CN114700000B - Magnetic liquid marble and preparation method and application thereof - Google Patents
Magnetic liquid marble and preparation method and application thereof Download PDFInfo
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- CN114700000B CN114700000B CN202210231275.0A CN202210231275A CN114700000B CN 114700000 B CN114700000 B CN 114700000B CN 202210231275 A CN202210231275 A CN 202210231275A CN 114700000 B CN114700000 B CN 114700000B
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- 239000007788 liquid Substances 0.000 title claims abstract description 110
- 239000004579 marble Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 52
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 42
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 29
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 28
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- -1 Polydimethylsiloxane Polymers 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 abstract description 8
- 230000008020 evaporation Effects 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 229910001566 austenite Inorganic materials 0.000 description 23
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 16
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000005389 magnetism Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- 235000005013 Pinus cembroides Nutrition 0.000 description 1
- 235000008575 Pinus pinea Nutrition 0.000 description 1
- 240000007789 Pinus pinea Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
Abstract
The invention belongs to the field of application of functional materials, and discloses a magnetic liquid marble and a preparation method and application thereof. The preparation method comprises the following steps: adjusting magnetic core Fe 2 O 3 @SiO 2 And the mass ratio of Polydimethylsiloxane (PDMS) is used for preparing magnetic super-hydrophobic powder with different particle sizes, and the magnetic liquid marbles are prepared by combining liquid drops with the magnetic super-hydrophobic powder. The magnetic liquid marbles can move directionally under the action of the magnetic field and can be opened and closed easily by magnetic force, and the reaction liquid is added and taken out easily, so that the reaction between the liquid in the marbles is realized, and the reaction products can be taken out easily. The magnetic liquid marbles prepared by the invention have stable performance and good mechanical property, can obviously slow down the evaporation of liquid in the marbles, can be used as a simple and convenient miniature reaction container, and is suitable for most reactions in aqueous solution.
Description
Technical Field
The invention belongs to the field of application of functional materials, and particularly relates to a magnetic liquid marble and a preparation method and application thereof.
Background
Liquid marbles are the concept proposed by aussillus and query in 2001, which is a stable liquid-solid complex consisting of tiny droplets with external non-wetting loose particles. Because of the existence of the super-hydrophobic particles, the liquid in the marble cannot be spread out, and a three-dimensional structure is presented. The particles of the outer layer can be in direct contact with other solid surfaces, so that the interface friction force is small; the gaps among the particles can keep the liquid in the gaps in contact with the air, so that the liquid marbles have wide application in the aspects of microfluid transportation, cell culture and gas sensing.
The method for preparing the liquid marbles by using the flexible super-hydrophobic surface paper (application number: 201510333757.7) specifically discloses a preparation method of the liquid marbles. The method comprises the steps of firstly preparing super-hydrophobic flexible paper, then adding super-hydrophobic powder such as copper stearate, titanium dioxide and the like to the paper, dripping liquid drops, and folding the paper to enable the liquid drops to roll to form liquid marbles. The preparation method limits the use conditions of the super-hydrophobic powder, and the recovery of the powder is a big problem and has big limitation.
A process for preparing water-carried microcapsule based on liquid marble includes such steps as preparing liquid marble from hydrophobic powder (201710232802.9), such as stone pine powder and polytetrafluoroethylene, freezing, sealing the liquid marble with instant adhesive, and coating photo-solidifying coating. Such a preparation method is complicated in process, difficult in liquid extraction, and easy in mixing of hydrophobic powder, and is disadvantageous in terms of final use.
Disclosure of Invention
Aiming at the problems of complex process, difficult taking process, difficult full recycling of materials and poor mechanical property in the prior art for preparing the liquid marble, the invention provides a magnetic liquid marble and a preparation method and application thereof.
The preparation method provided by the invention selects Fe 2 O 3 As magnetic source, with SiO 2 Fixing Fe 2 O 3 Clusters, make magnetism stable, and SiO 2 The resistance to strong acids is enhanced. By adjusting the magnetic core Fe 2 O 3 @SiO 2 The magnetic super-hydrophobic powder with different microscopic particle sizes is successfully prepared by the mass ratio of the magnetic super-hydrophobic powder and PDMS, and is prepared into magnetic liquid marbles, and the magnetic liquid marbles have good mechanical properties and can obviously slow down the evaporation rate of internal liquid.
The invention aims at realizing the following technical scheme:
a method for preparing powder of magnetic liquid marbles:
(1) Fe is added to 2 O 3 Adding the particles into absolute ethyl alcohol, adding ammonia water and tetraethoxysilane, stirring for reaction, and drying to obtain magnetic core Fe 2 O 3 @SiO 2 ；
(2) Magnetic core Fe 2 O 3 @SiO 2 And adding the polydimethylsiloxane into normal hexane, stirring for reaction, and drying to obtain the magnetic super-hydrophobic powder.
