CN106752933B - High density tungsten alloy wet-heat resisting anticorrosive paint - Google Patents
High density tungsten alloy wet-heat resisting anticorrosive paint Download PDFInfo
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- CN106752933B CN106752933B CN201611222943.4A CN201611222943A CN106752933B CN 106752933 B CN106752933 B CN 106752933B CN 201611222943 A CN201611222943 A CN 201611222943A CN 106752933 B CN106752933 B CN 106752933B
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
A kind of high density tungsten alloy wet-heat resisting anticorrosive paint, is made of priming paint and finishing coat, and the priming paint is made of isopropanol, softened water, silicon fluoride, acetic acid；The finishing coat is grouped as by first, second group, and wherein first component is made of epoxy resin, lemon yellow, titanium dioxide, talcum powder, kaolin, mica powder, dispersing agent, levelling agent, mixed solvent etc.；Component B is made of polyisocyanates, mixed solvent, catalyst.In use process, dip-coating processing first is carried out to tungsten alloy with priming paint, then carry out coating with finishing coat.By the high density tungsten alloy of anticorrosive coating, the requirement of long-time wet-heat resisting can satisfy, so that tungsten alloy be allow to be used for a long time in hygrothermal environment.
Description
Technical field
The present invention relates to anti-corrosion of metal fields, more particularly to a kind of high density tungsten alloy wet-heat resisting anticorrosive paint.
Background technique
High density tungsten alloy is a kind of powdered metallurgical material, has the characteristics such as high density, high intensity, low-expansion coefficient.Tungsten
Alloy material serves many purposes in aerospace and war industry, can be used to produce gyroscope, shrapnel, armor-piercing bullet,
The shielding material etc. of counterweight element and nuclear reactor in various instrument and engine.
It is influenced by powder metallurgical processing technique, high density tungsten alloy is a kind of porous material, is held in the natural environment
It is subject to corrode, especially in hygrothermal environment.Research shows that tungsten alloy is 24 hours in hygrothermal environment, surface can be corroded,
Black liquor is generated, post-etching obviously increases within 48 hours.For the antiseptic property for improving tungsten alloy, domestic currently used method with
Based on chemical plating, zinc-plated and nickel plating common are.But due to the porous particularity of tungsten alloy material itself, lead to base after plating
There is electroplating residual liquid in body material, is easy to corrode in hygrothermal environment.Meanwhile at micropore and the edge of tungsten alloy part plating
The anti-corrosion effect of layer is poor, this also cause tungsten alloy it is zinc-plated/antiseptic property of nickel material is well below common steel galvanization/nickel
Material.A plurality of commonly anticorrosive paints with excellent wet-hot aging performance are used for the coating of tungsten alloy, test its wet-heat resisting
Property, after 48 hours, coating surface blisters, and tungsten alloy generates corrosion, and these coating varieties all have on carbon steel base material
500 hours or more humidity resistances, existing coating products are not able to satisfy the requirement of shelter of tungsten alloy wet-heat resisting.
Summary of the invention
For the porous characteristic of high density tungsten alloy, the present inventor has developed a kind of hydrophobic that can be reacted with substrate
Property priming paint and the finishing coat with high-crosslinking-degree.In use process, dip-coating processing first carried out to tungsten alloy with priming paint, then with finishing coat into
Row coating.By the high density tungsten alloy of anticorrosive coating, the requirement of long-time wet-heat resisting can satisfy, to make tungsten alloy can be with
It is used for a long time in hygrothermal environment.
Present invention is generally directed to the requirement of shelter of high density tungsten alloy wet-heat resisting, have carried out the technical research of profession, preparation
A kind of etch primer with hydrophobicity and the finishing coat with high-crosslinking-degree.High density tungsten can be improved in the priming paint and finishing coat
The humidity resistance of alloy.
The high density tungsten alloy wet-heat resisting anticorrosive paint is made of priming paint and finishing coat.
The priming paint is made of isopropanol, softened water, silicon fluoride, acetic acid.
The finishing coat is grouped as by first, second group, and wherein first component is by epoxy resin, lemon yellow, titanium dioxide, talcum powder, height
The composition such as ridge soil, mica powder, dispersing agent, levelling agent, mixed solvent；Component B is by polyisocyanates, mixed solvent, catalyst group
At.
