CN108774562A - A kind of MOF-Ti/ polyaniline nano-composite materials ER fluid and preparation method thereof - Google Patents
A kind of MOF-Ti/ polyaniline nano-composite materials ER fluid and preparation method thereof Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 50
- 239000012530 fluid Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000002776 aggregation Effects 0.000 claims abstract description 9
- 238000004220 aggregation Methods 0.000 claims abstract description 9
- 229940008099 dimethicone Drugs 0.000 claims abstract description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 9
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000005457 optimization Methods 0.000 claims abstract 2
- 239000010936 titanium Substances 0.000 claims description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 230000005684 electric field Effects 0.000 abstract description 17
- 238000005253 cladding Methods 0.000 abstract description 5
- 239000011246 composite particle Substances 0.000 abstract description 4
- 241000549556 Nanos Species 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/18—Complexes with metals
-
- 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
- C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
- C10M157/10—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a compound containing atoms of elements not provided for in groups C10M157/02 - C10M157/08
-
- 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
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
-
- 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
- C10N2040/17—Electric or magnetic purposes for electric contacts
Abstract
The present invention relates to a kind of ER fluid material and preparation method thereof, more particularly to a kind of ER fluid material of MOF-Ti/ polyaniline nanos composite particles.The dispersed phase of the ER fluid is the cladding nanometer composite particles being combined with the polyaniline nanoparticles of growth thereon by MOF-Ti nano-particles, and continuous phase is dimethicone;Its preparation process is first to prepare MOF-Ti nano-particles as presoma using solvent-thermal method, recycles modified situ aggregation method to grow polyaniline in MOF-Ti nanoparticle precursors, prepares MOF-Ti/ polyaniline nano-composite materials.Prepared MOF-Ti/ polyaniline nano-composite materials pattern is unique, is approximately column.MOF-Ti nano-particles improve the performance of material after being combined with polyaniline, to make the comprehensive performance of material, especially ER properties obtain prodigious optimization.The relationship of MOF-Ti/ polyaniline nano-composite material ER fluid shear stress and electric field strength is shown in attached drawing.
Description
Technical field
The present invention relates to a kind of ER fluid materials and preparation method thereof, and in particular to a kind of MOF-Ti/ polyaniline nanos
Composite material by electric current becomes liquid and preparation method thereof.
Background technology
ER fluid (Electrorheological Fluids abbreviation ERF) is a kind of novel intellectual material, it is usually
It is the suspension system formed in the insulating oil of low-k by the solid particle dispersions of high-k, low conductivity.
The viscosity of the colloid can be significantly increased with the enhancing of electric field strength, when electric field increases to a threshold value, the rheology of the colloid
Characteristic will change.This process is very rapid, is usually happened in several milliseconds of process, and transition process have can
Inverse property.This also means that the rheological behavior of ER fluid can change with the variation of electric field.It is being not added with extra electric field
When, fluid shows the characteristic of Newtonian fluid, but when external electronic field is sufficiently high, can be transformed into " elastic solid (Hookean body) ", right
The outer property for showing Bingham fluid.Application range of the ER fluid in fields such as mechanical engineering, automobile engineering, control engineerings is non-
Often extensively.Under normal conditions, the property of solids determines the quality of ER fluid performance, is the key that ER fluid.Therefore
Studying the discrete state material with high current change effect becomes the critical issue that electric current becomes field.Correlative study in recent years is concentrated
In terms of becoming the preparation of dispersed phase of performance with high current, and achieve certain achievement.Nano particle ER fluid by
Can be of increased attention in its higher mechanics value and good resistance to settling, therefore, modified on micrometer structure
Nanostructure can obtain a kind of micrometer/nanometer clad structure material, the dual of micron and nano particle can be had concurrently simultaneously
Advantage, the mechanics and cutting performance of gained ER fluid are also greatly improved than micron particles ER fluid.
The metal organic framework (MOF) being made of metal ion and organic ligand is a kind of novel crystalline microporous body,
Have many advantages, such as that large specific surface area, structure are adjustable, due to its intrinsic porosity, adjustable skeleton and adjustable aperture,
Many fields show huge potentiality, therefore receive more and more attention in addition, different by selecting when preparing MOFs
Metal coordination centers and organic ligand, can not only obtain a large amount of different types of proton sources, but also can build effectively
Hydrogen bond transmit network structure, increase substantially proton conduction property.MIL-125 (a kind of MOF forming Ti) is as a kind of new
There is the porous material of type adjustable porosity, big specific surface area to show the characteristics such as excellent catalysis and hydrogen storage.
