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CN102899894A - Preparation method and use of shear thickening fluid - Google Patents

Preparation method and use of shear thickening fluid Download PDF

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Publication number
CN102899894A
CN102899894A CN2012101716594A CN201210171659A CN102899894A CN 102899894 A CN102899894 A CN 102899894A CN 2012101716594 A CN2012101716594 A CN 2012101716594A CN 201210171659 A CN201210171659 A CN 201210171659A CN 102899894 A CN102899894 A CN 102899894A
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shear thickening
preparation
thickening fluid
micro
nano granules
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CN102899894B (en
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来囯桥
张国栋
邬继荣
蒋剑雄
许文东
齐帆
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Hangzhou Normal University
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Hangzhou Normal University
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Abstract

The invention relates to the technical field of organic silicon polymer application and provides a preparation method of a shear thickening fluid. The preparation method realizes compatible matching of micro/nano-particles and a dispersion medium and improves system shear thickening effects and system storage stability. The shear thickening fluid is prepared by mixing micro/nano-particles and an organic silicon polymer, wherein a mass ratio of the micro/nano-particles to the organic silicon polymer is (1-3): (2-4). The preparation method is simple and has short preparation time. The shear thickening fluid obtained by the preparation method has stable quality, can be mass-produced easily, has low energy consumption, produces less three wastes and has a low cost. The invention also provides a use of the shear thickening fluid in a liquid protection composite material. The liquid protection composite material prepared from the shear thickening fluid has no toxicity and no pollution and is suitable for a human body and industrial production.