The magnetic liquid marble consists of magnetic super-hydrophobic powder and liquid drops, and the specific preparation method comprises the following steps: and (3) dripping the liquid drops on the magnetic super-hydrophobic powder to roll the liquid drops until the liquid drops are completely wrapped, so as to obtain the magnetic liquid marbles.
Said Fe 2 O 3 The mass ratio of the particles to the ammonia water to the tetraethoxysilane is (1-5): (4-15): (0.5-2); said Fe 2 O 3 @SiO 2 The mass ratio of the polydimethylsiloxane to the n-hexane is (1-2): (0.5-10): (40-150).
Said Fe 2 O 3 The mass ratio of the particles to the ammonia water to the tetraethoxysilane is 2:10:1, a step of; said Fe 2 O 3 @SiO 2 The mass ratio of the polydimethylsiloxane to the n-hexane is 1: (0.5-1.5): 60; the ethanol and Fe 2 O 3 The mass ratio of the particles is (70-500): (1-5).
The ethanol and Fe 2 O 3 The mass ratio of the particles is 400:1
Preferably, the Fe 2 O 3 Is gamma type with stronger magnetism, is ellipsoidal and has a particle size of 40-80nm.
Preferably, the type of the Polydimethylsiloxane (PMDS) is SYLGARD 184, and the PMDS prepolymer and the curing agent are composed, and the curing agent components are required to be added simultaneously when the PMDS prepolymer and the curing agent are used, wherein the mass ratio of the PMDS prepolymer to the curing agent is 10:1.
Preferably, the reaction time is 0.5h to 4h.
Preferably, the droplets may be water or an aqueous solution, and the volume of the droplets is less than 500 μl.
The magnetic liquid marble is used as a miniature reaction container for silver mirror reaction and displacement reaction.
The prepared magnetic super-hydrophobic powder has excellent magnetic and heat conducting properties, and the magnetic liquid marbles prepared by the magnetic super-hydrophobic powder can move directionally under the action of a magnetic field, and the magnetic force control can be easily opened and closed, so that the liquid can be easily added and taken out, and the magnetic super-hydrophobic powder can be used as a convenient miniature reaction container. By varying PDMS and gamma-Fe 2 O 3 @SiO 2 Can be used for preparing different granulesThe difference of the micro particle sizes of the materials finally leads to the difference of the mechanical properties of the liquid marbles and the evaporation rate of the internal liquid.
Compared with the prior art, the invention has the following advantages:
1) The liquid marble prepared by the Chinese patent application CN201510333757.7 has no magnetism, can not recover materials through magnetism, has low recovery utilization rate, can recover super-hydrophobic powder through magnetism, has high utilization rate and Fe 2 O 3 The addition of the material enhances the heat conduction property of the material, and plays a role in saving time and energy for the reaction needing heating.
2) The Chinese patent application CN201710232802.9 is complicated in preparation process, and needs to be packaged layer by layer, and the packaged liquid is difficult to take out. The preparation of the liquid marble is simple, only a few circles of the liquid marble need to roll on the magnetic super-hydrophobic powder, and the liquid marble can be opened and closed through magnetism, so that the operation of adding and taking out the coating liquid drops is realized.
3) The low surface energy substance selected by the raw materials of the invention is the fluorine-free polydimethylsiloxane, and the magnetism is the gamma-Fe which is preferable to have better biocompatibility and no toxic or side effect 2 O 3 Therefore, the preparation process of the invention does not need solvents or medicines harmful to the environment, and is environment-friendly.
Drawings
From left to right in fig. 1 are magnetic liquid marbles coated with water droplets of 20, 40, 100, 200, 300, 400, 500 μl prepared in example 1, respectively.
FIG. 2 is a graph showing the results of the magnetic liquid marble (A) prepared in example 2, the magnetic liquid marble (B) which was opened by the action of a magnet, and the removal (C1) and injection of the liquid (C2) using a pipette.
Fig. 3 is a graph of the opened magnetic liquid marbles coated with water droplets prepared in example 3 (left) and opened magnetic liquid marbles prepared in example 3 after a silver mirror reaction.
Fig. 4 is a view of the magnetic liquid marble (left) prepared in example 5 and the magnetic liquid marble (right) prepared in example 6.
Fig. 5 is a graph showing the evaporation rate of water droplets in the natural state, example 5, and example 6.
