CN106810993A - Self-healing mould assembly epoxy coating and its preparation and application based on the mesoporous container of micron order - Google Patents
Self-healing mould assembly epoxy coating and its preparation and application based on the mesoporous container of micron order Download PDFInfo
- Publication number
- CN106810993A CN106810993A CN201510845987.1A CN201510845987A CN106810993A CN 106810993 A CN106810993 A CN 106810993A CN 201510845987 A CN201510845987 A CN 201510845987A CN 106810993 A CN106810993 A CN 106810993A
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- container
- self
- component
- mould assembly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention relates to self-healing paint field, specially a kind of self-healing mould assembly epoxy coating and preparation method and application based on the mesoporous container of micron order.By mass percentage, component one is formulated by following component and quality proportioning：Epoxy resin 60%~80%；Mesoporous container 1%~10%；Organic solvent 10%~30%；Auxiliary agent 0.5%~5%；By mass percentage, component two is formulated by following component and quality proportioning：Organic solvent 25%~75%；Curing agent 25%~75%；Count in mass ratio, component one：Component two=2~4:1 mixing, obtains the self-healing mould assembly epoxy coating of containing mesopore container.Self-healing mould assembly epoxy coating is formed into self-healing mould assembly epoxy coating through spraying, brushing or dip-coating in substrate surface, normal temperature or heating cure.Corrosion Repair can be carried out to metal base when (fracture, machinery are scraped) is sustained damage using the coating of coating preparation of the present invention, extend the service life of coating.
Description
Technical field
The present invention relates to self-healing paint field, specially a kind of self-healing mould assembly ring based on the mesoporous container of micron order
Oxygen coating and preparation method and application, (can be broken, machinery is scraped using the coating of the coating preparation sustaining damage
Wipe) when, to metal base (such as：Aluminium alloy, magnesium alloy, steel or galvanized steel etc.) carry out Corrosion Repair.
Background technology
The self-healing technology of organic coating includes two aspects：First, coating self-healing in itself, i.e., using resin
Or the holiday that oligomer healing environmental damage brings；2nd, at coating damage or interface metal base corrosion
Self-healing.The meaning of the latter is to improve coating by slowing down or preventing the generation of metal erosion under coating
Service life.Shchukin et al. has loaded organic corrosion inhibitor with nano-porous materials first, and uses
Layer-by-Layer technologies can respond extraneous pH value and change and "ON" or " closing " in porous material surface preparation
Polyelectrolyte membrane, be prepared for " nano container ".The corrosion inhibitor of porous material release can be in metal surface
Protectiveness film is formed by chemical reaction, physical absorption or chemisorbed, the further of metal erosion reaction is prevented
Occur.Need that there is very strong adsorption capacity, larger specific surface area as the carrier of corrosion inhibitor, so
More corrosion inhibitors can be absorbed.
Up to the present, the healing coating containing corrosion inhibitor has been developed, and is all based on greatly relative
Thin sol- gel coating (<5μm).Because coating is relatively thin, sol- gel coating normally only can be used as surface
Process layer, also limit the size of corrosion inhibitor carrier.The container (nanoscale) of reduced size, in turn,
Also limit the load capacity of corrosion inhibitor.Therefore, to can be provided effective corrosion protection ability just low for container.
In this case, there is provided the amount of the nanoscale container that equal corrosion protection ability needs is big, high cost.
The content of the invention
It is an object of the invention to provide a kind of self-healing mould assembly epoxy coating based on the mesoporous container of micron order and preparation
Methods and applications, Corrosion Repair can be carried out using the coating of the coating preparation when coating is damaged to metal base.
In order to achieve the above object, the technical scheme is that：
A kind of self-healing mould assembly epoxy coating based on the mesoporous container of micron order, coating is uniform by component one and component two
Mix, wherein：
By mass percentage, component one is formulated by following component and quality proportioning：
By mass percentage, component two is formulated by following component and quality proportioning：
Organic solvent 25%~75%；
Curing agent 25%~75%；
Count in mass ratio, component one：Component two=2~4:1 mixing, obtains the self-healing mould assembly ring of containing mesopore container
Oxygen coating.
The described self-healing mould assembly epoxy coating based on the mesoporous container of micron order, it is preferred that by mass percentage,
Component one is formulated by following component and quality proportioning：The scope of epoxy resin is 65%~75%, mesoporous appearance
The scope of device is 1%~5%, and the scope of organic solvent is 20%~30%, and it is 1%~3% that auxiliary agent encloses.
The described self-healing mould assembly epoxy coating based on the mesoporous container of micron order, the mesoporous material that mesoporous container is used
It is micron-sized mesoporous silicon oxide, mesoporous TiO 2, mesoporous silicon carbide, mesoporous cerium oxide or mesoporous carbon.
The described self-healing mould assembly epoxy coating based on the mesoporous container of micron order, epoxy resin is bisphenol type epoxy
Resin or bisphenol f type epoxy resin, curing agent are amine curing agent.
