WO2007147347A1 - Elelctrorheological fluid of polar molecule type - Google Patents

Elelctrorheological fluid of polar molecule type Download PDF

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Publication number
WO2007147347A1
WO2007147347A1 PCT/CN2007/001890 CN2007001890W WO2007147347A1 WO 2007147347 A1 WO2007147347 A1 WO 2007147347A1 CN 2007001890 W CN2007001890 W CN 2007001890W WO 2007147347 A1 WO2007147347 A1 WO 2007147347A1
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polar
electrorheological fluid
particles
fluid
dispersed phase
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French (fr)
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Kunquan Lu
Rong Shen
Xuezhao Wang
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Institute of Physics of CAS
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Priority to EP07721463A priority Critical patent/EP2039743A4/en
Priority to JP2009514621A priority patent/JP2009540067A/ja
Publication of WO2007147347A1 publication Critical patent/WO2007147347A1/zh
Priority to US12/335,383 priority patent/US7981315B2/en
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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
    • 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
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants

Definitions

  • the invention relates to a novel electrorheological fluid, in particular to a polar molecular type electrorheological fluid.
  • Electroheological Fluids are suspensions of nano-micron-sized particles mixed with an insulating liquid.
  • the shear strength is continuously adjusted by an external electric field, which can be instantaneously changed from a liquid phase to a solid phase.
  • the electrorheological fluid has the characteristics of continuous adjustable shear strength, fast response and reversible transformation under the action of electric field. It is an intelligent material with adjustable softness and hardness. It has wide and important application value and can be used for clutch, damping system and reduction. Shock absorbers, brake systems, stepless speed change, liquid valves, electromechanical coupling control, robots, etc., to achieve mechatronics intelligent control, can be widely used in almost all industrial and technical fields, as well as military.
  • the working principle of the common electrorheological fluid is: Under the action of the electric field, the shearing strength of the electrorheological fluid increases with the increase of the electric field due to mutual attraction of the particles.
  • Such electrorheological fluids based on the mutual attraction principle of particle polarization are called "ordinary electrorheological fluids" or "dielectric electrorheological fluids”.
  • the shear yield strength limit of this type of electrorheological fluid is 10 kPa ( lkV / mm. This low shear strength electrorheological fluid cannot meet the requirements of technical and industrial applications.
  • the Institute of Physics of the Chinese Academy of Sciences developed Surface modified composite barium titanate electrorheological fluid (CN1190119) Under the action of an electric field of 3 kV/mm, the shear yield strength is only 30 kPa.
  • CN1490388 discloses a barium titanate electrorheological fluid coated with urea, which is called a giant electrorheological fluid. It discloses that the protective composite particles are promoters, including urea, butanamide and acetamide. Its static yield strength reaches 130 kPa, and its principle is based on the action of the particle surface coating, which is called the cladding saturation polarization principle. The main limitation of this electrorheological fluid is that it needs to be coated on the surface of the particles. The reported current density of the electrorheological fluid is large.
  • CN1944606 discloses a tantalum titanium dioxide electrorheological fluid and a preparation method thereof, which is mainly a catastrophic titanium dioxide electrorheological fluid.
  • the sol-gel method is used to form micron or nanometer-sized doped titanium dioxide particles by catastrophic and polar amides or their derivative molecules in titanium dioxide, and then prepared with methyl silicone oil, doped Ti0 2 Methyl silicone oil The number of integrals is formulated into a 30% electrorheological fluid to obtain a high yield strength electrorheological fluid.
  • CN1752195 discloses a calcium titanate electrorheological fluid and a preparation method thereof, which are mainly an anhydrous calcium titanate electrorheological fluid, which is prepared by preparing calcium titanate particles prepared by oxalic acid coprecipitation method and dimethicone oil, and has strong Current change effect.
  • the electrorheological fluid prepared by the calcium titanate particles and the dimethyl silicone oil by 30% by volume has a yield strength of more than 100 kPa.
  • the leakage current of the electrorheological fluid described in the above technology is large, and the preparation of the material is relatively limited, and cannot be widely applied. Summary of the invention
  • the technical problem to be solved by the invention is to provide a shortcoming that overcomes the existing low shear strength of the electrorheological fluid and can not meet the engineering requirements, overcomes the limitations of the preparation and material selection of the existing electrorheological fluid, has high shear strength and resists sedimentation.
  • the polar molecular type electrorheological fluid of the invention is mainly composed of a mixture of a solid particle dispersed phase and a liquid dispersion medium.
  • the surface of the dispersed solid particles and/or the liquid dispersion medium contains polar molecules or polar groups, and the polar or polar groups have a dipole moment of 0.5 to 10 Debey and a size of 0.1. ⁇ 0.8 nm;
  • the dispersed phase solid particles are spherical or spheroidal, having a particle size of 10 to 300 nm, preferably 20 to 100 nm, and a dielectric constant of more than 50;
  • the liquid dispersion medium has a conductivity lower than l ⁇ T 8 S/m and a dielectric constant lower than 10.
  • the polar molecules or polar groups on the surface of the dispersed phase solid particles of the present invention are added or retained during the preparation of the dispersed phase solid particles, or added or assembled on the surface of the prepared particles.
  • the molar fraction of the polar or polar group in the dispersed phase is from 0.01 to 50%.
  • the polar molecular or polar group in the liquid dispersion medium has a molar fraction of 0.1 to 100%.
  • the solid particle dispersed phase is sufficiently mixed with the liquid dispersion medium, and the volume fraction of the solid particle dispersed phase in the electrorheological fluid is 5 to 50%.
