CN116640615A - High-temperature hydraulic transmission medium at base end of molten metal as well as preparation method and application thereof - Google Patents
High-temperature hydraulic transmission medium at base end of molten metal as well as preparation method and application thereof Download PDFInfo
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- CN116640615A CN116640615A CN202310372986.4A CN202310372986A CN116640615A CN 116640615 A CN116640615 A CN 116640615A CN 202310372986 A CN202310372986 A CN 202310372986A CN 116640615 A CN116640615 A CN 116640615A
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- hydraulic transmission
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- transmission medium
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- 230000005540 biological transmission Effects 0.000 title claims abstract description 181
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 178
- 239000002184 metal Substances 0.000 title claims abstract description 178
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006263 metalation reaction Methods 0.000 title description 2
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- 238000000034 method Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
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- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001338 liquidmetal Inorganic materials 0.000 abstract description 38
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- 230000007774 longterm Effects 0.000 abstract description 5
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- 238000001291 vacuum drying Methods 0.000 description 6
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- 230000008595 infiltration Effects 0.000 description 4
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- 239000006249 magnetic particle Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 238000012986 modification Methods 0.000 description 4
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- 150000002739 metals Chemical class 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
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- 238000009834 vaporization Methods 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- -1 Al and Mg with Ga Chemical class 0.000 description 1
- 241000499895 Bloomeria Species 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F15—FLUID-PRESSURE ACTUATORS; HYDRAULICS OR PNEUMATICS IN GENERAL
- F15B—SYSTEMS ACTING BY MEANS OF FLUIDS IN GENERAL; FLUID-PRESSURE ACTUATORS, e.g. SERVOMOTORS; DETAILS OF FLUID-PRESSURE SYSTEMS, NOT OTHERWISE PROVIDED FOR
- F15B21/00—Common features of fluid actuator systems; Fluid-pressure actuator systems or details thereof, not covered by any other group of this subclass
- F15B21/06—Use of special fluids, e.g. liquid metal; Special adaptations of fluid-pressure systems, or control of elements therefor, to the use of such fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/05—Metals; Alloys
- C10M2201/053—Metals; Alloys used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/105—Silica
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/36—Seal compatibility, e.g. with rubber
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention discloses a high-temperature hydraulic transmission medium at a metal liquid base end and a preparation method and application thereof, and belongs to the technical field of fluid transmission. The high-temperature hydraulic transmission medium at the base end of the metal liquid comprises the metal liquid base and binary mixed nano particles, wherein the binary mixed nano particles comprise nano ceramic particles and the low-dimensional nano additive, and the nano ceramic particles are embedded between sheets of the low-dimensional nano additive; the binary mixed nano particles are uniformly dispersed in the metal liquid base liquid. The metal liquid base end high-temperature hydraulic transmission medium has the MHD function characteristic of conductive fluid, can meet the hydraulic transmission use requirement below 1300 ℃, especially the hydraulic transmission long-term use requirement at the extreme temperature above 400 ℃, has good wide-temperature-range lubricity and the capability of repairing abrasion, and breaks through the technical bottleneck of the existing high-temperature hydraulic transmission medium and the application limitation of liquid metal in the field of hydraulic transmission media.
Description
Technical Field
The invention belongs to the technical field of fluid transmission, and particularly relates to a high-temperature hydraulic transmission medium at a base end of molten metal as well as a preparation method and application thereof.
Background
The hydraulic transmission has the unique advantages of high power density, high power-weight ratio, easy realization of overload protection and the like, and is widely applied to various mechanical equipment. The hydraulic transmission medium plays roles of energy transmission, lubrication, cooling and the like in the hydraulic system, and is arterial blood of the hydraulic system. With the development of aviation, aerospace, naval vessels and military equipment technologies, resources such as deep land, deep sea, outer space and the like are developed and utilized, and a hydraulic transmission system is faced with more extreme high-temperature service environments, such as: the service environment temperature of the long-term rocket hydraulic servo system reaches 250 ℃, the deep sea hot spring temperature reaches more than 300 ℃, the steam temperature of the high-power plant steam turbine set exceeds 400 ℃, the average temperature of the golden star ground surface reaches 475 ℃, and the like. This places higher demands on the high temperature performance of the hydraulic medium, components and system. As the operating temperature increases, the physical parameters of the medium change, which causes the pressure and velocity profiles in the circuit to change, ultimately manifesting itself as a change in the control characteristics of the hydraulic system: (1) The viscosity of the medium is reduced, the lubricity and the tightness of the element matching interface are reduced, the abrasion and the leakage are increased, the volumetric efficiency is reduced, and the working efficiency and the control precision of the element are deteriorated; (2) The volume modulus of the medium is reduced, the compressibility is increased, and the control error is increased; (3) The saturated vapor pressure of the medium is increased, the critical condition of cavitation is reduced, and cavitation generated by cavitation leads to instability of medium power transmission, induces self-excited vibration of a valve core, a nozzle baffle plate and the like, and causes cavitation, thereby influencing the control characteristics of elements and systems and prolonging the service life.
The most widely used hydraulic transmission medium at present uses mineral oil as base liquid, and the mineral oil has inherent defects of evaporation, aging, decomposition, flammability and the like under the high temperature condition, so that the high temperature application of the mineral oil is limited. The fire-resistant hydraulic medium mostly uses water as base liquid, but the water-based hydraulic transmission medium has the problems of scaling, evaporation, boiling and the like at high temperature. In order to improve the high-temperature working performance of the medium, people sequentially develop a high-temperature flame-retardant hydraulic transmission medium which uses phosphate, silicone oil, synthetic hydrocarbon, perfluoropolyether and the like as base liquid, the maximum long-term working temperature of the current perfluoropolyether-based hydraulic transmission medium with the best high-temperature performance is 371 ℃, and the hydraulic transmission medium with the long-term working temperature exceeding 400 ℃ is rarely reported. Under the extreme high-temperature environment condition of more than 400 ℃ and the temperature impact of a high-temperature wide-temperature area, the medium has the problems of flammability, decomposition, aging, carbonization, toxicity and the like, and cannot meet the basic performance requirements of extreme high-temperature hydraulic transmission.
The metal liquid base liquid is prepared from low-melting-point metals such as gallium, bismuth, indium, tin, zinc, aluminum and the like through alloying, has metallic and room-temperature fluidity, has good fluidity, low saturated steam pressure, small temperature-viscosity change, small pressure-viscosity change, low thermal expansion rate, good shear stability, good heat conduction performance, good electric conduction performance, environmental protection and no toxicity, has excellent high-temperature heat stability, and is ideal extremely high-temperature hydraulic medium base liquid. However, the density of the pure liquid metal is generally in the range of 5.9 to 9.0g/cm 3 The dynamic viscosity is 2-5 mpa.s, and the dynamic viscosity is less than 1mm 2 And/s. Traditional mineral oilThe density of the base hydraulic transmission medium is only 0.875g/cm 3 About, the density of the water-based hydraulic medium is 0.9g/cm 3 About, in order to ensure the tightness and the lubricity, the kinematic viscosity of the hydraulic medium is not lower than 7mm 2 In general, should be greater than 25mm 2 And/s. The pure liquid metal has too high density, too low viscosity and unstable flow, and is not suitable for the hydraulic transmission environment.
In order to improve the application performance of liquid metal in hydraulic transmission media, the prior art has been studied to modify the liquid metal, specifically as follows.
