CN100448962C - Transition metal ion doped titanium dioxide electrorheological materials - Google Patents
Transition metal ion doped titanium dioxide electrorheological materials Download PDFInfo
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- CN100448962C CN100448962C CNB2003101058228A CN200310105822A CN100448962C CN 100448962 C CN100448962 C CN 100448962C CN B2003101058228 A CNB2003101058228 A CN B2003101058228A CN 200310105822 A CN200310105822 A CN 200310105822A CN 100448962 C CN100448962 C CN 100448962C
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Abstract
The present invention relates to electrorheological fluid material, particularly to anhydrous electrorheological fluid material doped with transition metal ion modified titanium dioxide. Compared with the previous rare earth doped modified titanium dioxide electrorheological fluid material, the present invention selects cheap and easy access transition metal ions such as chromium, iron, copper, etc. as doping agents; a normal-temperature sol-gel method is used for preparing the modified titanium dioxide electrorheological fluid material. The material not only has high mechanical property (an accompanying diagram displays the relation curve of the shearing stress and the shearing rate of titanium dioxide electrorheological fluid modified by doping the transition chromium metal ions at 25 DEG C and with the grain volume ratio of 18%) and simultaneously overcomes the problem that expensive rare earth elements are used as the doping agents; the present invention greatly reduces the cost of the original material and widens the varieties of the modified titanium dioxide electrorheological fluid material.
Description
Technical field
The present invention relates to a kind of electro-rheologic fluid material, particularly containing transition metal ionic electric titania rheological liquid material.
Background technology
Electrorheological fluid is made up of in transformer oil the particles dispersed of high-k usually.The electrorheological fluid oneself viscosity can be undergone mutation when being subjected to electric field action, when strength of electric field during greater than a certain value electrorheological fluid can change into by liquid state solid-state, thereby have stronger anti-shear ability.Particularly these variations of electrorheological fluid can be subjected to the outfield size modulations, have the characteristics such as fast reversible that respond.Therefore electrorheological fluid is with a wide range of applications at many industrial circles, as vibroshock, deoscillator, robot control, moment transmitting device etc.The late nineteen eighties, anhydrous electric rheological liquid was succeeded in developing, as electrorheological fluid such as polyaniline that English Patent 1501635,2100740A, 2170510B etc. reported and modified polyanilines; United States Patent (USP) 4,879, the 056 Aluminosilicates electrorheological fluid of being reported; The carbon containing class electrorheological fluid that Japanese Patent 63-97694,7-90287 etc. reported etc.The electrorheological fluid that these materials are prepared has overcome the shortcoming of moisture electrorheological fluid temperature stability difference preferably.But it is lower that the shortcoming of these electrorheological fluid is mechanical strengths, still can not satisfy the industrial application requirement.Developed some in recent years in succession and had the electric titania rheological liquid of the rare-earth-doped modification of higher mechanical strength, as Chinese patent 99115944.6 etc.Yet rare earth dopedly make that these electro-rheologic fluid materials cost an arm and a leg, less being difficult to of kind is widely used owing to using.
Summary of the invention
For solving the above-mentioned shortcoming of electric titania rheological liquid of rare-earth-doped modification, the invention provides a kind of with cheap and the transition metal ion-modified electric titania rheological liquid littler than titanium ion radius, its disperse phase is a containing transition metal ionic titanium dioxide dielectric grain, the external phase base fluid is a methyl-silicone oil, it is characterized in that titanium dioxide is as base matter in the disperse phase containing transition metal ionic titanium dioxide, to its adulterated transition metal ion is the chromium littler than titanium ion radius, a kind of in the cupric ion, transition metal ion encloses molten form with displacement and is present in the body material, the mol ratio of transition metal ion and titanium ion greater than 0 smaller or equal to 0.30; Prepare this material and adopt traditional sol gel reaction technology, simple to operate, because reaction is begun by solution, easily realize the even doping of oligo-elements, thereby control product component and performance easily, these transition metal ion-modified electric titania rheological liquids that obtain are suitable with the electric titania rheological liquid mechanics value of rare-earth-doped modification, make the too high shortcoming of electrorheological fluid cost with the rare-earth element modified of costliness but overcome.