  • the polar molecule or polar group may be a polar molecule or a polar group on the surface of the particle, and a polar molecule or a polar group on the surface of the particle may be in the particle.
  • the liquid dispersion medium is at least one selected from the group consisting of a conventional liquid dispersion medium such as silicone oil, mineral oil, engine oil, hydrocarbon oil, and the like, and a polar liquid containing the polar molecule or polar group.
  • the polar molecule or polar group may also be a polar molecule or a polar group contained in the dispersion medium.
  • the dispersion medium may be a polar liquid of a single chemical composition or a mixed liquid containing polar molecules or polar groups.
  • the dispersed phase of the solid particles may contain a polar molecule or a polar group, or may be free of a polar molecule or a polar group.
  • the high dielectric constant particles used may be inorganic substances, organic substances, or inorganic organic complexes, and the particles may be prepared by gas phase synthesis, liquid phase synthesis, solid phase synthesis. .
  • the solid particle dispersed phase and the liquid dispersion medium are sufficiently mixed by means of ultrasonic waves, a ball mill or the like.
  • the particles are polarized in the electrorheological fluid under the action of an electric field.
  • the local electric field between the particles increases as the particles approach, which is about a thousand times higher than the external electric field.
  • the polar molecules or polar groups between the particles in this region are oriented along the electric field under the action of a high local electric field. These oriented polar molecules and the polarized charges on the particles are strongly attracted to make the shear yield strength of the electrorheological fluid.
  • the polar molecular type electrorheological fluid of the invention has excellent electrorheological properties, and polar molecules or polar groups and high dielectric constant spherical particles play a key role in improving the electrorheological effect, high yield strength, yield strength and electric field strength. It has a linear relationship and high yield strength under low electric field. It is nearly 100 times higher than traditional electrorheological fluid.
  • the dynamic shear strength is high, and it can reach 60 kPa or more when the electric field strength is 3 kV/mm.
  • the anti-settling property was good, and no sedimentation was observed after standing for one month.
  • the leakage current is small.
  • the electric field strength is 5kV/mm, the current density is less than 20 ⁇ / ⁇ .
  • FIG 6 is a cut electrorheological fluid prepared by one of ordinary Ti0 2 particles do not contain polar molecules or polar groups of the yield strength of the electric field strength of the relationship;
  • Figure 9 is a comparison of the typical results of the surface-coated urea barium titanate electrorheological fluid with the polar molecular type electrorheological fluid of the present invention (Example 2): (a) The yield strength and electric field of the electrorheological fluid of the present invention The relationship between the strength, (b) the relationship between the yield strength of the barium titanate electrorheological fluid coated with urea and the electric field strength, (c) the relationship between the current density of the barium titanate electrorheological fluid coated with urea and the electric field strength;
  • Figure 10 is a scanning electron micrograph of the prepared titanium dioxide nanoparticles. detailed description
  • the titanium dioxide nanoparticles are spherical, have a size of 50 to 100 nm, and have a dielectric constant of 1000.
  • a titanium oxide nanoparticle containing a C-0 and C-NH 2 polar group is prepared by doping acetamide.
  • the granules are prepared by sol-gel method:
  • Component 1 30ml Ti (OC 4 H 9 ) 4 was dissolved in 210 ⁇ absolute ethanol, hydrochloric acid was added to adjust the pH of the solution to 1 ⁇ 3;
  • Component 2 40 ml deionized water and 150 ml absolute ethanol are mixed evenly
  • Component 3 30g acetamide dissolved in 20ml deionized water
  • component 2 was added to component 1 with vigorous stirring, component 3 was added immediately, and stirring was continued until a colorless transparent gel was formed.
  • the gel is aged at room temperature until a solution is precipitated, and vacuum-dried at a low temperature to obtain a white powder.
  • the size is 50 to 100 nm and the dielectric constant is about 1000.
  • the volume fraction of the particles in the total volume is 30%. Its shear yield strength can reach 100 kPa, and the current density is lower than ⁇ /cm 2 , as shown in Figure 1.
  • Figure 10 is a scanning electron micrograph of the prepared titanium dioxide nanoparticles having a spherical shape with an average size of 50 nm and a dielectric constant of about 500.
  • the granules are prepared by sol-gel method:
  • Component 1 30ml Ti(OC 4 H 9 ) 4 was dissolved in 150 ml of absolute ethanol, and hydrochloric acid was added to adjust the pH of the solution;
  • Component 2 40 ml of deionized water was dissolved in 250 ml of absolute ethanol, and 2 ml of diethanolamine was added to adjust the titanium. Hydrolysis condensation reaction of tetrabutyl acid;
  • Component 3 30 g of urea is dissolved in 20 ml of water;
  • (2) Mix the titanium dioxide nanoparticles with 10# silicone oil, stir vigorously for more than 3 hours with a ball mill, and fully disperse the particles to form a uniform electrorheological fluid with a volume fraction of 30%.
  • the shear yield strength can reach 200kPa or more. As shown in Fig. 2, when the electric field strength is 5 kV/mm, the current density is less than 20 ⁇ /cm 2 , and when the electric field strength is 2 kV/mm, the yield strength is up to 100 kPa. At 3kV/mm, the dynamic shear strength reaches 60 kPa or more, as shown in Figure 3.