For example, patent "high temperature hydraulic system using low melting point alloy as hydraulic medium", publication No. CN1033292C proposes to use low melting point alloy with melting point of 80 ℃ and boiling point of 700-760 ℃ as hydraulic transmission medium. However, when the melting point is too high and the transmission environment is lower than 80 ℃, hydraulic transmission cannot be realized, and the operation below 80 ℃ can be realized only by adding a heating device, so that the problems of high energy consumption and the like exist; and the metal in the liquid phase state is directly used as a hydraulic transmission medium, and as described above, the pure liquid gold has high density and low viscosity, is easy to generate turbulence, reduces the control performance of the system, has poor lubricity and is easy to cause element abrasion.
Liquid metal belongs to the category of atomic fluid, and is basically different from water, oil and other fluids, so that the performance of the conventional hydraulic medium additive cannot be regulated. With the development of nanotechnology, the incorporation of nanoparticles into a base liquid is increasingly studied in order to change the properties of the base liquid. For example, the published patent "hydraulic transmission based on liquid metal", publication number CN104343928A, proposes a hydraulic transmission designed using gallium-based or bismuth-based liquid metal as a hydraulic transmission medium, and gives a solution of doping magnetic particles having a particle size of 1 to 900 nm. The two solutions disclosed in this patent, firstly, using pure liquid metal as the hydraulic transmission medium, have the drawbacks consistent with those of CN1033292C, and are not described here again; secondly, liquid metal is used as base liquid, and magnetic particles with the particle size of 1-900 nm are doped, and the doping ensures that the final hydraulic transmission medium has magnetic performance, so that hydraulic transmission is controlled by an external magnetic field to move, but the addition of the magnetic particles cannot improve the defects of too high density, too low viscosity and the like of the liquid metal. In addition, in a hydraulic transmission medium, particles with submicron particle sizes larger than 100nm are easy to cause stagnation, seizing, strong abrasion and the like of key friction pairs such as plungers, sliding valves, hydraulic cylinder pistons and the like, and the performance and the service life of elements are seriously affected; the magnetic particles can perform alloying reaction with liquid metal, so that the magnetic performance of the medium is reduced or even eliminated; the micro-nano particles can increase electron scattering, so that the conductivity of the medium is reduced, and the functional characteristics are affected; and the magnetic material is demagnetized at high temperature, so that the magnetorheological performance of the magnetic material is weakened, and the magnetic material cannot be applied to an extremely high-temperature environment. The patent publication No. CN109022110B provides a liquid metal lubricant with non-magnetic or magnetic micro-nano powder as an additive, which adopts pasty liquid metal as a base liquid, has a grease-like base, high viscosity and insufficient fluidity, and is not suitable for being used as a hydraulic transmission medium. To achieve dispersion of solid phase particles in liquid phase metal: patent No. CN108085519B discloses a method for doping micro-nano particles into liquid metal, which comprises the steps of adding micro-nano particles and liquid metal in a mass ratio of 1:9-19 into an acidic, alkaline or conductive solution, stirring, and changing the wettability of the liquid metal through auxiliary metal and an external power supply so as to dope the micro-nano particles into the liquid metal. The externally-added power supply has the problems of high energy consumption, high preparation difficulty and the like; and the purity of the liquid metal can be influenced by introducing auxiliary metal, so that the physical properties such as melting point, viscosity, conductivity and the like of the liquid metal are changed, the wettability of the liquid metal is changed after a power supply is removed, and nano particles can be separated out under the action of surface tension.
In summary, the existing metal liquid based hydraulic transmission medium has a plurality of defects, and the development and research of a novel high-performance metal liquid based hydraulic transmission medium are significant.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to solve the technical problems that a metal liquid-based hydraulic transmission medium in the prior art is high in density, high in viscosity and poor in stability, and is limited in application in the field of hydraulic transmission media, and the technical problems that the high-temperature environment of the hydraulic transmission medium in the prior art is easy to change in control characteristics, cannot meet the requirements of high-temperature hydraulic transmission, especially the extreme high temperature of more than 400 ℃, the temperature impact resistance in a Gao Wenkuan temperature region is poor, the energy consumption is high and the preparation difficulty is high.
The nano ceramic particles have a microstructure formed by alternately stacking atoms in a layered manner, have good self-lubricating property and heat conductivity, have good compatibility with metal materials, cannot be corroded by metal base liquid, and have stable high-temperature property.
Graphene is a kind of graphene with sp 2 The material with the hybridized connection carbon atoms closely stacked into a single-layer two-dimensional honeycomb lattice structure has an ultrathin lamellar structure, is easy to enter a friction contact surface, is easy to slip between layers, has low shearing strength, has good self-lubricating performance, and has stable high-temperature property, excellent electric conduction and heat conduction performance and good compatibility with gallium-based alloy. The single-layer or few-layer graphene is used as an additive, so that the stability, lubricity, heat dissipation, conductivity and the like of the medium can be improved, and the viscosity of the medium can be regulated.
The nano ceramic particles and the low-dimensional nano additive graphene are prepared into binary mixed nano particles, so that the dispersibility and lubricity of a high-temperature hydraulic transmission medium at the base end of the metal liquid can be improved based on the synergistic effect of the binary mixed nano particles, and the problem of medium conductivity reduction caused by electronic scattering of the ceramic nano particles is solved.
The invention provides a high-temperature hydraulic transmission medium at a metal liquid base end, which comprises a metal liquid base and binary mixed nano particles, wherein the binary mixed nano particles comprise nano ceramic particles and low-dimensional nano additives, and the nano ceramic particles are embedded between sheets of the low-dimensional nano additives;
The binary mixed nano particles are uniformly dispersed in the metal liquid base liquid.
In some embodiments, the molten metal base end high temperature hydraulic transmission medium comprises the following raw materials in volume ratio: metal liquid base liquid: nano ceramic particles: low micro-nano additive= (80-95): 5-20;
the volume ratio of the nano ceramic particles to the low-dimensional nano additive is (1-2): 1.
In some embodiments, the binary mixed nano particles are coated with a nano metal oxide layer generated by the reaction of a metal liquid base solution and air, and the binary mixed nano particles coated with the nano metal oxide layer are uniformly distributed in the metal liquid base solution; the liquid metal oxide layer is a dispersing agent, and the mixed nano particles composed of nano ceramic particles/low-dimensional nano materials are a dispersing phase;
and/or the density of the high-temperature hydraulic transmission medium at the base end of the molten metal is 4-8 g/cm 3 The viscosity is 20-150 mPa.s;
and/or the thermal conductivity of the high-temperature hydraulic transmission medium at the base end of the molten metal is more than 20.9W/mK;
and/or the conductivity of the high-temperature hydraulic transmission medium at the base end of the molten metal is 2.2 x 10 6 Mu S/cm or more.
In some embodiments, the metal liquid base is preferably a lightweight liquid metal having a density of < 5g/cm 3 . The large density increases the hydraulic system energy consumption and reduces efficiency. By alloying low-density metals such as Al and Mg with Ga, in and the like, a lightweight metal liquid base liquid with lower density can be prepared. The density of the nano additive is far lower than that of the metal liquid base liquid, and the density of the high-temperature hydraulic transmission medium at the base end of the metal liquid can be reduced. Therefore, the density of the high-temperature hydraulic transmission medium at the base end of the molten metal is as low as 4g/cm 3 。
In some embodiments, the metal liquid base is a gallium alloy composed of gallium and at least one metal selected from indium, tin, zinc, aluminum, magnesium, bismuth; preferably, the melting of the metal liquid base liquidThe point is less than 30 ℃; to reduce the density of the metal liquid base liquid to reduce the energy consumption of the hydraulic system, gallium (5.9 g/cm is more preferable 3 ) With low density metallic aluminum (2.7 g/cm) 3 ) Magnesium (1.74 g/cm) 3 ) The alloy with the composition, such as Ga-Al alloy, ga-Mg alloy or Ga-Al-Mg alloy, is used as the metal liquid base liquid;
and/or the nano ceramic particles are in a spherical structure, and the particle size of the nano ceramic particles is 1-100 nm, so that the requirements of hydraulic transmission on the fluidity, the lubricity and the stability of the medium are met;
and/or the nano ceramic particles are SiO 2 、SiC、Si 3 N 4 One or more of the following;
and/or the low-dimensional nano additive is few-layer graphene with the thickness of a slice layer of 0.5-3.0 nm and the diameter of 0.1-5 mu m, and/or nano single-layer graphene with the thickness of 0.5-1.2 nm and the diameter of 100-500 nm.
