A kind of titanium oxyoxalate zinc current becomes liquid and preparation method thereof
Technical field
The present invention relates to a kind of electrorheological fluid and preparation method thereof, refer to that specifically a kind of titanium oxyoxalate zinc current becomes liquid and preparation method thereof.
Background technology
Electrorheological fluid is called as intelligent material, has the quality of controlled change, and its yielding stress, Young's modulus can change by changing ambient conditions.It usually is dispersed in the transformer oil of low-k by the solia particle with high-k and forms, and it is a kind of suspension under usual conditions, and it under the effect of electric field, the transformation of liquid-solid can occur.When electric field strength was significantly less than certain threshold value, electrorheological fluid was in a liquid state; When strength of electric field was much higher than this threshold value, it just became solid-state.Near the threshold value of strength of electric field, the viscosity of electrorheological fluid becomes greatly with the increase of strength of electric field, between also liquid also between solid states of matter.The character of particulate solid material has determined the quality of electrorheological fluid performance, is the key component of electrorheological fluid.
Electrorheological fluid is the even suspension liquid body that a kind of oneself viscosity can significantly increase under External Electrical Field.It has been generally acknowledged that this variation is because the small-particle that disperses in electrorheological fluid under electric field action is polarized to electric dipole, thereby produce the variation that strong electrostatic attraction causes the liquid macroscopic viscosity between these dipoles.In this process, particle becomes ordered arrangement by unordered stochastic distribution, usually forms certain chain and columnar structure, and this microtexture has a significant impact the macro-mechanical property of electrorheological fluid.The continuously adjustable peculiar character of electrorheological fluid soft or hard under electric field action has extensive and important using value, as clutch coupling, stopper, damping system, vibroshock, buncher, valve, electromechanical coupling control etc.Yet estimated current becomes liquid and not yet obtains practical application widely industrial, and its major cause is that the yielding stress of electrorheological fluid is low, complicated process of preparation.
Summary of the invention
Technical problem to be solved by this invention is the present situation for prior art, provides a kind of titanium oxyoxalate zinc current of high yield stress to become liquid.
Another technical problem to be solved by this invention is the present situation for prior art, provides the simple titanium oxyoxalate zinc current of a kind of preparation technology to become the preparation method of liquid.
The present invention solves the problems of the technologies described above the technical scheme that adopts: this titanium oxyoxalate zinc current becomes liquid, it is characterized in that: its be with nanometer to the titanium oxyoxalate zinc particle of micron-scale as disperse phase, be dispersed in the suspension liquid that forms in the silicone oil dispersion medium, and the volumetric concentration of this suspension liquid mesoxalic acid oxygen titanium zinc particle is 5~40%.
Preferably, described silicone oil can be selected methyl-silicone oil or hydroxy silicon oil.
The preparation method that above-mentioned titanium oxyoxalate zinc current becomes liquid first uses oxalic acid and titanium salt and zinc salt coprecipitation reaction to prepare titanium oxyoxalate zinc particle, more evenly is mixed with titanium oxyoxalate zinc suspension liquid with silicone oil.Detailed step is as follows:
1. the preparation of titanium oxyoxalate zinc particle
Titanium salt and the anhydrous organic alcohol solvent ratio take mol ratio as 1: 30~60 is mixed, obtain solution A;
To mix with anhydrous Organic Alcohol with the zinc salt of the mole numbers such as titanium salt, be mixed with the solution B of 0.2mol/l;
2 times of oxalic acid to the titanium salt mole number are dissolved in deionized water, are mixed with the solution C of 1mol/l;
Solution A is placed on stirrer stirs, be placed on simultaneously water-bath in 40-50 ℃ of constant temperature water bath; Solution B is added in solution A; Stir, get homogeneous mixture solotion AB;
Solution C is splashed in solution A B, form gradually precipitation; After reacting completely, with the sedimentation and filtration post-drying that generates, namely obtain the titanium oxyoxalate zinc particle that needed nanometer distributes to micron-scale;
2. the titanium oxyoxalate zinc current becomes the preparation of liquid
The titanium oxyoxalate zinc particle that 1. step is obtained evenly mixes with silicone oil, and the volumetric concentration that is mixed with the titanium oxyoxalate particle is 5~40% titanium oxyoxalate zinc suspension liquid.
