CN109679394A - A kind of preparation method of the sol-gel coating with corrosion monitoring function - Google Patents
A kind of preparation method of the sol-gel coating with corrosion monitoring function Download PDFInfo
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- CN109679394A CN109679394A CN201811617348.XA CN201811617348A CN109679394A CN 109679394 A CN109679394 A CN 109679394A CN 201811617348 A CN201811617348 A CN 201811617348A CN 109679394 A CN109679394 A CN 109679394A
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- salicylide
- corrosion monitoring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
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Abstract
The invention discloses the preparation methods that one kind can monitor the hybrid collosol gel film layer of aluminum alloy surface corrosion, and for this method using zirconium-n-propylate as presoma, dehydrated alcohol prepares zirconium colloidal sol as complexing agent as solvent, ethyl acetoacetate；Using silane coupling agent as presoma, as solvent, salicylide prepares the silica solution containing additive as corrosion monitoring substance for deionized water and dehydrated alcohol；By mixing two kinds of sol solutions, and nitric acid solution is added and adjusts pH, obtains mixed sols；After aluminium alloy carries out pre-treatment, mixed sols is immersed using dip-coating method and carries out film, is then repeatedly heat-treated under conditions of 60 DEG C, 90 DEG C, 110 DEG C in an oven, obtains the transparent hybrid collosol gel film layer with corrosion monitoring function.The present invention is using salicylide as fluorescer and provides suitable colloidal sol formula of liquid, so that the addition concentration of salicylide is in a very big range, therefore can adjust the addition concentration of salicylide according to demand.
Description
Technical field
The present invention relates to a kind of preparation methods of sol-gel coating with corrosion monitoring function, in particular to are corroding
The preparation method that the sol-gel coating of the corrosion monitoring function of aluminium alloy can be achieved under environment, belongs to function protecting coating material
Field.
Background technique
In a corrosive environment, aluminium alloy can corrode, therefore protect frequently with various corrosion protection means to it, often
The corrosion protection technology seen has plating, anodic oxidation, coating technology etc..Sol-gel coating is combined with paint film is enhanced significantly
The characteristic of power and green non-pollution is commonly used for the protection of aluminium alloy.And for sol-gel coating, suitable alcohol water when has
The ratio of machine inorganic constituents is particularly significant for the performance of coating, such as stability, the protective performance of coating of sol solutions.
When aluminium alloy corrodes, often occur in the form of spot corrosion, concealment is strong, harmfulness is big, therefore corrodes to it
Journey, which is monitored, to be extremely important.According to the difference of corrosion monitoring mechanism, currently used corrosion monitoring technology has
Physical monitoring technology, electrochemical monitoring technology and chemical monitoring technology.Fluorescence intelligent predicting technology is chemical monitoring technology
One kind.This technique functions derived from twentieth century end the U.S. and Canadian Navy, after the development of more than two decades, at present at
For a kind of very high corrosion monitoring technology of feasibility.Compared with traditional corrosion monitoring technology, fluorescence intelligent predicting technology, which has, to be seen
The advantages that surveying simple, high sensitivity and timeliness, increasingly by the attention of researcher.
In fluorescence Study On Intelligent Monitoring Techniques field, selects suitable fluorescer and its suitable addition concentration is the weight of research
Point.Mechanism is classified according to response, and fluorescer can be divided into metal ion response type fluorescer and pH response type fluorescer.With aluminium alloy
For, when aluminium alloy corrodes, anode can generate Al3+, OH can occur for cathode-Aggregation, by add to Al3+It is sensitive or right
The sensitive fluorescer of pH variation, can realize the monitoring to corrosion of aluminium alloy process.And classified according to fluorescence phenomenon, fluorescer can
It is divided into fluorescence generation type and fluorescent quenching type.In comparison, after corroding, fluorescent quenching can occur for fluorescent quenching type fluorescer
The phenomenon that, and fluorescence generation type fluorescer can also hold corrosion according to the variation of subsequent fluorescence intensity after generating fluorescence
Continuous monitoring, therefore fluorescence generation type fluorescer is often selected under study for action.
Further, improperly coating formula will lead to fluorescer and just react before corrosion with the component in coating,
Cause the failure of fluorescer corrosion monitoring function；In addition, the addition concentration of fluorescer can also significantly affect the sensitive of fluorescence monitoring
Property, low fluorescer concentration often makes fluorescence phenomenon unobvious, and high concentration fluorescer will lead to the crosslinking of coating itself
Degree reduces, and influences the protective performance of coating.
Salicylide, also referred to as salicylaldhyde, Benzaldehyde,2-hydroxy, molecular formula C6H4CHO-2-OH is colourless at room temperature
Oily liquids is often used as corrosion inhibiter in the research of field of corrosion prevention.Salicylide is to Al3+It is very sensitive, with Al3+Chelating
After can generate fluorescence.Therefore, the present invention is quasi- selects salicylide as fluorescer, passes through itself and Al3+Chelation with monitor because
The Al of corrosion and generation3+, and then realize the corrosion monitoring to alloy matrix aluminum.
To sum up, using salicylide as fluorescer, suitable addition concentration is selected, in conjunction with suitable colloidal sol formula of liquid and passes through conjunction
Suitable coating method and subsequent heat treatment technique, prepares a kind of sol-gel coating of corrosion monitoring function, is supervised by its corrosion
Brake can find the hot spot on alloy matrix aluminum in time, make counter-measure.
Summary of the invention
The present invention is intended to provide a kind of use salicylide to have corrosion prison as fluorescer, in conjunction with sol-gel technique preparation
The method of the sol-gel coating of brake.
Technical scheme is as follows:
Sol-gel coating prepared by the present invention has the function of corrosion monitoring, wherein being tried using salicylide as corrosion monitoring
Agent is prepared using dip coating.
The present invention utilizes sol-gel technique, makes to apply layer function by dip-coating method film, and by the way that salicylide is added
Change, by the alcohol water ratio of suitable sol solutions, silicon zirconium ratio etc., stablize the salicylide of a certain concentration range can in sol solutions and deposit
, and the sol-gel coating with corrosion monitoring function is obtained by suitable heat treatment process.
Preparation process of the invention the following steps are included:
(1) using zirconium-n-propylate as presoma, dehydrated alcohol is being stirred as solvent, ethyl acetoacetate as complexing agent
Under the conditions of prepare zirconium colloidal sol；
(2) using silane coupling agent as presoma, deionized water and dehydrated alcohol are as solvent, and salicylide is as corrosion monitoring
Substance, concentration 2.5mM-10mM prepare the silica solution of the substance containing corrosion monitoring under stirring conditions；
(3) the two kinds of colloidal sols prepared in step (1) and step (2) are mixed under stirring conditions, and nitric acid tune is added
PH is saved between 3.5-4.5, wherein volume ratio of alcohol to water is 2~3 in mixed sol solutions, silicon zirconium volume ratio is 2~6, and silicon
The volume ratio of alkane and solvent is 0.1~1；
(4) aluminum alloy specimen is subjected to first time film using dip-coating method, after standing 15 minutes in air, carries out two
Secondary film stands 30 minutes in air；
(5) sample after film obtained in (4) is heated in 60 DEG C and heats within 1 hour, 90 DEG C 30 minutes, 110 DEG C of heating 15
Minute, room temperature is cooling, obtains flat transparent zero defect coating.
The present invention has the advantages that having selected a kind of new fluorescer, i.e. salicylide, and when molten by suitable alcohol water
Glue formula be stabilized the salicylide of very big concentration range can in sol solutions, be had by suitable heat treatment process
There is the sol-gel coating of corrosion monitoring function.
Detailed description of the invention
Fig. 1: sol solutions optical photograph before film；
Fig. 2: it is the surface topography that 5mM heat treatment is observed by stereomicroscope (× 21) later that salicylide, which adds concentration,；
Phosphor dot photo after Fig. 3: 3 days immersion tests.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is described in further detail.
Embodiment 1
(1) 22mL dehydrated alcohol is added into the anhydrous beaker of drying, 13mL ethyl acetoacetate delays under agitation
It is slow that 19mL zirconium-n-propylate is added, about 30min is stirred at room temperature and prepares zirconium colloidal sol；
(2) using 50mL dehydrated alcohol as solvent, 2.5mM salicylide is added, is stirring evenly and then adding into 26ml deionized water,
42mL silane coupling agent is added under agitation can must contain the silica solution of corrosion monitoring substance after stirring 30 minutes；
(3) two kinds of colloidal sols prepared by step (1) and (2) are mixed under agitation, and with nitric acid tune pH to 3.5；
(4) aluminum alloy specimen is subjected to first time film using dip-coating method, after standing 15 minutes in air, carries out two
Secondary film stands 30 minutes in air；
(5) film sample obtained in (4) is heated 1 hour in 60 DEG C, 90 DEG C are heated 30 minutes, and 110 DEG C are heated 15 points
Clock, room temperature is cooling, obtains flat transparent zero defect coating.
Embodiment 2
(1) 24mL dehydrated alcohol is added into the anhydrous beaker of drying, 16mL ethyl acetoacetate delays under agitation
It is slow that 20mL zirconium-n-propylate is added, about 30min is stirred at room temperature and prepares zirconium colloidal sol；
(2) using 56mL dehydrated alcohol as solvent, 5mM salicylide is added, is stirring evenly and then adding into 26ml deionized water,
52mL silane coupling agent is added under stirring condition can must contain the silica solution of corrosion monitoring substance after stirring 30 minutes；
(3) two kinds of colloidal sols prepared by step (1) and (2) are mixed under agitation, and with nitric acid tune pH to 4；
(4) aluminum alloy specimen is subjected to first time film using dip-coating method, after standing 15 minutes in air, carries out two
Secondary film stands 30 minutes in air；
(5) film sample obtained in (4) is heated 1 hour in 60 DEG C, 90 DEG C are heated 30 minutes, and 110 DEG C are heated 15 points
Clock, room temperature is cooling, obtains flat transparent zero defect coating.
Embodiment 3
(1) 15mL dehydrated alcohol is added into the anhydrous beaker of drying, 10mL ethyl acetoacetate delays under agitation
It is slow that 10mL zirconium-n-propylate is added, about 30min is stirred at room temperature and prepares zirconium colloidal sol；
(2) using 60mL dehydrated alcohol as solvent, 10mM salicylide is added, is stirring evenly and then adding into 26ml deionized water,
60mL silane coupling agent is added under agitation can must contain the silica solution of corrosion monitoring substance after stirring 30 minutes；
(3) two kinds of colloidal sols prepared by step (1) and (2) are mixed under agitation, and with nitric acid tune pH to 4.5；
(4) aluminum alloy specimen is subjected to first time film using dip-coating method, after standing 15 minutes in air, carries out two
Secondary film stands 30 minutes in air；
(5) film sample obtained in (4) is heated 1 hour in 60 DEG C, 90 DEG C are heated 30 minutes, and 110 DEG C are heated 15 points
Clock, room temperature is cooling, obtains flat transparent zero defect coating.
Claims (3)
1. a kind of preparation method of the sol-gel coating with corrosion monitoring function, which is characterized in that include the following steps:
(1) using zirconium-n-propylate as presoma, dehydrated alcohol is as solvent, and ethyl acetoacetate is as complexing agent, in the item of stirring
Zirconium colloidal sol is prepared under part；
(2) using silane coupling agent as presoma, deionized water and dehydrated alcohol are as solvent, and salicylide is as corrosion monitoring object
Matter prepares the silica solution of the substance containing corrosion monitoring under stirring conditions；
(3) the two kinds of colloidal sols prepared in step (1) and step (2) are mixed under stirring conditions, and it is molten that nitric acid adjusting is added
The pH of glue is between 3.5-4.5；
(4) aluminum alloy specimen is subjected to first time film using dip-coating method, after standing 15 minutes in air, then carried out secondary
Film stands 30 minutes in air；
(5) sample after film obtained in (4) is heated 1 hour in 60 DEG C, 90 DEG C are heated 30 minutes, and 110 DEG C are heated 15 minutes
Heat treatment, room temperature is cooling, obtains the flawless coating of flat transparent.
2. preparation method as described in claim 1, which is characterized in that salicylide is molten as corrosion monitoring substance in step (2)
For solution in dehydrated alcohol, addition concentration is 2.5mM~10mM.
3. preparation method as described in claim 1, which is characterized in that alcohol water volume in mixed sol solutions in step (3)
Than being 2~3, silicon zirconium volume ratio is 2~6, and the volume ratio of silane and solvent is 0.1~1.
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| CN201811617348.XA CN109679394A (en) | 2018-12-28 | 2018-12-28 | A kind of preparation method of the sol-gel coating with corrosion monitoring function |
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| CN201811617348.XA CN109679394A (en) | 2018-12-28 | 2018-12-28 | A kind of preparation method of the sol-gel coating with corrosion monitoring function |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112742384A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Inorganic membrane catalyst, preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112742384A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Inorganic membrane catalyst, preparation method and application thereof |
| CN112742384B (en) * | 2019-10-31 | 2022-08-12 | 中国石油化工股份有限公司 | Inorganic membrane catalyst, preparation method and application thereof |
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