CN105289435B - A kind of preparation method of magnetism self-repairing microcapsule - Google Patents
A kind of preparation method of magnetism self-repairing microcapsule Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of magnetic self-repairing microcapsule, belongs to chemical high-molecular compound technical field.In order in coating microcapsules additive amount increase can cause coating mechanical performance decline the problem of, especially in intelligent corrosion-inhibiting coating preparation process, stirring, the technical process such as transport can introduce many stomatas, the problem of causing coating self-healing properties to decline, it is sequentially prepared oxidation carbon material, magnetic carbon material is prepared as functional stuffing, and the functional stuffing is added in urea-formaldehyde prepolymer solution, the preparation of microcapsules is completed using lotion synthetic method, solve the problems, such as that micro-capsulated magnetic targets, microcapsules are aligned in metal base surface using the magnetism of microcapsules, realize the preparation of gradient coating, enable microcapsules ordered arrangement in the coating, realize making full use of for microcapsules, reduce the defect of coating；The additive amount of microcapsules in the coating is advantageously reduced, realizes the function of coating selfreparing；It is widely used in the preparation process of microcapsules class material.
Description
Technical field
The present invention relates to Micro-Encapsulation Technique field, specifically a kind of preparation side of magnetic self-repairing microcapsule
Method.
Background technology
In recent years, the preparation and application study of intellectual material, is paid close attention to by more and more researchers.By " selfreparing
The failure that function " is introduced into corrosion-inhibiting coating inhibits and slows down in the research of Process of Metallic Corrosion, develops and acts on corrosion-inhibiting coating
The selfreparing anti-corrosion material of microdefect will bring the technological revolution of corrosion field.The preparation and application of intelligent corrosion-inhibiting coating are ground
Study carefully the research hotspot for having become domestic and international coatings art.As country is to the ever-expanding demand of ocean development scale, intelligence is anti-
Application prospect of the rotten coating in ocean development field is more wide, pipeline, hull, oil storage tank especially in marine environment and
Application on the marine steel structures such as oil gas platform is more urgent.
Early in 2011, the S.R.White et al. of Illinois universities of the U.S. proposed the general of microcapsules self-repair material
It reads.Then, it is applied to corrosion-inhibiting coating field, this type coating is allocated as two classes according to repair mechanisms.
The first kind is the selfreparing corrosion-inhibiting coating containing corrosion inhibiter microcapsules, and the microcapsules of heeling-in pass through outer in this type coating
Boundary's force effect triggering is damaged, causes capsule wall breakdown；Or external environment variation causes cyst wall permeability to change, corrosion inhibiter outflow
Passivating film can be generated at metallic matrix, to achieve the purpose that slow down metal erosion.
Second class is that the selfreparing corrosion-inhibiting coating of type microcapsules is filled up containing heeling-in, in this type coating heeling-in have and review one's lessons by oneself
The microcapsules of renaturation energy, by different triggering modes, such as：Heat triggering, radiation triggering, light triggering, machinery triggering, ion-trigger
The effects that cause capsule wall breakdown or because environmental parameter change lead to cyst wall permeability changes, cause renovation agent liquid in capsule-core
Body flows out, and reacts with the catalysis factor in catalyst or environment pre-buried in coating, final to realize renovation agent solidification, reaches
To the reparation purpose of filling crackle.
It is described according to above-mentioned two sections, in the process that the self-repairing microcapsule later stage is applied to coating, to be realized good
Selfreparing effect, need that more microcapsules are added, the mechanical performance of coating itself can be damaged in this way, be unfavorable for the reality of coating
Border is applied, and the repair ability of intelligent corrosion-inhibiting coating is reduced.
