a method according to claim 6, a composite gallium-based liquid metal according to claim 7 or a composite gallium-based liquid metal obtainable by a method according to any one of claims 8-9 for lubrication and wear resistance.
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