In some embodiments, the hydraulic drive temperature for the molten metal base end high temperature hydraulic drive medium is 1300 ℃ or less;
preferably, the hydraulic transmission temperature suitable for the high-temperature hydraulic transmission medium at the base end of the molten metal is 30-1300 ℃;
more preferably, the hydraulic transmission temperature applicable to the high-temperature hydraulic transmission medium at the base end of the molten metal is 30-700 ℃, and/or the hydraulic transmission temperature applicable to the high-temperature hydraulic transmission medium at the base end of the molten metal is 700-1300 ℃;
further preferably, the hydraulic transmission temperature suitable for the high-temperature hydraulic transmission medium at the base end of the molten metal is 30-400 ℃, and/or the hydraulic transmission temperature suitable for the high-temperature hydraulic transmission medium at the base end of the molten metal is 400-700 ℃.
The second aspect of the invention provides a method for preparing a high-temperature hydraulic transmission medium at a base end of molten metal, which comprises the following steps:
mixing nano ceramic particles and a low-dimensional nano additive according to the proportion of (1-2), adding the nano ceramic particles and the low-dimensional nano additive into a solvent according to the volume fraction of 0.5% -5%, preferably, using deionized water as the solvent, stirring and ultrasonic treatment at the temperature of 45-60 ℃, wherein the nano ceramic particles are embedded between the sheets of the low-dimensional nano additive, so as to obtain a binary mixed nano solution with stable dispersion;
Drying the binary mixed nano solution to obtain uniform mixed nano particles;
oxidizing the surface of the metal liquid base liquid in an oxygen-containing atmosphere to obtain a nano metal oxide layer, adding the binary mixed nano particles into the metal liquid base liquid, stirring at a constant temperature of 80 ℃, and infiltrating and cladding the nano metal oxide layer and the binary mixed nano particles to obtain a solution A;
pouring dilute hydrochloric acid into the solution A, stirring at constant temperature, and performing ultrasonic treatment to uniformly disperse the infiltrated and coated binary mixed nano particles in a metal liquid base solution to obtain a solution B;
separating out and removing the non-infiltrated and coated binary mixed nano particles to obtain the high-temperature hydraulic transmission medium at the base end of the molten metal.
In some embodiments, the volume ratio of the metal liquid base solution, the nano ceramic particles and the low-dimensional nano additive is (80-95): (5-20), and the volume ratio of the nano ceramic particles to the low-dimensional nano additive is (1-2): 1;
and/or the metal liquid base liquid is gallium alloy composed of gallium and at least one metal selected from indium, tin, zinc, aluminum, magnesium and bismuth; preferably, the melting point of the metal liquid base liquid is less than 30 ℃; more preferably, the metal liquid base liquid is a Ga-Al alloy, a Ga-Mg alloy, or a Ga-Al-Mg alloy.
In some embodiments, the binary mixed nanoparticle precipitation method without infiltration, coating, comprises:
removing hydrochloric acid in the solution B, adding an aqueous solution of acetic acid, standing at 40-60 ℃, and separating out binary mixed nano particles which are not fully coated to obtain a solution C;
and repeatedly flushing the solution C by using an acetic acid aqueous solution until all the binary mixed nano particles are removed, so as to obtain a solution D.
In some embodiments, the binary mixed nanoparticle precipitation method without infiltration, coating further comprises:
carrying out solid-liquid phase change treatment on the solution D for a plurality of times at the temperature of between 10 and 60 ℃, and separating out underwrapped binary mixed nano particles under the action of internal thrust of volume change of a phase change interface to obtain a solution E;
and repeatedly washing the solution E by using an acetic acid aqueous solution until the precipitated nano particles are completely removed, and obtaining the high-temperature hydraulic transmission medium at the base end of the metal liquid.
The third aspect of the invention provides the high-temperature hydraulic transmission medium for the molten metal base end and application of the high-temperature hydraulic transmission medium for the molten metal base end prepared by the preparation method in hydraulic transmission, energy storage batteries and electromagnetic flowmeters.
The invention principle of the invention is as follows:
the invention provides a performance regulation principle of a metal liquid-based high-temperature hydraulic transmission medium
The low-dimensional nano additive graphene has high electrical conductivity and good thermal conductivity, can improve the heat dissipation of a medium, and weakens the influence of nano ceramic particle electron scattering on the electromagnetic functional characteristics of the medium. The nano ceramic particles have excellent temperature resistance, corrosion resistance, thermal shock resistance, conductivity and excellent chemical inertness, and the gallium-based alloy is arranged on SiO 2 、SiC、Si 3 N 4 The wettability of the nano ceramic particles is superior to that of carbon, and the nano ceramic particles can easily infiltrate into graphene aggregates in the dispersing process to damage the formation of graphene clusters, so that the dispersion stability of the medium is improved. The presence of binary mixed nanoparticles formed by embedding the nano-ceramic particles into the low-dimensional nano-additives increases the flow resistance of the medium, thereby increasing the viscosity of the medium in appearance. Regulating and controlling the medium viscosity by controlling the addition amount of the binary mixed nano particles, wherein the larger the addition amount is, the larger the medium viscosity is and the smaller the density is; the smaller the addition amount, the smaller the viscosity of the medium and the greater the density. Therefore, the viscosity and density of the medium can be regulated and controlled by adding the nano ceramic particles and the low-dimensional nano additive, the problem that turbulence is easy to occur due to the higher density and smaller viscosity of the metal base solution is solved, The flow is made to tend to a stable laminar flow state, improving the system control characteristics.
(II) high-temperature resistant Wen Yuanli of the Metal liquid-based high-temperature hydraulic transmission Medium
The liquid metal base liquid adopts gallium base alloy, the boiling point is 1300-2400 ℃, the evaporation loss is almost avoided at the high temperature, the thermal expansion rate is low, and the temperature-viscosity characteristic is excellent; the low-dimensional nano additive graphene has excellent high-temperature stability, a melting point of up to 3852 ℃, and good compatibility with gallium-based alloy; nano ceramic particles, siO is adopted 2 、SiC、Si 3 N 4 The nano ceramic material has stable high temperature property, melting point higher than 1600 ℃ and good compatibility with gallium-based alloy. Therefore, the metal liquid-based high-temperature hydraulic transmission medium can meet the hydraulic transmission use requirement of a wide temperature range below 1300 ℃, and especially meet the hydraulic transmission requirement of an extremely high temperature above 400 ℃.