Invention content
The technical assignment of the present invention is to solve the deficiencies in the prior art, increases and can cause for microcapsules additive amount in coating
The problem of coating mechanical performance declines, especially in intelligent corrosion-inhibiting coating preparation process, the technical process such as stirring, transport can draw
The problem of entering many stomatas, coating self-healing properties is caused to decline provides a kind of preparation method of magnetic self-repairing microcapsule, with
The problem of improving self-repairing microcapsule during preparing intelligent corrosion-inhibiting coating, coating mechanical performance is caused to decline more additive amount.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of preparation method of magnetism self-repairing microcapsule, this method include preparing oxidation carbon material, preparing magnetic carbon materials
Expect and prepare three steps of microcapsules；
1) oxidation carbon material is prepared：Carbon material and strong oxidant solution are chosen, and carbon material and strong oxidant solution are pressed
According to 1: 10-100 ratio mixing, sonic oscillation 24 hours, then clean carbon material and Strong oxdiative repeatedly with acetone, alcohol therewith
The mixed liquor of agent solution, make mixed liquor pH value be 6, filtering, by this pH value be 6 mixed liquor in 60-90 DEG C of humidity province of baking oven
Between dry 6-12 hour, then toast 3-7 hours in 300-500 DEG C of temperature range, completion aoxidizes the preparation of carbon material；
2) magnetic carbon material is prepared：It chooses magnetic synthesis agent solution and sodium hydroxide solution, and will be prepared in step 1)
Oxidation carbon material is sufficiently mixed with magnetic synthesis agent solution according to 1: 1-1000 ratio, nitrogen protection, then in the mixed of acquisition
It closes in liquid and sodium hydroxide solution is added, adjust the pH value of the mixed liquor within the scope of 8-11, stir 1 hour later, then will mixing
Liquid stirs 4 hours at 70 DEG C, therewith wash with distilled water repeatedly, baking oven is put into after the completion of cleaning and carries out 40-90 DEG C of drying, complete
At the preparation of magnetic carbon material；
3) microcapsules are prepared：1. according to 0.2-2: 0.05-0.2: 0.05-0.6 ratio chooses isocyanate derivates, capsule
Core diluent, cosolvent are simultaneously mixed and made into core materials；
2. urea and the formaldehyde mixed solution that molar ratio is 1: 1.0-3.0 are then chosen, with triethanolamine or sodium hydroxide
Adjusting acid-base value within the scope of 7.5-11.8, is to slowly warm up to 60-85 DEG C and reacts 3 hours, generate clear viscous water therewith to pH
Dissolubility urea-formaldehyde prepolymer solution；
3. according to 0.02-1: 0.05-2: 0.05-2 ratio, which is chosen, prepares the core materials completed, magnetic carbon material, urea
Aldehyde prepolymer solution, and core materials and magnetic carbon material are sequentially added in urea-formaldehyde prepolymer solution, then 40-140ml is added to steam
Distilled water is stirred, and generates Lauxite pre-polymerization liquid；0.5%-2.5% adds emulsifier according to the ratio, with high-speed emulsifying machine with
The speed of 10000-30000r/min emulsifies 10-20 minutes, O/W type emulsions is formed, by Lauxite pre-polymerization liquid and emulsion
Mixing, being sufficiently stirred makes Lauxite pre-polymerization liquid be dispersed in aqueous medium, and dilute hydrochloric acid is added dropwise and sodium hydroxide adjusts pH to 1.0-
In 5.0 ranges, then cures 3 hours for 45-70 DEG C, repeatedly rinsed by particle suspension liquid obtained centrifugation, with alcohol later, vacuum
It is dry, obtain the microcapsules using magnetic surface modified carbonaceous components as functional stuffing；
Above-mentioned steps 1) in carbon material be single-walled carbon nanotube, multi-walled carbon nanotube, graphene, graphite powder, carbon fiber
One or more of；
Above-mentioned steps 1) in strong oxidizer be potassium permanganate, the concentrated sulfuric acid, concentrated hydrochloric acid, one kind in concentrated nitric acid.
