CN109181815B - Electrorheological fluid and preparation method thereof - Google Patents

Electrorheological fluid and preparation method thereof Download PDF

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CN109181815B
CN109181815B CN201811026409.5A CN201811026409A CN109181815B CN 109181815 B CN109181815 B CN 109181815B CN 201811026409 A CN201811026409 A CN 201811026409A CN 109181815 B CN109181815 B CN 109181815B
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electrorheological fluid
organic framework
titanium oxide
metal
organic
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CN109181815A (en
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程昱川
牛益民
华乐天
李志祥
刘丰华
孙爱华
郭建军
许高杰
晏育刚
陆祥芳
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Ningbo Xinfu Titanium Dioxide Co ltd
Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Xinfu Titanium Dioxide Co ltd
Ningbo Institute of Material Technology and Engineering of CAS
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    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/402—Castor oils
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • C10M2229/025—Unspecified siloxanes; Silicones used as base material
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/60—Electro rheological properties

Abstract

The invention discloses an electrorheological fluid and a preparation method thereof. The electrorheological fluid comprises a dispersion phase and a dispersion medium, wherein the dispersion phase comprises a metal organic framework-titanium oxide compound, the dispersion medium comprises an insulating liquid, and the dispersion phase is uniformly dispersed in the dispersion medium. The preparation method comprises the following steps: providing a first mixed system comprising a metal organic framework material, a surfactant, and a solvent; providing a second mixed system comprising an organotitanate; mixing the second mixed system with the first mixed system, and reacting to obtain a metal organic framework-titanium oxide compound; and uniformly dispersing the metal organic framework-titanium oxide compound in insulating liquid to obtain the electrorheological fluid. The electrorheological fluid has the advantages of high dynamic shear stress, good stability, low leakage current density, excellent anti-settling property, simple and easy preparation method and low cost.

Description

Electrorheological fluid and preparation method thereof
Technical Field
The invention relates to an electrorheological fluid, in particular to a metal organic framework/titanium oxide compound electrorheological fluid and a preparation method thereof, belonging to the technical field of electrorheological fluids.
Background
An electrorheological fluid is a suspension of dielectric particles (dispersed phase) dispersed in an insulating liquid (dispersion medium). After an electric field is applied, the dielectric particles in the dielectric particles can be arranged in a chain shape in a dispersion medium along the direction of the electric field, and the macroscopic expression is that the viscosity of the system is increased along with the increase of the electric field intensity, and the system can be converted from a liquid state to a solid-like state in a very short time; after the electric field is removed, the electrorheological fluid can be quickly converted from the solid-like structure to the liquid state. The electrorheological fluid is an intelligent material with great development potential, has the characteristics of adjustability and controllability, high response speed, reversible process, low energy consumption and the like, and has wide application prospects in the aspects of automatic control, electromechanical integration, flexible sensing and the like.
Patent CN107474913A discloses a giant electrorheological fluid of titanium oxide, which is prepared by reacting a dehydrated/ethanol mixed solution with an alcoholic solution of butyl titanate to prepare amorphous titanium oxide particles, then carrying out heat treatment at 120-200 ℃ to obtain titanium oxide particles, and mixing the titanium oxide particles with silicone oil.
Patent CN101838577A discloses a porous carbon electrorheological fluid with porous structure, which has improved dielectric polarization performance due to its internal hierarchical pore structure, and can obtain relatively low density, good electrorheological effect, but low dynamic shear stress.
The dynamic shear stress reflects the stress of the electrorheological fluid in the whole shear range, and the static yield stress only corresponds to the stress at the moment when the electrorheological fluid starts to flow, so that the working state of the electrorheological fluid material in the whole interval cannot be reflected. At present, most of electrorheological fluids with higher static yield stress have the problem of poorer dynamic shear stress stability. When the strain or shear rate exceeds the yield point, the dynamic shear stress exhibits a significant tendency to slip underground. The main reason is that when shearing at high speed, the dispersed phase of the electrorheological fluid and the dispersed medium are separated, the dispersed phase particles migrate to the edge of the electrode, and the solid content between the electrode plates is reduced, so that the dynamic shearing stress is reduced rapidly. This phenomenon is more pronounced the higher the static yield stress of the electrorheological fluid. This is a common disadvantage of electrorheological fluid materials, and has become a bottleneck to the development of electrorheological fluids.