The described self-healing mould assembly epoxy coating based on the mesoporous container of micron order, the preparation process of mesoporous container is as follows：
(1) organic corrosion inhibitor is scattered in water, the aqueous solution of ethanol or ethanol, then by mesoporous material
Add and be dispersed in above-mentioned solution, form mixed liquor；In the mixed liquor, by mass percentage,
Mesoporous material accounts for 1~10%, and organic corrosion inhibitor accounts for 0.1~10%, remaining be water, the aqueous solution of ethanol or
Ethanol；
(2) at ambient temperature, the mixed liquor that step (1) is obtained is vacuumized, makes organic corrosion inhibitor
Into in mesoporous material；The mesoporous material after load organic corrosion inhibitor is filtered out, is repeated to disperse and is taken out
Vacuum 3~4 times, the amount made into the organic corrosion inhibitor in mesoporous material reaches maximization, mesoporous material with
The mass ratio of organic corrosion inhibitor is 1:1~10:1；
(3) the mixed liquor filtering for obtaining step (2), obtains loading the mesoporous material of organic corrosion inhibitor；
(4) based on the characteristic that mesoporous material is electrically charged, the load organic corrosion inhibitor that step (3) is obtained
Mesoporous material be dispersed in the polyelectrolyte solution with opposite charges of 1~5g/L, with shaking table mix 15~
30min, obtains mixed liquor；
(5) the mixed liquor micro-filtrate membrane filtration for obtaining step (4), washing, it is unnecessary with electric charge to remove
Polyelectrolyte, obtain coat individual layer polyelectrolyte mesoporous material；
(6) mesoporous material that electric charge is carried after the cladding polyelectrolyte for again obtaining step (5) is distributed to 1~
In the polyelectrolyte solution with opposite charges of 5g/L, repeat and cladding first time polyelectrolyte identical step
Suddenly, that is, obtain coating the mesoporous container of double-deck polyelectrolyte film.
The described self-healing mould assembly epoxy coating based on the mesoporous container of micron order, in the preparation process of mesoporous container,
Organic corrosion inhibitor be 8-hydroxyquinoline, BTA, mercaptobenzothiazoler, methyl benzotriazazole,
One kind in imidazoline；Polyelectrolyte is polyacrylic acid, polyethyleneimine, kayexalate, polyene third
Two kinds of combinations of oppositely charged in base amine hydrochlorate, diallyl dimethyl ammoniumchloride；Polyelectrolyte is adopted
Solvent is water.
The preparation method of the described self-healing mould assembly epoxy coating based on the mesoporous container of micron order, comprises the following steps that：
1) epoxy resin, organic solvent, auxiliary agent are added in a reservoir, using 400~500rpm of high speed dispersor
Dispersion 10~20 minutes, adds mesoporous container, continues to be disperseed with 800~1500rpm of high speed centrifugation dispersion machine
10~30 minutes；
2) step 1) material that obtains ball mill grinding 4~8 hours, test fineness reach 20 μm with
Under, discharging, filtering obtains component one；
3) curing agent is added in organic solvent and is diluted, using 4000~5000rpm of high speed dispersor
Dispersion 5~20 minutes, discharging, obtains component two；
4) component two is added in component one, is mixing uniformly to form self-healing mould assembly epoxy coating.
The application of the described self-healing mould assembly epoxy coating based on the mesoporous container of micron order, self-healing mould assembly epoxy is applied
Material is through spraying, brushing or dip-coating in metal base：Aluminium alloy, magnesium alloy, steel or surface of galvanized steel, normal temperature or
Heating cure, forms self-healing mould assembly epoxy coating.
Design philosophy of the invention is：
In order to reduce the preparation cost of self-healing coating, the efficiency of the production process of container should be improved, while making certainly
Container amount used by agglutination is minimum.Generally, the epoxy coating of common anti-corrosion demand is applied to, it applies thickness
It is tens to one hundred microns to spend.For such thickness coatings, micron-sized mesoporous material compares nanoscale
Mesoporous material have efficiency higher.The present invention includes the load of corrosion inhibitor, the mesoporous container of micron order
Preparation, the preparation of self-healing coating, corrosion inhibitor load is with organic corrosion inhibitor as object, with micron
Level mesoporous material is main body, using vacuum filtration method, organic corrosion is completed in the aqueous solution or the aqueous solution of ethanol
The absorption and load of inhibitor；The mesoporous material after corrosion inhibitor is loaded with layer assembly (Layer-by-Layer)
Method cladding polyelectrolyte, formed controlled release corrosion inhibitor mesoporous " container "；Mesoporous container is doped to
In epoxy coating, the epoxy coating with healing metal base corrosion function is prepared.So as to micron order
Mesoporous material is used as carrier, it is possible to increase the load capacity of corrosion inhibitor, reduces the cost of self-healing coating, carries
The efficiency of high metal matrix corrosion healing.Mesoporous container with controlled release corrosion inhibitor function is used to make
Standby self-healing mould assembly organic coating, improves the decay resistance of coating, extends the service life of coating.