(III) the preparation dispersion principle of the high-temperature hydraulic transmission medium for the metal liquid base electrode provided by the invention:
because of intermolecular forces between the nano ceramic particles and the particles and van der Waals forces between the low-dimensional nano additive sheets, the single dispersed nano ceramic particles and the low-dimensional nano additive are easy to agglomerate and settle. According to the invention, the nano ceramic particles and the low-dimensional nano additives are embedded between the sheets of the low-dimensional nano additives (as shown in figure 4) through mechanical stirring, ultrasonic and other means, so that binary mixed nano particles are obtained, the stripping state and interlayer distance of the low-dimensional nano additives are changed, the interlayer Van der Waals force of the low-dimensional nano additives is weakened, the low-dimensional nano additives separate nano ceramic particle aggregates, the intermolecular acting force among the nano ceramic particle aggregates is weakened to a certain extent, the aggregation can be hindered, and the dispersion stability is improved. Because the surface tension of the liquid metal is large and the wettability is poor, binary mixed nano particles are difficult to enter the liquid metal, the mixed nano particles are wetted and coated by utilizing a nano metal oxide layer generated by the reaction of the metal liquid base solution and air, the coated binary mixed nano particles enter the liquid metal under the mechanical stirring and ultrasonic action, after the binary mixed nano particles are added, dilute hydrochloric acid is poured to prevent the metal liquid base solution from being further oxidized by air, and the nano particles coated by the oxide layer are uniformly dispersed in the liquid metal liquid base solution under the combined action of long-time ultrasonic wave and mechanical stirring. And then removing the nano particles which are not fully coated by the nano metal oxide layer from the liquid metal liquid base liquid through two-step treatment: firstly, standing to separate out uncoated mixed nano particles; then, the solution temperature is changed, and the insufficiently coated nano particles are separated out under the action of internal thrust of the volume change of a phase change interface through solid-liquid phase change treatment. Thus, the high-temperature hydraulic transmission medium with uniform dispersion and good stability at the base end of the metal liquid is prepared, and the dispersion state of the mixed nano particles in the metal liquid base is shown in figure 5.
Compared with the prior art, the invention has the following technical effects:
(1) According to the invention, the nano ceramic particles are embedded into the low-dimensional nano additive, and the existence of the formed binary mixed nano particles can increase the flow resistance of the medium, so that the viscosity of the medium is increased in appearance. Regulating and controlling the medium viscosity by controlling the addition amount of the binary mixed nano particles, wherein the larger the addition amount is, the larger the medium viscosity is and the smaller the density is; the smaller the addition amount, the smaller the viscosity of the medium and the greater the density. Therefore, the binary mixed nano particles formed by adding the nano ceramic particles and the low-dimensional nano additives can regulate and control the viscosity and density of the hydraulic transmission medium, improve the technical problem that turbulence is easy to occur due to the fact that the density of the metal base liquid is large and the viscosity is small, enable the flow of the hydraulic transmission medium to trend to a stable laminar state, improve the control characteristic of a system and provide conditions for the application of liquid metal in the extremely high-temperature hydraulic transmission medium.
(2) According to the invention, the gallium-based alloy is used as a base liquid of a medium, the boiling point is 1300-2400 ℃, the evaporation loss is almost avoided at the high temperature, the thermal expansion rate is low, the deformation of pipelines and elements caused by positive pressure due to the thermal expansion of the medium can be weakened, the application of a closed system is facilitated, the influence of temperature and pressure on viscosity is small, the compressibility is far lower than that of water and oil, and the control precision of a high-pressure system can be improved; low-dimensional nano additive stone The graphene has excellent high-temperature stability, the melting point is up to 3852 ℃, and the compatibility with gallium-based alloy is good; nano ceramic particles, siO is adopted 2 、SiC、Si 3 N 4 The nano ceramic material has stable high-temperature property, the melting point is more than 1600 ℃, and the compatibility with gallium-based alloy is good, so that the nano ceramic material can meet the use requirement of hydraulic transmission below 1300 ℃, especially the long-term use requirement of hydraulic transmission at the extreme temperature of more than 400 ℃, has good wide-temperature-range lubricity and the capability of repairing abrasion, and breaks through the technical bottleneck of the existing high-temperature hydraulic transmission medium.
(3) The high-temperature hydraulic transmission medium at the base end of the molten metal provided by the invention has good wear resistance and antifriction characteristics. The low-dimensional nano additive graphene has an ultrathin lamellar structure, is easy to enter a friction contact surface, is easy to slide between layers, has low shearing strength and has good self-lubricating performance; the adopted spherical nano ceramic particles have a micro rolling bearing effect on the surface of the friction pair and also have good self-lubricating performance. The unique lubricating advantages of the low-dimensional nano additive and the nano ceramic particles are utilized to exert the synergistic lubricating effect. In the friction process, (1) the nano ceramic particles roll and squeeze the low-dimensional nano additive graphene, and the graphene slides between layers, so that the friction resistance is further reduced; (2) the nano ceramic particles share partial load, so that the bearing capacity of the low-dimensional nano additive graphene is improved; (3) the deposition of the nano ceramic particles on the low-dimensional nano additive graphene reduces interlayer van der Waals force and enhances shearing resistance; (4) the nano ceramic particles and the low-dimensional nano additive graphene enter the abrasion surface and form a composite protective film, so that abrasion is repaired.
(4) The high-temperature hydraulic transmission medium at the base end of the molten metal can effectively improve the control characteristic of the valve core of the hydraulic valve. Compared with the existing hydraulic transmission medium, the high-temperature hydraulic transmission medium at the base end of the metal liquid has lower flow velocity in the valve cavity of the spool valve of the servo valve (as shown in figure 6), can improve the control stability of the servo valve, reduce the impact of fluid on a throttling orifice and prolong the service life of the spool; compared with the existing hydraulic transmission medium, the high-temperature hydraulic transmission medium at the base end of the metal liquid has extremely low vaporization pressure, can avoid cavitation, prevent cavitation of the medium on the valve core, and prolong the service life of the valve core; compared with the existing hydraulic transmission medium, the high-temperature hydraulic transmission medium at the base end of the molten metal can reduce the influence of turbulence intensity on the vibration of the valve core and reduce energy loss under the same pressure condition.
(5) Because the metal liquid base liquid has good conductivity, the low-dimensional nano additive can effectively weaken conductivity loss caused by nano ceramic particle electron scattering, therefore, the invention can recover throttle energy loss of a damping runner, a hydraulic cylinder buffer device and the like based on the MHD (magnetohydrodynamic effect) power generation principle, reduce system heating, can be used together with the traditional energy recovery modes of an energy accumulator and the like, and is energy-saving and efficient. The high-temperature hydraulic transmission medium at the base end of the molten metal passes through a magnetic field perpendicular to the flowing direction at a certain speed to cut magnetic force lines so as to generate electromotive force, thereby generating electric energy and storing the electric energy in a battery. The energy recovery mode has no relative movement and parts rotation, directly converts heat energy into electric energy, can reduce heat generation of the system, and has high energy conversion efficiency.
(6) The high-temperature hydraulic transmission medium at the base end of the molten metal can be driven by an electromagnetic pump, and when the high-temperature hydraulic transmission medium makes a magnetic force line cutting motion in a magnetic field, induced potential can be generated, the volume flow is in linear relation with the induced electromotive force and the section size of a measuring tube, and is inversely proportional to the magnetic induction intensity of the magnetic field. When the magnetic field is constant and the section of the pipeline is unchanged, the volume flow value at the moment can be represented by testing the magnitude of the induced electromotive force. The method has the characteristics of small pressure loss, large measurable flow range, high measurement precision and sensitivity and the like, and is beneficial to the development of an ultra-high precision hydraulic system.
(7) The high-temperature hydraulic transmission medium at the base end of the molten metal has good tightness, stable transmission and good silence. When the system leaks, the high-temperature hydraulic transmission medium at the base end of the metal liquid contacts with air, so that a high-viscosity oxide film can be formed at a sealing interface, the leakage is restrained, and the sealing performance of the element is improved.