Detailed Description
The invention will now be further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
0.2g of gamma-Fe purchased from Allatin and having a particle size of 40-80nm 2 O 3 Adding the nano particles into 80g of absolute ethyl alcohol, performing ultrasonic dispersion for 0.5h, adding 4g of 25% ammonia water and 0.1g of tetraethoxysilane into the solution, mechanically stirring for 3h, centrifuging at 3000-3500rpm, and vacuum drying the obtained product at 60 ℃ for 3h to obtain the magnetic core gamma-Fe 2 O 3 @SiO 2 。
0.1g of magnetic core gamma-Fe 2 O 3 @SiO 2 Adding 0.1g of PDMS prepolymer and 0.01g of curing agent into 6g of n-hexane, mechanically stirring for 0.5h, filtering the obtained suspension, and drying at 80 ℃ for 2h to obtain the magnetic super-hydrophobic powder. The polydimethylsiloxane in the embodiment of the invention is named as SYLGARD 184, which is a two-component commodity consisting of PDMS prepolymer and curing agent, and the mass ratio of the PDMS prepolymer to the curing agent is 10:1 when the polydimethylsiloxane is used.
And (3) dripping 20, 40, 100, 200, 300, 400 and 500 mu L of water drops on the magnetic super-hydrophobic powder, rolling the water drops until the water drops are completely wrapped, and obtaining the magnetic liquid marbles, wherein the result is shown in figure 1. From this, it was found that the liquid marble was gradually flattened as the drop volume increased, but the shape was maintained, isolating the contact of water with the solid interface.
Example 2
0.2g of gamma-Fe purchased from Allatin and having a particle size of 40-80nm 2 O 3 Adding the nano particles into 80g of absolute ethyl alcohol, performing ultrasonic dispersion for 0.5h, adding 4g of 25% ammonia water and 0.1g of tetraethoxysilane into the solution, mechanically stirring for 3h, centrifuging at 3000-3500rpm, and vacuum drying the obtained product at 60 ℃ for 3h to obtain the magnetic core gamma-Fe 2 O 3 @SiO 2 。
0.1g of magnetic core gamma-Fe 2 O 3 @SiO 2 Adding 0.15g of PDMS prepolymer and 0.015g of curing agent into 6g of n-hexane, mechanically stirring for 0.5h, filtering the obtained suspension, and drying at 80 ℃ for 2h to obtain the magnetic super-hydrophobic powder.
And (3) dripping 100 mu L of water drops on the magnetic super-hydrophobic powder, and rolling the water drops until the water drops are completely wrapped, so as to obtain the magnetic liquid marbles. Fig. 2 shows that the prepared magnetic liquid marble is placed on a glass sheet, a magnet is placed under the glass sheet, the magnetic super-hydrophobic powder is attracted by magnetic force, and the upper half part of powder is piled down, so that the liquid of the upper half part is exposed. The liquid can be injected into and taken out of the marble through the injector, and the whole volume is increased after the liquid is injected; the liquid is taken out so that only one shell is left on the magnetic liquid marble, and the magnetic liquid marble is in a bent and shrunken state.
Example 3
0.2g of gamma-Fe purchased from Allatin and having a particle size of 40-80nm 2 O 3 Adding the nano particles into 80g of absolute ethyl alcohol, performing ultrasonic dispersion for 0.5h, adding 4g of 25% ammonia water and 0.1g of tetraethoxysilane into the solution, mechanically stirring for 3h, centrifuging at 3000-3500rpm, and vacuum drying the obtained product at 60 ℃ for 3h to obtain the magnetic core gamma-Fe 2 O 3 @SiO 2 。
0.1g of magnetic core gamma-Fe 2 O 3 @SiO 2 And 0.15g of PDMS prepolymer and 0.015g of curing agent are added into 6g of n-hexane, the mixture is mechanically stirred for 0.5h, the obtained suspension is filtered, and the suspension is dried for 2h at 80 ℃ to obtain the magnetic super-hydrophobic powder.
Dropping 50 mu L of 2% silver ammonia solution onto the magnetic super-hydrophobic powder, and rolling the liquid drops until the liquid drops are completely wrapped to obtain magnetic liquid marbles; the magnetic liquid marbles were then opened in the manner described in example 2 and 2. Mu.L of 97% acetaldehyde solution purchased from Allatin was injected and heated at 80℃for 10min.
The silver ammonia solution is changed into water drops with the same volume to prepare the magnetic liquid marbles coated with the water drops. As shown in fig. 3, the left graph is a schematic view of the magnetic liquid marbles coated with the water droplets after being opened, and the right graph is the magnetic liquid marbles opened after the silver mirror reaction, and the silver mirror generated on the surfaces of the droplets can be observed.