Disclosure of Invention
The main purpose of the present invention is to provide an electrorheological fluid and a preparation method thereof, thereby overcoming the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
an embodiment of the present invention provides an electrorheological fluid, including: a dispersed phase comprising a metal organic framework-titanium oxide composite and a dispersion medium comprising an insulating liquid, the dispersed phase being uniformly dispersed in the dispersion medium.
The embodiment of the invention also provides a preparation method of the electrorheological fluid, which comprises the following steps:
providing a first mixed system comprising a metal organic framework material, a surfactant, and a solvent;
providing a second mixed system comprising an organotitanate;
mixing the second mixed system with the first mixed system, and reacting to obtain a metal organic framework-titanium oxide compound;
and uniformly dispersing the metal organic framework-titanium oxide compound in insulating liquid to obtain the electrorheological fluid.
The embodiment of the invention also provides the electrorheological fluid prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the electrorheological fluid provided by the invention adopts the metal organic framework-titanium oxide compound as a dispersion phase, and the metal organic framework-titanium oxide compound has a three-dimensional porous structure, large specific surface area, a large number of polar groups, excellent electrorheological property and large dynamic shear stress, so that the electrorheological fluid has the advantages of high dynamic shear stress, good stability, low leakage current density, excellent anti-settling property, simple and easy preparation method and low cost.
Drawings
FIG. 1 is a graph showing the relationship between the dynamic shear stress and the shear rate of an electrorheological fluid of an MIL-101(Cr) -titanium oxide composite in example 1 of the present invention.
FIG. 2 is a graph showing the relationship between the leakage current density and the electric field strength of an MIL-101(Cr) -titanium oxide composite electrorheological fluid in example 1 of the present invention.
FIG. 3 is a graph showing the settling rate of the MIL-101(Cr) -titanium oxide composite electrorheological fluid as a function of time in example 1 of the present invention.
FIG. 4 is a graph of the dynamic shear stress versus shear rate of an MIL-101(Fe) -titanium oxide composite electrorheological fluid according to example 2 of the present invention.
Fig. 5 is a graph of a leakage current density versus an electric field strength of the MIL-101(Fe) -titanium oxide composite electrorheological fluid in example 2 of the present invention.
FIG. 6 is a graph of the sedimentation rate of the MIL-101(Fe) -titanium oxide composite electrorheological fluid versus time in example 2 of the present invention.
FIG. 7 is a graph showing a relationship between a dynamic shear stress and a shear rate of a ZIF-8-titanium oxide composite electrorheological fluid according to example 3 of the present invention.
FIG. 8 is a graph showing a relationship between a leakage current density and an electric field strength of a ZIF-8-titanium oxide composite electrorheological fluid in example 3 of the present invention.
FIG. 9 is a graph showing a settling rate of the ZIF-8-titanium oxide composite electrorheological fluid with respect to time in example 3 of the present invention.
FIG. 10 is a graph of the dynamic shear stress versus shear rate of the HKUST-1-titanium oxide composite electrorheological fluid of example 4 of the present invention.
FIG. 11 is a graph showing the relationship between the leakage current density and the electric field strength of the HKUST-1-titanium oxide composite electrorheological fluid of example 4 of the present invention.
FIG. 12 is a graph of the settling rate of the HKUST-1-titanium oxide composite electrorheological fluid versus time in example 4 of the present invention.
FIG. 13 is a graph showing the relationship between the dynamic shear stress and the shear rate of an electrorheological fluid of an MIL-101(Cr) -titanium oxide composite according to example 5 of the present invention.