Polyaniline (PANI) has excellent physical and chemical performance, unique mechanism of doping effect and good environmental stability, and
And have many advantages, such as that raw material is cheap and easy to get, synthesis technology is easy, become the most a kind of conductive polymer of numerous scientists studies
Sub- material and the most possible conducting polymer for realizing industrial applications, conductivity can be by adulterating-going doping to be adjusted
Section.It is an object of the invention to provide a kind of nanometer/nano-core-shell structure material, the ER fluid of preparation has higher shear stress
Value, excellent resistance to settling energy, performance ratio micron particles and nano particle ER fluid all improve a lot.Using organic-inorganic
Nano combined mode had not only played the good feature of the small resistance to settling of organic matter density, but also big, the electric field that is utilized inorganic matter polarity
The strong feature of responding ability, the advantages of having fully demonstrated organic-inorganic nanocomposite.Preparation process uses solvent-thermal method and modification
Situ aggregation method be combined, preparation process is simple, easy to operate.
Goal of the invention and content
The object of the present invention is to provide a kind of novel MOF-Ti/ polyaniline-coateds type Nano composite granules ER fluids
Material, dispersed phase are the packets that similar columnar MOF-Ti nano-particles are combined with the polyaniline nanoparticles of growth thereon
Type Nano composite granules are covered, continuous phase is dimethicone.
The present invention also aims to provide a kind of method preparing MOF-Ti/ polyaniline nano-composite materials, this method
Gained nanocomposite is the cladded type being combined with the polyaniline nanoparticles of load thereon by MOF-Ti nano-particles
Nano composite granules, this Nano composite granules are combined to prepare using solvent-thermal method and modified in-situ polymerization growth method.
During preparing MOF-Ti nanoparticle precursors using solvent-thermal method method, its pattern is adjusted using CTAB.Grain diameter is about
Hundreds of nanometers, form is single uniformly, is approximately column.Then it is prepared by the simply modified situ aggregation method of preparation process
The core-shell material that MOF-Ti nano-particles are combined with polyaniline, so as to improve the performance of material, by coating a strata aniline
Material reduces its conductivity later, improves the polarizability of core-shell material, especially electric to make the comprehensive performance of the material
Rheological property is optimized.
The purpose of the present invention can be achieved through the following technical solutions:
ER fluid obtained by the present invention, dispersed phase are the polyaniline of column MOF-Ti nano-particles thereon with growth
Cladding nanometer composite particles made of nano-particles reinforcement, continuous phase are dimethicone.
Above-mentioned MOF-Ti presomas are prepared using solvent-thermal method, and preparation process is as follows:
(1) by 4.05~5.05g terephthalic acid (TPA)s be dissolved in 90~110ml N,N-dimethylformamides (DMF) and 10~
The in the mixed solvent of 20ml methanol, stirring to water white transparency;
(2) 4~6ml acetic acid is added before 2~4ml butyl titanates are added to prevent titanium precursor hydrolysis.Stir 10min
The solution of gained is transferred in autoclave afterwards and is heated for 24 hours at 150 DEG C;
(3) it finally reuses DMF and methanol solution carries out centrifuge washing, dry about 10h obtains MOF-Ti nanometers at 70 DEG C
Grain.
MOF-Ti/ polyaniline nano-composite materials and its ER fluid are prepared with the following method:
(1) under the conditions of strong stirring, a certain amount of MOF-Ti nano particles are dissolved in 90~110ml DMF solutions fully
Stirring, and 1~3ml aniline solutions are added;
(2) 0.5~1.5g ammonium persulfates are dissolved in the in the mixed solvent of 40~60ml DMF and very little water, after stirring clarification
It is poured slowly into the solution in step 1,3h is then stirred in ice-water bath;
(3) suspension deionized water being obtained after reaction and absolute ethyl alcohol carrying out multiple centrifuge washing, product is placed in 70
It is about 10 hours dry in DEG C baking oven;
(4) sample and dimethicone are configured to ER fluid by a certain percentage.
