CN1923986A - Intercalation kaolin/modified titanium oxide nano composite particles electrorheological fluid - Google Patents

Intercalation kaolin/modified titanium oxide nano composite particles electrorheological fluid Download PDF

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CN1923986A
CN1923986A CN 200510043181 CN200510043181A CN1923986A CN 1923986 A CN1923986 A CN 1923986A CN 200510043181 CN200510043181 CN 200510043181 CN 200510043181 A CN200510043181 A CN 200510043181A CN 1923986 A CN1923986 A CN 1923986A
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intercalation
titanium oxide
hours
electrorheological fluid
kaolin
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CN100396760C (en
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赵晓鹏
王宝祥
赵艳
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Northwestern Polytechnical University
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Northwestern Polytechnical University
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Abstract

The invention discloses a current liquid-changing material of intercalation kaolin/modified titanium oxide nanometer composite particle, which is characterized by the following: adopting formamide intercalation kaolin micrometer particle as core of dispersing phase; making chromium ion modified titanium oxide nanometer particle as micrometer/nanometer nuclear shell structure particle of clad layer; improving TauE/eta0 value of current liquid-changing material and physical value excited by electric field; increasing sediment-proof property; displaying the relationship of cutting stress and electric field strength of different dispersing particle currents in the accompanying diagram.