Description

A kind of preparation method of shear thickening fluid and application
Technical field
The present invention relates to the technical field that silicone oil with low viscosity is used, relate in particular to a kind of preparation that is scattered in the shear thickening suspension of silicone oil with low viscosity.
Background technology
The human possibility that faces injury in actual life is constantly increasing, and kind and the performance requirement of protective gear also improved day by day.Development along with high performance fibre material, the individual protection material also makes significant progress in recent years, by original hard, semi-rigid product, develop into present flexible products and up-to-date liquid-state protective equipment gradually, the liquid-state protective material has very large market prospects in the protection field.The shear thickening effect of this dispersion causes people's attention very early as a kind of macroscopic appearance, such as the obstruction of transmission pipeline, the destruction of instrument etc., and will avoid as possible the impact of this class ill-effect in production practices.Since late 1980s, how people utilizes this phenomenon to turn harm into good if beginning one's study, obtained wide application in shellproof and shockproof field.The people such as Fischer use the STF(shear thickening fluid) design sandwich beams, reach the purpose of control vibratory response, show that STF is in the using value that has in vibration field.The people such as Lee utilize STF to process Kevlar fabric, and have simulated the experiment that bullet is injected bulletproof jacket, confirm that STF can improve the intensity of bulletproof jacket greatly in the situation of equal hardness, namely can make the high safeguard of the good intensity of pliability.
Shear thickening fluid is a kind of non-newtonian fluid or is called dilatant fluid, generally is to be become with the inorganic gluey groups of grains of particle diameter with respect to homogeneous by suspension media, and at common low-energy state, when namely not being subject to clashing into, it can proper flow; When being triggered or colliding, STF just becomes hard solid, makes fabric more tough, and the protective action that can't estimate is provided.So, the Novel protective clothing that utilizes STF to make, soft comfortable at ordinary times, in case suffer cutting, sting or the impact of high velocity bullet, shell fragment of the sharp things such as cutter, will become tough and tensile incomparable in the moment of being impacted, and impulsive force can be spread out rapidly along fabric, greatly reduce the pressure of unit are.After impulsive force disappeared, shear thickening liquid recovered again liquid condition, and fabric is again deliquescing also.
At present, the STF of preparation liquid-state protective material is mostly by polyethylene glycol with silica is compound forms, and application number is that 201110062145.0 Chinese patent discloses a kind of based on SiO 2The preparation method of the shear thickening fluid of micro-nano ball, this patent disclosure the shear thickening fluid take polyethylene glycol as base material, but because the limitation of polyethylene glycol self structure, the system that forms exists owing to the polyethylene glycol hygroscopicity causes by force the unstable of system, and bond energy is low, the problem such as anti-shearing not.
Summary of the invention
For solving the compatible matching of micro-nano granules and decentralized medium, the effect of raising system shear thickening, the problems of stability in storage of reinforcement system, the invention provides a kind of preparation method of shear thickening fluid, preparation technology of the present invention is simple, preparation time weak point, product stay in grade, easy volume production, energy consumption is low, the three wastes are few, cost is low.
The present invention has also proposed a kind of shear thickening fluid in the application of liquid-state protective composite, and product is nontoxic, and is pollution-free, and suitable human body uses, and also is applicable to suitability for industrialized production simultaneously.
The present invention is achieved by the following technical solutions: a kind of shear thickening fluid, be mixed by micro-nano granules and silicone oil with low viscosity, and wherein the mass percent of micro-nano granules and silicone oil with low viscosity is respectively 20 ~ 60%, 40 ~ 80%.As preferably, the mass percent of micro-nano granules and silicone oil with low viscosity is respectively 30 ~ 40%, 60 ~ 70%, and this shear thickening fluid is a kind of solid particle suspension of high concentration.
Silicone oil with low viscosity is selected from hydroxy-end capped polysiloxanes, methoxyl group terminated polysiloxane, the ethyoxyl terminated polysiloxane one or more.The molecular weight of silicone oil with low viscosity is between 100 ~ 2000.
