CN115558535A - Modified titanium dioxide composite material, preparation method thereof, electrorheological fluid, preparation method and application thereof - Google Patents

Modified titanium dioxide composite material, preparation method thereof, electrorheological fluid, preparation method and application thereof Download PDF

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CN115558535A
CN115558535A CN202211331251.9A CN202211331251A CN115558535A CN 115558535 A CN115558535 A CN 115558535A CN 202211331251 A CN202211331251 A CN 202211331251A CN 115558535 A CN115558535 A CN 115558535A
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titanium dioxide
composite material
dioxide composite
modified titanium
electrorheological fluid
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丁奇
曹文辉
胡丽天
秦宝锋
张松伟
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/001—Electrorheological fluids; smart fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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    • 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
    • C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
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    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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Abstract

The invention belongs to the technical field of electric response materials, and particularly relates to a modified titanium dioxide composite material and a preparation method thereof, and an electrorheological fluid and a preparation method and application thereof. The invention provides a modified titanium dioxide composite material, which comprises titanium dioxide and polyion liquid coated on the surface of the titanium dioxide; the polyion liquid has a structural formula shown in a formula 1. In the invention, the titanium dioxide has high dielectric constant, and the long-chain polymeric part in the polyionic liquid has a binding effect on small-volume ions, so that the moving speed of the ions is reducedAnd reduces the conductivity of the polyionic liquid. According to the invention, the titanium dioxide and the polyion liquid are compounded, so that the responsivity of the modified titanium dioxide composite material in a low-voltage alternating current field is improved, and the viscosity of the modified titanium dioxide composite material can be rapidly adjusted according to the change of the electric field frequency.
Figure DDA0003913305770000011

Description

Modified titanium dioxide composite material and preparation method thereof, electrorheological fluid and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electric response materials, and particularly relates to a modified titanium dioxide composite material and a preparation method thereof, and an electrorheological fluid and a preparation method and application thereof.
Background
The intelligent response material is a material which can change the physical and chemical properties thereof under the external stimulation. The intelligent response material comprises a force response material, a light response material, a thermal response material and an electric response material, wherein the electric response material has the widest application range and can be applied to the fields of sensors, intelligent skin, biomedicine and the like.
The electrorheological fluid is a representative electrorheological fluid, and can enable yield stress, viscosity or elastic modulus to be changed violently according to the change of electric field intensity. The electrorheological fluid comprises a dispersion phase and a solvent, wherein the dispersion phase is polarizable nano particles, when the electric field intensity is zero, the dispersion phase is randomly distributed in the insulating fluid, after a certain electric field intensity is applied, the dispersion phase immediately forms linear arrangement in the insulating fluid, and after the applied electric field exceeds a certain intensity, the dispersion phase is more tightly arranged due to the electrostatic attraction effect to form a columnar structure, the mobility of the electrorheological fluid is gradually reduced and is finally converted into a solid-like body, the yield stress and the elastic modulus of the electrorheological fluid can also be changed along with the change of the mobility of the electrorheological fluid, namely the yield stress and the elastic modulus of the electrorheological fluid are changed along with the change of an external electric field.
At present, the dispersed phase of the electrorheological fluid is mainly titanium dioxide, but the responsivity of the electrorheological fluid only taking the titanium dioxide as the dispersed phase is lower. Researchers have improved the polarization characteristics of titanium dioxide by modifying the titanium dioxide, thereby improving its responsiveness. For example, chinese patent CN 106867629AOpen a TiO 2 /H 2 Ti 2 O 5 An electrorheological fluid material and a preparation method thereof, china patent CN 111004674A discloses an electrorheological fluid with a nanometer core-shell structure and a preparation method thereof, and China patent CN 109181815A discloses a preparation method of a metal organic framework-titanium oxide compound electrorheological fluid. In the prior art, the responsivity of the titanium dioxide is improved by modifying the structure and the composition of a titanium dioxide dispersion phase, but the existing modified titanium dioxide has higher responsivity only under higher electric field intensity, and the electro-rheological property is difficult to realize by responding to the electric field frequency in a low-voltage alternating current electric field.
Disclosure of Invention
In view of the above, the invention provides a modified titanium dioxide composite material and a preparation method thereof, an electrorheological fluid and a preparation method and application thereof.
In order to solve the technical problems, the invention provides a modified titanium dioxide composite material, which comprises titanium dioxide and polyion liquid coated on the surface of the titanium dioxide; the polyion liquid has a structural formula shown in a formula 1:
Figure BDA0003913305750000021
preferably, the average particle size of the modified titanium dioxide composite material is 200 to 500nm.