Advantages of the present invention and have the beneficial effect that：
1st, using micron order mesoporous material, load capacity of the mesoporous material to corrosion inhibitor is improved.
2nd, the present invention based on the method for preparing self-healing coating using mesoporous container it is simple, barrier propterty is good, cost
It is low, it is easy to promote.
Brief description of the drawings：
Fig. 1 (a)-Fig. 1 (b) is original mesoporous SiO2, load corrosion inhibitor and coat polyelectrolyte film
Mesoporous container.Wherein, Fig. 1 (a) is mesoporous SiO2End face shape；Fig. 1 (b) is mesoporous SiO2Container
Pattern.
Fig. 2 (a)-Fig. 2 (b) is the surface topography after the salt mist experiment of the epoxy coating with cut.Wherein,
Fig. 2 (a) epoxy coatings are through the surface topography after salt mist experiment 1 day, 4 days and 10 days；Fig. 2 (b) contains
Mesoporous SiO2The self-healing mould assembly epoxy coating of container is through the surface topography after salt mist experiment 1 day, 4 days and 10 days.
Fig. 3 (a)-Fig. 3 (b) is common epoxy coating and comprising mesoporous SiO2Container epoxy coating electrochemistry is handed over
The Bode figures of flow impedance spectrum.Wherein, Fig. 3 (a) epoxy coatings；Fig. 3 (b) contains mesoporous SiO2Container
Self-healing mould assembly epoxy coating.In figure, abscissa represents frequency, and left side ordinate represents impedance magnitude, and right side is indulged
Coordinate represents phase angle.
Specific embodiment
In specific implementation process, self-healing mould assembly epoxy coating of the present invention based on the mesoporous container of micron order, by group
Point one and component two is well mixed forms：
By mass percentage, component one is formulated by following component and quality proportioning：
By mass percentage, component two is formulated by following component and quality proportioning：
Organic solvent 25%~75%；
Curing agent 25%~75%；
Count in mass ratio, component one：Component two=2~4:1 mixing, obtains the self-healing mould assembly ring of containing mesopore container
Oxygen coating.
Wherein, the mesoporous material that mesoporous container is used can for micron-sized mesoporous silicon oxide, mesoporous TiO 2,
Mesoporous silicon carbide, mesoporous cerium oxide or mesoporous carbon etc..Epoxy resin is bisphenol A type epoxy resin or bisphenol-f type
Epoxy resin, curing agent is amine curing agent.Bisphenol A type epoxy resin can be E-12, E20, E44 or E54,
Bisphenol f type epoxy resin can be 6458,6445,6420 or 6412.Amine curing agent is aliphatic amine, virtue
Fragrant amine, cycloaliphatic amines or amide-type curing agent, aliphatic amine, such as：Diethylenetriamine, triethylene tetramine or four
The amine of ethene five；Aromatic amine, such as：M-phenylene diamine (MPD) or m-xylene diamine；Cycloaliphatic amines, such as：IPD；
Amide-type curing agent, such as：Shanghai Kailin Paint Factory 200,300,650 or the polyamide of 651 types, Tianjin swallow
TY-200, TY203, TY-300, TY-3051, TY-600, TY-650 or TY651 of extra large Chemical Co., Ltd.
Polyamide etc..Organic solvent is the solvent that coating is commonly used, such as：Toluene, dimethylbenzene, acetone, MEK,
Cyclohexanone or n-butanol etc..The auxiliary agent that auxiliary agent is commonly used for coating, including wetting dispersing agent, levelling agent or anti-settling agent
Deng can be using the serial auxiliary agents of the BYK of Bi Ke chemical companies of Germany；Dispersant, such as：BYK101 disperses
Agent, BYK104 dispersants, BYK110 dispersants, BYK130 dispersants, BYK141 dispersants or BYK161
Dispersant etc.；Levelling agent, such as：BYK 358N levelling agents, BYK300 levelling agents, BYK306 levelling agents,
BYK307 levelling agents, BYK310 levelling agents or BYK320 levelling agents etc.；Anti-settling agent, such as：BYK 410
Anti-settling agent, the anti-settling agents of BYK 420, the anti-settling agents of BYK 431 or the anti-settling agents of BYK 411 etc..
Outer unless specifically stated otherwise in the present invention, involved ratio is mass percent.
Preparation method of sample：The 2024-T3 aluminium alloy plates surface of some 150mm × 75mm × 2mm is by removing
After oil processing, together (thickness of dry film is 40 ± 2 μm), coating is respectively adopted and contains mesoporous SiO for spraying2Container,
Mesoporous SiO is not contained2The epoxy coating of container, air drying carries out coating performance test after 7 days.
The YWQ that the neutral salt spray sample of coating sample is produced using Jiangsu Huaian Central Asia testing equipment Co., Ltd
Type salt fog cabinet.NaCl solution concentration 5wt%, test temperature is 35 ± 2 DEG C.
The ac impedance measurement of coating uses EG＆G 273A potentiostats and 5210 lock-in amplifiers.Immersion is molten
Liquid：3.5wt%NaCl.Frequency range：10mHz~100KHz, disturbs current potential：20mV.