It is preferential to select above-mentioned steps 2 on the basis of strong oxidizer has been selected) in magnetic synthetics select chlorination
One or more of iron, frerrous chloride, ferrous sulfate, ferric sulfate, ferric nitrate, ferrous nitrate.
It is preferential that the ratio according to 1: 0.1: 0.06 is selected to choose isocyanate derivates, capsule-core diluent, cosolvent and mix
Core materials are made in conjunction.
It is preferential to select above-mentioned steps 3) in isocyanate derivates be 4,4 '-methyl diphenylene diisocyanates, toluene
In diisocyanate, Isosorbide-5-Nitrae '-phenylene diisocyanate, isophorone diisocyanate, 4,4'-Dicyclohexylmethane diisocyanate
One kind.
It is preferential to select above-mentioned steps 3 on the basis of isocyanate derivates have been selected) in capsule-core diluent be chlorine
One or more of benzene, benzyl alcohol, 1- butyl glycidyl ethers, ethyl acetic acid benzene fat, ethyl acetate.
It is preferential to select above-mentioned steps 3 on the basis of capsule-core diluent has been selected) in cosolvent be absolute ethyl alcohol,
One or more of chlorobenzene, hexamethylene, styrene, acetone.
It is preferential to select above-mentioned steps 3) in emulsifier be alkyl phenol polyoxyethylene ether compound, dodecyl benzene sulfonic acid
Calcium, sorbitan fatty acid ester, sorbitan monostearate, neopelex, lauryl sodium sulfate, benzene
One or more of ethylene maleic acid anhydride copolymer.
A kind of preparation method of magnetic self-repairing microcapsule of the present invention compared with prior art caused by advantageous effect
It is：
The present invention will prepare the core materials completed and magnetic carbon materials using magnetic surface modified carbonaceous components as functional stuffing
Material sequentially add in urea-formaldehyde prepolymer solution, using lotion synthetic method complete microcapsules preparation, have it is efficient, pollution it is small,
Quickly, energy saving feature solves the problems, such as micro-capsulated magnetic targeting, realizes the nanostructure advantage of carbon material, can utilize
The magnetism of microcapsules aligns microcapsules in metal base surface, it can be achieved that the preparation of gradient coating, enables microcapsules
Ordered arrangement in the coating, realizes making full use of for microcapsules, reduces the defect of coating；Advantageously reduce microcapsules in the coating
Additive amount, can realize the function of coating selfreparing；It is widely used in the preparation process of microcapsules class material.
Description of the drawings
Attached drawing 1 is the SEM figures of the present invention.
Specific implementation mode
By the way that example is embodied, the present invention will be further described.
Embodiment one：
A kind of preparation method of magnetism self-repairing microcapsule, this method include preparing oxidation carbon material, preparing magnetic carbon materials
Expect and prepare three steps of microcapsules；
1) oxidation carbon material is prepared：It chooses 1g single-walled carbon nanotubes and 20g concentrated hydrochloric acid solutions and mixes, therewith sonic oscillation
24 hours, above-mentioned mixed liquor is then cleaned repeatedly with acetone, alcohol, and it is 6 to make the pH value of mixed liquor, filtering, is 6 by this pH value
Mixed liquor is dried 9 hours in 80 DEG C of temperature ranges of baking oven, then is toasted 5 hours in 400 DEG C of temperature ranges, and oxidation carbon material is completed
Preparation；
2) magnetic carbon material is prepared：30g ferric chloride solutions and 0.01M sodium hydroxide solutions are chosen, and is weighed in step 1)
Oxidation carbon material and ferric chloride solution are sufficiently mixed, nitrogen protection by the oxidation carbon material 0.5g of preparation, then in oxidation carbon materials
0.01M sodium hydroxide solutions are added in the mixed liquor obtained after material and ferric chloride solution mixing, the pH value for adjusting the mixed liquor exists
It within the scope of 8-11, stirs 1 hour later, then mixed liquor is stirred 4 hours at 70 DEG C, it is multiple wash with distilled water therewith, clearly
It is put into baking oven after the completion of washing and carries out 70 DEG C of drying, completes the preparation of magnetic carbon material；
3) microcapsules are prepared：1. the ratio according to 1: 0.1: 0.06 chooses isocyanate derivates, capsule-core diluent, hydrotropy
Agent is simultaneously mixed and made into core materials；