Micro-nano granules is selected from silica, transition metal oxide or non-oxidized substance particle.The particle size range of micro-nano granules is 5nm ~ 10 μ m.Transition metal oxide comprises the metal oxides such as titanium, iron, copper, silver, gold, great majority are gluey or are spherical-like morphology, also can be the structure (ellipse of some other irregularity, cube or other polyhedral structures), these oxide surfaces can carry out modification through molecular surface, process such as carrying out silanization.The non-oxidized substance particle is selected from polymer or calcium carbonate, and polymer is selected from polymethyl methacrylate or polystyrene.As preferably, these grain diameter scopes are at 5nm ~ 8000nm, are scattered in the colloid to keep long flowability.
A kind of preparation method of shear thickening fluid is: add micro-nano granules in silicone oil with low viscosity, mix.Can adopt dispersing apparatus to carry out mixing; Can adopt vortex stirring, ultrasonic wave mixing plant, shaking table vibrations, ultrasonic wave processing, ultrasonic irradiation mixing; Processing time is 0.3 ~ 5 hour.
Add cosolvent in mixed process, cosolvent is selected from water, isopropyl alcohol, ethanol, the alkane compound one or more, and alkane is saturated hydrocarbons, is the chain hydrocarbon that only has carbon-carbon single bond, is the simplest class organic compound.In the alkane molecule, the number of hydrogen atom reaches maximum, and its general formula is C nH 2n+2Each carbon atom is sp3 hydridization in the molecule.The consumption of cosolvent and the mass ratio of micro-nano granules are 0.1 ~ 1:1.Cosolvent has promoted the dispersion of micro-nano granules in system, guarantee when cosolvent is selected simultaneously after mixing is complete, can be easy to remove through simple heating or the condition that vacuumizes, and the effect of guarantee system shear thickening is constant, thereby prepares final shear thickening fluid.
The application of a kind of shear thickening fluid in the liquid-state protective composite.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention has improved the compatible matching of decentralized photo and decentralized medium effectively, improves to interact, and has strengthened the effect of shear thickening, prevents the reunion of micro-nano granules and the Uniform Dispersion of realization particle;
(2) simple, the preparation time of preparation technology of the present invention weak point, product stay in grade, easy volume production, energy consumption is low, the three wastes are few, cost is low.
(3) product is nontoxic, and is pollution-free, and suitable human body uses, and also is applicable to suitability for industrialized production simultaneously.
Description of drawings
Fig. 1 is the steady-state flow varied curve that is scattered in the shear thickening fluid of dimethyl silicone polymer.
The specific embodiment
Below by specific embodiment the present invention is described in further detail, needed raw material is all commercially available, and following instance only is further detailed the present invention, should not be construed as limitation of the present invention.
Embodiment 1
(1) be 200 at hydroxyl endblocked polydimethylsiloxane 1.0kg(molecular weight) with the mixture of cosolvent absolute ethyl alcohol 0.2kg in to add average grain diameter be 450nm SiO 2Particle 0.3kg and average grain diameter are 250nm titanium dioxide granule 0.1kg, adopt the planet stirring device processes 3 hours, make the shear thickening fluid by the absolute ethyl alcohol dilution.
(2) then, the shear thickening fluid that the above-mentioned absolute ethyl alcohol that makes is diluted is warmed up to 55 ℃ of slow volatilization removal absolute ethyl alcohols that stir under vacuum condition, makes final shear thickening fluid A, and viscosity is 2500 ± 500cps.
Shear thickening fluid A has good shear thickening behavior, is well positioned to meet the needs of following process.
Embodiment 2
(1) be 500 at ethyoxyl end-blocking dimethyl silicone polymer 1.0kg(molecular weight) with the mixture of absolute ethyl alcohol 0.05kg in to add average grain diameter be 100nm SiO 2Particle 0.35kg and average grain diameter are 250nm titanium dioxide granule 0.08kg, adopt the ultrasonic agitation device processes 1 hour.Make the shear thickening fluid of absolute ethyl alcohol dilution.
(2) then, the shear thickening fluid that the above-mentioned absolute ethyl alcohol that makes is diluted is warmed up to 65 ℃, slowly stirs simultaneously volatilization removal absolute ethyl alcohol under the condition that vacuumizes, and makes final shear thickening fluid B, and viscosity is 3000 ± 500cps.
Shear thickening fluid B has good shear thickening behavior, is well positioned to meet the needs of following process.
Embodiment 3
(1) be 800 at hydroxyl endblocked polydimethylsiloxane 0.5kg(molecular weight), ethyoxyl end-blocking dimethyl silicone polymer 0.5kg(molecular weight is 250) with the mixture of anhydrous isopropyl alcohol 0.4kg in to add average grain diameter be 100nm SiO 2Particle 0.25kg and average grain diameter are 50nm SiO 2Particle 0.20kg adopted the planet stirring device processes 3.5 hours.