In such scheme, described anhydrous Organic Alcohol can be selected dehydrated alcohol or anhydrous isopropyl alcohol;
Described silicone oil can be selected from methyl-silicone oil or hydroxy silicon oil;
Described titanium salt can be selected from tetrabutyl titanate, titanium tetrachloride, tetraethyl titanate or titanium isopropylate.
Described zinc salt can be selected from zinc nitrate, zinc chloride, zinc acetate or zinc sulfate.
Compared with prior art, titanium oxyoxalate zinc current provided by the present invention becomes liquid, is that the titanium oxyoxalate zinc particle and the silicone oil that make with oxalic acid coprecipitation are formulated, and its required starting material very easily obtain, and with low cost, preparation technology is simple, and the cycle is short; The titanium oxyoxalate zinc current that makes becomes liquid and has strong electric rheopectic effect, and when extra electric field was 5kV/mm, its yielding stress reached 100kPa, and has the many merits such as current density is little, nontoxic, pollution-free, and good application prospect is arranged.
Description of drawings
Fig. 1 is that the titanium oxyoxalate zinc current of different volumes concentration in the embodiment of the present invention 1 becomes the yielding stress of liquid and the graph of a relation of strength of electric field;
Fig. 2 is that the titanium oxyoxalate zinc current of different volumes concentration in the embodiment of the present invention 1 becomes the current density of liquid and the graph of a relation of strength of electric field.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
0.05mol tetrabutyl titanate and dehydrated alcohol were mixed in 1: 30 in molar ratio, stir, obtain stabilizing solution A; The 0.05mol zinc nitrate is dissolved in dehydrated alcohol, is mixed with the zinc nitrate solution B of 0.2mol/l; 0.1mol oxalic acid is dissolved in deionized water, is mixed with 1mol/l oxalic acid solution C; Solution A is placed on stirrer stirs, be placed on simultaneously water-bath in 40 ℃ of water baths; Solution B is added in solution A; Stir, get homogeneous mixture solotion AB; Then solution C is splashed in solution A B, form gradually precipitation; After reacting completely, with the sedimentation and filtration post-drying that generates, namely obtain the titanium oxyoxalate zinc particle that needed nanometer distributes to micron-scale;
This titanium oxyoxalate zinc particle is evenly mixed with dimethyl silicone oil, be mixed with respectively volumetric concentration and be 10%, 20% and 30% titanium oxyoxalate zinc current and become liquid.Measure the relation of its yielding 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.
Embodiment 2
0.05mol titanium tetrachloride and anhydrous isopropyl alcohol were mixed in 1: 40 in molar ratio, stir, obtain stabilizing solution A; The 0.05mol zinc chloride is dissolved in anhydrous isopropyl alcohol, is mixed with the liquor zinci chloridi B of 0.2mol/l; 0.1mol oxalic acid is dissolved in deionized water, is mixed with 1mol/l oxalic acid solution C; Solution A is placed on stirrer stirs, be placed on simultaneously water-bath in 50 ℃ of water baths; Solution B is added in solution A; Stir, get homogeneous mixture solotion AB; Then solution C is splashed in solution A B, form gradually precipitation; After reacting completely, with the sedimentation and filtration post-drying that generates, namely obtain the titanium oxyoxalate zinc particle that needed nanometer distributes to micron-scale;
This titanium oxyoxalate zinc particle is evenly mixed with methyl-silicone oil, be mixed with respectively volumetric concentration and be 15%, 20% and 30% titanium oxyoxalate zinc current of the present invention and become liquid.When extra electric field V=4.0kV/mm, the yield strength that records 10% electrorheological fluid is 16kPa, and current density is 8uA/cm
2The yield strength of 20% electrorheological fluid is 60kPa, and current density is 18uA/cm
2The yield strength of 30% electrorheological fluid is 84kPa, and current density is 25uA/cm
2
Embodiment 3
0.05mol tetrabutyl titanate and anhydrous isopropyl alcohol were mixed in 1: 30 in molar ratio, stir, obtain stabilizing solution A; The 0.05mol zinc acetate is dissolved in anhydrous isopropyl alcohol, is mixed with the acetic acid zinc solution B of 0.2mol/l; 0.1mol oxalic acid is dissolved in deionized water, is mixed with 1mol/l oxalic acid solution C; Solution A is placed on stirrer stirs, be placed on simultaneously water-bath in 40 ℃ of water baths; Solution B is added in solution A; Stir, get homogeneous mixture solotion AB; Then solution C is splashed in solution A B, form gradually precipitation; After reacting completely, with the sedimentation and filtration post-drying that generates, namely obtain the titanium oxyoxalate zinc particle that needed nanometer distributes to micron-scale;