It is each in high density tungsten alloy wet-heat resisting anti-corrosion primer based on the gross mass of high density tungsten alloy wet-heat resisting anti-corrosion primer
The content of component are as follows:
The sum of each component content is 100%.
The silicon fluoride is the silicon fluoride that main chain has 8 or more carbon atoms.
Based on the gross mass of high density tungsten alloy wet-heat resisting antisepsis finishing paint first component, high density tungsten alloy wet-heat resisting anti-corrosion face
Paint the content of each component in first component are as follows:
The sum of each component content is 100%.
The epoxy resin is 607 resin of epoxy, any one or two kinds in 609 resin of epoxy with arbitrary proportion
Mixture.
The dispersing agent is at least one of BYK-110, BYK-104S.
The levelling agent is at least one of BYK-310, BYK-320.
The mixed solvent is at least one of cyclohexanone, acetone, butanone.
Based on the gross mass of high density tungsten alloy wet-heat resisting antisepsis finishing paint second component, high density tungsten alloy wet-heat resisting anti-corrosion face
The content of each component in Qi Yi component are as follows:
Polyisocyanates 84%~96%
Catalyst 0.06%~0.30%
Mixed solvent 5%~15%,
The sum of each component content is 100%.
The polyisocyanates is isocyanate compound of the degree of functionality 2 or more, NCO mass content 8%~
30%.
The catalyst is at least one of dibutyl tin dilaurate, stannous octoate, dibutyltin diacetate.
The mixed solvent is at least one of cyclohexanone, acetone, butanone, ethyl acetate, butyl acetate.
The preparation method of high density tungsten alloy wet-heat resisting anti-corrosion primer of the present invention, formula is stocked up as described above, work
Skill are as follows:
The mixed liquor of isopropanol and softened water is adjusted into pH value 5 or so with acetic acid, then heats to 55 DEG C ± 5 DEG C,
Under stirring, be slowly added to silicon fluoride within the used time 1 hour, after addition at this temperature insulation reaction 8 hours to get high density tungsten
Alloy wet-heat resisting anti-corrosion primer.
The preparation method of high density tungsten alloy wet-heat resisting antisepsis finishing paint of the present invention, formula is stocked up as described above, first
The preparation process of component are as follows:
(1) dissolution of epoxy resin.By etc. quality mixed solvent and epoxy resin be added to the container, be warming up to reflux shape
State, stirring and dissolving epoxy resin.Continue stirring 1 hour to after being uniformly dissolved, epoxy resin solution is made.
(2) component A is prepared.Dispersing agent, levelling agent, lemon are sequentially added into epoxy resin solution under stirring
Huang, titanium dioxide, talcum powder, kaolin, mica powder and remaining mixed solvent, are ground to fineness less than 30 μm, filtering and discharging, i.e.,
Obtain first component.
The preparation method of high density tungsten alloy wet-heat resisting antisepsis finishing paint of the present invention, formula is stocked up as described above, second
The preparation process of component are as follows:
Catalyst, mixed solvent are sequentially added into polyisocyanates under stirring, filter after mixing evenly to get
Second component.
In use, first tungsten alloy surface is wiped or is rinsed with dehydrated alcohol, it is ensured that be coated substrate table
Face is clean.The tungsten alloy cleaned up is submerged initially in high density tungsten alloy wet-heat resisting anti-corrosion primer, takes out and dries after 30 minutes
24 hours.It is 100 ︰ 10-20 according to the mass ratio of first component and second component, by high density tungsten alloy wet-heat resisting antisepsis finishing paint first and second
Component is uniformly mixed, and carries out the coating of finishing coat later.Finishing coat requires coating twice, and coating layer thickness is controlled in 60-100 micron
Between.
Compared with prior art, the present invention has the following advantages:
The present invention relates to a kind of high density tungsten alloy wet-heat resisting anticorrosive paints.Its priming paint can be sent out with tungsten alloy substrate
Biochemical reaction generates the priming paint with hydrophobicity, under the synergistic protective effect of high crosslinking finishing coat, plays well to tungsten alloy
Protective effect, use tungsten alloy for a long time in hygrothermal environment.This method has the following beneficial effects:
(1) there is reactive priming paint can react with the hydroxyl of substrate surface, forms one layer very in substrate surface
Thin protective film, the mode by then passing through chemical bonding realizes linking for film and substrate, strong to the protective effect of substrate.
Big using the C-F key bond energy in organofluorine compound simultaneously, fluorine atom makees scroll distribution along carbon key, has screen effect,
Low-surface-energy drops, to improve the hydrophobicity and chemical stability of priming paint.