(2) then, the shear thickening fluid that the above-mentioned anhydrous isopropyl alcohol that makes is diluted is warmed up to 70 ℃, the slow volatilization removal anhydrous isopropyl alcohol that stirs makes final shear thickening fluid C under the condition that vacuumizes simultaneously, and viscosity is at 4000 ± 600cps.
Shear thickening fluid C has good shear thickening behavior, is well positioned to meet the needs of following process.
Embodiment 4
(1) be 800 at methoxyl group end-blocking dimethyl silicone polymer 0.25kg(molecular weight), ethyoxyl end-blocking dimethyl silicone polymer 0.25kg(molecular weight is 800) with the mixture of anhydrous isopropyl alcohol 0.25kg in to add average grain diameter be the SiO of 10nm 2Particle 0.40kg and average grain diameter are 100nm SiO 2Particle 0.40kg adopted the planet stirring device processes 4.5 hours.
(2) then, the shear thickening fluid that the above-mentioned anhydrous isopropyl alcohol that makes is diluted is warmed up to 70 ℃, the slow volatilization removal anhydrous isopropyl alcohol that stirs makes final shear thickening fluid D under the condition that vacuumizes simultaneously, and viscosity is at 4200 ± 600cps.
Shear thickening fluid D has good shear thickening behavior, is well positioned to meet the needs of following process.
Embodiment 5
(1) be 400 at hydroxyl endblocked polydimethylsiloxane 1.0kg(molecular weight) with the mixture of cosolvent distilled water 0.6kg in to add average grain diameter be 450nm SiO 2Particle 0.5kg and average grain diameter are 250nm titanium dioxide granule 0.2kg, adopt the planet stirring device processes 3 hours, have made water-reducible shear thickening fluid.
(2) then, the above-mentioned water-reducible shear thickening fluid that makes is warmed up to 90 ℃ slowly stirs volatilization removal water under vacuum condition, make final shear thickening fluid E, viscosity is 8000 ± 1000cps.
Shear thickening fluid E has good shear thickening behavior, is well positioned to meet the needs of following process.
Embodiment 6
(1) be 400 at hydroxyl endblocked polydimethylsiloxane 0.5kg(molecular weight), methoxyl group end-blocking dimethyl silicone polymer 0.5kg(molecular weight is 350) with the mixture of cyclohexane 0.5kg in to add average grain diameter be 50nm SiO 2Particle 0.35kg and average grain diameter are 600nm SiO 2Particle 0.25kg adopted the planet stirring device processes 4.5 hours.
(2) then, the shear thickening fluid that the above-mentioned cyclohexane that makes is diluted is warmed up to 80 ℃, the slow volatilization removal cyclohexane that stirs makes final shear thickening fluid F under the condition that vacuumizes simultaneously, and viscosity is at 4000 ± 600cps.
Shear thickening fluid F has good shear thickening behavior, is well positioned to meet the needs of following process.
Embodiment 7
(1) be 300 at hydroxy-end capped polysiloxanes 1.0kg(molecular weight) with the mixture of cosolvent cyclohexane 0.2kg in to add average grain diameter be 300nm poly methyl methacrylate particle 0.55kg, adopt the planet stirring device processes 3.5 hours, and made the shear thickening fluid by the cyclohexane dilution.
(2) then, the shear thickening fluid that the above-mentioned cyclohexane that makes is diluted is warmed up to 80 ℃ of slow volatilization removal cyclohexanes that stir under vacuum condition, makes final shear thickening fluid G, and viscosity is 4500 ± 500cps.
Shear thickening fluid G has good shear thickening behavior, is well positioned to meet the needs of following process.
Will be by the shear thickening fluid of embodiment preparation, solid particle is homogeneously dispersed state in solution, shear thickening fluid has good shear thickening behavior, be well positioned to meet the needs of following process, Figure 1 shows that the steady-state flow varied curve of the shear thickening fluid that is scattered in dimethyl silicone polymer.
Can find out that from steady-state flow varied curve shown in Figure 1 the prepared shear thickening fluid of the present invention has good shear thickening behavior.
Application examples
With shear thickening fluid A, the B of above-described embodiment 1-7 preparation, C, D, E, F, G respectively with pbo fiber fabric or aramid fiber (Kevlar) cloth by the compound preparation liquid-state protective of mode composites such as immersion, coating or sprayings, the composite protection ability that obtains is strong, quality is little, softness is tough and tensile can satisfy that the individual protection material is comprehensive, comfortable, the requirement of easy.
By considering specification of the present disclosure and embodiment, to those skilled in the art, other embodiment of the present disclosure will be apparent.Above content is the further description of the present invention being done in conjunction with concrete embodiment, can not assert that implementation of the present invention is confined to these explanations.True scope of the present disclosure and essence are defined by the appended claims.