Description

Intercalation kaolin soil/modified titanium oxide nano composite particles electrorheological fluid
Technical field
The present invention relates to a kind of electro-rheologic fluid material, particularly a kind of intercalation kaolin soil/modified titanium oxide nano composite particles electrorheological fluid.
Background technology
Electrorheological fluid (Electrorheological Fluids is called for short ERF) is a kind of important intelligent material, and it has the quality of controlled change, and its yielding stress, Young's modulus change with the variation of extra electric field.Electrorheological fluid in a lot of fields as: have potential using value widely in the devices such as vibroshock, clutch coupling, deoscillator, driving mechanism, stepless speed regulation.In the design of electrorheological device, the field of use under certain shearing rate causes the ratio τ of shear-stress and electrorheological fluid zero electric field viscosity usually E/ η 0Weigh the performance quality of electrorheological fluid and the power modification scope (τ of definite electrorheological device EFor the shear yield stress kPa of electrorheological fluid is the zero electric field viscosity of electrorheological fluid).Also hope is enough big in addition, thereby can reduce the volume of electrorheological device, make it to replace original mechanical execution unit easily, even can be littler than original parts, to reduce the volume of complete machine.The τ of the various electrorheological fluid of being reported at present E/ η 0All smaller.Therefore study discrete state material and become electrorheological field problem demanding prompt solution with high electric rheological effect.Correlative study in recent years concentrates on the preparation aspect of the disperse phase with high ER properties, and has obtained certain achievement.The application of the maximum of micron particle electrorheological fluid hinders and comes from its relatively poor resistance to settling energy; And the nano particle electrorheological fluid is because its higher mechanics value and good resistance to settling can receive increasing concern.Therefore, the nanostructure of modifying on micrometer structure can access a kind of micrometer/nanometer clad structure material, can have the two-fold advantage of micron and nano particle simultaneously concurrently, the mechanics and the cutting performance of the electrorheological fluid of preparation also are greatly improved than micron particle electrorheological fluid.
The application of micron particle electrorheological fluid hinders and comes from its relatively poor resistance to settling energy; And the nano particle electrorheological fluid is because its higher static mechanical value and good resistance to settling can receive increasing concern.Purpose of the present invention provides a kind of micrometer/nanometer nucleocapsid structure material with micro-nano structure, can have the two-fold advantage of micron and nano particle simultaneously concurrently, and the electrorheological fluid of preparation has higher τ E/ η 0Value, good antisolvent precipitation performance.Performance all improves a lot than micron particle and nano particle electrorheological fluid.And this preparation method selects for use the abundant kaolin of China's reserves to make raw material, and cost is low.Preparation process adopts graft process and hydrolysis method, and preparation process is simple, and is easy to operate.
Summary of the invention
Technical problem to be solved by this invention provides a kind of intercalation kaolin soil/modified titanium oxide nano composite electrorheological fluid, the disperse phase of this electro-rheologic fluid material is for being nuclear with methane amide intercalation kaolin soil micron particle, chromium ion modified TiOx nano particle is the micrometer/nanometer core-shell structure particles of coating layer, and this particle helps improving the τ of electro-rheologic fluid material E/ η 0Mechanics value under value, the electric field excitation, the antisolvent precipitation performance of raising electrorheological fluid, the preparation cost of reduction electrorheological fluid, preparation process does not simply have particular requirement to equipment, has the two-fold advantage of micron and nano particle simultaneously concurrently, demonstrates good synergism.Particular requirement has the micron and the two-fold advantage of nano particle simultaneously concurrently, demonstrates good synergism.
For addressing the above problem the methane amide that the present invention proposes with high-k to the kaolin intercalation modification, select for use the chromium ion modified TiOx nano particle that itself just has better electric rheological effect to do coating layer again, thereby made intercalation kaolin soil/modified titanium oxide electrorheological fluid with supramaximal current change effect.
The preparation process of the inventive method is as follows:
1. measure 10ml~70ml methane amide, 30ml deionized water in the 100ml beaker, add 1.3~1.7g kaolin, magnetic agitation 48 hours~60 hours, centrifugation also uses deionized water rinsing to get methane amide intercalation kaolin soil 1~2 time;
With intercalation good kaolin be dispersed in the 200ml deionized water and add the 4g Sodium dodecylbenzene sulfonate and stirred 3 hours, obtain the finely dispersed intercalation kaolin soil aqueous solution;
3. 5ml butyl (tetra) titanate, 50ml dehydrated alcohol, 1ml Glacial acetic acid, 0.6g chromium nitrate are joined in the 100ml beaker in order, stir and obtained the transparent butyl (tetra) titanate alcoholic solution that contains chromium in 1 hour;
4. the butyl (tetra) titanate alcoholic solution that contains chromium in (3) slowly is added dropwise in the finely dispersed intercalation kaolin soil aqueous solution in (2), drip the back and continue reaction 10 hours~14 hours, the modified titanium oxide nano particle of generation fully is deposited on the intercalation kaolin soil micron particle, the vacuum filtration green filter cake that must loosen;
With filter cake 60 ℃~90 ℃ dry 3~5 hours down, in mortar behind the pulverize again 60 ℃~80 ℃ dry 2 hours~4 hours down, after abundant grinding, get final product intercalation kaolin soil/modified titanium oxide nano composite particles;
6. prepared Nano composite granules and methyl-silicone oil are mixed by 2g/1ml, 1.6g/4.5ml, be made into the intercalation kaolin soil/modified titanium oxide nano composite particles electrorheological fluid of two kinds of different concns.