The invention also provides a preparation method of the modified titanium dioxide composite material, which comprises the following steps:
mixing isopropyl titanate, 1-vinyl-3-ethylimidazole tetrafluoroborate, polyvinylpyrrolidone, azodiisobutyronitrile, ethanol and water, and carrying out one-pot reaction to obtain the modified titanium dioxide composite material.
Preferably, the mixing comprises the steps of:
dispersing isopropyl titanate in ethanol to obtain an ethanol dispersion of isopropyl titanate;
first mixing the ethanol dispersion of isopropyl titanate and 1-vinyl-3-ethylimidazole tetrafluoroborate to obtain a mixture dispersion;
and carrying out second mixing on the mixture dispersion liquid, the polyvinylpyrrolidone and the azobisisobutyronitrile, and adding water into a second mixed system.
Preferably, the volume ratio of the isopropyl titanate to the ethanol is 4.5-5.5 g;
the mass ratio of the isopropyl titanate to the 1-vinyl-3-ethylimidazole tetrafluoroborate is 4.5-5.5;
the mass ratio of the isopropyl titanate to the polyvinylpyrrolidone is 4.5-5.5;
the mass ratio of the isopropyl titanate to the azodiisobutyronitrile is 4.5-5.5;
the volume ratio of the ethanol to the water is 80-90.
Preferably, the temperature of the one-pot reaction is 65-80 ℃; the one-pot reaction time is 11-13 h.
The invention also provides an electrorheological fluid which comprises a dispersion phase and a solvent and is characterized in that the dispersion phase is the modified titanium dioxide composite material prepared by the preparation method of the technical scheme or the modified titanium dioxide composite material prepared by the preparation method of the technical scheme; the solvent is water.
Preferably, the volume ratio of the dispersed phase to the solvent is 10 to 20.
The invention also provides a preparation method of the electrorheological fluid in the technical scheme, which comprises the following steps:
ultrasonically dispersing the dispersed phase into water to obtain the electrorheological fluid; the power of the ultrasonic dispersion is 500-600W, the frequency of the ultrasonic dispersion is more than or equal to 40KHz, and the time of the ultrasonic dispersion is 20-40 min.
The invention also provides the application of the electrorheological fluid in the technical scheme or the electrorheological fluid prepared by the preparation method in the technical scheme as a lubricant.
The invention provides a modified titanium dioxide composite material, which comprises titanium dioxide and polyion liquid coated on the surface of the titanium dioxide; the polyion liquid has a structural formula shown in a formula 1:
Figure BDA0003913305750000031
in the invention, the titanium dioxide has high dielectric constant, and the long-chain polymeric part in the polyionic liquid is opposite to small-volume ions (-BF) 4 - ) Has a binding effect, reduces the moving speed of ions and reduces the conductivity of the polyion liquid. According to the invention, the responsivity of the modified titanium dioxide composite material in a low-voltage alternating current field is improved after the titanium dioxide and the polyion liquid are compounded, and the viscosity of the modified titanium dioxide composite material can be rapidly adjusted according to the change of current.
Drawings
FIG. 1 is an SEM image of a modified titanium dioxide composite material prepared in example 1;
FIG. 2 is an IR spectrum of a modified titanium dioxide composite material prepared in example 1;
FIG. 3 is a graph of the response of an electrorheological fluid prepared in example 1 to an electric current;
FIG. 4 is a graph of the response of an electrorheological fluid prepared in example 2 to an electric current;
fig. 5 is a graph of the response of an electrorheological fluid prepared in example 3 to an electric current.
Detailed Description
The invention provides a modified titanium dioxide composite material, which comprises titanium dioxide and polyion liquid coated on the surface of the titanium dioxide; the polyion liquid has a structural formula shown in formula 1:
Figure BDA0003913305750000041
in the present invention, the modified titanium dioxide composite material is preferably a powder; the average particle size of the modified titanium dioxide composite material is preferably 200 to 500nm, and more preferably 300 to 400nm.
The preparation method of the modified titanium dioxide composite material in the technical scheme of the invention comprises the following steps:
mixing isopropyl titanate, 1-vinyl-3-ethylimidazole tetrafluoroborate, polyvinylpyrrolidone, azodiisobutyronitrile, ethanol and water, and carrying out one-pot reaction to obtain the modified titanium dioxide composite material. In the present invention, the mixing preferably comprises the steps of:
dispersing isopropyl titanate in ethanol to obtain ethanol dispersion of isopropyl titanate;
first mixing the ethanol dispersion of isopropyl titanate and 1-vinyl-3-ethylimidazole tetrafluoroborate to obtain a mixture dispersion;
and carrying out second mixing on the mixture dispersion liquid, polyvinylpyrrolidone and azobisisobutyronitrile, and dripping water into the second mixed system to obtain a solution to be reacted.