In addition, the liquid of the liquid drop is changed into 100 mu L of 20wt% copper sulfate solution to prepare magnetic liquid marbles, a small iron wire is inserted into the marbles, and after 2 hours of reaction, red substances appear on the surface of the iron wire, namely substitution reaction occurs. This also illustrates that it is possible to perform a chemical reaction inside the magnetic liquid marble.
Example 4
0.2g of gamma-Fe purchased from Allatin and having a particle size of 40-80nm 2 O 3 Adding the nano particles into 80g of absolute ethyl alcohol, performing ultrasonic dispersion for 0.5h, adding 4g of 25% ammonia water and 0.1g of tetraethoxysilane into the solution, mechanically stirring for 3h, centrifuging at 3000-3500rpm, and vacuum drying the obtained product at 60 ℃ for 3h to obtain the magnetic core gamma-Fe 2 O 3 @SiO 2 。
0.1g of magnetic core gamma-Fe 2 O 3 @SiO 2 Adding 0.1g of PDMS prepolymer and 0.01g of curing agent into 6g of n-hexane, mechanically stirring for 0.5h, filtering the obtained suspension, and drying at 80 ℃ for 2h to obtain the magnetic super-hydrophobic powder.
And (3) dripping 100 mu L of water drops on the magnetic super-hydrophobic powder, and rolling the water drops until the water drops are completely wrapped, so as to obtain the magnetic liquid marbles. Further, 100. Mu.L of water was added dropwise to the glass sheet, and both were simultaneously placed in an oven at 80℃and, further, the temperature change of both was observed by an infrared camera. After 2min, the temperature of the water drop on the glass sheet was 38 ℃, while the surface of the magnetic liquid marble reached 69 ℃, and the temperature of the liquid inside was 55 ℃. This indicates that due to gamma-Fe 2 O 3 When the magnetic liquid marble is used as a reaction container, the heating time and energy can be effectively saved.
Example 5
0.2g of gamma-Fe purchased from Allatin and having a particle size of 40-80nm 2 O 3 Adding the nano particles into 80g absolute ethyl alcohol, dispersing for 0.5h by ultrasonic, adding 4g 25% ammonia water and 0.1g tetraethoxysilane into the solution, mechanically stirring for 3h,centrifuging at 3000-3500rpm, vacuum drying at 60deg.C for 3 hr to obtain magnetic core gamma-Fe 2 O 3 @SiO 2 。
0.1g of magnetic core gamma-Fe 2 O 3 @SiO 2 And 0.1g of PDMS prepolymer and 0.005g of curing agent are added into 6g of n-hexane, the mixture is mechanically stirred for 0.5h, the obtained suspension is filtered, and the suspension is dried for 2h at 80 ℃ to obtain the magnetic super-hydrophobic powder.
And (3) dripping 100 mu L of water drops on the magnetic super-hydrophobic powder, and rolling the water drops until the water drops are completely wrapped, so as to obtain the magnetic liquid marbles.
Example 6
In comparison with example 5, the difference is that the magnetic core is gamma-Fe 2 O 3 @SiO 2 And the mass ratio of PDMS is different.
0.1g of magnetic core gamma-Fe 2 O 3 @SiO 2 And 0.05g of PDMS prepolymer, 0.01g of curing agent are added into 6g of n-hexane, and the mixture is mechanically stirred for 0.5h, sprayed into a culture dish for 30cm, and the spraying pressure is 0.2Mpa. And (3) curing the sprayed culture dish at 80 ℃ for 2 hours to obtain the magnetic super-hydrophobic powder.
And (3) dripping 100 mu L of water drops on the magnetic super-hydrophobic powder, and rolling the water drops until the water drops are completely wrapped, so as to obtain the magnetic liquid marbles. Table 1 is a graph comparing the performances of the magnetic super-hydrophobic powders prepared in example 3, example 5 and example 6, and it can be seen from Table 1 that PDMS and gamma-Fe follow 2 O 3 @SiO 2 The mass ratio of @ PDMS is reduced, the particle size of the prepared super-hydrophobic powder is in a decreasing trend, and conversely, the contact angle with water is continuously increased, so that the super-hydrophobic powder has excellent hydrophobic property. In addition, different m (PDMS) were tested indirectly by magnetic liquid marbles drop-resistant height: m (gamma-Fe) 2 O 3 @SiO 2 The effect of PDMS) on the mechanical properties of the magnetic liquid marbles, it was evident that the drop-resistant height of the magnetic liquid marbles increased with decreasing particle size of the powder. An increase in PDMS content will result in more clustered gamma-Fe 2 O 3 @SiO 2 Are linked together so that the particle size of the powder increases. Meanwhile, PDMS containsAn increase in the amount will cover more of the cluster protrusions, resulting in a decrease in roughness and a decrease in contact angle. The distance between the powder on the surface of the liquid is increased along with the reduction of the particle size of the powder, and the coverage rate of the powder on the liquid drop in unit area is greatly improved, so that the super-hydrophobic powder at the contact point of the liquid marble and the interface can better block the liquid and the contact surface when the liquid marble falls down, the exposed surface of the liquid at the moment of collision is reduced, and the mechanical property of the liquid marble is improved.