Below, the present invention is further elaborated on by embodiment and comparative example.
Embodiment 1
Step one：Prepare the mesoporous SiO of mesoporous micron order2Container A
Corrosion inhibitor 8-hydroxyquinoline is dissolved in and is placed in ethanol, place into mesoporous SiO2(size~1 μm),
It is thoroughly mixed to form mixed liquor；In the mixed liquor, mesoporous material accounts for 1wt%, and organic corrosion inhibitor is accounted for
0.2wt%, remaining is ethanol.At ambient temperature, in being vacuumized in vacuum tank so that 8-hydroxyquinoline is adsorbed
In mesoporous SiO2In.After standing 30min, dispersion mixing liquid, vacuumizes again again.Repeat said process
Four times, until 8-hydroxyquinoline is fully adsorbed in mesoporous SiO2In.Take out resulting solution to be filtered, after filtering
Washing three times, gained filtering medium is used to coat (Layer-by-Layer) polyelectrolyte layer by layer.
Filtering medium is distributed in the 20mL aqueous solution, the polyethyleneimine (solvent is water) of the 2g/L of 20mL is taken
With filtering medium mixing, mixed liquor is formed, be placed in shaking table and hatch 15~30min.The suspension filtering that will be obtained
Three times, wash three times, obtain coating the mesoporous SiO of polyethyleneimine2.The polyphenyl of the 2g/L of 20mL is taken again
Vinyl sulfonic acid sodium (solvent is water) and the last filtering medium that is filtrated to get mix, and form mixed liquor, are placed in shaking table hatching
15~30min.The suspension that will be obtained is filtered three times, is washed three times, obtains coating kayexalate
Mesoporous SiO2.Through filtering, obtain coating the mesoporous SiO of double-deck polyelectrolyte film2Container A, dries, standby.
As shown in Fig. 1 (a)-Fig. 1 (b), from mesoporous SiO2End face shape and mesoporous SiO2Container pattern can be with
Find out, original mesoporous SiO2Mesoporous container is formed after load corrosion inhibitor and cladding polyelectrolyte film.
Step 2：Prepare self-healing mould assembly epoxy coating
The preparation method of component one：Bisphenol A epoxide resin E20 is added to account for 72wt%, solvent two in dispersion cylinder
Toluene accounts for 25wt%, and wetting dispersing agent (German Bi Ke chemical company DISPERBYK-163) accounts for 0.6wt%,
Levelling agent (German Bi Ke chemical company DISPERBYK-306) accounts for 0.2wt%, anti-settling agent (German Bi Keization
Company DISPERBYK-420) 0.2wt% is accounted for, disperseed 15 minutes using high speed dispersor 450rpm,
Add mesoporous SiO2Container A accounts for 2wt%, continues to be disperseed 20 minutes with high speed centrifugation dispersion machine 1000rpm.
The material for obtaining ball mill grinding 8 hours, test fineness reaches less than 20 μm, and discharging is filtered, and is obtained
To component one；
As needed, curing agent TY-650 is added in organic solvent toluene to be diluted and (is diluted to solidification
Agent accounts for 50wt%), disperseed 5~20 minutes in 4000~500rpm using high speed dispersor, discharging obtains group
Divide two.
Two components press component one：Component two=3：1 (weight ratio) is matched, and after stirring, is sprayed on 150mm
The 2024-T3 aluminum alloy base materials surface of × 75mm × 2mm, normal temperature cure 7 days, thickness of dry film is 40 ± 2 μm.
Embodiment 2
Step one：Prepare the mesoporous SiO of mesoporous micron order2Container B
During corrosion inhibitor BTA dissolved in into the distilled water being placed in container, mesoporous SiO is placed into2(chi
It is very little~1 μm), it is thoroughly mixed to form mixed liquor；In the mixed liquor, mesoporous material accounts for 1wt%, organic corrosion
Inhibitor accounts for 0.2wt%, and remaining is water.At ambient temperature, in being vacuumized in vacuum tank so that the nitrogen of benzo three
Azoles is adsorbed in mesoporous SiO2In.After standing 30min, dispersion mixing liquid, vacuumizes again again.In repetition
Process is stated four times, until BTA is fully adsorbed in mesoporous SiO2In.Resulting solution is taken out to be filtered,
Washed three times after filtering, gained filtering medium is used to coat (Layer-by-Layer) polyelectrolyte layer by layer.
Filtering medium is distributed in the 20mL aqueous solution, the polyethyleneimine (solvent is water) of the 2g/L of 20mL is taken
With filtering medium mixing, mixed liquor is formed, be placed in shaking table and hatch 15~30min.The suspension filtering that will be obtained
Three times, wash three times, obtain coating the mesoporous SiO of polyethyleneimine2.The polyphenyl of the 2g/L of 20mL is taken again
Vinyl sulfonic acid sodium (solvent is water) and the last filtering medium that is filtrated to get mix, and form mixed liquor, are placed in shaking table hatching
15~30min.The suspension that will be obtained is filtered three times, is washed three times, obtains coating kayexalate
Mesoporous SiO2.Through filtering, obtain coating the mesoporous SiO of double-deck polyelectrolyte film2Container B, dries, standby.