2. then choosing urea and the formaldehyde mixed solution that molar ratio is 1: 2.0, adjusted with triethanolamine or sodium hydroxide
Acid-base value within the scope of 7.5-11.8, is to slowly warm up to 75 DEG C and reacts 3 hours, generate clear viscous water soluble urea formaldehyde therewith to pH
Prepolymer solution；
3. it is molten to choose the core materials for preparing completion, magnetic carbon material, urea-formaldehyde prepolymer according to 0.5: 1: 1.2 ratio
Liquid, and core materials and magnetic carbon material are sequentially added in urea-formaldehyde prepolymer solution, then add 100ml distilled water, it is stirred,
Generate Lauxite pre-polymerization liquid；1.5% adds emulsifier according to the ratio, and 15 points are emulsified with the speed of 20000r/min with high-speed emulsifying machine
Clock forms O/W type emulsions, Lauxite pre-polymerization liquid is mixed with emulsion, and being sufficiently stirred makes Lauxite pre-polymerization liquid disperse
In aqueous medium, dilute hydrochloric acid is added dropwise and sodium hydroxide is adjusted within the scope of pH to 1.0-5.0, then cures 3 hours for 60 DEG C, later will
Particle suspension liquid obtained centrifuges, is repeatedly rinsed, is dried in vacuo with alcohol, obtains using magnetic surface modified carbonaceous components as function
The microcapsules of filler.
Embodiment two：
A kind of preparation method of magnetism self-repairing microcapsule, this method include preparing oxidation carbon material, preparing magnetic carbon materials
Expect and prepare three steps of microcapsules；
1) oxidation carbon material is prepared：It chooses 1g multi-walled carbon nanotubes and 30g concentrated sulfuric acid solutions and mixes, therewith sonic oscillation
24 hours, above-mentioned mixed liquor is then cleaned repeatedly with acetone, alcohol, and it is 6 to make the pH value of mixed liquor, filtering, is 6 by this pH value
Mixed liquor is dried 12 hours in 60 DEG C of temperature ranges of baking oven, then is toasted 7 hours in 300 DEG C of temperature ranges, and oxidation carbon materials are completed
The preparation of material；
2) magnetic carbon material is prepared：40g ferric chloride solutions and 0.01M sodium hydroxide solutions are chosen, and is weighed in step 1)
Oxidation carbon material and ferric chloride solution are sufficiently mixed, nitrogen protection by the oxidation carbon material 0.5g of preparation, then in oxidation carbon materials
0.01M sodium hydroxide solutions are added in the mixed liquor obtained after material and ferric chloride solution mixing, the pH value for adjusting the mixed liquor exists
It within the scope of 8-11, stirs 1 hour later, then mixed liquor is stirred 4 hours at 70 DEG C, it is multiple wash with distilled water therewith, clearly
It is put into baking oven after the completion of washing and carries out 40 DEG C of drying, completes the preparation of magnetic carbon material；
3) microcapsules are prepared：1. choosing isocyanate derivates according to 1.2: 0.1: 0.08 ratio, capsule-core diluent, helping
Solvent is simultaneously mixed and made into core materials；
2. then choosing urea and the formaldehyde mixed solution that molar ratio is 1: 1.5, adjusted with triethanolamine or sodium hydroxide
Acid-base value within the scope of 7.5-11.8, is to slowly warm up to 70 DEG C and reacts 3 hours, generate clear viscous water soluble urea formaldehyde therewith to pH
Prepolymer solution；
3. it is molten to choose the core materials for preparing completion, magnetic carbon material, urea-formaldehyde prepolymer according to 0.2: 0.7: 0.8 ratio
Liquid, and core materials and magnetic carbon material are sequentially added in urea-formaldehyde prepolymer solution, then add 80ml distilled water, it is stirred,
Generate Lauxite pre-polymerization liquid；1.5% adds emulsifier according to the ratio, and 15 points are emulsified with the speed of 20000r/min with high-speed emulsifying machine
Clock forms O/W type emulsions, Lauxite pre-polymerization liquid is mixed with emulsion, and being sufficiently stirred makes Lauxite pre-polymerization liquid disperse
In aqueous medium, dilute hydrochloric acid is added dropwise and sodium hydroxide is adjusted within the scope of pH to 1.0-5.0, then cures 3 hours for 55 DEG C, later will
Particle suspension liquid obtained centrifuges, is repeatedly rinsed, is dried in vacuo with alcohol, obtains using magnetic surface modified carbonaceous components as function
The microcapsules of filler.