  • Tetrabutyl titanate was used as a raw material, water was used as a reactant, and anhydrous ethanol was used as a solvent. Under vigorous stirring, the ethanol solution of water was added dropwise to a solution of tetrabutyl titanate in absolute ethanol, and stirring was continued after the addition was completed until the gel was formed. After the gel was aged for several days, it was vacuum-dried into a white powder. The powder was washed with a plurality of times, filtered, and placed in an oven at 50 ° C for more than 72 hours, and then dried at 120 ° C for 2 hours to obtain the desired nanometer. Ti0 2 particles. The particles are spherical with an average size of 50 nm.
  • the polar groups 0-H and C in the particles have a mole fraction of 5% and dipole moments of 1.51 Debey and 2.3 to 2.7 Debey, respectively.
  • An electrorheological fluid is prepared from calcium titanate nanoparticles containing polar groups, the dispersed phase being calcium titanate nanoparticles and the dispersing medium being silicone oil.
  • the calcium titanate nanoparticles are spherical with an average size of 50 nm and a dielectric constant of about 300.
  • Component 3 oxalic acid is dissolved in deionized water to prepare a 2 mol/l solution;
  • the component 3 was dropped into the mixed solution 1+2, and the mixed volume ratio of the three solutions was 2: 1:2.
  • the resulting precipitate was aged at 60 ° C for 12 hours, washed with deionized water, filtered, dried for 120 hours or more, and dried at 120 ° C for 3 hours to obtain 50-100 nm calcium titanate spherical particles.
  • the calcium titanate particles were mixed with 50# methyl silicone oil, and vigorously stirred by a ball mill for 3 hours or more to sufficiently disperse the particles to form an electrorheological fluid.
  • the particle volume fraction is 30%.
  • the electric field strength is 5kV/mm
  • the yield strength can reach 200 kPa or more
  • the current density is less than 1 ⁇ /cm 2
  • the electric field strength is 2 kV/mm
  • the yield strength can reach 90 kPa, as shown in Fig. 5.
  • An electrorheological fluid is prepared from lithium titanate nanoparticles containing polar groups, the dispersed phase is lithium titanate ruthenium nanoparticles, and the dispersion medium is silicone oil.
  • the particles are spherical with an average size of 50 nm and a dielectric constant of about 400.
  • the procedure for preparing lithium titanate ruthenium particles by co-precipitation method is as follows: LiCl.H 2 0, LaCl 3 -7H 2 0, Ti(OC 4 H 9 ) 4 are used as raw materials, oxalic acid ( ⁇ 2 0 4 ⁇ 23 ⁇ 40) is a coprecipitant.
  • the precipitated product was Li 3x La 2/3 _ x Ti(C 2 0 4 ) 2 , and the precipitate was washed several times with deionized water and ethanol, filtered and dried at 50 ° C for more than 48 hours, 120 ⁇ heating 3 In hours, white Li x La 2 / 3 . x Ti(C 2 0 4 ) 2 particles were obtained.
  • the particles are spherical with an average size of 50 nm.
  • An electrorheological fluid of formamide-attached barium titanate nanoparticles was prepared using commercially available barium titanate nanoparticles having a dielectric constant of 300.
  • the formamide liquid was uniformly mixed with the barium titanate nanoparticles at a molar ratio of 2:100, and the dipole moment of the formamide polar molecule was 3.73 Debey.
  • the formamide was attached to the barium titanate nanoparticles by baking at 50 ° C for 2 hours.
  • the particles are uniformly mixed with 200mm 2 /s of dimethyl silicone oil at a volume fraction of 30% to obtain an electrorheological fluid with a yield strength of up to 20 kPa, which is lower than the ordinary electrorheological fluid yield strength of the non-formamide polar molecule (less than 1 kPa). ) Greatly improve.
  • the purchased barium titanate nanoparticles are square, not spherical, and thus the yield strength cannot be made very high.
  • the barium titanate or barium titanate particles having a size of 100 to 200 nm used in the above Examples 6 and 7 are uniformly mixed with the dimethyl silicone oil having a viscosity of 200 mm 2 /s, and the barium titanate or barium titanate particles are used.
  • the volume fraction is 30%, and the shear yield strength of the obtained electrorheological fluid is less than 1 kPa. Comparative example 2
  • the ordinary Ti0 2 particles with a size of 200 nm are uniformly mixed with the dimethyl silicone oil having a viscosity of 200 mm 2 /s, and the volume fraction of the particles is 30%, and an electrorheological fluid containing no polar groups or polar molecules is obtained, and shearing is performed.
  • the yield strength is only a few tens of Pascals, as shown in Figure 6. This is a typical common electrorheological fluid.
  • a shearing yield of an electrorheological fluid prepared by heating a particle containing a polar group or a polar molecule at a high temperature to volatilize a polar group or a polar molecule, and losing a polar group or a polar molecule.
  • the strength is very low, fully indicating the shear yield strength ⁇ of the electrorheological fluid containing polar groups or polar molecules. Comparative example 4
  • An electrorheological fluid of surface-coated urea-coated barium titanate was prepared by the same method as described in CN1490388, and compared with the electrorheological fluid described in Example 2, and the results are shown in FIG.
  • the barium titanate electrorheological fluid coated with urea on the surface has a yield strength of about 30 kPa at 2 kV/mm, and the yield strength of the electrorheological fluid described in Example 2 is about 100 kPa at 2 kV/mm. Further, the yield strength of the electrorheological fluid of Example 2 is linear with respect to the electric field.
  • the leakage current density of the barium titanate electrorheological fluid coated with urea on the surface is 300 ⁇ at 5 kV/mm; i n 2 .