FIG. 14 is a graph of leakage current density versus electric field strength for an MIL-101(Cr) -titanium oxide composite electrorheological fluid of example 5 of the present invention.
FIG. 15 is a graph of the settling rate of the MIL-101(Cr) -titanium oxide composite electrorheological fluid versus time in example 5 of the present invention.
FIG. 16 is a graph showing a relationship between a dynamic shear stress and a shear rate of a ZIF-8-titanium oxide composite electrorheological fluid according to example 6 of the present invention.
FIG. 17 is a graph showing a relationship between a leakage current density and an electric field strength of a ZIF-8-titanium oxide composite electrorheological fluid in example 6 of the present invention.
FIG. 18 is a graph showing a settling rate of the ZIF-8-titanium oxide composite electrorheological fluid with respect to time in example 6 of the present invention.
Fig. 19 is a graph showing the dynamic shear stress versus shear rate of the titanium oxide electrorheological fluid of comparative example 1.
Fig. 20 is a graph showing the relationship between the leakage current density and the electric field strength of the titanium oxide electrorheological fluid of comparative example 1.
Fig. 21 is a graph showing the settling rate of the titanium oxide electrorheological fluid in comparative example 1 as a function of time.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose the technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc.
As an aspect of the technical solution of the present invention, it relates to an electrorheological fluid comprising: the dispersion medium comprises an insulating liquid, and the dispersed phase metal-organic framework-titanium oxide composite is uniformly dispersed in the insulating liquid of the dispersion medium.
In some embodiments, the content of the metal-organic framework-titanium oxide composite in the electrorheological fluid is 10 to 70wt%, preferably 20 to 60 wt%.
In some embodiments, the metal-organic framework-titanium oxide composite is formed by reacting a metal-organic framework material and an organotitanate. The metal organic framework-titanium oxide compound has a three-dimensional porous structure, is large in specific surface area, loads a large number of polar groups, and is excellent in electrorheological property and large in dynamic shear stress.
Wherein, the metal organic framework material can be any metal organic framework prepared by adopting a method known in the field.
Further, the metal organic framework material is preferably an organic-inorganic hybrid particle with intramolecular pores formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds, and the specific surface area is preferably more than 1500m2(ii) per gram of metal organic framework particles.
In some embodiments, the dielectric constant of the insulating liquid is 1 to 10(20 ℃, 10)-2Hz) and an electrical conductivity of 10-15～10-10(Ω·cm)-1Any one or a combination of two or more of silicone oil, castor oil, hydraulic oil, and the like is preferable, but not limited thereto.
The insulating liquid has good wettability to the metal organic framework-titanium oxide compound particles and can be spread on the surfaces of the metal organic framework-titanium oxide compound particles. The electric field is applied, the metal organic framework-titanium oxide composite particles are arranged into chains, polar groups on the surfaces of the particles form oriented dipole links along the direction of the electric field, and the insulating liquid film is penetrated to bridge the closed boundaries between adjacent particles, so that the metal organic framework-titanium oxide composite electrorheological fluid has excellent dynamic shear stress stability.
The thin layer of insulating liquid between two adjacent particles effectively prevents charge transfer between the particles under an applied electric field, so that the electrorheological fluid containing the metal-organic framework-titanium oxide composite exhibits a low leakage current density.
In conclusion, the electrorheological fluid has high dynamic shear stress, good stability, low leakage current density and excellent settling resistance.
As another aspect of the technical solution of the present invention, a method for preparing an electrorheological fluid is provided, which includes:
providing a first mixed system comprising a metal organic framework material, a surfactant, and a solvent;
providing a second mixed system comprising an organotitanate;
mixing the second mixed system with the first mixed system, and reacting to obtain a metal organic framework-titanium oxide compound;
and uniformly dispersing the metal organic framework-titanium oxide compound in insulating liquid to obtain the electrorheological fluid.
In some embodiments, the mass ratio of the metal organic framework material, surfactant, and organotitanate is 1: 0.1-4: 3 to 20.