Embodiment three：
A kind of preparation method of magnetism self-repairing microcapsule, this method include preparing oxidation carbon material, preparing magnetic carbon materials
Expect and prepare three steps of microcapsules；
1) oxidation carbon material is prepared：It chooses 1g multi-walled carbon nanotubes and 40g concentrated nitric acid solutions and mixes, therewith sonic oscillation
24 hours, above-mentioned mixed liquor is then cleaned repeatedly with acetone, alcohol, and it is 6 to make the pH value of mixed liquor, filtering, is 6 by this pH value
Mixed liquor is dried 6 hours in 90 DEG C of temperature ranges of baking oven, then is toasted 3 hours in 500 DEG C of temperature ranges, and oxidation carbon material is completed
Preparation；
2) magnetic carbon material is prepared：50g ferric chloride solutions and 0.01M sodium hydroxide solutions are chosen, and is weighed in step 1)
Oxidation carbon material and ferric chloride solution are sufficiently mixed, nitrogen protection by the oxidation carbon material 0.5g of preparation, then in oxidation carbon materials
0.01M sodium hydroxide solutions are added in the mixed liquor obtained after material and ferric chloride solution mixing, the pH value for adjusting the mixed liquor exists
It within the scope of 8-11, stirs 1 hour later, then mixed liquor is stirred 4 hours at 70 DEG C, it is multiple wash with distilled water therewith, clearly
It is put into baking oven after the completion of washing and carries out 90 DEG C of drying, completes the preparation of magnetic carbon material；
3) microcapsules are prepared：1. choosing isocyanate derivates according to 1.2: 0.1: 0.08 ratio, capsule-core diluent, helping
Solvent is simultaneously mixed and made into core materials；
2. then choosing urea and the formaldehyde mixed solution that molar ratio is 1: 2.5, adjusted with triethanolamine or sodium hydroxide
Acid-base value within the scope of 7.5-11.8, is to slowly warm up to 70 DEG C and reacts 3 hours, generate clear viscous water soluble urea formaldehyde therewith to pH
Prepolymer solution；
3. it is molten to choose the core materials for preparing completion, magnetic carbon material, urea-formaldehyde prepolymer according to 0.8: 1.5: 1.5 ratio
Liquid, and core materials and magnetic carbon material are sequentially added in urea-formaldehyde prepolymer solution, then add 80ml distilled water, it is stirred,
Generate Lauxite pre-polymerization liquid；1.5% adds emulsifier according to the ratio, and 15 points are emulsified with the speed of 20000r/min with high-speed emulsifying machine
Clock forms O/W type emulsions, Lauxite pre-polymerization liquid is mixed with emulsion, and being sufficiently stirred makes Lauxite pre-polymerization liquid disperse
In aqueous medium, dilute hydrochloric acid is added dropwise and sodium hydroxide is adjusted within the scope of pH to 1.0-5.0, then cures 3 hours for 55 DEG C, later will
Particle suspension liquid obtained centrifuges, is repeatedly rinsed, is dried in vacuo with alcohol, obtains using magnetic surface modified carbonaceous components as function
The microcapsules of filler.