Claims (10)

1. the preparation method of a shear thickening fluid is characterized in that, described shear thickening fluid is mixed by micro-nano granules and silicone oil with low viscosity, and wherein the mass percent of micro-nano granules and silicone oil with low viscosity is respectively 20 ~ 60%, 40 ~ 80%.
2. the preparation method of a kind of shear thickening fluid according to claim 1 is characterized in that, silicone oil with low viscosity is selected from hydroxy-end capped polysiloxanes, methoxyl group terminated polysiloxane, the ethyoxyl terminated polysiloxane one or more.
3. the preparation method of a kind of shear thickening fluid according to claim 2 is characterized in that, the molecular weight of silicone oil with low viscosity is between 100 ~ 2000.
4. the preparation method of a kind of shear thickening fluid according to claim 1 is characterized in that, micro-nano granules is selected from silica, transition metal oxide or non-oxidized substance particle.
5. the preparation method of a kind of shear thickening fluid according to claim 4 is characterized in that, the non-oxidized substance particle is selected from polymer or calcium carbonate, and polymer is selected from polymethyl methacrylate or polystyrene.
6. according to claim 4 or the preparation method of 5 described a kind of shear thickening fluids, it is characterized in that the particle size range of micro-nano granules is 5nm ~ 10 μ m.
7. the preparation method of a kind of shear thickening fluid according to claim 1 is characterized in that, adopts dispersing apparatus to carry out mixing in the preparation process, and incorporation time is 0.3 ~ 5 hour.
8. the preparation method of a kind of shear thickening fluid according to claim 7 is characterized in that: dispersing apparatus employing vortex stirring, ultrasonic wave mixing plant, shaking table vibrations, ultrasonic wave processing or ultrasonic irradiation.
9. according to claim 7 or the preparation method of 8 described a kind of shear thickening fluids, it is characterized in that: in mixed process, add cosolvent, cosolvent is selected from one or more in water, isopropyl alcohol, ethanol, the alkane compound, and the quality of cosolvent and the mass ratio of micro-nano granules are 0.1 ~ 1:1.
10. the application of an a kind of shear thickening fluid as claimed in claim 1 in the liquid-state protective composite.
CN201210171659.4A 2012-05-30 2012-05-30 Preparation method and use of shear thickening fluid Expired - Fee Related CN102899894B (en)

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Cited By (16)

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CN103614903A (en) * 2013-11-27 2014-03-05 中南大学 Method for preparing micrometer/nanometer calcium carbonate in situ and shear thickening fluid of micrometer/nanometer calcium carbonate
CN104047162A (en) * 2014-06-26 2014-09-17 浙江理工大学 Preparation method of novel shearing and thickening fluid
CN104862975A (en) * 2015-05-18 2015-08-26 西安理工大学 Shear thickening gel, preparation methods and splinterproof fabric with shear thickening effect
CN106344318A (en) * 2016-09-24 2017-01-25 矫云 Rapid fixing blanket for pediatric nursing
CN107502288A (en) * 2017-08-28 2017-12-22 湖南沃美新材料科技有限公司 A kind of preparation method of nano silicon STF
CN107579503A (en) * 2017-08-24 2018-01-12 国网陕西省电力公司西安供电公司 A kind of cable connector explosion-protection equipment based on silicone oil STF
CN108221382A (en) * 2018-02-01 2018-06-29 江南大学 A kind of electromagnetic masking shear thickening liquid and preparation method thereof
CN109371695A (en) * 2018-09-20 2019-02-22 天津工业大学 A kind of preparation method of uvioresistant flexibility stab-resistant material
CN109795445A (en) * 2019-03-28 2019-05-24 西北工业大学 A kind of safety belt braking method and brake driven using shear thickening liquid
CN110896641A (en) * 2016-11-15 2020-03-20 沙特阿拉伯石油公司 Nanoparticle-based shear thickening materials
CN111150196A (en) * 2020-01-21 2020-05-15 翁秋梅 Electronic device package containing dilatant component
CN112321831A (en) * 2020-11-26 2021-02-05 济宁学院 Preparation method of colorless transparent shear thickening methyl silicone oil
CN113999616A (en) * 2021-11-12 2022-02-01 山东理工大学 Magnetic shear thickening polishing medium and preparation method thereof
CN114250629A (en) * 2021-12-02 2022-03-29 西安工程大学 Preparation method of intelligent stab-resistant fabric, product and application thereof
CN114552448A (en) * 2022-04-27 2022-05-27 南通宇元智能科技有限公司 Explosion-proof electrical appliance control device for extremely cold area
PL445847A1 (en) * 2023-08-18 2024-04-22 Politechnika Warszawska System for preparing shear thickening fluids and method of preparing shear thickening fluids