Wherein, the metal organic framework material can be any metal organic framework prepared by adopting a method known in the field.
In some embodiments, the metal-organic framework material is preferably an organic-inorganic hybrid particle with intramolecular pores formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds, preferably with a specific surface area greater than 1500m2(ii) per gram of metal organic framework particles.
Further, the concentration of the metal-organic framework material in the first mixed system is 0.6-1.2 g/L.
In some embodiments, the surfactant includes any one or a combination of two or more of sodium dodecylbenzene sulfonate, stearic acid, lauric acid, and the like, but is not limited thereto. The surfactant has a surface modification effect, can prevent the aggregation of the metal organic framework material, and can improve the wettability of the insulating liquid to the metal organic framework-titanium oxide compound.
Further, the solvent comprises a mixed solvent of an organic solvent and water, wherein the volume ratio of the organic solvent to the water is 1: 0.05 to 0.2.
Further, the organic solvent is preferably, but not limited to, absolute ethanol.
In some embodiments, the organic titanate includes any one or a combination of two or more of butyl titanate, ethyl titanate, isopropyl titanate, and the like, but is not limited thereto.
Furthermore, the concentration of the organic titanate in the second mixed system is 5-15 g/L.
Further, the second mixed system includes an organic titanate and an organic solvent, wherein the organic solvent is preferably, but not limited to, absolute ethanol.
In some embodiments, the preparation method specifically comprises: and dropwise adding the second mixed system into the first mixed system, stirring, aging, centrifuging, washing and drying to obtain the metal organic framework-titanium oxide compound.
Furthermore, the stirring treatment is not strictly limited in time, and is preferably 0.5-5 h.
Furthermore, the aging treatment has no strict time limit, and is preferably 10-24 h.
In some embodiments, the dielectric constant of the insulating liquid is 1 to 10(20 ℃, 10)-2Hz) and an electrical conductivity of 10-15～10-10(Ω·cm)-1Any one or a combination of two or more of silicone oil, castor oil, hydraulic oil, and the like is preferable, but not limited thereto.
In some more specific embodiments, the method for preparing the metal organic framework-titanium oxide composite electrorheological fluid specifically comprises the following steps:
1) dispersing a metal organic framework material in an absolute ethyl alcohol/water mixed solvent, and adding a surfactant to obtain a suspension A;
2) dissolving organic titanate in absolute ethyl alcohol to obtain a solution B;
3) dropwise adding the solution B into the suspension A, stirring, aging, centrifuging, washing and drying to obtain a metal organic framework-titanium oxide compound;
4) and dispersing the obtained metal organic framework-titanium oxide compound in insulating liquid to obtain the electrorheological fluid.
Wherein, the steps are operated at room temperature.
As another aspect of the technical solution of the present invention, it relates to an electrorheological fluid prepared by the aforementioned method.
In conclusion, the electrorheological fluid has high dynamic shear stress, good stability, low leakage current density, excellent settling resistance, simple and easy preparation method and low cost.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. In the following examples, experimental methods without specific conditions noted are generally performed under conventional conditions or conditions recommended by the manufacturer, based on a full understanding of the present invention.
Example 1
(1) Weighing 0.055g MIL-101(Cr) (specific surface area 2483 m)2In a solvent (volume ratio 1: 0.1), then 0.0055g of sodium dodecyl benzene sulfonate is added to obtain a suspension A;
(2) measuring 0.5g of tetrabutyl titanate, dissolving in 50mL of absolute ethyl alcohol, and stirring for half an hour to obtain a solution B;
(3) dropwise adding the solution B into the solution A, continuously stirring for four hours after the dropwise adding is completed, and then standing and aging for 10 hours; and filtering, washing and drying the precipitate to obtain the required MIL-101(Cr) -titanium oxide composite particles.