The invention disperses isopropyl titanate in ethanol to obtain the ethanol dispersion of isopropyl titanate. In the present invention, the ethanol is preferably anhydrous ethanol. In the present invention, the volume ratio of the isopropyl titanate (TTIP) to ethanol is preferably 4.5 to 5.5g, more preferably 4.5 to 5.2 g. In embodiments of the invention, the mass to volume ratio of isopropyl titanate to ethanol is 5 g. In the present invention, the dispersion is preferably carried out under stirring conditions, and the rotation speed of the stirring is preferably 280 to 320r/min, more preferably 300r/min; the stirring time is preferably 8 to 12min, more preferably 10min.
In the present invention, the isopropyl titanate is hydrolyzed to produce titanium dioxide in a one-pot reaction process.
After the ethanol dispersion of isopropyl titanate is obtained, the ethanol dispersion of isopropyl titanate and 1-vinyl-3-ethylimidazole tetrafluoroborate are subjected to first mixing to obtain a mixture dispersion. In the present invention, the isopropyl titanate and 1-vinyl-3-ethylimidazole tetrafluoroborate ([ VEIm)][BF 4 ]) The mass ratio of (b) is preferably 4.5 to 5.55-5.5, more preferably 4.5-5.2. In the embodiment of the invention, the mass ratio of the isopropyl titanate to the 1-vinyl-3-ethylimidazole tetrafluoroborate is 1.
In the invention, the 1-vinyl-3-ethylimidazole tetrafluoroborate monomer is polymerized in a one-pot reaction to generate polyion liquid.
In the present invention, the first mixing is preferably performed under stirring conditions, and the rotation speed of the stirring is preferably 280 to 320r/min, more preferably 300r/min; the stirring time is preferably 8 to 12min, more preferably 10min.
After the mixture dispersion liquid is obtained, the mixture dispersion liquid, the polyvinylpyrrolidone and the azobisisobutyronitrile are subjected to second mixing, and water is dripped into a system obtained after the second mixing to obtain a solution to be reacted. In the present invention, the mass ratio of isopropyl titanate to polyvinylpyrrolidone (PVP) is preferably 4.5 to 5.5, more preferably 4.5 to 5.2. In the embodiment of the present invention, the mass ratio of the isopropyl titanate to the polyvinylpyrrolidone is specifically 5.
In the present invention, the mass ratio of isopropyl titanate to Azobisisobutyronitrile (AIBN) is preferably 4.5 to 5.5, more preferably 4.5 to 5.2. In the embodiment of the present invention, the mass ratio of isopropyl titanate to azobisisobutyronitrile is specifically 5.
In the invention, the polyvinylpyrrolidone and the azodiisobutyronitrile are used as initiators of polymerization reaction.
In the present invention, the second mixing is preferably performed under stirring conditions, and the rotation speed of the stirring is preferably 280 to 320r/min, and more preferably 300r/min; the stirring time is preferably 18 to 22min, more preferably 20min.
In the present invention, the water is preferably deionized water. In the present invention, the volume ratio of ethanol to water is preferably 80 to 90. In the present invention, the rate of the dropwise addition is preferably 5 to 10mL/min, more preferably 7 to 8mL/min.
In the invention, the stirring ensures that the raw materials are uniformly mixed and can remove oxygen in a solution system to be reacted, thereby being beneficial to the subsequent reaction.
In the present invention, the one-pot reaction is preferably carried out under a protective gas; the protective gas preferably comprises nitrogen. In the present invention, it is preferable to introduce a protective gas into the solution to be reacted. The invention can prevent oxidation in the reaction process by carrying out one-pot reaction under the protective gas. In the present invention, the one-pot reaction includes a hydrolysis reaction and a polymerization reaction.
In the invention, the temperature of the one-pot reaction is preferably 65-80 ℃, and more preferably 70-75 ℃; the time for the one-pot reaction is preferably 11 to 13 hours, and more preferably 12 hours. In the present invention, the one-pot reaction is preferably accompanied by stirring, and the rotation speed of the stirring is not particularly limited as long as sufficient reaction can be ensured.