As shown in Fig. 1 (a)-Fig. 1 (b), from mesoporous SiO2End face shape and mesoporous SiO2Container pattern can be with
Find out, original mesoporous SiO2Mesoporous container is formed after load corrosion inhibitor and cladding polyelectrolyte film.
Step 2：Prepare self-healing mould assembly epoxy coating
The preparation method of component one：Bisphenol A epoxide resin E20 is added to account for 72wt%, solvent two in dispersion cylinder
Toluene accounts for 25wt%, and wetting dispersing agent (German Bi Ke chemical company DISPERBYK-163) accounts for 0.6wt%,
Levelling agent (German Bi Ke chemical company DISPERBYK-306) accounts for 0.2wt%, anti-settling agent (German Bi Keization
Company DISPERBYK-420) 0.2wt% is accounted for, disperseed 10 minutes using high speed dispersor 480rpm,
Add mesoporous SiO2Container B accounts for 2wt%, continues to be disperseed 15 minutes with high speed centrifugation dispersion machine 1200rpm.
The material for obtaining ball mill grinding 6 hours, test fineness reaches less than 20 μm, and discharging is filtered, and is obtained
To component one；
As needed, curing agent TY-650 is added in organic solvent toluene to be diluted and (is diluted to solidification
Agent accounts for 50wt%), disperseed 5~20 minutes in 4000~500rpm using high speed dispersor, discharging obtains group
Divide two.
Two components press component one：Component two=3：1 (weight ratio) is matched, and after stirring, is sprayed on 150mm
The 2024-T3 aluminum alloy base materials surface of × 75mm × 2mm, normal temperature cure 7 days, thickness of dry film is 40 ± 2 μm.
Comparative example 1
The preparation method of component one：Bisphenol A epoxide resin E20 is added to account for 73wt%, solvent two in dispersion cylinder
Toluene accounts for 26wt%, and wetting dispersing agent (German Bi Ke chemical company DISPERBYK-163) accounts for 0.6wt%,
Levelling agent (German Bi Ke chemical company DISPERBYK-306) accounts for 0.2wt%, anti-settling agent (German Bi Keization
Company DISPERBYK-420) 0.2wt% is accounted for, disperseed 15 minutes using high speed dispersor 450rpm.
The material for obtaining ball mill grinding 8 hours, test fineness reaches less than 20 μm, and discharging is filtered, and is obtained
To component one；
As needed, curing agent TY-650 is added in organic solvent toluene to be diluted and (is diluted to solidification
Agent accounts for 50wt%), disperseed 5~20 minutes in 4000~500rpm using high speed dispersor, discharging obtains group
Divide two.
Two components press component one：Component two=3：1 (weight ratio) is matched, and after stirring, is sprayed on 150mm
The 2024-T3 aluminum alloy base materials surface of × 75mm × 2mm, normal temperature cure 7 days, thickness of dry film is 40 ± 2 μm.
Neutral salt spray test 10 days and electrochemical AC impedance 7 days the results are shown in Table 1 and Fig. 2 (a)-Fig. 2
(b).By table 1 and Fig. 2 (a)-Fig. 2 (b) as can be seen that embodiment 1 and 2 adds mesoporous container ring
The salt spray resistance of oxygen coating sample is substantially better than the common epoxy coating sample of comparative example 1.And, addition is situated between
The low-frequency impedance modulus value of the epoxy coating (embodiment 1 and 2) of pore volume device also will be apparently higher than common epoxy coating
(comparative example 1).From Fig. 3 (a)-Fig. 3 (b), the impedance magnitude containing mesoporous container epoxy coating exists
Increase in 3.5wt%NaCl solution with soak time gradually rises, and indicates corrosion inhibitor release to coating
The self-healing of lower base material corrosion.
The result of the test such as following table of embodiment 1,2 and comparative example 1：
The corrosion-resistant evaluation of the epoxy coating of table 1
| Salt fog resistance (level) | ||
| Embodiment 1 | 0 | |
| Embodiment 2 | 0 | |
| Comparative example 1 | 1 |
The result of embodiment and comparative example shows that the present invention proposes the self-healing mould assembly ring based on micron order mesoporous material
Oxygen coating, by adding the mesoporous container of micron order, the corrosion resistance of epoxy coating is significantly improved.
Claims (8)
1. a kind of self-healing mould assembly epoxy coating based on the mesoporous container of micron order, it is characterised in that coating is by component
One and component two be uniformly mixed, wherein：
By mass percentage, component one is formulated by following component and quality proportioning：
By mass percentage, component two is formulated by following component and quality proportioning：
Organic solvent 25%~75%；
Curing agent 25%~75%；
Count in mass ratio, component one：Component two=2~4:1 mixing, obtains the self-healing mould assembly ring of containing mesopore container
Oxygen coating.
