CN101691518B - Magnetorheological fluid using high molecular microgel as anti-sedimentation agent and preparation method thereof - Google Patents
Magnetorheological fluid using high molecular microgel as anti-sedimentation agent and preparation method thereof Download PDFInfo
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- CN101691518B CN101691518B CN200910194654A CN200910194654A CN101691518B CN 101691518 B CN101691518 B CN 101691518B CN 200910194654 A CN200910194654 A CN 200910194654A CN 200910194654 A CN200910194654 A CN 200910194654A CN 101691518 B CN101691518 B CN 101691518B
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Abstract
The invention belongs to the technical field of magnetic materials and functional materials, and in particular relates to magnetorheological fluid using high molecular microgel as an anti-sedimentation agent and a preparation method thereof. The magnetorheological fluid is prepared from raw material components of magnetic particles, basic load fluid and the high molecular microgel in a certain weight ratio. The magnetorheological fluid has the advantages of simple preparation process, convenient operation, good sedimentation stability, low zero field viscosity, high shear strain and wide range of usage temperature.
Description
Technical field
The invention belongs to magneticsubstance and technical field of function materials, be specifically related to a kind of high anti-sedimentation magnetic flow liquid and preparation method thereof.
Background technology
Magnetic flow liquid is a kind of new function material.Under the effect in magnetic field, its AV has the variation of 2～3 one magnitude, shows similar " liquid-solid " phase transforming process; After removing magnetic field, AV is replied, and material is reversed to liquid.Can come the viscosity of accurate control material in the whole process through controlling magnetic field intensity.Because magnetic flow liquid has characteristics such as power consumption is few, damping force is big, dynamicrange is wide, frequency response is high, widely applicable; Particularly it can produce optimum damping power according to the vibration performance of system, thereby it has a wide range of applications in fields such as vibroshock, braking devices, fixed support, aviation and wide, polishing technologies.
Because the density of magnetic particle often differs greatly with the density of carrier fluid in the magnetic flow liquid; The system that uniform magnetorheological suspension-s system is a thermodynamic instability; Sedimentation and reunion can take place in magnetic particle inevitably, and magnetorheological performance is disappeared.For avoiding sedimentation, tend to add additives (Lord Corp., thixotropic magnetorheological materials, Chinese invention patent CN1088020, on June 15th, 1994) such as a certain proportion of tensio-active agent, thixotropic agent and thickening material in the magnetic flow liquid.These additives are generally the tensio-active agent of organic small molecules or mineral-type; Or the particle of modified-high polymer (letter spit of fland, Pu; Jiang Fengjing, the progress of magnetic flow liquid material and application prospect. chemical industry progress, 2005; 24 (2): 132), and adopt simple polymer microgel class material not see bibliographical information as settled the present of the method for magnetic flow liquid antisettling agent.
The present invention is as the antisettling agent in the magnetic flow liquid with the polymer microgel; Promptly utilize polymer microgel swelling (so-called swelling in the base load liquid of magnetic flow liquid; Be meant that the polymer microgel is under the effect of the good solvent of correspondence; The physical action that can polymer segment be extended) the three-dimensional space network structure that is had; And utilize functional group that the carboxyl that has in the three-dimensional net structure, sulfonic group etc. can adsorb magnetic particle to hinder the sedimentation behavior of magnetic particle, improve the sedimentation stability of magnetic flow liquid material.
Summary of the invention
The object of the present invention is to provide magnetic flow liquid material that a kind of sedimentation stability is good, the magnetic response performance is good, shear-stress is high and preparation method thereof.
The high anti-sedimentation magnetic flow liquid material that the present invention proposes is to utilize polymer microgel ability swelling in good solvent corresponding with it, forms the characteristic of three-dimensional net structure, and as antisettling agent, its raw material composition by weight is following with the polymer microgel:
Magnetic-particle 30-95 part
Base load liquid 10-70 part
Polymer microgel 0.1-10 part.
Described magnetic-particle is one or more the mixture in the oxide compound, carbonyl iron dust, nitrided iron, iron carbide, stainless iron, cobalt, nickel, ferrocobalt, iron-nickel alloy of iron powder, iron, and the particulate median size is 0.1-50 μ m.