These electrorheological fluid raw material sources are rich and easy to get, cost is low, the preparation method is simple to operation, the discrete state material structure that makes is unique to be the micrometer/nanometer core-shell particle of micro-nano structure: promptly the methane amide intercalation modifying kaolin particle with high-k is a nuclear, and the chromium ion modified nano-titanium oxide is a coating layer.The dielectric properties of the electro-rheologic fluid material that is made into by this disperse phase improve a lot, and have some excellent characteristics, as: extremely strong electric rheological effect especially dynamic shearing stress, very high τ E/ η 0, preferably antisolvent precipitation stability, wide operation temperature area, current density is low, chemical stability good.
Description of drawings
Fig. 1 intercalation kaolin soil/modified titanium oxide nano composite particles electrorheological fluid, methane amide intercalation kaolin soil/titanium oxide nano composite particles electrorheological fluid, kaolin/modified titanium oxide nano composite particles electrorheological fluid, modified titanium oxide nano electrorheological fluid, the shear-stress of washed kaolin electrorheological fluid electrorheological fluid and the relation of strength of electric field.
The shear-stress of Fig. 2 intercalation kaolin soil/modified titanium oxide nano composite particles electrorheological fluid and the relation of shearing rate.
Specific embodiment
Used chemical feedstocks is the chemical pure except that kaolin, butyl (tetra) titanate, and all the other are analytical pure entirely, and deionized water is the laboratory self-control.
Below in conjunction with embodiment and description of drawings the present invention is described in further detail:
Embodiment one: (intercalation kaolin soil/modified titanium oxide nano composite particles electrorheological fluid)
Measure 10ml~70ml methane amide, 30ml deionized water in the 100ml beaker, add 1.5g kaolin, magnetic agitation 48 hours~60 hours, centrifugation and with product with deionized water rinsing 1~2 time methane amide intercalation kaolin soil.Be dispersed in the kaolin behind the intercalation in the 200ml deionized water and add the 4g Sodium dodecylbenzene sulfonate and stirred 5 hours.In addition 5ml butyl (tetra) titanate, 50ml dehydrated alcohol, 1ml Glacial acetic acid, 0.6g chromium nitrate are joined successively to stir after 3 hours in the 100ml beaker and slowly splash in the above-mentioned 200ml aqueous solution, drip the back and continue reaction 10 hours~14 hours, the vacuum filtration green filter cake that must loosen.With filter cake 60 ℃~90 ℃ dry 3 hours~5 hours down, in mortar behind the pulverize again 60 ℃~80 ℃ dry 2~4 hours down, after abundant grinding, get final product intercalation kaolin soil/modified titanium oxide nano composite particles.Prepared Nano composite granules and methyl-silicone oil are mixed by 2g/1ml, and the relation that is made into the shear-stress of electrorheological fluid and strength of electric field as shown in Figure 1.Prepared Nano composite granules and methyl-silicone oil are mixed by 1.6g/4.5ml, be made into the shear-stress of electrorheological fluid and the relation such as the accompanying drawing 2 of shearing rate.
Embodiment two: (methane amide intercalation kaolin soil/titanium oxide nano composite particles electrorheological fluid)
Measure 10ml~70ml methane amide, 30ml deionized water in the 100ml beaker, add 1.5g kaolin, magnetic agitation 48 hours~60 hours, centrifugation and with product with deionized water rinsing 1~2 time methane amide intercalation kaolin soil.Be dispersed in the kaolin behind the intercalation in the 200ml deionized water and add the 4g Sodium dodecylbenzene sulfonate and stirred 5 hours.In addition 5ml butyl (tetra) titanate, 50ml dehydrated alcohol, 1ml Glacial acetic acid are joined successively to stir after 3 hours in the 100ml beaker and slowly splash in the above-mentioned 200ml aqueous solution, drip the back and continue reaction 10 hours~14 hours, the vacuum filtration filter cake that must loosen.With filter cake 60 ℃~90 ℃ dry 3~5 hours down, in mortar behind the pulverize again 60 ℃~80 ℃ dry 2 hours~4 hours down, through fully getting methane amide intercalation kaolin soil/titanium oxide nano composite particles after the grinding.Prepared Nano composite granules and methyl-silicone oil are mixed by 2g/1ml, and the relation that is made into the shear-stress of electrorheological fluid and strength of electric field as shown in Figure 1.
Embodiment three: (kaolin/modified titanium oxide nano composite particles electrorheological fluid)
Be dispersed in 1.5g kaolin in the 200ml deionized water and add the 4g Sodium dodecylbenzene sulfonate and stirred 5 hours.In addition 5ml butyl (tetra) titanate, 50ml dehydrated alcohol, 1ml Glacial acetic acid, 0.6g chromium nitrate are joined successively to stir after 3 hours in the 100ml beaker and slowly splash in the above-mentioned 200ml aqueous solution, drip the back and continue reaction 10 hours~14 hours, the vacuum filtration green filter cake that must loosen.With filter cake 60 ℃~90 ℃ dry 3 hours~5 hours down, in mortar behind the pulverize again 60 ℃~80 ℃ dry 2~4 hours down, after abundant grinding, get final product kaolin/modified titanium oxide nano composite particles.Prepared Nano composite granules and methyl-silicone oil are mixed by 2g/1ml, and the shear-stress of institute's distribution rheology liquid and the relation of strength of electric field are as shown in Figure 1.
Embodiment four: (modified titanium oxide nano electrorheological fluid)
10ml tetrabutyl titanate, 1ml Glacial acetic acid, 1.2g chromium nitrate are joined in the 100ml ethanol, stirred 3 hours, be made into pure phase solution; Simultaneously 7.5g Sodium dodecylbenzene sulfonate (SDBS), 4g acrylamide are joined in the 400ml deionized water, stirred 3 hours, be made into aqueous phase solution; Slowly splash in the aqueous phase solution at following pure phase solution of powerful condition of stirring then, drip off the back and continue to stir 6 hours, behind the vacuum filtration filter cake was vacuumized under 80 ℃ dry 9 hours, take out through carefully grind slick chromium ion modified TiOx nano particle.Prepared Nano composite granules and methyl-silicone oil are mixed by 2g/1ml, and the relation that is made into the shear-stress of electrorheological fluid and strength of electric field as shown in Figure 1.
Embodiment five: (washed kaolin electrorheological fluid)
Will 120 ℃ down kaolin and the methyl-silicone oil after dry 2 hours mix by 2g/1ml, be made into the washed kaolin electrorheological fluid, the relation of measuring its shear-stress and shearing rate as shown in Figure 1.