2. the self-healing mould assembly epoxy coating based on the mesoporous container of micron order according to claim 1, its feature
It is, it is preferred that by mass percentage that component one is formulated by following component and quality proportioning：Epoxy
The scope of resin is 65%~75%, and the scope of mesoporous container is 1%~5%, the scope of organic solvent for 20%~
30%, it is 1%~3% that auxiliary agent encloses.
3. the self-healing mould assembly epoxy coating based on the mesoporous container of micron order according to claim 1, its feature
It is that the mesoporous material that mesoporous container is used is micron-sized mesoporous silicon oxide, mesoporous TiO 2, mesoporous
Carborundum, mesoporous cerium oxide or mesoporous carbon.
4. the self-healing mould assembly epoxy coating based on the mesoporous container of micron order according to claim 1, its feature
It is that epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin, and curing agent is amine curing agent.
5. the self-healing mould assembly epoxy coating based on the mesoporous container of micron order according to claim 1, its feature
It is that the preparation process of mesoporous container is as follows：
(1) organic corrosion inhibitor is scattered in water, the aqueous solution of ethanol or ethanol, then by mesoporous material
Add and be dispersed in above-mentioned solution, form mixed liquor；In the mixed liquor, by mass percentage,
Mesoporous material accounts for 1~10%, and organic corrosion inhibitor accounts for 0.1~10%, remaining be water, the aqueous solution of ethanol or
Ethanol；
(2) at ambient temperature, the mixed liquor that step (1) is obtained is vacuumized, makes organic corrosion inhibitor
Into in mesoporous material；The mesoporous material after load organic corrosion inhibitor is filtered out, is repeated to disperse and is taken out
Vacuum 3~4 times, the amount made into the organic corrosion inhibitor in mesoporous material reaches maximization, mesoporous material with
The mass ratio of organic corrosion inhibitor is 1:1~10:1；
(3) the mixed liquor filtering for obtaining step (2), obtains loading the mesoporous material of organic corrosion inhibitor；
(4) based on the characteristic that mesoporous material is electrically charged, the load organic corrosion inhibitor that step (3) is obtained
Mesoporous material be dispersed in the polyelectrolyte solution with opposite charges of 1~5g/L, with shaking table mix 15~
30min, obtains mixed liquor；
(5) the mixed liquor micro-filtrate membrane filtration for obtaining step (4), washing, it is unnecessary with electric charge to remove
Polyelectrolyte, obtain coat individual layer polyelectrolyte mesoporous material；
(6) mesoporous material that electric charge is carried after the cladding polyelectrolyte for again obtaining step (5) is distributed to 1~
In the polyelectrolyte solution with opposite charges of 5g/L, repeat and cladding first time polyelectrolyte identical step
Suddenly, that is, obtain coating the mesoporous container of double-deck polyelectrolyte film.
6. the self-healing mould assembly epoxy coating based on the mesoporous container of micron order according to claim 5, its feature
It is that in the preparation process of mesoporous container, organic corrosion inhibitor is 8-hydroxyquinoline, BTA, mercapto
One kind in base benzothiazole, methyl benzotriazazole, imidazoline；Polyelectrolyte is polyacrylic acid, polyethylene
Two kinds in imines, kayexalate, PAH, diallyl dimethyl ammoniumchloride
The combination of oppositely charged；The solvent that polyelectrolyte is used is water.
7. the preparation side of the self-healing mould assembly epoxy coating based on the mesoporous container of micron order described in a kind of claim 1
Method, it is characterised in that comprise the following steps that：
1) epoxy resin, organic solvent, auxiliary agent are added in a reservoir, using 400~500rpm of high speed dispersor
Dispersion 10~20 minutes, adds mesoporous container, continues to be disperseed with 800~1500rpm of high speed centrifugation dispersion machine
10~30 minutes；
2) step 1) material that obtains ball mill grinding 4~8 hours, test fineness reach 20 μm with
Under, discharging, filtering obtains component one；
3) curing agent is added in organic solvent and is diluted, using 4000~5000rpm of high speed dispersor
Dispersion 5~20 minutes, discharging, obtains component two；
4) component two is added in component one, is mixing uniformly to form self-healing mould assembly epoxy coating.