Claims (6)
1. a kind of preparation method of magnetism self-repairing microcapsule, which is characterized in that this method includes preparing oxidation carbon material, preparing
Magnetic carbon material and prepare three steps of microcapsules；
1) oxidation carbon material is prepared：Carbon material and strong oxidant solution are chosen, and by carbon material and strong oxidant solution according to 1:
The ratio of 10-100 mixes, and sonic oscillation 24 hours, then clean carbon material with acetone, alcohol and strong oxidizer is molten repeatedly therewith
The mixed liquor of liquid, it is 6 to make the pH value of mixed liquor, and filtering does the mixed liquor that this pH value is 6 in 60-90 DEG C of temperature range of baking oven
It is 6-12 hours dry, then toasted 3-7 hours in 300-500 DEG C of temperature range, complete the preparation of oxidation carbon material；
2) magnetic carbon material is prepared：Choose magnetic synthesis agent solution and sodium hydroxide solution, and the oxidation that will be prepared in step 1)
Carbon material is sufficiently mixed with magnetic synthesis agent solution according to 1: 1-1000 ratio, nitrogen protection, then in the mixed liquor of acquisition
Middle addition sodium hydroxide solution adjusts the pH value of the mixed liquor within the scope of 8-11, stirs 1 hour later, then mixed liquor is existed
It is stirred at 70 DEG C 4 hours, therewith wash with distilled water repeatedly, baking oven is put into after the completion of cleaning and carries out 40-90 DEG C of drying, completes magnetic
The preparation of property carbon material；
3) microcapsules are prepared：1. according to 0.2-2: it is dilute that 0.05-0.2: 0.05-0.6 ratio chooses isocyanate derivates, capsule-core
It releases agent, cosolvent and is mixed and made into core materials；
2. then choosing urea and the formaldehyde mixed solution that molar ratio is 1: 1.0-3.0, adjusted with triethanolamine or sodium hydroxide
Acid-base value within the scope of 7.5-11.8, is to slowly warm up to 60-85 DEG C and reacts 3 hours, it is water-soluble to generate clear viscous therewith to pH
Urea-formaldehyde prepolymer solution；
3. according to 0.02-1: it is pre- that 0.05-2: 0.05-2 ratio chooses the core materials for preparing completion, magnetic carbon material, ureaformaldehyde
Oligomer solution, and core materials and magnetic carbon material are sequentially added in urea-formaldehyde prepolymer solution, then add 40-140ml distilled water,
It is stirred, generates Lauxite pre-polymerization liquid；0.5%-2.5% adds emulsifier according to the ratio, with high-speed emulsifying machine with 10000-
The speed of 30000r/min emulsifies 10-20 minutes, forms O/W type emulsions, Lauxite pre-polymerization liquid is mixed with emulsion, is filled
Divide stirring that Lauxite pre-polymerization liquid is made to be dispersed in aqueous medium, dilute hydrochloric acid is added dropwise and sodium hydroxide adjusts pH to 1.0-5.0 ranges
It is interior, then cure 3 hours for 45-70 DEG C, repeatedly rinses, is dried in vacuo by particle suspension liquid obtained centrifugation, with alcohol later, obtain
To the microcapsules using magnetic surface modified carbonaceous components as functional stuffing；
Above-mentioned steps 1) in carbon material select single-walled carbon nanotube, multi-walled carbon nanotube, graphene, graphite powder, in carbon fiber
One or more；
Above-mentioned steps 1) in strong oxidizer select potassium permanganate, the concentrated sulfuric acid, concentrated hydrochloric acid, one kind in concentrated nitric acid；
Above-mentioned steps 2) in magnetic synthetics select iron chloride, frerrous chloride, ferrous sulfate, ferric sulfate, ferric nitrate, nitric acid sub-
One or more of iron.