  • the current density of the electrorheological fluid of Example 2 was 20 ⁇ M at 5 kV/mm; below i n 2 , some were lower than ⁇ /cm 2 , as shown in FIG. 5 .
  • the leakage current density of the barium titanate electrorheological fluid coated with urea is 10 times to 100 times lower than that of the surface. It is fully explained that the polar molecular type electrorheological fluid of the present invention has high yield strength, high dynamic shear strength, small leakage current, linear relationship between yield strength and electric field strength, and yield strength under low electric field.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Lubricants (AREA)
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Description

极性分子型电流变液 技术领域
本发明涉及一种新型的电流变液， 特别涉及一种极性分子型电流变液。 背景技术
电流变液 （Electrorheological Fluids) 是纳米至微米尺寸的颗粒与绝缘液体混合组 成的悬浮液， 其剪切强度用外电场连续调节， 可由液相瞬间变为固相。 电流变液在电 场作用下剪切强度连续可调、 快速响应和可逆转变的奇特性质， 是软硬程度可调节的 智能材料， 具有广泛和重要的应用价值， 可以用于离合器、 阻尼系统、 减震器、 制动 系统， 无级变速、 液体阀门、 机电耦合控制、 机器人等， 实现机电一体化智能控制， 几乎所有工业和技术领域， 以及军事上均可广泛应用。
但自 20世纪 40年代 Winslow发现电流变液至今， 电流变液并没有得到预期的应 用， 主要原因是其剪切强度较低， 一般约为几 kPa， 最高为 10 kPa， 漏电流大， 抗沉 降性低。 通常的电流变液工作原理是： 在电场作用下， 由于颗粒极化发生相互吸引， 电流变液的剪切强度随电场增大而增高。 这类基于颗粒极化相互吸引原理的电流变液 称为"普通电流变液 "或"介电电流变液"。这类电流变液的剪切屈服强度极限为 lOkPa ( lkV/mm 这种低剪切强度的电流变液不能达到技术和工业应用的要求。 在上世纪 90年代末， 中国科学院物理研究所研制的表面改性复合钛酸锶电流变液（CN1190119) 在 3kV/mm的电场作用下， 剪切屈服强度仅达 30kPa。
现有文献和专利绝大部分是关于传统电流变液的材料和技术。 CN1490388公开了 一种表面包覆尿素的钛酸钡电流变液， 称之为巨电流变液， 其公开了保护复合颗粒的 是促进剂 （promoter) , 包括了尿素、 丁酰胺、 乙酰胺。 其静态屈服强度达 130kPa， 其原理是基于颗粒表面包覆层的作用， 称之为包覆层饱和极化原理。 这种电流变液主 要局限是需在颗粒表面进行包覆， 所报导的电流变液的电流密度大， 在 5kV/mm时， 电流密度达数百 μΑ/cm2, 在低电场时屈服强度低， 如 2kV/mm 时的屈服强度约为 30-40kPa, 同时钛酸钡在 120°C左右会发生相变， 影响其实际应用。 CN1944606公幵 了一种糁质二氧化钛电流变液及其制备方法， 主要是一种惨质二氧化钛电流变液。 釆 用溶胶一凝胶法， 通过在二氧化钛中惨质强极性的酰胺类或其衍生物分子， 形成微米 或纳米尺寸的掺质二氧化钛颗粒， 再与甲基硅油配制而成， 掺质 Ti02与甲基硅油按体 积分数配制成 30%电流变液， 获得高屈服强度的电流变液。 CN1752195公开了一种钛 酸钙电流变液及其制备方法， 主要是无水钛酸钙电流变液， 是以草酸共沉淀法制备的 钛酸钙颗粒与二甲基硅油配制而成， 具有强电流变效应。 钛酸钙颗粒与二甲基硅油按 体积分数 30%配制成的电流变液，其屈服强度可达 lOOkPa以上。但是以上技术所述的 电流变液的漏电流较大， 制备选材比较局限， 不能得到广泛的应用。 发明内容
本发明所要解决的技术问题是提供一种克服现有的电流变液剪切强度低、 不能满 足工程要求的缺点， 克服现有电流变液制备和选材的局限性、 剪切强度高、 抗沉降性 好、 漏电流小的极性分子型电流变液。