(8) The high-temperature hydraulic transmission medium raw materials at the base end of the metal liquid have flame resistance, are suitable for various complex environments, and can improve the battlefield viability of military hydraulic equipment; the high-temperature hydraulic transmission medium at the base end of the molten metal has good adaptability to low temperature, and can work at a temperature lower than room temperature by arranging heating equipment.
(9) The preparation method adopted by the invention is simple and efficient, has the advantages of easily available raw materials, low cost, safety, no toxicity, environmental protection and easy realization of expanded production.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a high-temperature hydraulic transmission medium at a base end of a molten metal in the invention;
FIG. 2 is a photograph of the materials of the high temperature hydraulic transmission medium at the base end of the molten metal in example 1 of the present invention;
FIG. 3 is a photograph of a high temperature hydraulic medium at the base end of the molten metal prepared in examples 1-3 of the present invention;
FIG. 4 is an SEM image of a high temperature hydraulic transmission medium at the base end of molten metal prepared in example 1 of the present invention;
FIG. 5 is a graph showing the dispersion phase of the high-temperature hydraulic transmission medium at the base end of the molten metal prepared in examples 1 to 3 by SEM-EDS;
FIG. 6 is a cloud chart showing the distribution of a high-temperature hydraulic transmission medium at the base end of a molten metal prepared in the embodiment 2 of the invention in a flow field of a valve cavity of a sliding valve;
FIG. 7 is a graph showing the comparison of the viscosity reduction rate between 40 and 100 ℃ of the hydraulic transmission medium according to the embodiment 1 of the present invention;
FIG. 8 is a graph showing the comparison of the viscosity reduction rate between 40 and 100℃of the hydraulic transmission medium according to example 2 of the present invention;
FIG. 9 is a graph showing the comparison of the viscosity reduction rate between 40 and 100 ℃ of the hydraulic transmission medium according to the embodiment 3 of the present invention;
FIG. 10 is a graph showing the comparison of the heat-weight curve of example 1 of the present invention and the prior art hydraulic transmission medium at 0-700 ℃;
FIG. 11 is a graph showing the heat-weight curve of example 2 of the present invention versus the prior art hydraulic transmission medium at 0-700 ℃;
FIG. 12 is a graph showing the heat-weight curve of example 3 of the present invention versus the prior art hydraulic transmission medium at 0-700 ℃;
FIG. 13 is a photograph showing the friction test of the high temperature hydraulic transmission medium at the base end of the molten metal prepared in examples 1-3 of the present invention;
FIG. 14 is a graph showing the temperature-coefficient of friction characteristics of the high-temperature hydraulic transmission medium at the base end of molten metal prepared in examples 1-3 of the present invention;
FIG. 15 is a schematic diagram of the MHD energy recovery principle;
fig. 16 is a schematic diagram of the testing principle of an MHD electromagnetic flowmeter.
Detailed Description
The technical scheme of the invention is described below through specific embodiments with reference to the accompanying drawings. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
In some embodiments, the preparation method of the high-temperature hydraulic transmission medium at the base end of the molten metal provided by the invention is shown in fig. 1, and specifically comprises the following steps:
step1: adding nano ceramic particles and a low-dimensional nano additive into deionized water according to the volume ratio (1-2) of 1, wherein the volume fractions of the nano ceramic particles and the low-dimensional nano additive are respectively 0.5-5%, mechanically stirring and ultrasonically dispersing under the condition of constant-temperature water bath, so that the nano ceramic particles are embedded between sheets of the low-dimensional nano additive, and a binary mixed nano solution with stable dispersion is obtained; preferably, the mechanical stirring and ultrasonic dispersing time is 30-120 min, and the stirring rotating speed is 200-1000 r/min; the Brownian movement of the nanometer particle in the base liquid can raise the dispersion stability, and this results in proper raised base liquid temperature, enhanced Brownian movement and beneficial dispersing effect, but deionized water with temperature over 60 deg.c may be used to form scale and promote evaporation, so that the temperature in the constant temperature water bath is 45-60 deg.c.
Step2: and drying the binary mixed nano solution by using a blast drying box or vacuum drying equipment at 70-150 ℃ until the moisture is completely evaporated, and obtaining uniform binary mixed nano particles.
Step3: slowly adding 5-20% of mixed nano particles prepared by Step2 into a metal liquid base solution in volume fraction under an air atmosphere, and mechanically stirring at a constant temperature of 80 ℃ to fully wet and coat the mixed nano particles by a nano metal oxide layer generated by the contact of the metal liquid base solution and air to obtain a solution A; the liquid metal has large surface tension, weak infiltration and coating capability, is difficult to be fused with nano ceramic particles, low-dimensional nano additives and binary mixed nano particles formed by the nano ceramic particles and the low-dimensional nano additives, and the surface tension of nano metal oxide generated after the liquid metal is oxidized is reduced, so that the wettability is enhanced, and the binary mixed nano particles are fully wetted and coated; preferably, the stirring time is 30-45 min, and the stirring rotating speed is 200-500 r/min.
Step4: and pouring dilute hydrochloric acid with the volume fraction of 3-10% and the concentration of 0.2mol/L into the solution A of Step 3. The dilute hydrochloric acid is used to isolate air, and meanwhile, as the hydrochloric acid can react with the oxide of the liquid metal, the oxidation of the liquid metal by oxygen in water can be avoided, so that the hydrochloric acid is used to effectively avoid the further oxidation of the liquid metal base solution. The Brownian movement of the nano particles in the base liquid can improve the dispersion stability, the temperature of the base liquid is properly improved, the Brownian movement can be enhanced, the dispersion effect is benefited, and preferably, the mixed nano particles are uniformly dispersed in the metal liquid base liquid by ultrasonic and mechanical stirring under the constant temperature condition of 80 ℃ to obtain a solution B; preferably, the stirring time is 45-60 min, and the stirring rotating speed is 300-500 r/min.
Step5: drying the dilute hydrochloric acid on the upper layer of the solution B by using a blast drying box or vacuum drying equipment, adding an acetic acid aqueous solution according to 3-10% of the volume fraction of the dried solution, standing for 48h at 40-60 ℃, and separating out nano particles which are not fully coated by the nano oxide layer due to the fact that the surface tension of liquid metal is high, and the infiltration and coating capability are weak, so that the solution C is obtained.
Step6: and (3) washing the solution C for 3-8 times by using an acetic acid aqueous solution until the precipitated nano particles are completely removed to obtain a solution D, carrying out solid-liquid phase change treatment on the solution D for 6-10 times by using an industrial refrigerator at the temperature of-10-60 ℃, wherein the solid-liquid phase change can cause volume change, and the volume change of a phase change interface causes the binary mixed nano particles to be subjected to an internal thrust action in the phase change process, so that the coating layer of the binary mixed nano particles which are not fully coated is easily broken to cause the precipitation of the nano particles, thereby obtaining the solution E.
Step7: and (3) washing the solution E for 3-8 times by using an acetic acid aqueous solution until the precipitated nano particles are completely removed, and obtaining the high-temperature hydraulic transmission medium at the base end of the metal liquid.
And (3) storing the prepared metal liquid base extreme high-temperature hydraulic transmission medium sample in a storage liquid, wherein the storage liquid is a weak acid solvent, the weak acid solvent is used for isolating air on one hand, and on the other hand, the weak acid solvent can be used for carrying out weak reaction with a liquid metal oxide layer to remove the oxide layer. Preferably, the stock solution is an aqueous acetic acid solution having a pH of 3.0 to 4.5.