In the present invention, it is preferable that the one-pot reaction further comprises:
cooling and carrying out solid-liquid separation on the system after one pot is used to obtain a solid;
and washing and drying the solid to obtain the modified titanium dioxide composite material.
In the present invention, the temperature of the system after cooling is preferably 20 to 35 ℃, more preferably 25 to 30 ℃. The invention has no special requirement on the cooling mode as long as the required temperature can be achieved.
In the present invention, the solid-liquid separation is preferably centrifugation; the rotating speed of the centrifugation is preferably 5000-10000 r/min, more preferably 8000-10000 r/min; the time for the centrifugation is preferably 6 to 10min, more preferably 6 to 8min.
In the present invention, the washing preferably includes sequentially performing an absolute ethanol washing and a deionized water washing. In the present invention, the number of washing with anhydrous ethanol is preferably 2 to 4, more preferably 3; the number of washing with deionized water is preferably 2 to 4, more preferably 3.
In the present invention, the drying is preferably vacuum freeze-drying, and the temperature of the vacuum freeze-drying is preferably-20 to-40 ℃, and more preferably-25 to-35 ℃; the freeze-drying time is preferably 22 to 26 hours, and more preferably 23 to 24 hours.
In the present invention, it is preferable that the drying further comprises: and grinding the dried product. In the present invention, the average particle diameter of the ground product is preferably 200 to 500nm, more preferably 300 to 400nm. The grinding mode of the invention has no special requirement as long as the required particle size can be achieved.
The invention also provides an electrorheological fluid which comprises a dispersion phase and a solvent, wherein the dispersion phase is the modified titanium dioxide composite material prepared by the technical scheme or the modified titanium dioxide composite material prepared by the preparation method of the technical scheme. In the present invention, the solvent is water, and the water is preferably deionized water.
In the present invention, the volume ratio of the dispersed phase to the solvent is preferably 10 to 20, more preferably 15 to 18.
The invention also provides a preparation method of the electrorheological fluid in the technical scheme, which comprises the following steps:
and ultrasonically dispersing the dispersed phase into water to obtain the electrorheological fluid. In the invention, the power of the ultrasonic dispersion is 500-600W, preferably 550-580W; the ultrasonic frequency of the ultrasonic dispersion is more than or equal to 40KHz, preferably 45-50 KHz; the time of ultrasonic dispersion is 20-40 min, preferably 25-35 min, and more preferably 30min.
The invention also provides the application of the electrorheological fluid prepared by the preparation method of the technical scheme or the electrorheological fluid as a lubricant. In the present invention, the lubricant is preferably a lubricant in a machine-lubricated part; the mechanical lubrication means preferably comprises a thrust bearing or a hydrodynamic bearing involving an electrical scene. The invention can regulate and control the viscosity of the lubricant by controlling the change of the low-voltage alternating current electric field, thereby realizing the regulation and control of the lubricating performance of the mechanical lubricating part.
In the invention, when the electrorheological fluid is used as a lubricant, the lubricant is added to a friction interface, and a low-frequency and low-voltage alternating-current electric field is applied, so that the viscosity of the electrorheological fluid can be controlled, the friction coefficient can be regulated, and the required different lubricating performances can be regulated.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
5g of isopropyl titanate is dispersed in 85mL of absolute ethyl alcohol and stirred for 10min under the condition that the rotating speed is 300r/min, so as to obtain an ethyl alcohol dispersion liquid of isopropyl titanate;
stirring the ethanol dispersion of isopropyl titanate and 5g of 1-vinyl-3-ethylimidazole tetrafluoroborate for 10min at the rotating speed of 300r/min to obtain a mixture dispersion;
stirring the mixture dispersion liquid, 0.32g of polyvinylpyrrolidone and 0.12g of azodiisobutyronitrile for 20min under the condition that the rotating speed is 300r/min, and then dropwise adding 3g of deionized water into the system according to the dropping speed of 7mL/min to obtain a solution to be reacted; carrying out one-pot reaction on the solution to be reacted for 12h at 75 ℃ with stirring;
cooling the system after reaction to 25 ℃, and centrifuging for 8min at the rotating speed of 8000r/min to obtain a solid; washing the solid with absolute ethyl alcohol for 3 times, and then washing with deionized water for 3 times; freeze-drying the washed solid at-35 deg.C for 24h; the dried product was ground to a modified titanium dioxide composite with an average particle size of 300nm, noted as TiO 2 -p[VEIm][BF 4 ]；
Ultrasonically dispersing the obtained modified titanium dioxide composite material in deionized water to obtain electrorheological fluid; the volume ratio of the modified titanium dioxide composite material to the deionized water is 15; the ultrasonic dispersion power is 550W, and the ultrasonic frequency is 45KHz; the ultrasonic dispersion time is 30min.