本发明的极性分子型电流变液，主要由固体颗粒分散相和液体分散介质混合组成，
( 1 ) 分散相固体颗粒表面和 /或液体分散介质中含有极性分子或极性基团， 极性 分子或极性基团的偶极矩为 0.5〜10德拜 （Debey), 尺寸为 0.1〜0.8纳米；
(2) 分散相固体颗粒为球形或类球形， 颗粒尺寸为 10〜300纳米， 优选为 20〜 100纳米， 介电常数大于 50;
(3 ) 液体分散介质电导率低于 l{T8S/m， 介电常数低于 10。
本发明所述的极性分子或极性基团中起作用的极性键选自 C=0、 0-H、 N-H、 F-H、 C-OH、 C-N02、 C-H、 C-OCH3、 C-N¾、 C-COOH、 C-CU N=0中的至少一种。
本发明所述的分散相固体颗粒表面的极性分子或极性基团是在分散相固体颗粒的 制备过程中添加或保留的， 或在制备好的颗粒表面上添加或组装的。 极性分子或极性 基团在分散相中的摩尔分数为 0.01~50%。
对于本发明的极性分子型电流变液， 所述液体分散介质中的极性分子或极性基团 的摩尔分数为 0. 1〜100%。
对于本发明的极性分子型电流变液， 固体颗粒分散相与液体分散介质充分混合， 固体颗粒分散相在电流变液中的体积分数为 5〜50%。
对于本发明的极性分子型电流变液， 所述极性分子或极性基团可为颗粒表面的极 性分子或极性基团， 颗粒表面的极性分子或极性基团可在颗粒的制备过程中加入或故 意保留， 也可以在制备好的颗粒上添加或组装， 即分散相固体颗粒自身含有的极性分 子或极性基团， 或者在制备好的固体颗粒的表面添加， 或者在固体颗粒的制备过程中 添加极性分子或极性基团， 无论以何种方式添加的极性分子或极性基团， 在电路变液 中起作用的都是附着或裸露在固体颗粒表面的那部分极性分子或极性基团。 此时， 所 述的液体分散介质选自硅油、 矿物油、 机油、 烃油等常规液体分散介质以及含所述极 性分子或极性基团的极性液体中的至少一种。
对于本发明的极性分子型电流变液， 所述极性分子或极性基团也可为分散介质中 包含的极性分子或极性基团。 所述分散介质可为单一化学组成的极性液体， 或包含极 性分子或极性基团的混合液体。 极性分子或极性基团为分散介质所包含时， 固体颗粒 分散相可含有极性分子或极性基团， 也可不含极性分子或极性基团。
对于本发明的极性分子型电流变液， 所用的高介电常数颗粒可为无机物、有机物， 或无机有机复合物， 所述的颗粒可以用气相合成、 液相合成、 固相合成法制备。
对于本发明的极性分子型电流变液， 在其制备过程中， 采用超声、 球磨机等方式 充分混合固体颗粒分散相与液体分散介质。
本发明通过在分散相和 /或分散介质中加入极性分子或极性基团，或选用含极性键 的分散相和 /或分散介质， 在电场作用下， 电流变液中颗粒发生极化相互吸引而靠近， 颗粒间局域电场随着颗粒靠近而增强， 可比外电场约高千倍。 此区域颗粒间的极性分 子或极性基团在高局域电场作用下沿电场取向， 这些取向极性分子与颗粒上极化电荷 发生很强吸引作用， 使电流变液的剪切屈服强度比传统电流变液大大提高。 起作用的 极性分子或极性基团的偶极矩愈大， 尺寸愈小， 或数目愈多， 屈服强度愈高。 当电场 切断时， 颗粒间局域电场消失， 取向极性分子恢复到无规吸附状态， 极化电荷也消失， 电场引起的电流变效应随之消失。
本发明的极性分子型电流变液具有优良的电流变特性， 极性分子或极性基团和高 介电常数球形颗粒对提高电流变效应起关键作用， 屈服强度高， 屈服强度与电场强度 呈线性关系， 在低电场下具有高屈服强度等特点， 比传统电流变液提高近百倍， 可达
200kPa以上， 动态剪切强度高， 在电场强度为 3kV/mm时可达到 60kPa以上。 抗沉降 性好， 在静置一月后观察不到出现沉降。 漏电流小， 在电场强度为 5kV/mm时， 电流 密度小于 20 μΑ/οηα 附图说明
图 1是由一种含 C=0和 C-NH2极性基团的二氧化钛纳米颗粒制备的电流变液的剪 切屈服强度与电场强度关系图 （左图）， 电流密度与电场强度关系图 （右图）；
图 2是由另一种含 C=0和 C-NH2极性基团的二氧化钛纳米颗粒制备的电流变液的 剪切屈服强度及电流密度与电场强度的关系；
图 3是以含 C=0和 C-NH2极性基团的二氧化钛纳米颗粒制备的电流变液，在不同 电场强度下的动态剪切强度与切变速率的关系；
图 4是由包含 0-H， C=0极性基团的二氧化钛纳米颗粒制备的电流变液的剪切屈 服强度及电流密度与电场强度关系；
图 5是由包含 0-H， C=0极性基团的钛酸钙纳米颗粒制备的电流变液的剪切屈服 强度及电流密度与电场强度关系；
图 6是由不包含极性基团或极性分子的普通 Ti02颗粒制备的电流变液的剪切屈服 强度与电场强度关系；
图 7是在不同温度加热的含 C=0和 C-NH2极性基团的二氧化钛纳米颗粒制备的电 流变液的剪切屈服强度特性；
图 8是包含 0-H及 C=0极性基团的钛酸钙纳米颗粒，在 500°C加热 2小时制备的 电流变液的剪切屈服强度特性；