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CN103614903A (en) * 2013-11-27 2014-03-05 中南大学 Method for preparing micrometer/nanometer calcium carbonate in situ and shear thickening fluid of micrometer/nanometer calcium carbonate
CN103614903B (en) * 2013-11-27 2015-11-25 中南大学 A kind of original position prepares the method for micro-/ nano calcium carbonate and shear thickening fluid thereof
CN104047162A (en) * 2014-06-26 2014-09-17 浙江理工大学 Preparation method of novel shearing and thickening fluid
CN104047162B (en) * 2014-06-26 2016-03-23 浙江理工大学 A kind of preparation method of novel shear thickening fluid
CN104862975A (en) * 2015-05-18 2015-08-26 西安理工大学 Shear thickening gel, preparation methods and splinterproof fabric with shear thickening effect
CN104862975B (en) * 2015-05-18 2017-01-11 西安理工大学 Shear thickening gel, preparation methods and splinterproof fabric with shear thickening effect
CN106344318B (en) * 2016-09-24 2019-06-28 王文学 The quick fixed blanket of pediatric nursing
CN106344318A (en) * 2016-09-24 2017-01-25 矫云 Rapid fixing blanket for pediatric nursing
US11242728B2 (en) 2016-11-15 2022-02-08 Saudi Arabian Oil Company Nanoparticle-based shear-thickening materials
CN110896641A (en) * 2016-11-15 2020-03-20 沙特阿拉伯石油公司 Nanoparticle-based shear thickening materials
US11781400B2 (en) 2016-11-15 2023-10-10 Saudi Arabian Oil Company Nanoparticle-based shear-thickening materials
CN107579503A (en) * 2017-08-24 2018-01-12 国网陕西省电力公司西安供电公司 A kind of cable connector explosion-protection equipment based on silicone oil STF
CN107502288A (en) * 2017-08-28 2017-12-22 湖南沃美新材料科技有限公司 A kind of preparation method of nano silicon STF
CN108221382A (en) * 2018-02-01 2018-06-29 江南大学 A kind of electromagnetic masking shear thickening liquid and preparation method thereof
CN108221382B (en) * 2018-02-01 2020-04-14 江南大学 Electromagnetic shielding type shear thickening liquid and preparation method thereof
CN108221382B9 (en) * 2018-02-01 2020-06-12 江南大学 Electromagnetic shielding type shear thickening liquid and preparation method thereof
CN109371695A (en) * 2018-09-20 2019-02-22 天津工业大学 A kind of preparation method of uvioresistant flexibility stab-resistant material
CN109371695B (en) * 2018-09-20 2021-05-14 天津工业大学 Preparation method of anti-ultraviolet flexible stab-resistant material
CN109795445A (en) * 2019-03-28 2019-05-24 西北工业大学 A kind of safety belt braking method and brake driven using shear thickening liquid
CN111150196A (en) * 2020-01-21 2020-05-15 翁秋梅 Electronic device package containing dilatant component
CN112321831A (en) * 2020-11-26 2021-02-05 济宁学院 Preparation method of colorless transparent shear thickening methyl silicone oil
CN113999616A (en) * 2021-11-12 2022-02-01 山东理工大学 Magnetic shear thickening polishing medium and preparation method thereof
CN114250629A (en) * 2021-12-02 2022-03-29 西安工程大学 Preparation method of intelligent stab-resistant fabric, product and application thereof
CN114552448A (en) * 2022-04-27 2022-05-27 南通宇元智能科技有限公司 Explosion-proof electrical appliance control device for extremely cold area
CN114552448B (en) * 2022-04-27 2022-07-01 南通宇元智能科技有限公司 Explosion-proof electrical appliance control device for extremely cold area
PL445847A1 (en) * 2023-08-18 2024-04-22 Politechnika Warszawska System for preparing shear thickening fluids and method of preparing shear thickening fluids

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