(4) Dispersing the obtained composite particles in silicone oil to prepare the MIL-101(Cr) -titanium oxide composite electrorheological fluid with the mass fraction of 40 wt%. As shown in figures 1-3, the electrorheological fluid has a shear rate of 100s in an electric field of 4kV/mm-1The dynamic shear stress was 40.5kPa, and the leakage current density was 4.5. mu.A/cm2. The anti-settling rate of the electrorheological fluid is more than 96 percent after the electrorheological fluid is placed for 30 days.
Example 2
(1) 0.084g MIL-101(Fe) (specific surface area 2265 m) was weighed2In 105mL of an absolute ethanol/water mixed solvent (volume ratio of 1: 0.05), then 0.336g of sodium dodecyl sulfate is added to obtain suspension A;
(2) measuring 0.25g of ethyl titanate, dissolving in 50mL of absolute ethyl alcohol, and stirring for half an hour to obtain a solution B;
(3) dropwise adding the solution B into the solution A, continuously stirring for four hours after the dropwise adding is completed, and then standing and aging for 10 hours; and filtering, washing and drying the precipitate to obtain the required MIL-101(Fe) -titanium oxide composite particles.
(4) And dispersing the obtained composite particles in castor oil to prepare the MIL-101(Fe) -titanium oxide composite electrorheological fluid with the mass fraction of 20 wt%. As shown in figures 4-6, the electrorheological fluid has a shear rate of 100s in an electric field of 4kV/mm-1The dynamic shear stress at that time was 39.8kPa, and the leakage current density was 4.7. mu.A/cm2. The anti-settling rate of the electrorheological fluid is more than 94 percent after the electrorheological fluid is placed for 30 days.
Example 3
(1)0.05g of ZIF-8 (specific surface area 2034 m) was weighed2In 60mL of an absolute ethanol/water mixed solvent (volume ratio of 1: 0.2), then 0.1g of stearic acid is added to obtain a suspension A;
(2) measuring 0.75g of isopropyl titanate, dissolving in 50mL of absolute ethyl alcohol, and stirring for half an hour to obtain a solution B;
(3) dropwise adding the solution B into the solution A, continuously stirring for four hours after the dropwise adding is completed, and then standing and aging for 10 hours; and filtering, washing and drying the precipitate to obtain the required ZIF-8-titanium oxide compound particles.
(4) And dispersing the obtained composite particles in hydraulic oil to prepare the ZIF-8-titanium oxide composite electrorheological fluid with the mass fraction of 40 wt%. As shown in figures 7-9, the electrorheological fluid has a shear rate of 100s in an electric field of 4kV/mm-1The dynamic shear stress was 37.9kPa, and the leakage current density was 4.4. mu.A/cm2. The anti-settling rate of the electrorheological fluid is more than 95 percent after the electrorheological fluid is placed for 30 days.
Example 4
(1) Weighing 0.055g HKUST-1 (specific surface area 1783 m)2In a solvent (volume ratio 1: 0.1), then 0.11g of lauric acid was added to obtain suspension a;
(2) measuring 0.5g of tetrabutyl titanate, dissolving in 50mL of absolute ethyl alcohol, and stirring for half an hour to obtain a solution B;
(3) dropwise adding the solution B into the solution A, continuously stirring for four hours after the dropwise adding is completed, and then standing and aging for 10 hours; and filtering, washing and drying the precipitate to obtain the required HKUST-1-titanium oxide compound particles.
(4) The composite particles obtained above are dispersed in hydraulic oil to prepare HKUST-1-titanium oxide composite electrorheological fluid with the mass fraction of 30 wt%. As shown in figures 10-12, the electrorheological fluid has a shear rate of 100s in an electric field of 4kV/mm-1The dynamic shear stress was 37.1kPa, and the leakage current density was 4.8. mu.A/cm2. The anti-settling rate of the electrorheological fluid is more than 94 percent after the electrorheological fluid is placed for 30 days.