图 9是表面包覆尿素的钛酸钡电流变液与本发明的极性分子型电流变液的典型结 果 （实施例 2) 的比较： （a)本发明的电流变液的屈服强度与电场强度的关系， （b) 表 面包覆尿素的钛酸钡电流变液屈服强度与电场强度的关系， （c)表面包覆尿素的钛酸钡 电流变液电流密度与电场强度的关系；
图 10是制备的二氧化钛纳米颗粒的扫描电镜照片。 具体实施方式
实施例 1
通过加入乙酰胺制备含 C=0和 C-NH2极性基团的二氧化钛纳米颗粒的电流变液， 分散相为二氧化钛纳米颗粒，分散介质为硅油。二氧化钛纳米颗粒为球形，尺寸为 50〜 100纳米， 介电常数为 1000。 C=0和 C-NH2极性基团的偶极矩为 2.3〜2.76 Debey和 1.2-1.5 Debey。 在制备成的二氧化钛纳米颗粒中， C=0和 C-NH2极性基团的摩尔分 数为 20%。
( 1 ) 通过掺质乙酰胺制备含 C-0和 C-NH2极性基团的二氧化钛纳米颗粒。
颗粒釆用溶胶凝胶法制备：
组份 1 : 将 30ml Ti(OC4H9)4溶解于 210ηιΓ无水乙醇中， 加入盐酸调节溶液的 pH 值到 1〜3； 组份 2: 40ml去离子水和 150ml无水乙醇均匀混合
组份 3 : 30g乙酰胺溶于 20ml去离子水中
在强力搅拌下将组份 2加入组份 1后， 立即加入组份 3， 继续搅拌直到形成无色 透明的凝胶。 将凝胶在室温下老化直到有溶液析出， 低温真空干燥得到白色粉末， 将 此粉末多次洗涤、 离心分离、 抽滤后， 在箱式炉中于 50°C下干燥 48小时以上， 再在 120°C干燥 3小时， 得到含 D=0和 C-N¾极性基团的球形二氧化钛纳米颗粒。尺寸为 50〜100纳米， 介电常数约为 1000。 在制备成的二氧化钛纳米颗粒中， C=0和 C-NH2 极性基团摩尔分数为 20%。
(2)将含 C=0和 C-NH2极性基团的二氧化钛纳米颗粒与 10#硅油混合， 用球磨 机强力搅拌 3小时以上， 使颗粒充分分散， 形成电流变液。 颗粒占总体积的体积分数 为 30%。 其剪切屈服强度可达 100kPa， 电流密度低于 ΙΟμΑ/cm2, 如图 1所示。 实施例 2
通过掺质尿素制备含 C=0和 C-NH^ 性基团的二氧化钛纳米颗粒的电流变液，分 散相为二氧化钛纳米颗粒，分散介质为硅油。图 10所示为制备的二氧化钛纳米颗粒的 扫描电镜照片， 颗粒为球形， 平均尺寸为 50纳米， 介电常数约为 500。 C=0和 C-NH2 极性基团的偶极矩为 2.3〜2.76 Debey和 1.2〜1.5 Debey。 二氧化钛纳米颗粒中 C=0 和 C-NH2极性基团的摩尔分数为 15%。
( 1 ) 通过惨质尿素制备含 C=0和 C-NH2极性基团的二氧化钛纳米颗粒。
颗粒采用溶胶凝胶法制备：
组份 1： 30mlTi(OC4H9)4溶解于 150ml无水乙醇中， 加入盐酸调节溶液的 pH值； 组份 2: 40ml去离子水溶于 250ml无水乙醇， 再加入 2 ml二乙醇胺调节钛酸四丁 酯的水解缩合反应；
组份 3： 30g尿素溶于 20ml水中；
将组份 2在强力搅拌下滴加入组份 1后， 立即加入第三组份， 继续搅拌直到形成 无色透明的凝胶。 将凝胶在室温下陈化 7天后， 在真空下低温干燥得到白色粉末， 将 此粉末用去离子水和无水乙醇多次洗涤、离心分离、抽滤后， 于 50°C下干燥 48小时， 再在 120°C干燥 3小时， 得到含 C=0和 C-N¾极性基团的球形二氧化钛纳米颗粒， 平均尺寸为 50纳米，介电常数约为 500。 C=0和 C-NH2极性基团的偶极矩为 2.3〜2.76 Debey和 1.2〜1.5 Debey。 颗粒中 C=0和 C-NH2极性基团摩尔分数为 15%。 (2) 将二氧化钛纳米颗粒与 10#硅油混合， 用球磨机强力搅拌 3小时以上， 使 颗粒充分分散， 形成均匀电流变液， 体积分数为 30%， 其剪切屈服强度可达 200kPa 以上， 如图 2所示， 在电场强度为 5kV/mm时， 电流密度小于 20 μΑ/cm2, 在电场强 度为 2kV/mm时， 屈服强度可达 100kPa。 在 3kV/mm时， 动态剪切强度达到 60kPa 以上， 如图 3所示。
实施例 3
由包含 0-H及 C=0极性基团的二氧化钕纳米颗粒制备电流变液，分散相为二氧化 钛， 分散介质为硅油， 极性基团在二氧化钛纳米颗粒制备过程中保留， 二氧化钛纳米 颗粒为球形， 平均尺寸为 50纳米， 介电常数约为 500。 0-H及 C=0极性基团的偶极 矩为 2.3〜2.76 Debey和 1.51 Debey。颗粒中的极性基团 0-H及 C=0的摩尔分数为 5%。
( 1 ) 采用溶胶凝胶法制备颗粒：