Description of drawings
The relation of Fig. 1 containing transition metal ionic electric titania rheological liquid yielding stress and strength of electric field (direct current) (25 ℃)
The relation of the chromium-doped ionic titanium dioxide of Fig. 2 (Cr/Ti=0.08) electrorheological fluid current density and strength of electric field (direct current) (25 ℃)
The relation (25 ℃) of the shearing resistance of the chromium-doped ionic titanium dioxide of Fig. 3 (Cr/Ti=0.08) electrorheological fluid and shearing rate
The relation (25 ℃) of the apparent viscosity of the chromium-doped ionic titanium dioxide of Fig. 4 (Cr/Ti=0.08) electrorheological fluid and shearing rate
The yielding stress of the chromium-doped ionic electric titania rheological liquid of Fig. 5 and the relation of granule density (25 ℃)
The yielding stress of the chromium-doped ionic electric titania rheological liquid of Fig. 6 and the relation of chromium ion concentration (25 ℃)
Embodiment
The concrete enforcement of the present invention is as follows: select the chemical pure tetrabutyl titanate for use, and the muriate of analytical pure chromium nitrate, cupric nitrate or respective metal, secondary deionized water is made reaction raw materials, and the analytical pure dehydrated alcohol is made organic solvent, and analytical pure nitric acid or hydrochloric acid are made catalyzer; The mole proportioning of reactant is a tetrabutyl titanate: dehydrated alcohol: water: nitric acid or hydrochloric acid=and 1: 20: 0.625: 0.1～0.2, take by weighing above-mentioned nitrate or chlorate by certain transition metal ion/titanium ion mol ratio; The pH value of solution is 2～3, and temperature of reaction is between 15～35 ℃; At first half dehydrated alcohol of tetrabutyl titanate and total amount is mixed and obtain first component; The dehydrated alcohol that the nitrate or the chlorate of secondary deionized water, respective metal is dissolved in remaining half amount is as second component; Form clear solution among second component slowly is added drop-wise to first component, and to regulate the pH value be 2～3; This clear solution left standstill gelling in 12～48 hours and with gel 80 ℃ of vacuum-dryings 7～8 hours, obtain the xerogel blocky-shaped particle; With mortar it is ground into fine powder, changes crucible over to and carry out continuous heat treatment, promptly obtain containing transition metal ion electric titania rheological liquid discrete state material by 2 hours, 400 ℃ calcinings of 200 ℃ of calcinings 2 hours and 4 hours technology of 550 ℃ of calcinings; At last this particle is mixed by certain particle/silicone oil volume ratio after 8 hours with through 150 ℃ of methyl-silicone oils after smoking 2 hours 150 ℃ of dryings, promptly obtain containing transition metal ion electric titania rheological liquid.
The performance of implementation procedure of the present invention and material is by embodiment and description of drawings:
Embodiment one: (pure TiO
2Electrorheological fluid)
(density is about 1.0g/cm with the 13.6ml tetrabutyl titanate
3) join in the 20ml dehydrated alcohol, and constantly stirring makes it to mix as first component; A small amount of nitric acid and 0.5ml secondary deionized water mixed to join in addition partly measure in the 20ml dehydrated alcohol as second component.Under room temperature and the vigorous stirring second component slowly being added drop-wise to dropper among first component, adjust pH value=2～3.After waiting to dropwise, continue to stir 5～10 minutes, make reactant mix the formation clear solution, and put into stink cupboard and left standstill 12 hours, allow its gelling.After treating gel formation, put it into 80 ℃ of vacuum drying oven inner dryings 7～8 hours, the dry gel particle that obtains loosening, put into crucible with mortar after with its porphyrize and change chamber type electric resistance furnace over to, handled continuously in 4 hours by 2 hours, 400 ℃ calcinings of 200 ℃ of calcinings 2 hours and 550 ℃ of calcinings, obtain the pure titinium dioxide powder of white.The pure titinium dioxide powder that obtains white mixed by the volume ratio 18% of particle/silicone oil promptly obtain electric titania rheological liquid.The relation of measuring its dynamic yield stress and strength of electric field as shown in Figure 1.