This titanium oxyoxalate zinc particle is evenly mixed with dimethyl silicone oil, be mixed with volumetric concentration and be 10%, 20% and 30% titanium oxyoxalate zinc current of the present invention and become liquid.When extra electric field V=5.0kV/mm, the yield strength of 10% electrorheological fluid is 10kPa, and current density is 8uA/cm
2The yield strength of 20% electrorheological fluid can reach 68kPa, and current density is 15uA/cm
2The yield strength of 30% electrorheological fluid can reach 96kPa, and current density is 20uA/cm
2
Embodiment 4
0.05mol titanium tetrachloride and dehydrated alcohol were mixed in 1: 60 in molar ratio, stir, obtain stabilizing solution A; 0.05mol zinc sulfate is dissolved in dehydrated alcohol, is mixed with the solution of zinc sulfate B of 0.2mol/l; 0.1mol oxalic acid is dissolved in deionized water, is mixed with 1mol/l oxalic acid solution C; Solution A is placed on stirrer stirs, be placed on simultaneously water-bath in 40 ℃ of water baths; Solution B is added in solution A; Stir, get homogeneous mixture solotion AB; Then solution C is splashed in solution A B, form gradually precipitation; After reacting completely, with the sedimentation and filtration post-drying that generates, namely obtain the titanium oxyoxalate zinc particle that needed nanometer distributes to micron-scale;
This titanium oxyoxalate zinc particle is evenly mixed with dimethyl silicone oil, be mixed with volumetric concentration and be 15%, 25% and 35% titanium oxyoxalate zinc current of the present invention and become liquid.When extra electric field V=4.0kV/mm, the yield strength of 10% electrorheological fluid is 16kPa, and current density is 8uA/cm
2The yield strength of 20% electrorheological fluid can reach 70kPa, and current density is 18uA/cm
2The yield strength of 30% electrorheological fluid can reach 90kPa, and current density is 25uA/cm
2
Embodiment 5
0.05mol tetraethyl titanate and anhydrous isopropyl alcohol were mixed in 1: 30 in molar ratio, stir, obtain stabilizing solution A; The 0.05mol zinc nitrate is dissolved in anhydrous isopropyl alcohol, is mixed with the zinc nitrate solution B of 0.2mol/l; 0.1mol oxalic acid is dissolved in deionized water, is mixed with 1mol/l oxalic acid solution C; Solution A is placed on stirrer stirs, be placed on simultaneously water-bath in 40 ℃ of water baths; Solution B is added in solution A; Stir, get homogeneous mixture solotion AB; Then solution C is splashed in solution A B, form gradually precipitation; After reacting completely, with the sedimentation and filtration post-drying that generates, namely obtain the titanium oxyoxalate zinc particle that needed nanometer distributes to micron-scale.This titanium oxyoxalate zinc particle is evenly mixed with methyl-silicone oil, be mixed with volumetric concentration and be 35% titanium oxyoxalate zinc current of the present invention and become liquid.When extra electric field V=4.0kV/mm, the yield strength of electrorheological fluid can reach 90kPa, and current density is 20uA/cm
2
Embodiment 6
0.05mol titanium isopropylate and anhydrous isopropyl alcohol were mixed in 1: 45 in molar ratio, stir, obtain stabilizing solution A; The 0.05mol zinc nitrate is dissolved in anhydrous isopropyl alcohol, is mixed with the zinc nitrate solution B of 0.2mol/l; 0.1mol oxalic acid is dissolved in deionized water, is mixed with 1mol/l oxalic acid solution C; Solution A is placed on stirrer stirs, be placed on simultaneously water-bath in 50 ℃ of water baths; Solution B is added in solution A; Stir, get homogeneous mixture solotion AB; Then solution C is splashed in solution A B, form gradually precipitation; After reacting completely, with the sedimentation and filtration post-drying that generates, namely obtain the titanium oxyoxalate zinc particle that needed nanometer distributes to micron-scale.This titanium oxyoxalate zinc particle is evenly mixed with methyl-silicone oil, be mixed with volumetric concentration and be 40% titanium oxyoxalate zinc current of the present invention and become liquid.When extra electric field V=4.0kV/mm, the yield strength of electrorheological fluid can reach 95kPa, and current density is 25uA/cm
2