Example 2
Dispersing 4.5g of isopropyl titanate in 85mL of absolute ethyl alcohol, and stirring for 10min under the condition that the rotating speed is 300r/min to obtain an ethanol dispersion liquid of isopropyl titanate;
stirring ethanol dispersion of isopropyl titanate and 4.5g of 1-vinyl-3-ethylimidazole tetrafluoroborate for 10min at the rotating speed of 300r/min to obtain mixture dispersion;
stirring the mixture dispersion liquid, 0.3g of polyvinylpyrrolidone and 0.11g of azodiisobutyronitrile for 20min under the condition that the rotating speed is 300r/min, and then dripping 2.8g of deionized water into the system according to the dripping speed of 8mL/min to obtain a solution to be reacted; carrying out one-pot reaction on the solution to be reacted for 12h at 75 ℃ with stirring;
cooling the system after reaction to 25 ℃, and centrifuging for 6min under the condition that the rotating speed is 10000r/min to obtain solid; washing the solid with absolute ethyl alcohol for 3 times, and then washing with deionized water for 3 times; vacuum freeze-drying the washed solid at-30 deg.C for 24 hr; the dried product was ground to a modified titanium dioxide composite material with an average particle size of 400nm, noted as TiO 2 -p[VEIm][BF 4 ]；
Ultrasonically dispersing the obtained modified titanium dioxide composite material in deionized water to obtain electrorheological fluid; the volume ratio of the modified titanium dioxide composite material to the deionized water is 10; the ultrasonic dispersion power is 600W, and the ultrasonic frequency is 50KHz; the ultrasonic dispersion time is 20min.
Example 3
5.2g of isopropyl titanate is dispersed in 88mL of absolute ethyl alcohol, and stirred for 10min under the condition that the rotating speed is 300r/min, so as to obtain an ethanol dispersion liquid of isopropyl titanate;
stirring the ethanol dispersion of isopropyl titanate and 5.2g of 1-vinyl-3-ethylimidazole tetrafluoroborate for 10min at the rotating speed of 300r/min to obtain a mixture dispersion;
stirring the mixture dispersion liquid, 0.33g of polyvinylpyrrolidone and 0.13g of azodiisobutyronitrile for 20min under the condition that the rotating speed is 300r/min, and then dripping 3.3g of deionized water into the system according to the dripping speed of 5mL/min to obtain a solution to be reacted; carrying out one-pot reaction on the solution to be reacted for 12h at 75 ℃ with stirring;
cooling the system after reaction to 25 ℃, and centrifuging for 10min at the rotating speed of 6000r/min to obtain solid; washing the solid with absolute ethyl alcohol for 3 times, and then washing with deionized water for 3 times; the washed solid is filteredVacuum freeze drying at 25 deg.C for 24 hr; modified titanium dioxide composite material, denoted TiO, having a mean particle size of 500nm from the dried product 2 -p[VEIm][BF 4 ]；
Ultrasonically dispersing the obtained modified titanium dioxide composite material in deionized water to obtain electrorheological fluid; the volume ratio of the modified titanium dioxide composite material to the deionized water is 20; the ultrasonic dispersion power is 500W, and the ultrasonic frequency is 40KHz; the ultrasonic dispersion time was 40min.
Scanning electron microscope detection is carried out on the modified titanium dioxide composite material prepared in example 1, and an SEM picture is obtained and is shown in figure 1. As can be seen from figure 1, the modified titanium dioxide composite material is granular and uniform in shape, a layer of substance is obviously coated on the surface of the granules, and the substance is determined to be polyion liquid, namely, the titanium dioxide is coated by the polyion liquid.
The modified titanium dioxide composite material prepared in example 1 was subjected to infrared detection to obtain an infrared spectrum, which is shown in fig. 2. As can be seen from FIG. 2, 1649cm -1 ，1369cm -1 ，1167cm -1 And 1084cm -1 The characteristic peak is consistent with the stretching vibration peak of the key functional group of the polyion liquid, which indicates that the product contains polyion liquid components. 400-1000cm -1 The large peak is the characteristic vibration peak of Ti-O, which indicates that TiO exists in the modified titanium dioxide composite material 2 And infrared results show that the modified titanium dioxide composite material is successfully synthesized.
