Background technology
Electrorheological fluid is the complex fluid that is mixed by dielectric grain and insulating liquid, and the structural transformation of similar liquid-solid phase transformation can take place under electric field, is a frontier of material and colloid science research.This shearing resistance of electrorheological fluid is adjustable continuously, the response and the peculiar character of reversible transition fast, can be used for realizing electromechanical integration (mechantronics) intelligent control, be the adjustable intelligent material of unique soft or hard degree, it is considered to make the material that change takes place such as many departments such as the vehicles, hydraulic efficiency installation, machinery manufacturing industry, sensor technology.Found that at present multiple electrorheological fluid can produce electric rheological effect, but because synthetic electro-rheologic fluid material shearing resistance is too low before this, the highest about 10kPa; And the general requirement that engineering is used is greater than 30kPa.In order to reach practical requirement, electrorheological fluid should have high as far as possible yielding stress, secondly also must possess excellent comprehensive performances, comprise that combination, the time of response between resistance to settling, low null field viscosity, low-leakage current density, the strong electrorheological fluid-battery lead plate is short, temperature stability is high, pollution-free and long service life etc.In addition, also require stable performance, yield rate height, technical process that cost is low aspect material preparation, just can obtain can practical electrorheological fluid.Traditional micron electrorheological fluid exists problems such as the mechanics value is not high, resistance to settling is poor, complicated process of preparation, cost height, hinders it and is extensive use of.And the nanometer electro-rheologic fluid material has fundamentally overcome above-mentioned shortcoming, wherein the most outstanding advantage is that yielding stress is significantly improved, substantially exceeded the micron electrorheological fluid, simultaneously, resistance to settling also increases, as the calcium titanate electric rheological liquid of inventions such as Inst. of Physics, CAS land, the titanium-calcium oxyoxalate electrorheological fluid that the urea of report such as Hong Kong University of Science and Thchnology's temperature coats.
Titanium oxide, perovskite inorganic oxide have high specific inductivity, have established good basis for the preparation high-performance current becomes material; The coating of particularly mixing waits modified method to regulate its electricity and leads the further optimization that can realize the electro-rheologic fluid material performance.China has carried out a large amount of work aspect electric titania rheological liquid.Patent CN1944606A has formed the admixture titanium dioxide granule of micron and nanoscale by the strong polar amides of admixture molecule in titanium dioxide, has effectively improved the electrorheological fluid yield strength of titanium dioxide, and preparation technology is simple, not free settling.Patent CN1769403A passes through to change the crystal formation of nano-titanium oxide and changes adjusting and the optimization of acid amides kind realization to ER properties.The alcoholic solution of patent CN1768914A by butyl (tetra) titanate and methane amide hydrolysis reaction in containing the aqueous solution of urea obtains to be compounded with the nano titania particle of urea/methane amide, and the yield value of stress of electrorheological fluid under the effect of 4KV/mm DC electric field that the common grinding of this nano particle and methyl-silicone oil obtains can reach 70KPa.Yet there are no report and have electric titania rheological liquid high ER properties, non-modified or admixture.
Summary of the invention
Technical problem to be solved by this invention is the present situation at prior art, excellent properties such as the high-performance nano electric titania rheological liquid that provides a kind of titanium dioxide not need modification or admixture, this electrorheological fluid have that null field viscosity is low, high yield stress, antisolvent precipitation performance are good; And preparation technology is simple for this electrorheological fluid, and raw material is easy to get.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this nano titanium dioxide electrorheological liquid is characterized in that with the Nano titanium dioxide particle as disperse phase, silicone oil is external phase; The volumetric concentration of Nano titanium dioxide is 5~50% in this electrorheological fluid;
Wherein, described Nano titanium dioxide particulate preparation method is as follows:
1. with titanium salt and dehydrated alcohol or anhydrous isopropyl alcohol 1:1~10 uniform mixing by volume, add a small amount of glacial acetic acid then, obtain solution T; Preferably, described titanium salt can be selected titanium tetrachloride, titanium tetrabromide, tetrabutyl titanate, tetraethyl titanate or titanium isopropylate for use; Usually the volume ratio of titanium salt and glacial acetic acid is 300~400:1;
2. with organic alkane and the water mixed of 1:10~30 by volume, obtain solution O; Preferably, described organic alkane can be selected Skellysolve A, normal hexane, normal heptane, octane or octane-iso for use;
3. by volume for the ratio of T:O=5~20:1 is added drop-wise to solution O among the solution T, form precipitation gradually; After reacting completely, be deposited in 20~50 ℃ of ageings 8~12 hours with what generate;
4. for several times, filter the precipitate with deionized water after the ageing and absolute ethanol washing, in 50~60 ℃ of following vacuum-dryings 20~30 hours, and then 105~120 ℃ dry 3~5 hours down, promptly obtain described Nano titanium dioxide particle.