(2) in high density tungsten alloy wet-heat resisting antisepsis finishing paint select molecular backbone on multiple hydroxyls epoxy resin and
Polyisocyanates realizes high cross-linking system as binder resin.The finishing coat has good shielding properties, can effectively prevent steam
Equal diffusion of the corrosive mediums to ground.
Specific embodiment
Embodiment 1:
(1) 50kg isopropanol and 32kg the preparation of high density tungsten alloy wet-heat resisting anti-corrosion primer: are added in a kettle
The acetic acid of 0.4kg is added in softened water, after tested pH value about 5.55 DEG C ± 2 DEG C are warming up to, under stiring, 1 hour used time slowly added
Enter heptadecafluorodecyl triethoxysilane 2kg, insulation reaction 8 hours, obtained high density tungsten are closed at this temperature after addition
Golden wet-heat resisting anti-corrosion primer.
(2) preparation of high density tungsten alloy wet-heat resisting antisepsis finishing paint component A: in a kettle be added 20kg cyclohexanone,
The butanone of 5kg is warming up to reflux state, and the epoxy resin 607 of 25kg is added in three times, and reflux state keeps the temperature 2 hours, and ring is made
Oxygen resin solution.Prepare dispersant B YK-110, the 0.15kg for sequentially adding 0.5kg under stirring into epoxy resin solution
The cyclohexanone of levelling agent BYK-320,8kg, the butanone of 8kg, 12kg lemon yellow, 12kg titanium dioxide, 6kg talcum powder, 4kg kaolinite
The mica powder of soil, 4kg, after stirring 30 minutes, grinding distribution to fineness is 20 μm, and filtering and discharging is to get first component.
(3) NCO the preparation of high density tungsten alloy wet-heat resisting antisepsis finishing paint component B: is added into scuffing of cylinder bore under stirring
The dibutyl tin dilaurate of the butanone of HDI trimer 90kg, 10kg, 0.1kg that mass content is 18%, is stirred 25 minutes
Afterwards, filtering and discharging is to get second component.
In use, first by tungsten alloy surface dehydrated alcohol wiped clean.The tungsten alloy cleaned up is first soaked
Enter in high density tungsten alloy wet-heat resisting anti-corrosion primer, takes out and dry 24 hours after 30 minutes.According to first component: the quality of second component
Than for 100 ︰ 10, high density tungsten alloy wet-heat resisting the first and second component of antisepsis finishing paint is uniformly mixed, the coating of finishing coat is carried out later.Face
Coating twice are painted, coating layer thickness is controlled at 75 microns.
Embodiment 2:
(1) 50kg isopropanol and 40kg the preparation of high density tungsten alloy wet-heat resisting anti-corrosion primer: are added in a kettle
The acetic acid of 0.45kg is added in softened water, after tested pH value about 5.55 DEG C ± 2 DEG C are warming up to, under stiring, 1 hour used time is slow
Heptadecafluorodecyl triethoxysilane 2.5kg is added, high density is made in insulation reaction 8 hours at this temperature after addition
Tungsten alloy wet-heat resisting anti-corrosion primer.
(2) preparation of high density tungsten alloy wet-heat resisting antisepsis finishing paint component A: in a kettle be added 23kg cyclohexanone,
The butanone of 2kg is warming up to reflux state, and the epoxy resin 607 of 20kg, the epoxy resin 609 of 5kg are added in three times, and flow back shape
State keeps the temperature 2 hours, and epoxy resin solution is made.Prepare point for sequentially adding 0.4kg under stirring into epoxy resin solution
The cyclohexanone of powder BYK-110,0.15kg levelling agent BYK-320,8kg, the butanone of 8kg, 13kg lemon yellow, 12kg titanium dioxide,
6kg talcum powder, 4kg kaolin, 4kg mica powder, stirring 30 minutes after, grinding distribution to fineness be 25 μm, filtering and discharging, i.e.,
Obtain first component.
(3) NCO the preparation of high density tungsten alloy wet-heat resisting antisepsis finishing paint component B: is added into scuffing of cylinder bore under stirring
The dibutyl tin dilaurate of the butanone of HDI trimer 92kg, 8kg, 0.13kg that mass content is 16.8%, is stirred 20 minutes
Afterwards, filtering and discharging is to get second component.