The electrorheological properties of the electrorheological fluids prepared in examples 1 to 3 were examined as follows: an alternating current electric field is introduced between rheometer clamps to serve as an electrode plate, an alternating current electric field of 15V/mm is applied between the electrode plates, and a rheometer is used for viscosity test (the shear rate of the rheometer is 10-30 r/s) on the electrorheological fluid under the electric field frequency of 0Hz and 10Hz respectively to obtain response curves of the electrorheological fluids prepared in the embodiments 1-3 to the current, as shown in fig. 3-5, wherein fig. 3 is the response curve of the electrorheological fluid prepared in the embodiment 1 to the current, fig. 4 is the response curve of the electrorheological fluid prepared in the embodiment 2 to the current, and fig. 5 is the response curve of the electrorheological fluid prepared in the embodiment 3 to the current. The data for some of the results in FIGS. 3-5 are shown in Table 1.
TABLE 1 electrorheological Properties of the electrorheological fluids obtained in examples 1 to 3
Figure BDA0003913305750000091
Figure BDA0003913305750000101
It can be seen from table 1 and fig. 3 to 5 that, after the 10Hz alternating current electric field is added, the viscosity of the electrorheological fluid is rapidly increased, and meanwhile, the viscosity of the electrorheological fluid is changed almost without hysteresis, and the viscosity is changed when the electric field is applied, which shows that the electrorheological fluid provided by the invention has different viscosity along with the change of the low-voltage alternating current electric field, and the response speed is very high.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments are included in the scope of the present invention.

Claims (10)

1. A modified titanium dioxide composite material comprises titanium dioxide and polyion liquid coated on the surface of the titanium dioxide; the polyion liquid has a structural formula shown in formula 1:
Figure FDA0003913305740000011
2. the modified titanium dioxide composite material according to claim 1, wherein the modified titanium dioxide composite material has an average particle diameter of 200 to 500nm.
3. A process for preparing the modified titanium dioxide composite material according to claim 1 or 2, comprising the steps of:
mixing isopropyl titanate, 1-vinyl-3-ethylimidazole tetrafluoroborate, polyvinylpyrrolidone, azodiisobutyronitrile, ethanol and water, and carrying out one-pot reaction to obtain the modified titanium dioxide composite material.
4. The method of claim 3, wherein the mixing comprises the steps of:
dispersing isopropyl titanate in ethanol to obtain an ethanol dispersion of isopropyl titanate;
first mixing the ethanol dispersion of isopropyl titanate and 1-vinyl-3-ethylimidazole tetrafluoroborate to obtain a mixture dispersion;
and carrying out second mixing on the mixture dispersion liquid, the polyvinylpyrrolidone and the azobisisobutyronitrile, and adding water into a second mixed system.
5. The preparation method according to claim 3 or 4, wherein the volume ratio of the isopropyl titanate to the ethanol is 4.5-5.5g;
the mass ratio of the isopropyl titanate to the 1-vinyl-3-ethylimidazole tetrafluoroborate is 4.5-5.5;
the mass ratio of the isopropyl titanate to the polyvinylpyrrolidone is 4.5-5.5;
the mass ratio of the isopropyl titanate to the azodiisobutyronitrile is 4.5-5.5;
the volume ratio of the ethanol to the water is 80-90.
6. The preparation method according to claim 3, wherein the temperature of the one-pot reaction is 65-80 ℃; the one-pot reaction time is 11-13 h.
7. An electrorheological fluid comprising a dispersed phase and a solvent, wherein the dispersed phase is the modified titanium dioxide composite material according to claim 1 or 2 or the modified titanium dioxide composite material prepared by the preparation method according to any one of claims 3 to 6; the solvent is water.
8. The electrorheological fluid of claim 7, wherein the volume ratio of the dispersed phase to the solvent is from 10 to 20.
9. A method for preparing an electrorheological fluid according to claim 7 or 8, comprising the steps of:
ultrasonically dispersing the dispersed phase in water to obtain the electrorheological fluid; the power of the ultrasonic dispersion is 500-600W, the frequency of the ultrasonic dispersion is more than or equal to 40KHz, and the time of the ultrasonic dispersion is 20-40 min.
10. Use of an electrorheological fluid according to claim 7 or 8 or produced by the production method according to claim 9 as a lubricant.
CN202211331251.9A 2022-10-28 2022-10-28 Modified titanium dioxide composite material, preparation method thereof, electrorheological fluid, preparation method and application thereof Pending CN115558535A (en)

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