选用钛酸四丁酯作为原料， 水作为反应剂， 无水乙醇作为溶剂。 在强力搅拌的条 件下， 将水的乙醇溶液滴加到钛酸四丁酯的无水乙醇溶液中， 滴加完毕后继续搅拌直 到凝胶生成。 凝胶陈化若干天后， 真空干燥成白色粉末， 将该粉末多次洗涤抽滤后置 于 50°C的烘箱中干燥 72小时以上， 再在 120°C烘干 2小时， 得到所需的纳米 Ti02颗 粒。颗粒为球形， 平均尺寸为 50纳米。通过洗涤时间和次数控制颗粒中极性基团 0-H 及 C=0的存留量。 颗粒中极性基团 0-H及 C )摩尔分数为 5%， 偶极矩分别为 1.51 Debey和 2.3〜2.7 Debey。
(2) 将该纳米 Ti02颗粒与粘度为 200mm2/s的二甲基硅油混合， 用球磨机强力 搅拌 3小时以上， 使颗粒充分分散， 形成电流变液。 颗粒体积分数为 30%， 得到的 电流变液的剪切屈服强度可达 150kPa以上，如图 4所示。在电场强度为 2kV/mm时， 屈服强度可达近 100kPa， 在电场强度为 5kV/mm时， 电流密度小于 20 μΑΑ;πι2。 实施例 4
由包含极性基团的钛酸钙纳米颗粒制备电流变液， 分散相为钛酸钙纳米颗粒， 分 散介质为硅油。 0-Η及 C=0极性基团在钛酸钙纳米颗粒的制备过程中保留。钛酸钙纳 米颗粒为球形， 平均尺寸为 50纳米， 介电常数约为 300。 0-H及 C=0极性基团的偶 极矩分别为 1.51Debey和 2.3~2.7 Debey。 颗粒中极性基团 0-H及 C=0的摩尔分数为 25%。
( 1 ) 用共沉淀法制备钛酸钙纳米颗粒： 组份 1 : 将 30ml四氯化钛与无水乙醇按摩尔比 1 : 25混合均匀； 组份 2: 将无水氯化钙以 2mol/l溶于去离子水， 配制成水溶液；
在 60°C水浴中搅拌， 将组份 1和组份 2充分混合， 用盐酸调节溶液 pH值为 4, 得 混合溶液 1+2;
组份 3: 将草酸以溶解于去离子水中， 配制成 2mol/l 溶液；
将组份 3滴入混合溶液 1+2中， 三种溶液的混合体积比为 2: 1： 2。 将生成的沉 淀在 60°C下陈化 12小时， 用去离子水洗涤、 过滤， 干燥 120小时以上， 再在 120°C干 燥 3小时， 即得到 50-100纳米的钛酸钙球形颗粒。通过洗涤时间和次数控制颗粒中极 性基团 0-H及 C=0的存留量。 0-H和 C )极性基团由红外光谱分析 (红外光谱仪的型 号为： Digilab FTS3000)验证， 颗粒中的极性基团 0-H及 C=0的摩尔分数约为 25%。
0-H和 C=0极性基团的偶极矩分别为 1.51 Debey和 2.3-2.7 Debey。
(2) 将该钛酸钙颗粒与 50#甲基硅油混合， 用球磨机强力搅拌 3小时以上， 使颗 粒充分分散， 形成电流变液。 颗粒体积分数为 30%。 在电场强度为 5kV/mm时， 屈服 强度可达 200kPa以上， 电流密度小于 1 μΑ/cm2, 在电场强度为 2kV/mm时， 屈服强 度可达 90kPa， 如图 5所示。 . 实施例 5
由包含极性基团的钛酸锂镧纳米颗粒制备电流变液， 分散相为钛酸锂镧纳米颗 粒，分散介质为硅油。 0-H及 C=0极性基团在钛酸锂镧纳米颗粒的制备过程中保留。 颗粒为球形， 平均尺寸为 50纳米， 介电常数约为 400。 颗粒中的极性基团 0-H及 C=0的摩尔分数为 15%， 0-H及 C=0极性基团的偶极矩分别为 1.51 Debey和 2.3~ 2.7 Debey。
( 1 ) 釆用共沉淀法制备钛酸锂镧颗粒的步骤如下： 选用 LiCl.H20， LaCl3-7H20, Ti(OC4H9)4为原料， 草酸 ( Η204·2¾0)为共沉淀剂。 沉淀产物为 Li3xLa2/3_xTi(C204)2, 将沉淀用去离子水和乙醇多次洗涤， 抽滤后在 50°C下洪干 48小时以上， 120 Ό加热 3 小时， 得到白色的 LixLa2/3.xTi(C204)2颗粒。 颗粒为球形， 平均尺寸为 50纳米。 颗粒 中包含 0-H和 C=0极性基团， 摩尔分数为 15%。
(2) 将合成的钛酸锂镧颗粒与粘度为 200mm2/s的二甲基硅油以体积分数 30%混合， 用球磨机强力搅拌 3小时以上， 使颗粒充分分散， 得到电流变液。 电流变液屈服强度 可达 90kPa以上， 电流密度小于 20μΑΑ;πι2。 实施例 6
制备甲酰胺附着的钛酸锶纳米颗粒的电流变液， 用购买的钛酸锶纳米颗粒， 介电 常数为 300。 按摩尔比为 2: 100的比例， 将甲酰胺液体与钛酸锶纳米颗粒均匀混合， 甲酰胺极性分子的偶极矩为 3.73 Debey。 在 50°C烘 2小时， 使甲酰胺附着在钛酸锶纳 米颗粒上。将颗粒与 200mm2/s的二甲基硅油以体积分数 30%均匀混合，得到电流变液， 屈服强度可达 20kPa， 比不加甲酰胺极性分子的普通电流变液屈服强度 （低于 lkPa) 大大提高。 但购买的钛酸锶纳米颗粒为方形， 并非球形， 因而屈服强度不能达到很高。 实施例 7
制备在分散介质中包含极性分子或极性基团的电流变液， 将乙酸乙酯与粘度为