Described Nano titanium dioxide particle is mixed with silicone oil, make the Nano titanium dioxide volumetric solid concentration and be 5~50% electrorheological fluid; The viscosity of described silicone oil is 5~800mm
2/ s.
Compared with prior art, nano titanium dioxide electrorheological liquid provided by the invention, need not titanium dioxide is modified or admixture, suppress the titanium salt hydrolysis rate by adding a small amount of glacial acetic acid, the Nano titanium dioxide particle that obtains with control is the sphere of rule, this nano particle helps reducing the null field viscosity of electro-rheologic fluid material, improves the mechanics value under electro-rheologic fluid material resistance to settling and the electric field excitation; Use the electrorheological fluid that this Nano titanium dioxide particle and silicone oil mixed configuration form, have extremely strong electric rheological effect, low, nontoxic, pollution-free, the no burn into chemical stability of current density is good.And Nano titanium dioxide electrorheological fluid preparation method of the present invention is simple, easy to operate, cost is low.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1:
With 34ml tetrabutyl titanate and anhydrous isopropyl alcohol by volume 1:4 mix, add the glacial acetic acid of 0.1mL, stir, obtain stable solution T; Octane-iso 1ml with after 30ml water mixes, is obtained solution O; Under stirring condition, under the room temperature,, solution O is added drop-wise among the solution T with the volume ratio of T:O=5:1, precipitation forms gradually.After reacting completely, this was precipitated ageing at normal temperatures 10 hours, then with precipitate with deionized water and absolute ethanol washing 4 times, filter, dry 60 ℃ of following dryings are 20 hours in vacuum, through 120 ℃ of dry 4h, promptly obtain the titanium dioxide granule that required nano-scale distributes.
With this titanium dioxide granule and viscosity 50mm
2The dimethyl silicone oil uniform mixing of/s is made into volume fraction and is 10% electric titania rheological liquid of the present invention.When extra electric field V=3kV/mm, the shearing resistance of 10% electrorheological fluid can reach 80kPa, and current density is 6 μ A, and null field viscosity is 5Pas.
Embodiment 2:
With 34ml tetrabutyl titanate and anhydrous isopropyl alcohol by volume 1:7 mix, add the glacial acetic acid of 0.1mL, stir, obtain stable solution T; Octane-iso 1ml with after 12.6ml water mixes, is obtained solution O; Under stirring condition, under the room temperature, solution O is added drop-wise among the solution T with the volume ratio of T:O=20:1, precipitation forms gradually.After reacting completely, this was precipitated ageing at normal temperatures 10 hours, then with precipitate with deionized water and absolute ethanol washing 4 times, filter, dry 60 ℃ of following dryings are 25 hours in vacuum, through 120 ℃ of dry 4h, promptly obtain the titanium dioxide granule that required nano-scale distributes.
With this titanium dioxide granule and viscosity 100mm
2The dimethyl silicone oil uniform mixing of/s is made into volume fraction and is 30% electric titania rheological liquid of the present invention.When extra electric field V=3kV/mm, the shearing resistance of 30% electrorheological fluid can reach 150kPa, and current density is 10 μ A, and null field viscosity is 11Pas.
Embodiment 3:
With 34ml tetrabutyl titanate and anhydrous isopropyl alcohol by volume 1:9 mix, add the glacial acetic acid of 0.1mL, stir, obtain stable solution T; Octane-iso 1ml with after 19ml water mixes, is obtained solution O; Under stirring condition, under the room temperature, solution O is added drop-wise among the solution T with the volume ratio of T:O=17:1, precipitation forms gradually.After reacting completely, this was precipitated ageing at normal temperatures 10 hours, then with precipitate with deionized water and absolute ethanol washing 4 times, filter, dry 60 ℃ of following dryings are 30 hours in vacuum, through 120 ℃ of dry 4h, promptly obtain the titanium dioxide granule that required nano-scale distributes.
With this titanium dioxide granule and viscosity 200mm
2The dimethyl silicone oil uniform mixing of/s is made into volume fraction and is 50% electric titania rheological liquid of the present invention.When extra electric field V=3kV/mm, the shearing resistance of 50% electrorheological fluid can reach 210kPa, and current density is 20 μ A, and null field viscosity is 16Pas.
Embodiment 4:
With 30ml titanium tetrachloride and dehydrated alcohol by volume 1:5 mix, add the glacial acetic acid of 0.1mL, stir, obtain stable solution T; Octane 1ml with after 24ml water mixes, is obtained solution O; Under stirring condition, in 30 ℃ of water-baths, solution O is added drop-wise among the solution T with the volume ratio of T:O=7.2:1, precipitation forms gradually.After reacting completely, this was deposited in 30 ℃ of water-baths ageing 12 hours, then with precipitate with deionized water and absolute ethanol washing 4 times, filter, dry 60 ℃ of following dryings are 23 hours in vacuum, through 120 ℃ of dry 4h, promptly obtain the titanium dioxide granule that required nano-scale distributes.