8. the application of the self-healing mould assembly epoxy coating based on the mesoporous container of micron order described in a kind of claim 1,
Characterized in that, by self-healing mould assembly epoxy coating through spraying, brushing or dip-coating in metal base：Aluminium alloy, magnesium
Alloy, steel or surface of galvanized steel, normal temperature or heating cure, form self-healing mould assembly epoxy coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510845987.1A CN106810993B (en) | 2015-11-27 | 2015-11-27 | Self-healing type epoxy coating and its preparation and application based on the mesoporous container of micron order |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510845987.1A CN106810993B (en) | 2015-11-27 | 2015-11-27 | Self-healing type epoxy coating and its preparation and application based on the mesoporous container of micron order |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106810993A true CN106810993A (en) | 2017-06-09 |
| CN106810993B CN106810993B (en) | 2019-10-22 |
Family
ID=59103001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510845987.1A Active CN106810993B (en) | 2015-11-27 | 2015-11-27 | Self-healing type epoxy coating and its preparation and application based on the mesoporous container of micron order |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106810993B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107991181A (en) * | 2017-11-09 | 2018-05-04 | 大连理工大学 | A kind of breaked self-healing method of carborundum amorphous nanometer wire |
| CN108912960A (en) * | 2018-07-10 | 2018-11-30 | 山东格物新材料科技有限公司 | A kind of selfreparing anticorrosive paint |
| WO2019034915A1 (en) * | 2017-08-17 | 2019-02-21 | Khalifa University of Science and Technology | Mesoporous carbon based nanocontainer coatings for corrosion protection of metal structures |
| CN111205745A (en) * | 2020-01-09 | 2020-05-29 | 厦门双瑞船舶涂料有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN111234566A (en) * | 2020-01-22 | 2020-06-05 | 湖南大学 | Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating |
| CN112144287A (en) * | 2020-09-28 | 2020-12-29 | 江南大学 | Method for preparing super-smooth antifouling surface by grafting modified hollow microsphere with lubricating oil |
| CN112280419A (en) * | 2019-07-25 | 2021-01-29 | 天津大学 | Intelligent epoxy coating containing halloysite nanotube loaded 8-hydroxyquinoline and preparation method and application thereof |
| CN112646451A (en) * | 2020-12-08 | 2021-04-13 | 沈阳化工大学 | Hierarchical-pore nano-zeolite modified epoxy ceramic coating |
| CN113337210A (en) * | 2021-05-28 | 2021-09-03 | 上海应用技术大学 | Corrosion inhibitor-loaded pH-responsive silicon dioxide nano container composite silane film and preparation and application thereof |
| CN114213940A (en) * | 2022-01-27 | 2022-03-22 | 广德辉龙环保科技有限公司 | Coating for protecting surfaces of rhombic bag cages |
| CN114539870A (en) * | 2022-01-06 | 2022-05-27 | 内江师范学院 | Self-healing coating based on covalent organic framework material and preparation method thereof |
| CN114716890A (en) * | 2022-01-12 | 2022-07-08 | 南京大学 | Preparation method of self-healing coating taking overdue drug cefalexin as corrosion inhibitor |
| CN115637071A (en) * | 2022-10-19 | 2023-01-24 | 武汉材料保护研究所有限公司 | Titanium dioxide micro-nano container, corrosion-resistant water-based epoxy coating and preparation method |
| CN115651533A (en) * | 2022-11-02 | 2023-01-31 | 佛山科学技术学院 | Super-hydrophobic self-repairing silane coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
| CN103980802A (en) * | 2014-05-22 | 2014-08-13 | 国家电网公司 | Self-repair epoxy residual rust paint and preparation method thereof |
| CN104927583A (en) * | 2015-07-06 | 2015-09-23 | 江苏固格澜栅防护设施有限公司 | Preparation method and application of intelligent anti-corrosion coating capable of being automatically repaired |
-
2015
- 2015-11-27 CN CN201510845987.1A patent/CN106810993B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
| CN103980802A (en) * | 2014-05-22 | 2014-08-13 | 国家电网公司 | Self-repair epoxy residual rust paint and preparation method thereof |
| CN104927583A (en) * | 2015-07-06 | 2015-09-23 | 江苏固格澜栅防护设施有限公司 | Preparation method and application of intelligent anti-corrosion coating capable of being automatically repaired |
Non-Patent Citations (1)
| Title |
|---|
| MINGDONG WANG,ET AL: "An intelligent anticorrosion coating based on pH-responsive smart nanocontainers fabricated via a facile method for protection of carbon steel", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019034915A1 (en) * | 2017-08-17 | 2019-02-21 | Khalifa University of Science and Technology | Mesoporous carbon based nanocontainer coatings for corrosion protection of metal structures |
| CN111247214A (en) * | 2017-08-17 | 2020-06-05 | 哈里发科学技术大学 | Mesoporous carbon-based nanocontainer coating for corrosion protection of metal structures |
| US11859104B2 (en) | 2017-08-17 | 2024-01-02 | Khalifa University of Science and Technology | Mesoporous carbon based nanocontainer coatings for corrosion protection of metal structures |
| CN107991181A (en) * | 2017-11-09 | 2018-05-04 | 大连理工大学 | A kind of breaked self-healing method of carborundum amorphous nanometer wire |
| CN108912960A (en) * | 2018-07-10 | 2018-11-30 | 山东格物新材料科技有限公司 | A kind of selfreparing anticorrosive paint |