2. a kind of preparation method of magnetic self-repairing microcapsule according to claim 1, which is characterized in that according to 1: 0.1:
0.06 ratio chooses isocyanate derivates, capsule-core diluent, cosolvent and is mixed and made into core materials.
3. a kind of preparation method of magnetic self-repairing microcapsule according to claim 1 or 2, which is characterized in that above-mentioned step
It is rapid 3) in isocyanate derivates select 4,4 '-methyl diphenylene diisocyanates, toluene di-isocyanate(TDI), Isosorbide-5-Nitrae '-benzene two
One kind in isocyanates, isophorone diisocyanate, 4,4'-Dicyclohexylmethane diisocyanate.
4. a kind of preparation method of magnetic self-repairing microcapsule according to claim 3, which is characterized in that above-mentioned steps 3)
In capsule-core diluent select chlorobenzene, benzyl alcohol, 1- butyl glycidyl ethers, ethyl acetic acid benzene fat, one kind in ethyl acetate
Or it is two or more.
5. a kind of preparation method of magnetic self-repairing microcapsule according to claim 4, which is characterized in that above-mentioned steps 3)
In cosolvent select absolute ethyl alcohol, chlorobenzene, hexamethylene, styrene, one or more of acetone.
6. a kind of preparation method of magnetic self-repairing microcapsule according to claims 1 or 2 or 4 or 5, which is characterized in that
Above-mentioned steps 3) in emulsifier select alkyl phenol polyoxyethylene ether compound, calcium dodecyl benzene sulfonate, Sorbitan alcohol ester
Fat acid esters, sorbitan monostearate, neopelex, lauryl sodium sulfate, phenylethylene-maleic anhydride are total
One or more of polymers.
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| CN106732222A (en) * | 2017-03-24 | 2017-05-31 | 天津双君智材科技发展有限公司 | Pitch crack autogenous healing microcapsules and preparation method thereof |
| CN107233852A (en) * | 2017-06-28 | 2017-10-10 | 常州汉唐文化传媒有限公司 | A kind of preparation method of magnetic self-repairing microcapsule |
| CN107216774B (en) * | 2017-07-19 | 2019-02-19 | 陕西延长石油(集团)有限责任公司研究院 | A kind of magnetism anti-corrosion self-healing coatings and its application in the erosion of oil gas field casing tube anti-corrosive |
| CN109622581B (en) * | 2018-12-28 | 2020-09-15 | 江西夏氏春秋环境股份有限公司 | Method for removing heavy metals in polluted soil by using magnetically modified biochar |
| CN111029023B (en) * | 2019-12-16 | 2021-08-10 | 东莞市领亚智能科技有限公司 | Vulcanization-free rubber insulated cable |
| CN111499251B (en) * | 2020-04-24 | 2024-01-05 | 河海大学 | Magnetic concrete self-healing capsule, preparation method and differential device |
| CN111584225B (en) * | 2020-05-25 | 2021-09-21 | 南通华兴磁性材料有限公司 | Forming method of flat ultra-thin power transformer magnetic core |
| CN113070466B (en) * | 2021-03-22 | 2022-05-10 | 江苏竣昌科技有限公司 | Surface treatment method for lightweight aluminum alloy die casting |
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| CN102728288B (en) * | 2012-06-27 | 2014-07-23 | 中国船舶重工集团公司第七二五研究所 | Method for enhancing capsule wall toughness of self-repairing microcapsules, and self-repairing microcapsules prepared by the same |
| KR101461320B1 (en) * | 2013-05-31 | 2014-11-17 | 연세대학교 산학협력단 | Self healing complex capsules with magnetic nature and conductivity and preparing method of the same |
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