Claims (4)

1. intercalation kaolin soil/modified titanium oxide nano composite particles electrorheological fluid material, the disperse phase that it is characterized in that this material is a kind of micrometer/nanometer core-shell particle: its nuclear is methane amide intercalation kaolin soil mixture, shell is a chromium ion modified TiOx nano particle, and external phase is dimethyl silicone oil.
2. according to the described intercalation kaolin soil of claim 1/modified titanium oxide nano composite particles electrorheological fluid material, it is characterized in that the preparation condition of methane amide intercalation kaolin soil mixture is as follows: with 1.3g~1.7g particle diameter is that to be dispersed in 60ml~100ml concentration be to carry out intercalation in 25%~70% the methane amide deionized water solution for the laminate structure kaolin of 500nm~3 μ m.
3. according to the described intercalation kaolin soil of claim 1/modified titanium oxide nano composite particles electrorheological fluid material, it is characterized in that the Cr/Ti mol ratio is 0.08~0.11 in the shell chromium ion modified TiOx nano particle.
4. according to the described intercalation kaolin soil of claim 1/modified titanium oxide nano composite particles electrorheological fluid material, it is characterized in that preparation technology may further comprise the steps:
(1) measure 10ml~70ml methane amide, 30ml deionized water in the 100ml beaker, add 1.5g kaolin, magnetic agitation 48 hours~60 hours, centrifugation also uses deionized water rinsing to get methane amide intercalation kaolin soil 1~2 time;
(2) with intercalation good kaolin be dispersed in the 200ml deionized water and add the 4g Sodium dodecylbenzene sulfonate and stirred 3 hours, obtain the finely dispersed intercalation kaolin soil aqueous solution;
(3) 5ml butyl (tetra) titanate, 50ml dehydrated alcohol, 1ml Glacial acetic acid, 0.6g chromium nitrate are joined in the 100ml beaker in order, stir and obtained the transparent butyl (tetra) titanate alcoholic solution that contains chromium in 1 hour;
(4) the butyl (tetra) titanate alcoholic solution that contains chromium in (3) slowly is added dropwise in the finely dispersed intercalation kaolin soil aqueous solution in (2), drip the back and continue reaction 10 hours~14 hours, the modified titanium oxide nano particle of generation fully is deposited on the intercalation kaolin soil micron particle, the vacuum filtration green filter cake that must loosen;
(5) with filter cake 60 ℃~90 ℃ dry 3~5 hours down, in mortar behind the pulverize again 60 ℃~80 ℃ dry 2 hours~4 hours down, after abundant grinding, get final product intercalation kaolin soil/modified titanium oxide nano composite particles;
(6) prepared Nano composite granules and methyl-silicone oil are mixed by 2g/1ml, 1.6g/4.5ml, be made into the intercalation kaolin soil/modified titanium oxide nano composite particles electrorheological fluid of two kinds of different concns.
CNB2005100431817A 2005-09-02 2005-09-02 Intercalation kaolin/modified titanium oxide nano composite particles electrorheological fluid Expired - Fee Related CN100396760C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101469286B (en) * 2007-12-28 2011-05-25 西北工业大学 Polyaniline intercalated titanium oxide nano-tube ER fluid
CN106753722A (en) * 2017-01-16 2017-05-31 中国科学院宁波材料技术与工程研究所 A kind of giant electro-rheological liquid and preparation method thereof
CN110055125A (en) * 2019-05-31 2019-07-26 青岛科技大学 A kind of hud typed composite material by electric current of anisotropic TS-1 molecular sieve/TiOx nano becomes liquid and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100448962C (en) * 2003-10-13 2009-01-07 西北工业大学 Transition metal ion doped titanium dioxide electrorheological materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101469286B (en) * 2007-12-28 2011-05-25 西北工业大学 Polyaniline intercalated titanium oxide nano-tube ER fluid
CN106753722A (en) * 2017-01-16 2017-05-31 中国科学院宁波材料技术与工程研究所 A kind of giant electro-rheological liquid and preparation method thereof
CN110055125A (en) * 2019-05-31 2019-07-26 青岛科技大学 A kind of hud typed composite material by electric current of anisotropic TS-1 molecular sieve/TiOx nano becomes liquid and preparation method thereof
CN110055125B (en) * 2019-05-31 2021-10-22 青岛科技大学 Anisotropic TS-1 molecular sieve/titanium oxide nano core-shell composite electrorheological fluid and preparation method thereof

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