Embodiment two:
The 13.6ml tetrabutyl titanate is joined in the 20ml dehydrated alcohol, and constantly stirring makes it to mix as first component; With a small amount of nitric acid acid, the 0.5ml secondary deionized water, 0.48 gram chromium nitrate mixes to join partly to measure in addition and forms clear solution in the 20ml dehydrated alcohol as second component.Under room temperature and the vigorous stirring second component slowly being added drop-wise to dropper among first component, adjust pH value=2～3 with nitric acid.After waiting to dropwise, continue to stir 5～10 minutes, make reactant mix the formation clear solution, leave standstill and allowed its gelling in 24 hours.After treating gel formation, put it into 80 ℃ of vacuum drying oven inner dryings 7～8 hours, the dry gel particle that obtains loosening, put into crucible with mortar after with its porphyrize and change chamber type electric resistance furnace over to, handled continuously in 4 hours by the calcining of 2 hours, 400 ℃ calcinings of 200 ℃ of calcinings 2 hours and 550 ℃, the chromium/titanium mol ratio that contains that obtains brown is 8% chromium ion-doped titanium dioxide powder.Mix and promptly obtain electric titania rheological liquid obtaining the volume ratio 18% of powder by particle/silicone oil.The relation of measuring its dynamic yield stress and strength of electric field as shown in Figure 1, the relation of current density and strength of electric field as shown in Figure 2, the relation of shearing resistance and shearing rate as shown in Figure 3, the relation of apparent viscosity and shearing rate is as shown in Figure 4.
Embodiment three:
Press the preparation process of embodiment two, prepare chromium ion blended titanium dioxide granule material, and be mixed with electrorheological fluid by above-mentioned particle/silicone oil volume ratio 10%, 18%, 23%, 17%, 34%.The relation of measuring its yielding stress and strength of electric field as shown in Figure 5.
Embodiment four:
Press the preparation process of embodiment two, take by weighing the chromium ion blended titanium dioxide granule material that chromium nitrate 0.32 restrains, 0.64 gram, 1.76 restrains, 2.40 restraints are equipped with different volumetric molar concentrations, and be mixed with electrorheological fluid by above-mentioned particle/silicone oil volume ratio 18%.The relation of measuring its dynamic yield stress and strength of electric field as shown in Figure 6.
Embodiment five:
Press the preparation process of embodiment two, cupric ion titanium dioxide granule material is mixed in the preparation that takes by weighing 0.50 gram cupric nitrate, and is mixed with electrorheological fluid by above-mentioned particle/silicone oil volume ratio 18%.The relation of measuring its dynamic stress and strength of electric field as shown in Figure 1.As a comparison, we are also by above-mentioned technological process, take by weighing 0.51 gram zinc nitrate and prepared and mix zine ion titanium dioxide granule material, and be mixed with electrorheological fluid by above-mentioned particle/silicone oil volume ratio 18%, the relation of measuring its dynamic stress and strength of electric field as shown in Figure 1.Contrasting electric titania rheological liquid as seen chromium-doped, cupric ion has than pure titinium dioxide and zine ion electric titania rheological liquid better properties.
Claims (2)
1, a kind of containing transition metal ionic electric titania rheological liquid material, its disperse phase is a containing transition metal ionic titanium dioxide dielectric grain, the external phase base fluid is a methyl-silicone oil; It is characterized in that titanium dioxide is as base matter in the disperse phase containing transition metal ionic titanium dioxide, to its adulterated transition metal is a kind of in chromium, the cupric ion, transition metal ion is present in the body material with displacement solid solution form, the mol ratio of transition metal ion and titanium ion greater than 0 smaller or equal to 0.30.