Example 5
(1) 0.064g MIL-101(Cr) (specific surface area)2483m2In 105mL of an absolute ethanol/water mixed solvent (volume ratio of 1: 0.05), then 0.064g of sodium dodecyl benzene sulfonate is added to obtain a suspension A;
(2) measuring 0.75g of ethyl titanate, dissolving in 50mL of absolute ethyl alcohol, and stirring for half an hour to obtain a solution B;
(3) dropwise adding the solution B into the solution A, continuously stirring for four hours after the dropwise adding is completed, and then standing and aging for 10 hours; and filtering, washing and drying the precipitate to obtain the required MIL-101(Cr) -titanium oxide composite particles.
(4) Dispersing the obtained composite particles in castor oil to prepare the MIL-101(Cr) -titanium oxide composite electrorheological fluid with the mass fraction of 50 wt%. As shown in FIGS. 13-15, the electrorheological fluid has a shear rate of 100s in an electric field of 4kV/mm-1The time dynamic shear stress is 38.8KPa, and the leakage current density is 5.0 muA/cm2. The anti-settling rate of the electrorheological fluid is more than 95 percent after the electrorheological fluid is placed for 30 days.
Example 6
(1) 0.072g ZIF-8 (specific surface area 2034 m) was weighed2In 60mL of an absolute ethanol/water mixed solvent (volume ratio of 1: 0.2), then 0.144g of sodium dodecyl sulfate is added to obtain suspension A;
(2) measuring 0.25g of isopropyl titanate, dissolving in 50mL of absolute ethyl alcohol, and stirring for half an hour to obtain a solution B;
(3) dropwise adding the solution B into the solution A, continuously stirring for four hours after the dropwise adding is completed, and then standing and aging for 10 hours; and filtering, washing and drying the precipitate to obtain the required ZIF-8-titanium oxide compound particles.
(4) And dispersing the obtained composite particles in hydraulic oil to prepare the ZIF-8-titanium oxide composite electrorheological fluid with the mass fraction of 40 wt%. As shown in FIGS. 16-18, the electrorheological fluid has a shear rate of 100s in an electric field of 4kV/mm-1The dynamic shear stress was 39.6kPa, and the leakage current density was 4.5. mu.A/cm2. The anti-settling rate of the electrorheological fluid is more than 96 percent after the electrorheological fluid is placed for 30 days.
Comparative example 1
(1) Mixing absolute ethyl alcohol with water to obtain 60mL of an absolute ethyl alcohol/water mixed solvent (volume ratio is 1: 0.2);
(2) measuring 0.6g of tetrabutyl titanate, dissolving in 60mL of absolute ethyl alcohol, and stirring for half an hour to obtain a solution B;
(3) dropwise adding the solution B into 60mL of absolute ethyl alcohol/water mixed solvent, continuously stirring for four hours after dropwise adding is completed, and then standing and aging for 10 hours; and filtering, washing and drying the precipitate to obtain the required titanium oxide particles.
(4) The titanium oxide particles obtained above are dispersed in hydraulic oil to prepare titanium oxide electrorheological fluid with the mass fraction of 20 wt%. As shown in FIGS. 19-21, the electrorheological fluid has a shear rate of 100s in an electric field of 4kV/mm-1The dynamic shear stress was 5.7kPa, and the leakage current density was 10.9. mu.A/cm2. The anti-settling rate of the electrorheological fluid is more than 83 percent after the electrorheological fluid is placed for 30 days, and the performance of the electrorheological fluid is obviously inferior to that of the electrorheological fluids obtained in examples 1 to 6.
In conclusion, by the technical scheme, the electrorheological fluid has the advantages of high dynamic shear stress, good stability, low leakage current density, excellent anti-settling property, simple and easy preparation method and low cost.
In addition, the present inventors have also made experiments with other materials and conditions, etc. listed in this specification, in the manner of examples 1 to 6, and have also succeeded in obtaining an electrorheological fluid having high dynamic shear stress, good stability, low leakage current density, and excellent settling resistance.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.

Claims (28)

1. An electrorheological fluid characterized by comprising a dispersed phase comprising a metal organic framework-titanium oxide composite and a dispersion medium comprising an insulating liquid, the dispersed phase being uniformly dispersed in the dispersion medium.
2. Electrorheological fluid according to claim 1, characterized in that: the content of the metal organic frame-titanium oxide compound in the electrorheological fluid is 10-70 wt%.
3. Electrorheological fluid according to claim 2, characterized in that: the content of the metal organic frame-titanium oxide compound in the electrorheological fluid is 20-60 wt%.
4. Electrorheological fluid according to claim 1 or 2, characterized in that: the metal-organic framework-titanium oxide composite is formed by reacting a metal-organic framework material and an organotitanate.
5. Electrorheological fluid according to claim 4, characterized in that: the metal organic framework material is formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds.
6. Electrorheological fluid according to claim 4, characterized in that: the metal-organic framework material includes organic-inorganic hybrid particles having intramolecular pores.
7. Electrorheological fluid according to claim 4, characterized in that: the specific surface area of the metal organic framework material is more than 1500m2/g。
8. Electrorheological fluid according to claim 1, characterized in that: the dielectric constant of the insulating liquid is 1-10, and the conductivity is 10-15～10-10（Ω·cm）-1。
9. Electrorheological fluid according to claim 1, characterized in that: the insulating liquid comprises any one or the combination of more than two of silicone oil, castor oil and hydraulic oil.
10. A preparation method of electrorheological fluid is characterized by comprising the following steps:
providing a first mixed system comprising a metal organic framework material, a surfactant, and a solvent;
providing a second mixed system comprising an organotitanate;
mixing the second mixed system with the first mixed system, and reacting to obtain a metal organic framework-titanium oxide compound;
and uniformly dispersing the metal organic framework-titanium oxide compound in insulating liquid to obtain the electrorheological fluid.
11. The method of manufacturing according to claim 10, wherein: the mass ratio of the metal organic framework material to the surfactant to the organic titanate is 1: 0.1-4: 3 to 20.
12. The method of manufacturing according to claim 10, wherein: the metal organic framework material is formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds.
13. The method of manufacturing according to claim 10, wherein: the metal-organic framework material includes organic-inorganic hybrid particles having intramolecular pores.
14. The method of manufacturing according to claim 10, wherein: the specific surface area of the metal organic framework material is more than 1500m2/g。
15. The method of manufacturing according to claim 10, wherein: the concentration of the metal-organic framework material in the first mixed system is 0.6-1.2 g/L.
16. The method of manufacturing according to claim 10, wherein: the surfactant comprises any one or the combination of more than two of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, stearic acid and lauric acid.
17. The method of manufacturing according to claim 10, wherein: the solvent includes a mixed solvent of an organic solvent and water.
18. The method of claim 17, wherein: the volume ratio of the organic solvent to the water is 1: 0.05 to 0.2.
19. The method of claim 17, wherein: the organic solvent comprises absolute ethyl alcohol.
20. The method of manufacturing according to claim 10, wherein: the organic titanate comprises any one or the combination of more than two of butyl titanate, ethyl titanate and isopropyl titanate.
21. The method of manufacturing according to claim 10, wherein: the concentration of organic titanate in the second mixed system is 5-15 g/L.
22. The method of manufacturing according to claim 10, wherein: the second mixed system includes an organic titanate and an organic solvent.
23. The method of claim 22, wherein: the organic solvent comprises absolute ethyl alcohol.
24. The method of manufacturing according to claim 10, wherein: the dielectric constant of the insulating liquid is 1-10, and the conductivity is 10-15～10-10（Ω·cm）-1。
25. The method of manufacturing according to claim 10, wherein: the insulating liquid comprises any one or the combination of more than two of silicone oil, castor oil and hydraulic oil.
26. The method of manufacturing according to claim 10, wherein: the preparation method is carried out at room temperature.
27. The method according to claim 10, comprising: and dropwise adding the second mixed system into the first mixed system, stirring, aging, centrifuging, washing and drying to obtain the metal organic framework-titanium oxide compound.
28. An electrorheological fluid prepared by the method of any one of claims 10 to 27.
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