With this titanium dioxide granule and viscosity 400mm
2The methyl-silicone oil uniform mixing of/s is made into volume fraction and is 20% electric titania rheological liquid of the present invention.When extra electric field V=3kV/mm, the shearing resistance of 20% electrorheological fluid can reach 110kPa, and current density is 12 μ A, and null field viscosity is 8Pas.
Embodiment 5:
With 34ml tetraethyl titanate and dehydrated alcohol by volume 1:6 mix, add the glacial acetic acid of 0.1mL, stir, obtain stable solution T; Normal heptane 1ml with after 15ml water mixes, is obtained solution O; Under stirring condition, in 30 ℃ of water-baths, solution O is added drop-wise among the solution T with the T:O=14.9:1 volume ratio, precipitation forms gradually.After reacting completely, this was deposited in 50 ℃ of water-baths ageing 10 hours, then with precipitate with deionized water and absolute ethanol washing 4 times, filter, dry 60 ℃ of following dryings are 28 hours in vacuum, through 120 ℃ of dry 4h, promptly obtain the titanium dioxide granule that required nano-scale distributes.
With this titanium dioxide granule and viscosity 700mm
2The methyl-silicone oil uniform mixing of/s is made into volume fraction and is 40% electric titania rheological liquid of the present invention.When extra electric field V=3kV/mm, the shearing resistance of 40% electrorheological fluid can reach 160kPa, and current density is 18 μ A, and null field viscosity is 18Pas.
Embodiment 6:
With 34ml titanium tetrabromide and dehydrated alcohol by volume 1:1 mix, add the glacial acetic acid of 0.1mL, stir, obtain stable solution T; Normal hexane 1ml with after 8 water mix, is obtained solution O; Under stirring condition, in 40 ℃ of water-baths, solution O is added drop-wise among the solution T with the volume ratio of T:O=7.6:1, precipitation forms gradually.After reacting completely, this was deposited in 40 ℃ of water-baths ageing 12 hours, then with precipitate with deionized water and absolute ethanol washing 4 times, filter, dry 60 ℃ of following dryings are 25 hours in vacuum, through 120 ℃ of dry 4h, promptly obtain the titanium dioxide granule that required nano-scale distributes.
With this titanium dioxide granule and viscosity 800mm
2The hydroxy silicon oil uniform mixing of/s is made into volume fraction and is 5% electric titania rheological liquid of the present invention.When extra electric field V=3kV/mm, the shearing resistance of 5% electrorheological fluid can reach 50kPa, and current density is 11 μ A, and null field viscosity is 9Pas.
Embodiment 7:
With 34ml titanium isopropylate and anhydrous isopropyl alcohol by volume 1:3 mix, add the glacial acetic acid of 0.1mL, stir, obtain stable solution T; Skellysolve A 1ml with after 15ml water mixes, is obtained solution O; Under stirring condition, in 50 ℃ of water-baths,, solution O is added drop-wise among the solution T with the volume ratio of T:O=8.5:1, precipitation forms gradually.After reacting completely, this was deposited in 50 ℃ of water-baths ageing 8 hours, then with precipitate with deionized water and absolute ethanol washing 4 times, filter, dry 60 ℃ of following dryings are 24 hours in vacuum, through 120 ℃ of dry 4h, promptly obtain the titanium dioxide granule that required nano-scale distributes.
With this titanium dioxide granule and viscosity 300mm
2The hydroxy silicon oil uniform mixing of/s is made into volume fraction and is 40% electric titania rheological liquid of the present invention.When extra electric field V=3kV/mm, the shearing resistance of 40% electrorheological fluid can reach 220kPa, and current density is 15 μ A, and null field viscosity is 16Pas.The relation of measuring its yielding stress and strength of electric field as shown in Figure 2, the SEM picture of its pattern scanning is as shown in Figure 1.
Embodiment 8:
With 34ml titanium isopropylate and anhydrous isopropyl alcohol by volume 1:2 mix, add the glacial acetic acid of 0.1mL, stir, obtain stable solution T; Octane-iso 1ml with after 5.5ml water mixes, is obtained solution O; Under stirring condition, under the room temperature condition,, solution O is added drop-wise among the solution T with the volume ratio of T:O=15.7:1, precipitation forms gradually.After reacting completely, this was precipitated ageing at room temperature 10 hours, then with precipitate with deionized water and absolute ethanol washing 4 times, filter, dry 60 ℃ of following dryings are 26 hours in vacuum, through 120 ℃ of dry 4h, promptly obtain the titanium dioxide granule that required nano-scale distributes.
With this titanium dioxide granule and viscosity 500mm
2The dimethyl silicone oil uniform mixing of/s is made into volume fraction and is 30% electric titania rheological liquid of the present invention.When extra electric field V=3kV/mm, the shearing resistance of 30% electrorheological fluid can reach 180kPa, and current density is 12 μ A, and null field viscosity is 12Pas.