Example 1
A high-temp hydraulic drive medium for the base end of molten metal is prepared from GaAl 0.9 Liquid metal base solution, si 3 N 4 Nano ceramic particles and low-dimensional nano additives of few-layer graphene (FLG-Ls). A physical photograph of each raw material is shown in FIG. 2, and few layers of graphene and Si can be seen 3 N 4 The nano ceramic particles have uniform color and luster, and the metal liquid base solution has bright metallic luster under the soaking of dilute hydrochloric acid.
The preparation method of the high-temperature hydraulic transmission medium at the base end of the molten metal comprises the following steps:
step1: the volume fraction of the nano ceramic particles is 5 percent, and the low-dimensional nano additive is prepared according to the volume ratio of 1:1, adding the nano ceramic particles into deionized water, mechanically stirring and ultrasonically dispersing for 30min under the condition of constant-temperature water bath at 45 ℃ at the stirring speed of 200r/min, so that the nano ceramic particles are embedded between the low-dimensional nano additive sheets to obtain a binary mixed nano solution with stable dispersion;
step2: and drying the binary mixed nano solution by using a blast drying box at the temperature of 70 ℃ until the moisture is completely evaporated, and obtaining uniform mixed nano particles.
Step3: under the air atmosphere, slowly adding 5% of mixed nano particles prepared by Step2 into the metal liquid base liquid, mechanically stirring for 30min at the constant temperature of 80 ℃, and stirring at the rotation speed of 200r/min to enable the mixed nano particles to be fully wetted and coated by a nano oxide layer generated by the contact of the metal liquid base liquid and air, thereby obtaining solution A.
Step4: and (3) pouring dilute hydrochloric acid with the volume fraction of 3% and the concentration of 0.2mol/L into the solution A of Step3, avoiding further oxidation of the metal liquid base solution, carrying out ultrasonic and mechanical stirring for 45min at the constant temperature of 80 ℃, and uniformly dispersing mixed nano particles in the metal liquid base solution at the stirring speed of 300r/min to obtain the solution B.
Step5: drying the upper layer of the solution B by using a blast drying box or vacuum drying equipment, adding an acetic acid aqueous solution according to the volume fraction of 3% of the dried solution, standing at 40 ℃ for 48 hours, and separating out the nano particles which are not fully coated to obtain a solution C.
Step6: and (3) washing the solution C for 3-8 times by using an acetic acid aqueous solution until the precipitated nano particles are completely removed to obtain a solution D, carrying out 6 times of solid-liquid phase change treatment on the solution D at the temperature of minus 10-60 ℃ by using an industrial refrigerator, wherein the solid-liquid phase change can cause volume change, and in the phase change process, the volume change of a phase change interface generates internal thrust, so that the fully coated and the incompletely coated binary mixed nano particles are subjected to the internal thrust, the coating layer is easy to break, the incompletely coated nano particles are precipitated, and the solution E is obtained.
Step7: and (3) washing for 3 times by using an acetic acid aqueous solution E until the precipitated nano particles are completely removed, and obtaining a high-temperature hydraulic transmission medium sample at the base end of the metal liquid.
Example 2
A high-temperature hydraulic transmission medium at the base end of molten metal is prepared from the same materials as in example 1.
The preparation method of the high-temperature hydraulic transmission medium at the base end of the molten metal comprises the following steps:
step1: the volume fraction of the nano ceramic particles is 5 percent, and the low-dimensional nano additive is prepared according to the volume ratio of 1:1, adding the nano ceramic particles into deionized water, mechanically stirring and ultrasonically dispersing for 30min under the condition of constant-temperature water bath at 45 ℃ at the stirring speed of 200r/min, so that the nano ceramic particles are embedded between the low-dimensional nano additive sheets to obtain a binary mixed nano solution with stable dispersion;
step2: and drying the binary mixed nano solution by using a blast drying box or vacuum drying equipment at the temperature of 70 ℃ until the moisture is completely evaporated, and obtaining uniform mixed nano particles.
Step3: under the air atmosphere, slowly adding 10% of mixed nano particles prepared by Step2 into the metal liquid base liquid, mechanically stirring for 40min at the constant temperature of 80 ℃, and stirring at the rotation speed of 400r/min to enable the mixed nano particles to be fully wetted and coated by a nano oxide layer generated by the contact of the metal liquid base liquid and air, thereby obtaining solution A.
Step4: and (3) pouring dilute hydrochloric acid with the volume fraction of 6% and the concentration of 0.2mol/L into the solution A of Step3 to prevent the metal liquid base solution from being further oxidized, carrying out ultrasonic and mechanical stirring for 50min at the constant temperature of 80 ℃ at the stirring speed of 400r/min, and uniformly dispersing the mixed nano particles in the metal liquid base solution to obtain the solution B.
Step5: drying the dilute hydrochloric acid on the upper layer of the solution B by using a blast drying box or vacuum drying equipment, adding an acetic acid aqueous solution according to the volume fraction of 3-10% of the dried solution, standing at 50 ℃ for 48 hours, and separating out the nano particles which are not fully coated to obtain a solution C.
Step6: and (3) washing the solution C for 6 times by using an acetic acid aqueous solution until the precipitated nano particles are completely removed to obtain a solution D, carrying out 8 times of solid-liquid phase change treatment on the solution D at the temperature of-10 ℃ to 60 ℃ by using an industrial refrigerator, and precipitating the nano particles which are not fully coated under the action of internal thrust of volume change of a phase change interface to obtain a solution E.
Step7: and (3) washing for 6 times by using an acetic acid aqueous solution E until the precipitated nano particles are completely removed, and obtaining a high-temperature hydraulic transmission medium sample at the base end of the metal liquid.
Example 3
A high-temperature hydraulic transmission medium at the base end of molten metal is prepared from the same materials as in example 1.
The preparation method of the high-temperature hydraulic transmission medium at the base end of the molten metal comprises the following steps:
the preparation method comprises the following steps:
step1: the volume fraction of the nano ceramic particles is 5 percent, and the low-dimensional nano additive is prepared according to the volume ratio of 1:1, adding the nano ceramic particles into deionized water, mechanically stirring and ultrasonically dispersing for 30min under the condition of constant-temperature water bath at 45 ℃ at the stirring speed of 200r/min, so that the nano ceramic particles are embedded between the low-dimensional nano additive sheets to obtain a binary mixed nano solution with stable dispersion;
step2: and drying the binary mixed nano solution by using a blast drying box at the temperature of 70 ℃ until the moisture is completely evaporated, and obtaining uniform mixed nano particles.
Step3: under the air atmosphere, slowly adding 20% of the mixed nano particles prepared by Step2 into the metal liquid base liquid, mechanically stirring for 45min at the constant temperature of 80 ℃ at the stirring speed of 500r/min, so that the mixed nano particles are fully wetted and coated by a nano oxide layer generated by the contact of the metal liquid base liquid and air, and obtaining solution A.
Step4: and (3) pouring dilute hydrochloric acid with the volume fraction of 10% and the concentration of 0.2mol/L into the solution A of Step3 to prevent the metal liquid base solution from being further oxidized, and carrying out ultrasonic and mechanical stirring for 60min at the constant temperature of 80 ℃ at the stirring speed of 500r/min to uniformly disperse the mixed nano particles in the metal liquid base solution to obtain the solution B.
Step5: drying the dilute hydrochloric acid on the upper layer of the solution B by using a blast drying box or vacuum drying equipment, adding an acetic acid aqueous solution according to the volume fraction of 3-10% of the dried solution, standing at 60 ℃ for 48 hours, and separating out the nano particles which are not fully coated to obtain a solution C.