200mm2/s的二甲基硅油以摩尔比 3: 10均匀混合， 配制成包含极性分子的均匀液体， 以此作为分散介质。 乙酸乙酯极性分子的偶极矩为 1.78 Debey。 用购买的尺寸为 100-200纳米， 介电常数为 300的钛酸锶颗粒作为分散相， 以体积分数 30%均匀混合。 得到电流变液， 屈服强度可达 30kPa。 比用纯硅油与钛酸锶颗粒配制的普通电流变液 的屈服强度 （低于 1 kPa)大大提高。 但购买的钛酸锶纳米颗粒为方形， 并非球形， 因 而屈服强度不能达到很高。
将乙酸乙酯与粘度为 200mm2/s的二甲基硅油以摩尔比为 0.5: 10， 1： 10, 2: 10 进行混合， 可获得类似结果。 比较例 1
将上述实施例 6、 7中所使用的尺寸为 100〜200纳米的钛酸钡或钛酸锶颗粒与粘 度为 200mm2/s的二甲基硅油均匀混合，钛酸钡或钛酸锶颗粒的体积分数为 30%，得到 的电流变液的剪切屈服强度均低于 lkPa。 比较例 2
将尺寸为 200纳米的普通 Ti02颗粒与粘度为 200mm2/s的二甲基硅油均匀混合， 颗粒体积分数为 30%， 得到不包含极性基团或极性分子的电流变液， 剪切屈服强度仅 为几十帕， 如图 6所示。 这是典型的普通电流变液。
比较例 3
将实施例 2中掺质尿素制备的含 C=0和 C-NH2极性基团的二氧化钕纳米颗粒，实 施例 4中的包含 0-H及 C )极性基团的钛酸钙纳米颗粒在 500〜800°C加热 2小时。 红外光谱分析表明， 极性分子和极性基团均已挥发'掉。 用这些高温处理过的颗粒， 与 粘度为 200mm2/S的二甲基硅油均勾混合，颗粒体积分数为 30%，得到的电流变液失去 剪切屈服强度特性。
将含 C=0和 C-NH2极性基团的二氧化钛纳米颗粒在 800°C加热 2小时后，制成的 电流变液完全失去剪切屈服强度特性， 如图 7所示。
将包含 0-H及 C= 极性基团的钛酸钙纳米颗粒在 500°C加热 2小时后， 制成的 电流变液完全失去剪切屈服强度特性， 如图 8所示。
将包含极性基团或极性分子的颗粒， 在高温加热， 使极性基团或极性分子挥发掉， 失去极性基团或极性分子的颗粒制备成的电流变液的剪切屈服强度很低， 充分说明含 有极性基团或极性分子的电流变液的剪切屈服强度髙。 比较例 4
通过与 CN1490388中所述的方法相同的方法制备表面包覆尿素的钛酸钡的电流变 液， 并将其与实施例 2所述的电流变液进行比较， 结果如图 9所示。 表面包覆尿素的钛 酸钡电流变液在 2kV/mm 时屈服强度约为 30kPa, 实施例 2所述的电流变液的屈服强度 在 2kV/mm 时约为 100kPa。而且实施例 2的电流变液的屈服强度与电场呈线性关系。表 面包覆尿素的钛酸钡电流变液的漏电流密度在 5kV/mm时为 300μΑΑ;ιη2。 实施例 2的电 流变液的电流密度在 5kV/mm时， 为 20μΑΑ;ιη2以下， 有些低于 ΙμΑ/cm2, 如图 5所示。 比表面包覆尿素的钛酸钡电流变液的漏电流密度低 10倍到 100倍以上。充分说明本发明 的极性分子型电流变液具有屈服强度高， 动态剪切强度高， 漏电流小， 屈服强度与电 场强度呈线性关系， 在低电场下具有髙屈服强度等特点。

Claims

权 利 要 求
1、 一种极性分子型电流变液， 主要由固体颗粒分散相和液体分散介质混合组成， 其特征是，
( 1 ) 分散相固体颗粒表面和 /或液体分散介质中含有极性分子或极性基团， 极性 分子或极性基团的偶极矩为 0.5〜10德拜， 尺寸为 0.i〜0.8纳米；
(2)分散相固体颗粒为球形或类球形， 颗粒尺寸为 10〜300纳米， 介电常数大于
50；
(3 ) 液体分散介质的电导率低于 10—sS/m， 介电常数低于 10。
2、根据权利要求 1所述的极性分子型电流变液， 其特征在于， 所述的分散相固体 颗粒的尺寸为 20〜！ 00纳米。
3、根据权利要求 1所述的极性分子型电流变液， 其特征在于， 所述极性分子或极 性基团中起作用的极性键选自 C=0、 0-H、 N-H、 F-H、 C-OH、 C-N02、 C-H、 C-OCH3、 C-NH2、 C-COOH、 C-C1、 N-O中的至少一种。
4、根据权利要求 1所述的极性分子型电流变液， 其特征在于， 所述分散相固体颗 粒表面的极性分子或极性基团是在分散相固体颗粒的制备过程中添加或保留， 或在制 备好的颗粒表面上添加或组装的。
5、根据权利要求 4所述的极性分子型电流变液， 其特征在于， 所述极性分子或极 性基团在分散相中的摩尔分数为 0.01〜50%。
6、根据权利要求 1所述的极性分子型电流变液， 其特征在于， 所述液体分散介质 中的极性分子或极性基团的摩尔分数为 0. 1〜100%。
7、根据权利要求 1所述的极性分子型电流变液， 其特征在于， 固体颗粒分散相与 液体分散介质充分混合， 固体颗粒分散相在电流变液中的体积分数为 5〜50%。
8、根据权利要求 1所述的极性分子型电流变液， 其特征在于， 所述分散相固体颗 粒包括二氧化钛颗粒、 钛酸钙颗粒、 钛酸锂镧颗粒或钛酸锶颗粒。
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