Compared with prior art, the present invention having following significant technological merit:
1, the preparation process that preparation method of the present invention is combined using the situ aggregation method of solvent-thermal method and modification, by MOF-
Ti nano-particles and polyaniline nanoparticles are compounded to form cladding nanometer composite particles, the Nano composite granules grain size of preparation compared with
Small, in-stiu coating grows polyaniline nanoparticles on MOF-Ti, is in the form of a column, and size is about hundreds of nanometers, and pattern is single uniformly.
2, the ER fluid prepared by the material and methyl-silicone oil not only has higher mechanical property and resistance to settling, and
And its operating temperature range is wider, manufacturing cost is relatively low, and reaction process is easily controllable, nontoxic, is wanted without special to equipment
It asks.The speciality for having given full play to Organic/Inorganic Composite Nanomaterials is a kind of er material of high comprehensive performance.It prepares
Simple for process, raw material is easy to get, and component is easily controllable with performance, and product is nontoxic, is easy to industrialized production and extensive use.
Description of the drawings
The scanning electron microscopic picture of the pure MOF-Ti of Fig. 1.
The XRD diagram of the pure MOF-Ti of Fig. 2.
Relationship of the pure MOF-Ti nano particles ER fluids of Fig. 3 in different electric field strength down cut stress and shear rate
Figure.
Fig. 4 DMF do the scanning electron microscope (SEM) photograph of the MOF-Ti/ polyaniline nano-composite materials of solvent preparation.
Fig. 5 DMF do the transmission electron microscope picture of the MOF-Ti/ polyaniline nano-composite materials of solvent preparation.
Fig. 6 DMF do the XRD diagram of the MOF-Ti/ polyaniline nano-composite materials of solvent preparation.
Fig. 7 MOF-Ti/ polyanilines (DMF) nano particle ER fluid is in different electric field strength down cut intensity and shearing
The relational graph of rate.
Fig. 8 water does the scanning electron microscope (SEM) photograph of the MOF-Ti/ polyaniline nano-composite materials of solvent preparation.
Fig. 9 water does the XRD diagram of the MOF-Ti/ polyaniline nano-composite materials of solvent preparation.
Figure 10 MOF-Ti/ polyanilines (water) nano particle ER fluid is in different electric field strength down cut intensity and shearing
The relational graph of rate.
Figure 11 hydrochloric acid does the scanning electron microscope (SEM) photograph of the MOF-Ti/ polyaniline nano-composite materials of solvent preparation.
Figure 12 hydrochloric acid does the XRD diagram of the MOF-Ti/ polyaniline nano-composite materials of solvent preparation.
Figure 13 MOF-Ti/ polyanilines (hydrochloric acid) nano particle ER fluid is in different electric field strength shear strengths and shearing
The relational graph of rate.
Specific implementation mode
Embodiment one (preparation of presoma MOF-Ti nano particles):
1, by 4.05~5.05g terephthalic acid (TPA)s be dissolved in 90~110ml N,N-dimethylformamides (DMF) and 10~
The in the mixed solvent of 20ml methanol, stirring to water white transparency;
2,4~6ml acetic acid is first added before 2~4ml butyl titanates are added to above-mentioned solution to prevent titanium precursor water
Solution.The solution of gained is transferred in autoclave after stirring 10min and is heated for 24 hours at 150 DEG C;
3, it finally reuses DMF and methanol solution carries out centrifuge washing, dry about 10h obtains MOF-Ti nanometers at 70 DEG C
Grain.
The stereoscan photograph of obtained presoma MOF-Ti particles is as shown in Fig. 1.Obtained MOF-Ti particles are in
Column, particle morphology are uniform.Grain size is about in hundreds of rans, polydispersion and grain size is uneven.Presoma MOF-Ti particles
XRD spectrum it is as shown in Fig. 2, it can be seen that the intensity at its peak is it is obvious that meet the standard diagram of MOF-Ti.At room temperature, it takes
The pure MOF-Ti samples of 0.15g, which are placed in 1.5mL silicone oil, obtains the ER fluid that weight ratio is 10% after grinding uniformly, use electric current
Become tester to test ER properties of the sample in the case where applying different external electrical field effects, obtains shear stress and shearing
The relationship of rate such as attached drawing 3.Attached drawing shows that pure MOF electric rheological effects are very weak, and because of its conductivity very greatly and so that can not
It is added to high voltage.