Step6: and (3) washing the solution C for 8 times by using an acetic acid aqueous solution until the precipitated nano particles are completely removed to obtain a solution D, carrying out solid-liquid phase change treatment on the solution D for 10 times by using an industrial refrigerator at the temperature of-10 ℃ to 60 ℃, and precipitating the nano particles which are not fully coated under the action of internal thrust of volume change of a phase change interface to obtain a solution E.
Step7: and (3) washing for 8 times by using the acetic acid aqueous solution E until the precipitated nano particles are completely removed, and obtaining a high-temperature hydraulic transmission medium sample at the base end of the metal liquid.
Sample characterization and analysis
The high-temperature hydraulic transmission medium at the base end of the molten metal prepared in the examples 1-3 has a physical photo shown in figure 3, and it can be seen that the samples in the examples 1 and 2 have uniform colors, and the sample in the example 3 has a small amount of impurities on the surface. Because the addition amount of the binary mixed nano particles in the embodiment 3 is more, the good dispersing effect cannot be achieved through the preparation step and the washing step, so that more binary mixed nano particles are separated out to form impurities, and the effect of removing the excessive binary mixed nano particle impurities can be achieved through further solid-liquid treatment and washing.
SEM：SEM (scanning electron microscope) scan of the high-temperature hydraulic transmission medium sample at the base end of the molten metal prepared in example 1, the result is shown in FIG. 4, and Si is visible 3 N 4 The nano ceramic particles are embedded between the sheets of the low-dimensional nano additive graphene. The high-temperature hydraulic transmission medium samples at the base end of the molten metal prepared in example 2 and example 3 were subjected to SEM, and the results were the same as those in example 1, and no description thereof is repeated here.
SEM+EDS：Characterization of the dispersed phase of the high temperature Metal liquid base end Transmission Medium prepared in examples 1-3 by SEM+EDS, as shown in FIG. 5, two hybrid nanoparticles in the high temperature Metal liquid base end Transmission Medium prepared in examples 1-3All exist in the form of agglomerates, the dispersion is uniform, and the particle size of the agglomerates is small. Among them, example 1 had the best dispersion uniformity, the smallest particle size of the agglomerates, better uniformity than example 2 and example 3, and smaller particle size of the agglomerates than example 3.
Flow field distribution:taking example 2 as an example, fig. 6 shows the flow characteristics of the high-temperature hydraulic transmission medium sample at the base end of the molten metal prepared in example 2 and the existing high-temperature hydraulic transmission medium in the valve cavity of the spool valve of the servo valve, and it can be seen that: the vaporization pressure of the high-temperature hydraulic transmission medium at the base end of the metal liquid prepared by the embodiment 2 of the invention is extremely low, so that cavitation can be avoided, cavitation of the medium on the valve core can be prevented, and the service life of the valve core can be prolonged. The high-temperature hydraulic transmission medium at the base end of the molten metal prepared by the invention has lower flow velocity in the valve cavity, can improve the control stability of the servo valve and reduce the impact of fluid on the throttle orifice. Under the same pressure condition, the high-temperature hydraulic transmission medium at the base end of the molten metal prepared by the invention can reduce the influence of turbulence intensity on the vibration of the valve core and reduce energy loss.
Sample Performance test 1-basic Performance parameter test and comparison
The base end high temperature hydraulic transmission medium samples of the molten metal prepared in examples 1-3 were subjected to performance testing and compared with pure water, mineral oil, phosphate esters, PAO (poly alpha olefins), as shown in Table 1.
Table 1 comparison of basic Performance parameters of examples 1-3 with existing Hydraulic Transmission Medium
As can be seen from Table 1, the boiling point of the high-temperature hydraulic transmission medium sample at the base end of the molten metal prepared in examples 1-3 is higher than 1300 ℃, and is far higher than that of the existing hydraulic transmission medium; the melting point is 25.0 ℃, and the product can be used at normal temperature; the viscosity of the high-temperature hydraulic transmission medium sample at the base end of the metal liquid is close to that of the existing hydraulic medium, and the metal liquid has good fluidityThe method comprises the steps of carrying out a first treatment on the surface of the The heat conductivity is far higher than that of the existing hydraulic medium, so that the heat dissipation of the system is facilitated; conductivity is up to 2.3 x 10 6 Mu S/cm or more, has the MHD functional characteristic of the conductive fluid, which is not possessed by the existing hydraulic transmission medium.
Sample Performance test 2-temperature-viscosity characteristic test
Temperature-viscosity characteristics are key characteristics of the hydraulic medium. The temperature-viscosity characteristics of several traditional high-temperature hydraulic transmission media and the high-temperature hydraulic transmission media at the metal liquid base end prepared in the embodiment 1-3 of the invention are tested, and the results are shown in fig. 7-9, the viscosity reduction rate of the several traditional high-temperature hydraulic transmission media is more than 55% along with the temperature rise from the temperature of 40 ℃ to the temperature of 100 ℃, and the viscosity reduction rates of the high-temperature hydraulic transmission media at the metal liquid base end prepared in the embodiment 1-3 are respectively about 20%, 38% and 46%, which shows that the viscosity of the high-temperature hydraulic transmission media at the metal liquid base end prepared in the invention is small along with the temperature change, thereby being beneficial to improving the control stability of a hydraulic system under the conditions of high temperature wide temperature area and temperature impact.
Sample Performance test 3-thermal stability test
Thermal stability is an essential property of high temperature hydraulic media. Under the condition of heating, the weight loss conditions of the traditional high-temperature hydraulic transmission media and the high-temperature hydraulic transmission media at the base end of the metal liquid prepared by the embodiment 1-3 of the invention are monitored, as shown in the figures 10-12, pure water is completely evaporated in 150 ℃, and the base liquids of the hydrocarbon hydraulic media are decomposed in sequence in the range of 100-270 ℃ and are completely decomposed when the temperature exceeds 400 ℃. The high-temperature hydraulic transmission medium sample at the base end of the metal liquid prepared in the embodiment 1-3 has no mass attenuation in the range of 25-700 ℃, which indicates that the evaporation property is extremely low and the thermal stability is good in the temperature range, and binary mixed nano particles are not thermally decomposed.
Sample Performance test 4-lubricity test
Lubricity is also a key property of hydraulic transmission media. The friction loss test is carried out on several traditional high-temperature hydraulic transmission media and the high-temperature hydraulic transmission media at the base end of the metal liquid prepared in the embodiment 1-3 of the invention, and fig. 13 is a physical photograph of the friction wear test, and the measured temperature-friction coefficient characteristics are shown in fig. 14, and it can be seen from the graph that in terms of lubricity, the friction coefficient of the high-temperature hydraulic transmission media at the base end of the metal liquid prepared in the embodiment 1-3 of the invention is slightly changed by temperature, the friction coefficient is slightly higher than PAO-6 lubricating liquid and LH-M68# mineral hydraulic oil below 100 ℃, and the friction coefficient is lower than PAO-6 lubricating liquid and LH-M68# mineral hydraulic oil at the high temperature of 200 ℃, so that the high-temperature lubricating characteristic is superior to that of the existing hydraulic media.
Example 4 application based on the principle of energy recovery
Taking the high-temperature hydraulic transmission medium at the base end of the molten metal prepared in example 1 as an example, as shown in fig. 15, the high-temperature hydraulic transmission medium at the base end of the molten metal passes through a magnetic field perpendicular to the flowing direction at a certain speed to cut magnetic lines of force to generate electromotive force, thereby generating electric energy, and the electric energy is stored in a battery. The nano ceramic particles are embedded into the low-dimensional nano additive graphene, so that the problem of conductivity reduction caused by adding the nano ceramic particles can be effectively solved, and the high-temperature hydraulic transmission medium at the base end of the metal liquid can keep good electromagnetic induction performance. The energy recovery mode has no relative movement and parts rotation, directly converts heat energy into electric energy, can reduce heat generation of the system, and has high energy conversion efficiency. The throttling energy loss of a damping runner, a hydraulic cylinder buffer device and the like can be recovered.