In addition, in comparison with the morphology, fig. 4 shows that the magnetic liquid marbles prepared in example 5 (left) and example 6 (right) are significantly different in the roughness of the outermost layer, the magnetic liquid marbles prepared in example 6 are smooth and fine in surface, have no large protrusions, and the magnetic liquid marbles prepared in example 5 are much rough.
Fig. 5 is a graph showing comparison of evaporation rates of water droplets in the magnetic liquid marbles of examples 5 and 6, wherein the evaporation rates of water in the natural state are stable and almost straight. The magnetic liquid marbles prepared in example 5 showed nearly 1-fold slower evaporation rate of the liquid than that of the liquid in the natural state, which proves that the water drops still contact with the outside air under the coating of the magnetic super-hydrophobic powder, but the contact area is greatly reduced, which is advantageous for the micro-reaction vessel. The evaporation rate of example 6 was further slowed down because the powder particle size in the magnetic superhydrophobic powder coating prepared in example 6 was finer and more hydrophobic, and accordingly the superhydrophobic powder coating comprising the outer layer of liquid marbles was denser with further reduced contact of the liquid with air.
Table 1 shows the comparison of the properties of the powders prepared in example 3, example 5 and example 6 with those of the magnetic liquid marbles
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. The application of the magnetic liquid marble on the miniature reaction container is characterized in that the magnetic liquid marble consists of magnetic super-hydrophobic powder and liquid drops;
the preparation method of the magnetic liquid marble comprises the following steps: dripping the liquid drops on the magnetic super-hydrophobic powder to enable the liquid drops to roll until the liquid drops are completely wrapped, so as to obtain magnetic liquid marbles;
the magnetic super-hydrophobic powder is prepared by the following method:
(1) Fe is added to 2 O 3 Adding the particles into absolute ethyl alcohol, adding ammonia water and tetraethoxysilane, stirring for reaction, and drying to obtain magnetic core Fe 2 O 3 @SiO 2 ；
(2) Magnetic core Fe 2 O 3 @SiO 2 Adding the magnetic super-hydrophobic powder and polydimethylsiloxane into normal hexane, stirring for reaction, and drying to obtain the magnetic super-hydrophobic powder;
the Fe is 2 O 3 @SiO 2 The mass ratio of the polydimethylsiloxane to the n-hexane is (1-2): 0.5: (40-150).
2. The use according to claim 1, wherein Fe 2 O 3 The mass ratio of the particles to the ammonia water to the tetraethoxysilane is (1-5): (4-15): (0.5-2).
3. The use according to claim 2, wherein Fe 2 O 3 The mass ratio of the particles to the ammonia water to the tetraethoxysilane is 2:10:1, a step of; the ethanol and Fe 2 O 3 The mass ratio of the particles is (70-500): (1-5).
4. Use according to any one of claims 1 to 3, wherein the type of polydimethylsiloxane is SYLGARD 184; the ethanol and Fe 2 O 3 The mass ratio of the particles is 400:1.
5. the use according to claim 4, wherein the reaction in step (1) takes from 0.5h to 4h; said Fe 2 O 3 The particle size is 40-80 and nm.
6. The use according to claim 5, wherein the droplet has a volume of less than 500 μl.
7. The use according to claim 6, wherein the magnetic liquid marble is used as a micro reaction vessel for silver mirror reaction and displacement reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210231275.0A CN114700000B (en) | 2022-03-09 | 2022-03-09 | Magnetic liquid marble and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210231275.0A CN114700000B (en) | 2022-03-09 | 2022-03-09 | Magnetic liquid marble and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114700000A CN114700000A (en) | 2022-07-05 |
| CN114700000B true CN114700000B (en) | 2024-03-29 |
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| CN111956524A (en) * | 2020-08-21 | 2020-11-20 | 中国药科大学 | Composition of nicotinamide and ascorbic acid or derivatives thereof based on 'dry water' technology |
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