Embodiment two (MOF-Ti/ polyaniline nano-composite materials 1. and its preparation of ER fluid):
1, under the conditions of strong stirring, 2.5-3.5gMOF-Ti nano particles is dissolved in 90~110ml DMF solutions and are filled
Divide stirring, and 1~3ml aniline solutions are added;
2,0.5~1.5g ammonium persulfates are dissolved in 40~60ml DMF and very little water (accounts for the 0.1%-1.5% of solvent total amount
Volume ratio) in the mixed solvent, stirring clarification after be poured slowly into the solution in step 1,3h is then stirred in ice-water bath;
3, suspension deionized water will be obtained after reaction and absolute ethyl alcohol carries out multiple centrifuge washing, and product is placed in 70 DEG C
It is about 10 hours dry in baking oven;
4, the sample and dimethicone are configured to ER fluid by weight 10%.
Pass through the scanning electron microscope (SEM) photograph such as attached drawing of MOF-Ti/ polyaniline nano-composite materials prepared by modified situ aggregation method
Shown in 4, transmission electron microscope picture as shown in figure 5, as can be seen from Figure 4 coated one layer of nano polyaniline layer on MOF-Ti particles,
The pattern stable homogeneous of particle, is uniformly dispersed, and grain size is about in hundreds of rans.Packet can be evident that from Fig. 5
The nucleocapsid covered, the thickness of clad is in 50nm-100nm.XRD spectra is as shown in Fig. 6, we can also from XRD
The intensity for going out diffraction maximum significantly reduces, and from the success of the cladding of side illustration polyaniline, polyaniline makes MOF-Ti in cladding
The strength reduction of diffraction maximum.Using electric current become tester to ER properties of the sample in the case where applying the effect of different external electrical fields into
Row test, obtains shear stress and the relationship such as attached drawing 7 of shear rate, as can be seen that being not powered on field from rheological curve
In the case of, shear stress linearly increases with shear rate, and slope is about 1, and ER fluid shows typical Newtonian fluid
Characteristic;After applying electric field, shear stress increased dramatically under the action of extra electric field, especially within the scope of low shear rate,
Show the characteristic of similar Bingham liquid.Attached drawing 7 shows that the MOF-Ti/ polyanilines prepared by modified situ aggregation method are received
The electric rheological effect of nano composite material is very strong, and when voltage reaches 3kV, shear strength has been more than 200Pa.Occur significantly flat
Taiwan area, electric rheological effect are many higher than pure MOF ER fluids.
In addition, it is intuitive expression shear stress increasing degree size under different electric field actions that electric current, which becomes efficiency,
Parameter, while being also the parameter for weighing electric rheological effect power, it can be expressed as with formula (1):
E=[(τ E- τ 0)/τ 0] (1)
In formula, e is that electric current becomes effectτ E and τ 0 is respectively under different electric field strengths and to be not powered on shear stress off field,
From figure 7 it can be seen that being 3kV/mm, shear rate 0.1s in electric field strength-1When, the electric current of ER fluid becomes efficiency and is up to
74。
Embodiment three (MOF-Ti/ polyaniline nano-composite materials 2. and its preparation of ER fluid):
1, under the conditions of strong stirring, 2.5-3.5gMOF-Ti nano particles are dissolved in 90~110ml deionized water solvents
In be sufficiently stirred, and be added 1~3ml aniline solutions;
2,0.5~1.5g ammonium persulfates are dissolved in 40~60ml deionized waters, are poured slowly into step 1 after stirring clarification
Solution in, 3h is then stirred in ice-water bath;
3, suspension deionized water will be obtained after reaction and absolute ethyl alcohol carries out multiple centrifuge washing, and product is placed in 70 DEG C
It is about 10 hours dry in baking oven;
4, the sample and dimethicone are configured to ER fluid by weight 10%.
The scanning electron microscope (SEM) photograph of the MOF-Ti/ polyaniline nano-composite materials prepared by modified situ aggregation method 2. is for example attached
Shown in Fig. 8, we significantly can be seen that the pattern of MOF has occurred certain destruction and reunited from Fig. 8.XRD
Spectrogram is as shown in Fig. 9, we can therefrom find out that the structure of MOF has been destroyed, only several very weak diffraction maximums.It is cut
The relationship of shearing stress and shear rate is as shown in Fig. 10, and therefrom we can significantly find out that its electric rheological effect is very poor,
Its shear strength is very low when low shear rate.
Example IV (MOF-Ti/ polyaniline nano-composite materials 3. and its preparation of ER fluid):
1, under the conditions of strong stirring, 2.5-3.5g MOF-Ti nano particles are dissolved in a concentration of 1mol/L of 90~110ml
Hydrochloric acid solution in be sufficiently stirred, and be added 1~3ml aniline solutions;
2,0.5~1.5g ammonium persulfates are dissolved in the hydrochloric acid solution of a concentration of 1mol/L of 40~60ml, delayed after stirring clarification
Slowly it pours into the solution in step 1,3h is then stirred in ice-water bath;
3, suspension deionized water will be obtained after reaction and absolute ethyl alcohol carries out multiple centrifuge washing, and product is placed in 70 DEG C
It is about 10 hours dry in baking oven;
4, the sample and dimethicone are configured to ER fluid by weight 10%.
The scanning electron microscope (SEM) photograph of the MOF-Ti/ polyaniline nano-composite materials prepared by modified situ aggregation method 3. is for example attached
Shown in Figure 11, XRD spectra is as shown in Fig. 12.As can be seen from Figure 11 MOF patterns have been destroyed completely substantially, only remaining
Polymerize the polyaniline fiber of institute, in Figure 12 it is also seen that only there are one 20 degree or so very weak diffraction maximum, be polyaniline
Diffraction maximum.The relationship of its shear stress and shear rate is as shown in Fig. 13, and therefrom we can significantly find out its electric current
Change effect is very poor, and land regions are unstable and its shear strength is very low, and electric current becomes inefficiency.
Claims (3)
1. the dispersed phase of a kind of MOF-Ti/ polyaniline nanoparticles ER fluid material, the material is a kind of MOF-Ti/ polyanilines
Nano particle, continuous phase are dimethicone;The pattern of the MOF-Ti/ polyaniline nanoparticles ER fluid materials is approximate column
Shape;The dispersed phase of the ER fluid is the cladded type being combined with the polyaniline nanoparticles of growth thereon by MOF-Ti
Nano composite granules are combined using solvent-thermal method and modified in-situ polymerization growth method to prepare;Prepare MOF-Ti nanoparticles
The core-shell material that son is combined with polyaniline, as a kind of nanometer/nano-core-shell structure material, the ER fluid of preparation is with higher
Shear stress values, excellent resistance to settling energy, improve the performance of material, to make the comprehensive performance of material, especially electric current
Become performance and obtains prodigious optimization.
2. MOF-Ti/ polyaniline nanoparticles ER fluid material as described in claim 1, which is characterized in that preparation process packet
Include the following steps:
(1) 4.05~5.05g terephthalic acid (TPA)s are dissolved in 90~110ml N,N-dimethylformamides (DMF) and 10~20ml first
The in the mixed solvent of alcohol, stirring to water white transparency;4~6ml acetic acid is added before 2~4ml butyl titanates are added to prevent
Titanium precursor hydrolysis;The solution of gained is transferred in autoclave after stirring 10min and is heated for 24 hours at 150 DEG C;Finally reuse
DMF and methanol solution carry out centrifuge washing, and dry about 10h obtains MOF-Ti nano particles at 70 DEG C;
(2) under the conditions of strong stirring, 2.5-3.5g MOF-Ti nano particles are dissolved in 90~110ml DMF solutions fully
Stirring, and 1~3ml aniline solutions are added;The mixing that 0.5~1.5g ammonium persulfates are dissolved in 40~60ml DMF and very little water is molten
In agent, it is poured slowly into the solution in step 1 after stirring clarification, 3h is then stirred in ice-water bath;It will be suspended after reaction
Liquid deionized water and absolute ethyl alcohol carry out multiple centrifuge washing, and product is placed in 70 DEG C of baking ovens about 10 hours dry;
(3) sample and dimethicone are configured to ER fluid by weight 10%.
3. MOF-Ti/ polyaniline nanoparticles ER fluid material as described in claim 1, which is characterized in that described
The best reaction dissolvent of the situ aggregation method of its modification is DMF in MOF-Ti/ polyaniline ER fluid material preparation process.
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