| CN112280419A (en) * | 2019-07-25 | 2021-01-29 | 天津大学 | Intelligent epoxy coating containing halloysite nanotube loaded 8-hydroxyquinoline and preparation method and application thereof |
| CN111205745A (en) * | 2020-01-09 | 2020-05-29 | 厦门双瑞船舶涂料有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN111234566A (en) * | 2020-01-22 | 2020-06-05 | 湖南大学 | Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating |
| CN111234566B (en) * | 2020-01-22 | 2021-04-20 | 湖南大学 | Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating |
| CN112144287B (en) * | 2020-09-28 | 2021-09-28 | 江南大学 | Method for preparing super-smooth antifouling surface by grafting modified hollow microsphere with lubricating oil |
| CN112144287A (en) * | 2020-09-28 | 2020-12-29 | 江南大学 | Method for preparing super-smooth antifouling surface by grafting modified hollow microsphere with lubricating oil |
| CN112646451A (en) * | 2020-12-08 | 2021-04-13 | 沈阳化工大学 | Hierarchical-pore nano-zeolite modified epoxy ceramic coating |
| CN113337210A (en) * | 2021-05-28 | 2021-09-03 | 上海应用技术大学 | Corrosion inhibitor-loaded pH-responsive silicon dioxide nano container composite silane film and preparation and application thereof |
| CN114539870A (en) * | 2022-01-06 | 2022-05-27 | 内江师范学院 | Self-healing coating based on covalent organic framework material and preparation method thereof |
| CN114716890A (en) * | 2022-01-12 | 2022-07-08 | 南京大学 | Preparation method of self-healing coating taking overdue drug cefalexin as corrosion inhibitor |
| CN114213940A (en) * | 2022-01-27 | 2022-03-22 | 广德辉龙环保科技有限公司 | Coating for protecting surfaces of rhombic bag cages |
| CN115637071A (en) * | 2022-10-19 | 2023-01-24 | 武汉材料保护研究所有限公司 | Titanium dioxide micro-nano container, corrosion-resistant water-based epoxy coating and preparation method |
| CN115637071B (en) * | 2022-10-19 | 2024-01-23 | 中国机械总院集团武汉材料保护研究所有限公司 | Titanium dioxide micro-nano container, corrosion-resistant water-based epoxy paint and preparation method |
| CN115651533A (en) * | 2022-11-02 | 2023-01-31 | 佛山科学技术学院 | Super-hydrophobic self-repairing silane coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106810993B (en) | 2019-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106810993A (en) | Self-healing mould assembly epoxy coating and its preparation and application based on the mesoporous container of micron order | |
| CN105440884B (en) | A kind of preparation and application of aqueous epoxy resins selfreparing erosion shield | |
| CN102942835B (en) | A kind of high throwing power cathode electrophoresis dope and preparation method thereof and using method | |
| CN108192472B (en) | Polyaniline grafted graphene oxide water-based epoxy zinc-rich primer and preparation method thereof | |
| CN104630749A (en) | Corrosion-resistant self-assembled doped film layer on aluminum alloy surface and preparation method of corrosion-resistant self-assembled doped film layer | |
| CN103555137B (en) | Doped polyaniline-epoxy-zinc powder composite coating and preparation method thereof | |
| CN105038440A (en) | Polytetrafluoroethylene modified chromium-free Dacromet paint and preparation method of composite coating thereof | |
| CN113088162B (en) | Wear-resistant epoxy resin coating and preparation method thereof | |
| CN111822296A (en) | Preparation method of super-hydrophobic composite coating on surface of aluminum alloy | |
| WO2022141935A1 (en) | Steel bar corrosion-resistant coating for marine concrete and preparation method therefor | |
| CN104817929B (en) | A kind of track traffic water-base epoxy dual-component coating and preparation method thereof | |
| CN103469286B (en) | A kind of metal surface Organic-inorganic composite coating and preparation technology thereof | |
| CN105820706B (en) | A kind of power transmission and transforming equipment high-performance nano anticorrosive paint and preparation method thereof | |
| CN115044279B (en) | Two-dimensional polydopamine reinforced waterborne epoxy composite anticorrosive paint and preparation method and application thereof | |
| CN106128744B (en) | A kind of Sintered NdFeB magnet surface temporary protection organic coating and preparation method | |
| CN114106608A (en) | Low-VOC (volatile organic compound) water-based two-component epoxy zinc-rich coating and preparation method thereof | |
| CN110885617A (en) | Rust conversion coating and preparation method thereof | |
| CN112680056A (en) | Anticorrosive paint and preparation method and application thereof | |
| CN109608983A (en) | A kind of anticorrosive coating and preparation method thereof for underground petroleum storage tank | |
| CN114276707A (en) | Water-based graphene zinc powder anticorrosive paint and preparation method thereof | |
| CN108912960A (en) | A kind of selfreparing anticorrosive paint | |
| CN103805027B (en) | A kind of zinc rich primer and preparation method thereof | |
| CN112852262A (en) | Lignocellulose-containing anti-corrosion self-repairing coating and preparation method thereof | |
| CN116970295A (en) | Corrosion-resistant phosphate composite coating with 'brick-mud' layered structure and preparation method and application thereof | |
| CN111247214A (en) | Mesoporous carbon-based nanocontainer coating for corrosion protection of metal structures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |