CN104559669A - Organic graphene anticorrosive paint applied to marine ship - Google Patents
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- CN104559669A CN104559669A CN201510010658.5A CN201510010658A CN104559669A CN 104559669 A CN104559669 A CN 104559669A CN 201510010658 A CN201510010658 A CN 201510010658A CN 104559669 A CN104559669 A CN 104559669A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with 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
- C09D115/00—Coating compositions based on rubber derivatives
- C09D115/02—Rubber derivatives containing halogen
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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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
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
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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
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
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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
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Abstract
The invention relates to an organic graphene anticorrosive paint applied to a marine ship. The organic graphene anticorrosive paint of the marine ship is prepared from the following steps: adding graphene to a single component of marine paint or two components of marine paint to be mutually mixed and stirred uniformly to form the novel anticorrosive paint; and brushing and coating the mixed anticorrosive paint on the surface of a sample and carrying out air drying to obtain a product brushed and coated by the novel marine anticorrosive paint. The preparation method is simple, the cost is low, and the obtained novel grapheme marine ship anticorrosive paint is proper in price, good in mechanical performance, simple in process, good in bioantifouling and preservative effect, long in service life and the like.
Description
Technical field
The present invention relates to a kind of Graphene organic anti-corrosive erosion coating, particularly a kind of Graphene organic anti-corrosive erosion coating being applied to marine ship.
Technical background
Earth surface about have the part of 71% cover by seawater, useful area be the 5-10 on land doubly, seafaring and marine industries have become current world economy and have developed indispensable mainstay.But ocean environment is very harsh corrosive environment, boats and ships are in such ocean environment for a long time, corrosion is extremely serious, and corrosion not only can reduce the intensity of ship steel structure, shortens ship's life, also can increase running resistance, reduce the speed of a ship or plane, affect ship performance and safety of navigation.Because corrosion causes structural failure and destruction, the property even loss of life are of common occurrence, can say that marine corrosion is one of maximum factor affecting its life-span.Corrosion failure or fracture not only cause the leakage of objectionable impurities, pollute environment, sometimes also can cause the catastrophic failure of burst, jeopardize the safety of the mankind.Concerning boats and ships, antiseptic and rustproof is one global problem perplexing people all the time.Pertinent data shows: the annual corrosion loss of China at least reaches several hundred billion yuans.Therefore, the anticorrosive work of boats and ships is very urgent.
The anticorrosion of current boats and ships generally smears marine paint to intercept contacting of seawater and boats and ships at hull and hull bottom, tradition coating for watercraft is due to the restriction by own material character and technique, fine and close not, the problems such as water proof anti-seepage permeability is bad, and poor adhesive force, sea water resistance, protecting against shock are bad.Not satisfactory to the corrosion prevention effect of matrix metal, and have quite a few coating because of harmful toxic matters such as leaded or chromic salt, in preparation and use procedure, there is the danger of contaminate environment, the requirement of this and Sustainable Socioeconomic Development strategy is incompatible.
Graphene is chemically inert material, can protecting group bottom material from the impact of violent chemical reaction.The antibacterial of Graphene, resistance of oxidation, excellent to the barrier property of corrosive medium, so add the characteristic that appropriate Graphene effectively can utilize Graphene in anti-corrosive organic coatings, improve the corrosion resisting property of matrix metal.
Chinese patent notification number CN103589282A, date of publication on February 19th, 2014, name marine anticorrosion anti-pollution paint being called a kind of graphene-containing and preparation method thereof, this application case discloses one and add in epoxy resin Graphene as marine anticorrosion anti-pollution paint to, compound is carried out by Graphene and epoxy resin, the anti-microbial property of Graphene and the antiseptic property of epoxy resin are organically combined, develops with this novel anti-pollution paint having protection against corrosion and antifouling property concurrently.Its weak point is, do not fully take into account the popularity of marine finish kind and the complicacy of component, only select epoxypaint to show slightly not enough, have that bioantifouling preservative effect is not good, expensive, seriously polluted, the defect of complex process and high cost.
Summary of the invention
The object of the invention is to overcome problems of the prior art, a kind of Graphene organic anti-corrosive erosion coating being applied to marine ship is provided.
Through long-term research find Graphene be carbon atom tightly packed individual layer two dimension laminated structure a kind of carbonaceous novel material.Graphene has small-size effect, in the hole that can be filled into anticorrosive coating and defect, thus delays even to stop small molecules corrosive medium to enter metallic matrix, has good physical isolation preservative activity.In addition, the surface effects of Graphene makes it very large with the contact angle of water, very poor to the wetting property of water, therefore has good water-repellancy, and in seawater corrosion prevention, isolation action is obvious.And because Graphene is not perfectly laminar structured, there is more defect, the degree of order is poor, and its defect makes it more easily can be combined with coating, thus improve the bonding force of coating.After contriver finds Graphene and marine ship anti-corrosive organic coatings to be uniformly mixed according to a best mass ratio, mixture formation novel sea boats and ships protective system, can brush at specimen surface.
For achieving the above object, the present invention adopts following technical scheme:
Be applied to a Graphene organic anti-corrosive erosion coating for marine ship, with single-component marine paint for priming paint, it is characterized in that in described single-component marine paint by single-component marine paint: Graphene=1000:(0.1 ~ 6) quality than Uniform Doped Graphene.
Above-mentioned single-component marine paint is: the yellow chlorinated rubber antiseptic finish paint of lead red alcohol acid paint, iron red alcohol acid paint, epoxy resin-based paint or lemon.
A kind of Graphene organic anti-corrosive erosion coating being applied to marine ship, with two component marine paint for priming paint, to it is characterized in that in the grease paint part of described two component marine paints by grease paint: Graphene: powder additive=800: 200:(0.1 ~ 6) quality than Uniform Doped Graphene and powder additive.
Above-mentioned two component marine paints are epoxy zinc rich primer or bituminous varnish.
Above-mentioned powder additive is at least one in titanium valve, silica flour, zinc powder, silver powder, aluminium powder.
Described Graphene marine ship anti-corrosive organic coatings can be applied in the marine anticorrosion erosion aspect of marine surface.The present invention compared with prior art has following beneficial effect: the novel graphite alkene boats and ships anti-corrosive organic coatings prepared of the present invention compensate for traditional coating for watercraft in prior art due to the restriction by own material character and technique, fine and close not, water proof anti-seepage permeability is bad, the problems such as poor adhesive force, sea water resistance, protecting against shock are bad, contaminate environment., the former patent achievement is improved meanwhile, fully take into account the popularity of marine finish kind and the complicacy of component.
Accompanying drawing explanation
Fig. 1 to be Fe be substrate sea-water corrosion is after 62 days, the digit microscope figure of common double component epoxy zinc rich primer anti-corrosive organic coatings.
Fig. 2 to be Fe be substrate sea-water corrosion is after 62 days, the digit microscope figure of the two component epoxy zinc rich primer anti-corrosive organic coatings of Graphene modification.
Fig. 3 to be Fe be substrate sea-water corrosion is after 25 days, the scanning electronic microscope SEM figure of common lead red alcohol acid anti-corrosive organic coatings.
Fig. 4 to be Fe be substrate sea-water corrosion is after 25 days, the scanning electronic microscope SEM figure of the lead red alcohol acid anti-corrosive organic coatings of Graphene modification.
Fig. 5 is Fe is under substrate corrosive environment of sea water, the polarization curve of the lead red alcohol acid anti-corrosive organic coatings of common lead red alcohol acid anti-corrosive organic coatings and Graphene modification.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Comparative example 1:
Utilize cut mechanically that Fe sheet is processed into the square coupons of 10mm × 10mm × 1mm.Polish to No. 4 step by step with SiC silicon carbide paper, then deionized water and alcohol washes is used successively, and inlay sample with XQ-2B metallic phase sample inlaying machine, finally directly brush at the specimen surface inlayed the common double component epoxy zinc rich primer anti-corrosive organic coatings that one deck mixes.Carry out chemical immersion after air-dry, under 3.5wt% NaCl solution environment, place sample 62 days (simulated marine corrosion environment), after experiment terminates, take out sample, utilize VHX-100 digital micrograph sem observation coatingsurface situation.
Embodiment 1:
(1) Graphene additive is prepared: under the condition that ice bath cools and stirs, toward the dense H of 69ml
2sO
4in add 1.5gNaNO
3(grinding), waits NaNO
3be dissolved in H completely
2sO
4in after, by 3g graphite limit stir just add wherein.Then 9g KMnO is slowly added
4, add speed and strictly control, to ensure that temperature is lower than 20 DEG C, then removes ice bath, use water-bath and maintain the temperature at about 35 DEG C, being incubated 2 hours.Stir lower slowly (starting very slow) and add 137ml deionized water, system is fiercely warmed up to 98 DEG C, 15 minutes are kept afterwards with 98 DEG C of water-baths, then 420ml is diluted to further with warm (60 DEG C) deionized water, then add 30% hydrogen peroxide 11ml(refer to excessive) with potassium permanganate remaining in reduction system with for Manganse Dioxide, obtain glassy yellow system.Filtered while hot, then washs once with the hydrochloric acid soln that volume ratio is 1:10, washes three times.45 DEG C of dryings in an oven.By freshly prepd graphite oxide grind into powder, to ensure abundant expanded by heating, be progressively warming up to 200 DEG C, load in tube furnace, heating mouth of pipe place sealing (using glycerine oil sealing), thermopair with contact bottom heating tube to ensure that thermometric is accurate.After thermal expansion terminates, obtain Graphene.
(2) Graphene marine ship anti-corrosive organic coatings is prepared: joined by 10mg Graphene in 10g two component epoxy zinc rich primer anti-corrosive organic coatings, now 10mg Graphene and 8g grease paint are first mixed, the condition of sonic oscillation 30min(high-energy ultrasonic: the frequency of high-energy ultrasonic pulverization process is 40KHz, output power range is 100W), again 2g zinc powder additive is poured into and wherein stir, obtain the novel ship anti-corrosive organic coatings mixing more uniform Graphene modification.
Utilize cut mechanically that Fe sheet is processed into the square coupons of 10mm × 10mm × 1mm.Polish to No. 4 step by step with SiC silicon carbide paper, then deionized water and alcohol washes is used successively, and inlay sample with XQ-2B metallic phase sample inlaying machine, the novel ship anti-corrosive organic coatings of the Graphene modification that one deck mixes finally directly is brushed at the specimen surface inlayed.Carry out chemical immersion after air-dry, under 3.5wt% NaCl solution environment, place sample 62 days (simulated marine corrosion environment), after experiment terminates, take out sample, utilize VHX-100 digital micrograph sem observation coatingsurface situation.
Fig. 1 and Fig. 2 sets forth the substrate surface corrosion area situation of sea-water corrosion after 62 days when comparative example 1 and embodiment 1 take Fe as substrate.Contrasted from Fig. 1 and Fig. 2, Graphene boats and ships organic anti-corrosive coating more common marine ship of substrate surface corrosion condition after sea-water corrosion for some time has base corrosion protection coating slight, and surface corrosion is not serious.
Comparative example 2:
Utilize cut mechanically that Fe sheet is processed into the square coupons of 10mm × 10mm × 1mm.Polish to No. 4 step by step with SiC silicon carbide paper, then use deionized water and alcohol washes successively, prepare electrochemical sample and chemical immersion sample respectively, finally directly brush one deck common lead red alcohol acid boats and ships anti-corrosive organic coatings at the specimen surface prepared.Air-dry rear portion carries out chemical immersion, sample is placed 25 days (simulated marine corrosion environment) under 3.5wt% NaCl solution environment, after experiment terminates, take out sample, utilize HITACHI SU-1500 tungsten filament sem observation coatingsurface situation; A part carries out electrochemistry experiment, soaks sample (simulated marine corrosion environment), utilize HCP-803 electrochemical workstation to record polarization curve under 3.5wt% NaCl solution environment.
Embodiment 2:
(1) Graphene additive is prepared: under the condition that ice bath cools and stirs, toward the dense H of 69ml
2sO
4in add 1.5gNaNO
3(grinding), waits NaNO
3be dissolved in H completely
2sO
4in after, by 3g graphite limit stir just add wherein.Then 9g KMnO is slowly added
4, add speed and strictly control, to ensure that temperature is lower than 20 DEG C, then removes ice bath, use water-bath and maintain the temperature at about 35 DEG C, being incubated 2 hours.Stir lower slowly (starting very slow) and add 137ml deionized water, system is fiercely warmed up to 98 DEG C, 15 minutes are kept afterwards with 98 DEG C of water-baths, then 420ml is diluted to further with warm (60 DEG C) deionized water, then add 30% hydrogen peroxide 11ml(refer to excessive) with potassium permanganate remaining in reduction system with for Manganse Dioxide, obtain glassy yellow system.Filtered while hot, then washs once with the hydrochloric acid soln that volume ratio is 1:10, washes three times.45 DEG C of dryings in an oven.By freshly prepd graphite oxide grind into powder, to ensure abundant expanded by heating, be progressively warming up to 200 DEG C, load in tube furnace, heating mouth of pipe place sealing (using glycerine oil sealing), thermopair with contact bottom heating tube to ensure that thermometric is accurate.After thermal expansion terminates, obtain Graphene.
(2) Graphene marine ship anti-corrosive organic coatings is prepared: joined by 10mg Graphene in 10g lead red alcohol acid paint coating, the condition of sonic oscillation 30min(high-energy ultrasonic: the frequency of high-energy ultrasonic pulverization process is 40KHz, output power range is 100W), obtain the novel ship anti-corrosive organic coatings mixing more uniform Graphene modification.
Utilize cut mechanically that Fe sheet is processed into the square coupons of 10mm × 10mm × 1mm.Polish to No. 4 step by step with SiC silicon carbide paper, then deionized water and alcohol washes is used successively, prepare electrochemical sample and chemical immersion sample respectively, finally directly brush the lead red alcohol acid boats and ships anti-corrosive organic coatings of a layer graphene modification at the specimen surface prepared.Air-dry rear portion carries out chemical immersion, sample is placed 25 days (simulated marine corrosion environment) under 3.5wt% NaCl solution environment, after experiment terminates, take out sample, utilize HITACHI SU-1500 tungsten filament sem observation coatingsurface situation; A part carries out electrochemistry experiment, soaks sample (simulated marine corrosion environment), utilize HCP-803 electrochemical workstation to record polarization curve under 3.5wt% NaCl solution environment.
Fig. 3 and Fig. 4 sets forth the substrate surface corrosion condition of sea-water corrosion after 25 days when comparative example 2 and embodiment 2 take Fe as substrate.Contrasted from Fig. 3 and Fig. 4, Graphene boats and ships organic anti-corrosive coating is substrate comparatively common ship organic anti-corrosive coating small area local corrosion after sea-water corrosion for some time, and substrate is more smooth, does not have obvious slight crack, corrodes not too obvious.
Fig. 5 sets forth the polarization curve of sea-water corrosion when comparative example 2 and embodiment 2 take Fe as substrate, is about 0.04uA/cm by the iron red alcohol acid lacquering corrosion current of the visible Graphene modification of upper figure
2, and common iron red alcohol acid lacquering corrosion current is about 0.4uA/cm
2, erosion rate obviously reduces by 9 times, has good erosion resistance.
Claims (5)
1. at a kind of Graphene organic anti-corrosive erosion coating being applied to marine ship, with single-component marine paint for priming paint, to it is characterized in that in described single-component marine paint by single-component marine paint: Graphene=1000:(0.1 ~ 6) quality than Uniform Doped Graphene.
2. the Graphene organic anti-corrosive erosion coating being applied to marine ship according to claim 1, is characterized in that described single-component marine paint is: the yellow chlorinated rubber antiseptic finish paint of lead red alcohol acid paint, iron red alcohol acid paint, epoxy resin-based paint or lemon.
3. one kind is applied to the Graphene organic anti-corrosive erosion coating of marine ship, with two component marine paint for priming paint, to it is characterized in that in the grease paint part of described two component marine paints by grease paint: Graphene: powder additive=800:200:(0.1 ~ 6) quality than Uniform Doped Graphene and powder additive.
4. the Graphene organic anti-corrosive erosion coating being applied to marine ship according to claim 3, is characterized in that described two component marine paints are epoxy zinc rich primer or bituminous varnish.
5. the Graphene organic anti-corrosive erosion coating being applied to marine ship according to claim 3, is characterized in that described powder additive is at least one in titanium valve, silica flour, zinc powder, silver powder, aluminium powder.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105086762A (en) * | 2015-08-22 | 2015-11-25 | 江苏万源新材料有限公司 | Aluminum-base graphene oily epoxy paint composite material and preparation method thereof |
| CN105363993A (en) * | 2015-10-21 | 2016-03-02 | 南京润屹电子科技有限公司 | Graphene enhanced cast-penetrated combination for test experimental equipment units and use method of graphene enhanced cast-penetrated combination |
| CN105713426A (en) * | 2016-04-19 | 2016-06-29 | 中山大学惠州研究院 | Method for preparing ocean anticorrosion coating |
| CN105838187A (en) * | 2016-04-23 | 2016-08-10 | 上海大学 | Ball milling preparation method and application of graphene oxide anticorrosive coating |
| CN105949828A (en) * | 2016-05-31 | 2016-09-21 | 无锡伊佩克科技有限公司 | Red lead antirust coating for steel and iron and preparation method of red lead antirust coating |
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| CN106752886A (en) * | 2016-12-05 | 2017-05-31 | 江西龙正科技发展有限公司 | A kind of marine ship Graphene anti-corrosive organic coatings |
| CN108250906A (en) * | 2018-01-24 | 2018-07-06 | 洛阳大豫实业有限公司 | A kind of watersoluble plumbago alkene coating and preparation method thereof |
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