Described polymer microgel can be polymer microgels such as polyurethanes, styrenic as antisettling agent, or the polymer microgel of acrylic acid or the like, acrylic amide.Or several kinds the microgel of multipolymer in the above-mentioned polymkeric substance.The microgel particle diameter is 10nm～20 μ m, can be in good solvent corresponding with it swelling and form three-dimensional space network structure, star structure or the dendritic structure of internal crosslinking.Can also contain the functional group that carboxyl or sulfonic group etc. can be adsorbed on the magnetic-particle surface in this microgel cross-linking system.
The mixture of one or more that described base load liquid is non-polar solvents such as silicone oil, glycerine, Yellow Protopet 2A, polyolefin oil, polyester, polyethers can make polyurethanes and styrenic hydrophobic nature polymer microgel swelling wherein.Perhaps be one or more mixture of high polarity solvents such as terepthaloyl moietie, water, can make hydrophilic macromolecule microgel swellings such as acrylic acid or the like and acrylic amide wherein; Base load liquid needs chemical property to stablize, difficulty is volatilized and can be with corresponding polymer microgel swelling therein.
The preparation of this high sedimentation stability magnetic flow liquid can be adopted following method, and concrete steps are:
1. the preparation of polymer microgel.
The synthetic of polymer microgel can be adopted conventional method, like (anti-phase) letex polymerization, and (anti-phase) micro-emulsion polymerization, emulsifier-free emulsion polymerization or cationoid polymerisation etc.Usually adopt the method synthesising macromolecule copolymer microgel of emulsifier-free emulsion polymerization.For example, with the polymer monomer of 90～95 weight parts and the mixture of linking agent, 3～6 parts of tensio-active agents, 2～4 parts of initiators are dissolved in the corresponding good solvent.The under agitation logical nitrogen of this mixture was elevated to 70～80 ℃ with temperature of reaction after 25～40 minutes, continued to stir 4～6 hours.The polymer particles of dry gained is polymer microgel.
2. the polymer microgel of 0.1-10 weight part is placed the base load liquid of 10-70 part, stirred 3～5 hours, make its abundant swelling.Stirring velocity with 200～500rpm for well.
3. the magnetic-particle of 30-95 weight part has been joined fully in the swollen polymer microgel solution, stirred,, promptly obtained resisting settled magnetic flow liquid up to they being uniformly dispersed (stirring velocity is with 2500-3500rpm, churning time 20～40 minutes for well).
Utilize the polymer microgel to have characteristics such as sedimentation stability is good, the magnetic response performance is good, shear-stress height by the present invention as the magnetic flow liquid of antisettling agent preparation.
Description of drawings
Fig. 1 is with the sedimentation stability of acrylic amide-methylacrylic acid copolymerization microgel as the water based magnetic rheologic liquid of antisettling agent.
Fig. 2 with acrylic amide-methylacrylic acid copolymerization microgel as the AV of the water based magnetic rheologic liquid of antisettling agent change curve with magnetic field.
Fig. 3 is with the dependency curve of urethane microgel as silicone oil (molecular weight 1000) based magnetic rheologic liquid apparent viscosity temperature under zero magnetic field and the magneticstrength at 15.26T of antisettling agent.
Embodiment
Following examples are to be merely further to specify the present invention, are not violating under the purport of the present invention, and the present invention should be not limited to the content that following examples are specifically shown clearly.
Embodiment 1
Embodiment is as follows raw materials used:
Carbonyl iron dust, Tianyi Superfine Metal Powders Co., Ltd., Jiangsu provides.
Deionized water, Fudan University's purified water factories provides.
The copolymerized macromolecule microgel of acrylic amide and methylacrylic acid is pressed document preparation (Zhang Y, Liu H; Zhao Y; Etal, Controllable synthesis of CuS-P (AM-co-MAA) composite microspheres with patternedsurface structures, Journal of Colloid and Interface Science; 2008,325:391.).
Raw materials used proportioning is following:
49 parts of carbonyl iron dusts (weight)
50 parts of deionized waters (weight)
Acrylic amide-1 part of methylacrylic acid copolymerization microgel (weight)
The preparation of magnetic flow liquid:
Acrylic amide-methylacrylic acid copolymerization the microgel of preparation is joined in the deionized water, keep the stirring velocity of 200-500rmp to stir 4 hours, make fully swelling of microgel.Then reduced iron powder is joined in the middle of microgel-aqueous systems, under the high-speed stirring of 2500-3500rmp, stir half a hour, system is mixed.The mixture system of this method gained is the magnetic flow liquid of acrylic amide-methylacrylic acid copolymerization microgel as antisettling agent.
The performance characterization of magnetic flow liquid:
(1) the prepared magnetic flow liquid of the present invention has lower null field viscosity, at room temperature uses NDJ-79 type rotational viscosimeter (dynamo-electric factory of Tongji University), and recording its null field AV is 15mPas.
(2) temperature applicable range of the magnetic flow liquid of the present invention's preparation and water coupling.
(3) magnetic flow liquid of the present invention's preparation has good sedimentation stability.The rate of descent that left standstill when reaching final settlement in 4～6 days is 8.4%.Fig. 1 is the settling property curve of the prepared magnetic flow liquid of the present invention.The settling property of magnetic flow liquid representes with rate of descent V, V=b/ (a+b) * 100% wherein, and a is the volume of supernatant liquid, b is the volume of the muddy liquid of lower floor.
(4) adopt the NDJ-79 type rotational viscosimeter (dynamo-electric factory of Tongji University) of reequiping to test its magnetorheological performance.The result is as shown in Figure 2.
Embodiment 2
Raw materials used proportioning is following:
95 parts of carbonyl iron dusts (weight)
50 parts of deionized waters (weight)
Acrylic amide-1 part of methylacrylic acid copolymerization microgel (weight)
The preparation of magnetic flow liquid:
Acrylic amide-methylacrylic acid copolymerization the microgel of preparation is joined in the deionized water, keep the stirring velocity of 200-500rmp to stir 5 hours, make fully swelling of microgel.Then reduced iron powder is joined in the middle of microgel-aqueous systems, under the high-speed stirring of 2500-3500rmp, stir half a hour, system is mixed.The mixture system of this method gained is the magnetic flow liquid of acrylic amide-methylacrylic acid copolymerization microgel as antisettling agent.
The performance of the magnetic flow liquid that makes and embodiment 1 are similar.
Embodiment 3
Raw materials used proportioning is following:
30 parts of carbonyl iron dusts (weight)
70 parts of deionized waters (weight)
Acrylic amide-1.5 parts of methylacrylic acid copolymerization microgels (weight)
The preparation of magnetic flow liquid:
Acrylic amide-methylacrylic acid copolymerization the microgel of preparation is joined in the deionized water, keep the stirring velocity of 200-500rmp to stir 3 hours, make fully swelling of microgel.Then reduced iron powder is joined in the middle of microgel-aqueous systems, under the high-speed stirring of 2500-3500rmp, stir half a hour, system is mixed.The mixture system of this method gained is the magnetic flow liquid of acrylic amide-methylacrylic acid copolymerization microgel as antisettling agent.
The performance of the magnetic flow liquid that makes and embodiment 1 are similar.
Embodiment 4
Embodiment is as follows raw materials used:
Carbonyl iron dust, Tianyi Superfine Metal Powders Co., Ltd., Jiangsu provides.
Silicone oil (molecular weight 1000), China (medicine) Shanghai chemical reagents corporation provides.
The polyurethanes microgel, press document self-control (Huang Zhihong, Zhong Wenjun, the preparation of unsaturated polyurethanes microgel and self-stable function research thereof. functional polymer journal, 2005,18 (3): 17).
Raw materials used proportioning is following:
34.1 parts of carbonyl iron dusts (weight)
Silicone oil (molecular weight 1000) 64.5 parts (weight)
1.4 parts of urethane microgels (weight)
The preparation of magnetic flow liquid:
The urethane microgel of preparation is joined in the silicone oil, keep the stirring velocity of 200-500rmp to stir 4 hours, make fully swelling of microgel.Then carbonyl iron dust is joined in the middle of urethane microgel-silicone oil system, under the high-speed stirring of 2500-3500rmp, stir half a hour, system is mixed.The mixed system of this method gained is the magnetic flow liquid of urethane microgel as antisettling agent.
The performance characterization of magnetic flow liquid:
(5) the prepared magnetic flow liquid of the present invention has lower null field viscosity, at room temperature uses NDJ-79 type rotational viscosimeter (dynamo-electric factory of Tongji University), and recording its null field AV is 64.5 * 100Pas.
(6) temperature applicable range and the silicone oil of the magnetic flow liquid of the present invention's preparation are complementary.
(7) adopt the AV of NDJ-79 type rotational viscosimeter (dynamo-electric factory of Tongji University) test magnetic flow liquid reequip under zero magnetic field, to reach under the magnetic field at 15.26T and the dependence of temperature.The result is as shown in Figure 3.
Raw materials used proportioning is following:
34.1 parts of carbonyl iron dusts (weight)
Silicone oil (molecular weight 1000) 63.1 parts (weight)
2.8 parts of urethane microgels (weight)
The preparation of magnetic flow liquid:
The urethane microgel of preparation is joined in the silicone oil, keep the stirring velocity of 200-500rmp to stir 4 hours, make fully swelling of microgel.Then carbonyl iron dust is joined in the middle of urethane microgel-silicone oil system, under the high-speed stirring of 2500-3500rmp, stir half a hour, system is mixed.The mixed system of this method gained is the magnetic flow liquid of urethane microgel as antisettling agent.
The performance of the magnetic flow liquid that makes and embodiment 4 are similar.
Embodiment 6
Raw materials used proportioning is following:
51.1 parts of carbonyl iron dusts (weight)
Silicone oil (molecular weight 1000) 46.1 parts (weight)
2.8 parts of urethane microgels (weight)
The preparation of magnetic flow liquid:
The urethane microgel of preparation is joined in the silicone oil, keep the stirring velocity of 200-500rmp to stir 5 hours, make fully swelling of microgel.Then carbonyl iron dust is joined in the middle of urethane microgel-silicone oil system, under the high-speed stirring of 2500-3500rmp, stirred 40 minutes, system is mixed.The mixed system of this method gained is the magnetic flow liquid of urethane microgel as antisettling agent.
The performance of the magnetic flow liquid that makes and embodiment 4 are similar.
Embodiment 7
Embodiment is as follows raw materials used:
Reduced iron powder, chemical reagent Shanghai ltd of traditional Chinese medicines group provides.
Silicone oil (molecular weight 1000), China (medicine) Shanghai chemical reagents corporation provides.
The vinylbenzene microgel; Press document self-control (Antonietti M, Pakula T, Bremser W; Rheology of SmallSpherical Polystyrene Microgels:A Direct Proof for a New Transport Mechanism in BulkPolymers besides Reptation; Macromolecules, 1995,18:4227.)
Raw materials used proportioning is following:
60 parts of reduced iron powders (weight)
Silicone oil (molecular weight 1000) 39.5 parts (weight)
0.5 part of vinylbenzene microgel (weight)
The preparation of magnetic flow liquid:
The vinylbenzene microgel of preparation is joined in the silicone oil (molecular weight 1000), keep the stirring velocity of 200-500rmp to stir 3 hours, make fully swelling of microgel.Then reduced iron powder is joined in the middle of vinylbenzene microgel-silicone oil system, under the high-speed stirring of 2500-3500rmp, stirred 25 minutes, system is mixed.The mixed system of this method gained is the magnetic flow liquid of vinylbenzene microgel as antisettling agent, has sedimentation stability preferably.
Embodiment is as follows raw materials used:
Reduced iron powder, chemical reagent Shanghai ltd of traditional Chinese medicines group provides.
Deionized water, Fudan University's purified water factories provides.
Acroleic acid microgel; Press document self-control (Bromberg L and Alakhov V; Effects of polyether-modifiedpoly (acrylic acid) microgels on doxorubicin transport in human intestinal epithelial Caco-2celllayers; Journal of Controlled Release, 2003,88:11.)
Raw materials used proportioning is following:
60 parts of reduced iron powders (weight)
39.5 parts of deionized waters (weight)
0.5 part of acroleic acid microgel (weight)
The preparation of magnetic flow liquid:
The acroleic acid microgel of preparation is joined in the deionized water, keep the stirring velocity of 200-500rmp to stir 4 hours, make fully swelling of microgel.Then reduced iron powder is joined in acroleic acid microgel-deionized water system, under the high-speed stirring of 2500-3500rmp, stir half a hour, system is mixed.The mixed system of this method gained is the magnetic flow liquid of acroleic acid microgel as antisettling agent, has sedimentation stability preferably.
In the foregoing description, the parameter of each component raw material and consumption and preparation process only is the representative of choosing in order to describe invention.In fact a large amount of experiments show, in summary of the invention part institute restricted portion, all can obtain the similar magnetic flow liquid of the foregoing description.
Claims (3)
1. magnetic flow liquid with high sedimentation stability is characterized in that with the polymer microgel as the antisettling agent in the magnetic flow liquid, its component is by weight:
Magnetic-particle 30-95 part;
Base load liquid 10-70 part;
Polymer microgel 0.1-10 part;
Described magnetic-particle is one or more in the oxide compound, carbonyl iron dust, nitrided iron, iron carbide, stainless iron, cobalt, nickel, ferrocobalt, iron-nickel alloy of iron powder, iron, and the particulate median size is 0.1-50 μ m;
As the polymer microgel of antisettling agent be particle diameter be 10nm-20 μ m, can be in good solvent corresponding with it swelling form the polymer particle of three-dimensional space network structure, star structure or the dendritic structure of internal crosslinking; This polymkeric substance is a kind of in acrylic acid or the like, acrylic amide, polyurethanes, the styrenic, perhaps is several kinds multipolymer wherein;
Described base load liquid is and the corresponding good solvent of corresponding polymer microgel chemical ingredients; Wherein, can make acrylic acid or the like, acrylic amide hydrophilic macromolecule microgel swelling base load liquid therein is polar solvent, and can make polyurethanes, styrenic hydrophobic nature polymer microgel swelling base load liquid therein is nonpolar solvent.
2. magnetic flow liquid according to claim 1 is characterized in that containing carboxyl or sulfonic group functional group in the cross-linking system of described polymer microgel.
3. preparation method with magnetic flow liquid of high sedimentation stability as claimed in claim 1 is characterized in that concrete steps are:
1. prepare the polymer microgel;
2. the polymer microgel of 0.1-10 weight part is placed the base load liquid of 10-70 part, stirred 3 ~ 5 hours, make its abundant swelling;
3. the magnetic particle of 30-95 part has been joined fully in the swollen polymer microgel dispersion, stirred,, promptly obtained anti-settled magnetic flow liquid up to they are uniformly dispersed.
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| EP3889458A4 (en) * | 2018-11-26 | 2022-09-14 | Nippon Paint Holdings Co., Ltd. | Magnetic viscoelastic fluid and device |
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| CN110223816B (en) * | 2019-06-27 | 2020-10-02 | 中国人民解放军陆军勤务学院 | Magnetorheological fluid based on magnetic organogel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1595558A (en) * | 2004-06-22 | 2005-03-16 | 上海大学 | A magnetic rheological fluid and preparing method thereof |
| CN101266861A (en) * | 2008-01-04 | 2008-09-17 | 重庆大学 | A magneto-rheological liquid without sediment |
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| CN1595558A (en) * | 2004-06-22 | 2005-03-16 | 上海大学 | A magnetic rheological fluid and preparing method thereof |
| CN101266861A (en) * | 2008-01-04 | 2008-09-17 | 重庆大学 | A magneto-rheological liquid without sediment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3889458A4 (en) * | 2018-11-26 | 2022-09-14 | Nippon Paint Holdings Co., Ltd. | Magnetic viscoelastic fluid and device |
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