2, containing transition metal ion electric titania rheological liquid material according to claim 1 is characterized in that this electro-rheologic fluid material prepares by following steps:
1. select tetrabutyl titanate to make the precursor of base matter titanium dioxide, one of in adulterated transition metal ion employing chromium nitrate, cupric nitrate or chromium chloride, the cupric chloride, secondary deionized water is made reaction raw materials, and dehydrated alcohol is made organic solvent, and nitric acid or hydrochloric acid are made catalyzer;
2. the mole proportioning of reactant is a tetrabutyl titanate: dehydrated alcohol: water: nitric acid or hydrochloric acid=and 1: 20: 0.625: 0.1～0.2, the nitrate or the chlorate of transition metal ion on request/titanium mol ratio selected respective metal in taking by weighing 1.; The pH value of solution is 2～3, and temperature of reaction is between 15～35 ℃;
3. half dehydrated alcohol of tetrabutyl titanate and total amount is mixed and obtain first component; Secondary deionized water, respective metal nitrate or chlorate are dissolved in the dehydrated alcohol of remaining half amount as second component; Form clear solution among second component slowly is added drop-wise to first component, and to regulate the pH value be 2～3; This clear solution left standstill gelling in 12～48 hours and with gel 80 ℃ of vacuum-dryings 7～8 hours, obtain the xerogel blocky-shaped particle; With mortar it is ground into fine powder, changes crucible over to and carry out continuous heat treatment, promptly obtain containing transition metal ion electric titania rheological liquid dispersion particle material by 2 hours, 400 ℃ calcinings of 200 ℃ of calcinings 2 hours and 4 hours technology of 550 ℃ of calcinings;
4. with the dry back of this particle 150 ℃/8 hours with mix by certain particle/silicone oil volume ratio through the 150 ℃/methyl-silicone oil smoked in 2 hours, promptly obtain containing transition metal ion electric titania rheological liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100396760C (en) * | 2005-09-02 | 2008-06-25 | 西北工业大学 | Intercalation kaolin/modified titanium oxide nano composite particles electrorheological fluid |
| CN101318694B (en) * | 2008-06-20 | 2010-06-16 | 浙江大学 | Method for preparing titanium dioxide nanocrystalline with highlight catalytic activity in low-temperature |
| CN108865384B (en) * | 2018-07-19 | 2021-10-26 | 中山大学 | Conductor dispersed electrorheological fluid and preparation method thereof |
| CN114574274B (en) * | 2022-03-24 | 2022-12-13 | 中国科学院物理研究所 | Preparation method of conductor micelle dominant giant electrorheological fluid and giant electrorheological fluid thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05194973A (en) * | 1992-01-22 | 1993-08-03 | Toyohisa Fujita | Electric-field-responsive fluid |
| EP0626003A1 (en) * | 1992-01-31 | 1994-11-30 | Lord Corporation | Atomically polarizable electrorheological materials |
| CN1130675A (en) * | 1995-12-01 | 1996-09-11 | 清华大学 | Mica series electric rheologic liquid |
| CN1094636C (en) * | 1999-12-21 | 2002-11-20 | 西北工业大学 | Electric rheopectic liquid containing TiO2 modified by doping rare earth and its preparing process |
-
2003
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05194973A (en) * | 1992-01-22 | 1993-08-03 | Toyohisa Fujita | Electric-field-responsive fluid |
| EP0626003A1 (en) * | 1992-01-31 | 1994-11-30 | Lord Corporation | Atomically polarizable electrorheological materials |
| CN1130675A (en) * | 1995-12-01 | 1996-09-11 | 清华大学 | Mica series electric rheologic liquid |
| CN1094636C (en) * | 1999-12-21 | 2002-11-20 | 西北工业大学 | Electric rheopectic liquid containing TiO2 modified by doping rare earth and its preparing process |
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