Example 5 application of electromagnetic flowmeter-based test principle
Taking the high-temperature hydraulic transmission medium at the base end of the molten metal prepared in the example 1 as an example, as shown in fig. 16, when the high-temperature hydraulic transmission medium at the base end of the molten metal makes a motion of cutting magnetic lines in a magnetic field, induced potential is generated, and the volume flow is in linear relation with the induced electromotive force and the section size of the measuring tube and is inversely proportional to the magnetic induction intensity of the magnetic field. When the magnetic field is constant and the section of the pipeline is unchanged, the volume flow value at the moment can be represented by testing the magnitude of the induced electromotive force. The method has the characteristics of small pressure loss, large measurable flow range, high measurement precision and sensitivity and the like, and is beneficial to the development of an ultra-high precision hydraulic system.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The high-temperature hydraulic transmission medium for the metal liquid base end is characterized by comprising metal liquid base liquid and binary mixed nano particles, wherein the binary mixed nano particles comprise nano ceramic particles and the low-dimensional nano additive, and the nano ceramic particles are embedded between sheets of the low-dimensional nano additive;
the binary mixed nano particles are uniformly dispersed in the metal liquid base liquid.
2. The molten metal base end high temperature hydraulic transmission medium according to claim 1, wherein the molten metal base end high temperature hydraulic transmission medium comprises the following raw materials in volume ratio: metal liquid base liquid: nano ceramic particles: low-dimensional nano additive= (80-95): (5-20);
The volume ratio of the nano ceramic particles to the low-dimensional nano additive is (1-2): 1.
3. The high-temperature hydraulic transmission medium at the base end of the metal liquid according to claim 1, wherein the binary mixed nano particles are coated with a nano metal oxide layer generated by the reaction of the metal liquid base and air, and the binary mixed nano particles coated with the nano metal oxide layer are uniformly distributed in the metal liquid base;
and/or the density of the high-temperature hydraulic transmission medium at the base end of the molten metal is 4-8 g/cm 3 The viscosity is 20-150 mPa.s;
and/or the thermal conductivity of the high-temperature hydraulic transmission medium at the base end of the molten metal is more than 20.9W/mK;
and/or the conductivity of the high-temperature hydraulic transmission medium at the base end of the molten metal is 2.2 x 10 6 Mu S/cm or more.
4. The high-temperature hydraulic transmission medium at the base end of the metal liquid according to claim 1, wherein the metal liquid base is a gallium alloy composed of gallium and at least one metal selected from indium, tin, zinc, aluminum, magnesium and bismuth; preferably, the melting point of the metal liquid base liquid is less than 30 ℃; more preferably, the metal liquid base liquid is a Ga-Al alloy, a Ga-Mg alloy, or a Ga-Al-Mg alloy;
And/or the nano ceramic particles are in a spherical structure, and the particle size of the nano ceramic particles is 1-100 nm;
and/or the nano ceramic particles are SiO 2 、SiC、Si 3 N 4 One or more of the following;
and/or the low-dimensional nano additive is few-layer graphene with the thickness of a slice layer of 0.5-3.0 nm and the diameter of 0.1-5 mu m, and/or nano single-layer graphene with the thickness of 0.5-1.2 nm and the diameter of 100-500 nm.
5. The molten metal base end high temperature hydraulic transmission medium according to any one of claims 1 to 4, wherein the suitable hydraulic transmission temperature of the molten metal base end high temperature hydraulic transmission medium is 1300 ℃ or lower;
preferably, the hydraulic transmission temperature suitable for the high-temperature hydraulic transmission medium at the base end of the molten metal is 30-1300 ℃;
more preferably, the hydraulic transmission temperature applicable to the high-temperature hydraulic transmission medium at the base end of the molten metal is 30-700 ℃, and/or the hydraulic transmission temperature applicable to the high-temperature hydraulic transmission medium at the base end of the molten metal is 700-1300 ℃;
further preferably, the hydraulic transmission temperature suitable for the high-temperature hydraulic transmission medium at the base end of the molten metal is 30-400 ℃, and/or the hydraulic transmission temperature suitable for the high-temperature hydraulic transmission medium at the base end of the molten metal is 400-700 ℃.
6. The preparation method of the high-temperature hydraulic transmission medium at the base end of the molten metal is characterized by comprising the following steps:
mixing nano ceramic particles and a low-dimensional nano additive according to the proportion of (1-2) 1, adding the mixture into a solvent according to the volume fraction of 0.5% -5%, stirring and ultrasonic treatment at the temperature of 45-60 ℃, and fully embedding the nano ceramic particles between the sheets of the low-dimensional nano additive to obtain a binary mixed nano solution with stable dispersion;
drying the binary mixed nano solution to obtain uniform mixed nano particles;
oxidizing the surface of the metal liquid base liquid in an oxygen-containing atmosphere to obtain a nano metal oxide layer, adding the binary mixed nano particles into the metal liquid base liquid, stirring at a constant temperature of 80 ℃, and infiltrating and cladding the nano metal oxide layer and the binary mixed nano particles to obtain a solution A;
pouring dilute hydrochloric acid into the solution A, stirring at constant temperature, and performing ultrasonic treatment to uniformly disperse the infiltrated and coated binary mixed nano particles in a metal liquid base solution to obtain a solution B;
separating out and removing the non-infiltrated and coated binary mixed nano particles to obtain the high-temperature hydraulic transmission medium at the base end of the molten metal.
7. The preparation method according to claim 6, wherein the volume ratio of the metal liquid base liquid, the nano ceramic particles and the low-dimensional nano additive is (80-95): (5-20), and the volume ratio of the nano ceramic particles to the low-dimensional nano additive is (1-2): 1;
and/or the metal liquid base liquid is gallium alloy composed of gallium and at least one metal selected from indium, tin, zinc, aluminum, magnesium and bismuth; preferably, the melting point of the metal liquid base liquid is less than 30 ℃; more preferably, the metal liquid base liquid is a Ga-Al alloy, a Ga-Mg alloy or a Ga-Al-Mg alloy.
8. The method according to claim 6, wherein the precipitation method of the non-infiltrated, coated binary mixed nanoparticles comprises:
removing hydrochloric acid in the solution B, adding an aqueous solution of acetic acid, standing at 40-60 ℃, and separating out binary mixed nano particles which are not fully coated to obtain a solution C;
and repeatedly flushing the solution C by using an acetic acid aqueous solution until all the binary mixed nano particles are removed, so as to obtain a solution D.
9. The method of claim 8, wherein the non-infiltrated, coated binary mixed nanoparticle precipitation method further comprises:
Carrying out solid-liquid phase change treatment on the solution D for a plurality of times at the temperature of between 10 and 60 ℃, and separating out underwrapped binary mixed nano particles under the action of internal thrust of volume change of a phase change interface to obtain a solution E;
and repeatedly washing the solution E by using an acetic acid aqueous solution until the precipitated nano particles are completely removed, and obtaining the high-temperature hydraulic transmission medium at the base end of the metal liquid.
10. The high-temperature hydraulic transmission medium of the metal liquid base end prepared by the preparation method of claims 1-5 is applied to hydraulic transmission, energy recovery and electromagnetic flow meters.
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