In use, first by tungsten alloy surface dehydrated alcohol wiped clean.The tungsten alloy cleaned up is first soaked
Enter in high density tungsten alloy wet-heat resisting anti-corrosion primer, takes out and dry 24 hours after 30 minutes.According to first component: the quality of second component
Than for 100 ︰ 15, high density tungsten alloy wet-heat resisting the first and second component of antisepsis finishing paint is uniformly mixed, the coating of finishing coat is carried out later.Face
Coating twice are painted, coating layer thickness is controlled at 80 microns.
Embodiment 3:
(1) 60kg isopropanol and 36kg the preparation of high density tungsten alloy wet-heat resisting anti-corrosion primer: are added in a kettle
The acetic acid of 0.5kg is added in softened water, after tested pH value about 5.55 DEG C ± 2 DEG C are warming up to, under stiring, 1 hour used time slowly added
Enter tridecafluoro-n-octyltriethoxysilane 2kg, insulation reaction 8 hours, obtained high density tungsten are closed at this temperature after addition
Golden wet-heat resisting anti-corrosion primer.
(2) preparation of high density tungsten alloy wet-heat resisting antisepsis finishing paint component A: in a kettle be added 20kg cyclohexanone,
The butanone of 5kg is warming up to reflux state, and the epoxy resin 609 of 25kg is added in three times, and reflux state keeps the temperature 2 hours, and ring is made
Oxygen resin solution.Prepare dispersant B YK-110,0.2kg stream for sequentially adding 0.6kg under stirring into epoxy resin solution
The cyclohexanone of flat agent BYK-320,12kg, the butanone of 4kg, 15kg lemon yellow, 10kg titanium dioxide, 6kg talcum powder, 4kg kaolin,
The mica powder of 4kg, after stirring 30 minutes, grinding distribution to fineness is 28 μm, and filtering and discharging is to get first component.
(3) NCO the preparation of high density tungsten alloy wet-heat resisting antisepsis finishing paint component B: is added into scuffing of cylinder bore under stirring
The dibutyl tin dilaurate of the butyl acetate of HDI trimer 85kg, 15kg, 0.1kg that mass content is 23%, stirs 25 points
Zhong Hou, filtering and discharging is to get second component.
In use, first by tungsten alloy surface dehydrated alcohol wiped clean.The tungsten alloy cleaned up is first soaked
Enter in high density tungsten alloy wet-heat resisting anti-corrosion primer, takes out and dry 24 hours after 30 minutes.According to first component: the quality of second component
Than for 100 ︰ 20, high density tungsten alloy wet-heat resisting the first and second component of antisepsis finishing paint is uniformly mixed, the coating of finishing coat is carried out later.Face
Coating twice are painted, coating layer thickness is controlled at 90 microns.
Comparative example 1:
In addition to by the epoxy resin 607 in embodiment 1 replace with tetrafluoroethene base resin GK507 and epoxy resin E-51 by
The mixture that mass ratio 6.5:3.5 is mixed, it is other same as Example 1.
Comparative example 2:
It is other same as Example 1 in addition to the epoxy resin 607 in embodiment 1 is replaced with epoxy resin E-51.
Implementation result
Carrying out wet-hot aging performance test to the tungsten alloy after coating in embodiment 1-3 and comparative example 1-2, (GJB150 is wet
Heat test).Test result is as follows:
Claims (6)
1. a kind of high density tungsten alloy wet-heat resisting anticorrosive paint, is made of priming paint and finishing coat, it is characterised in that:
Based on the gross mass of high density tungsten alloy wet-heat resisting anti-corrosion primer, each component in high density tungsten alloy wet-heat resisting anti-corrosion primer
Content are as follows:
The sum of each component content is 100%；
Priming paint the preparation method comprises the following steps: as described above content stock up, with acetic acid by the mixed liquor of isopropanol and softened water adjust
PH value is 5, then heats to 55 DEG C ± 5 DEG C, under stiring, is slowly added to silicon fluoride within the used time 1 hour, warm herein after addition
Lower insulation reaction 8 hours are spent to get high density tungsten alloy wet-heat resisting anti-corrosion primer；
The finishing coat is grouped as by first component and second group,
Based on the gross mass of high density tungsten alloy wet-heat resisting antisepsis finishing paint first component, high density tungsten alloy wet-heat resisting antisepsis finishing paint first
The content of each component in component are as follows:
The sum of each component content is 100%；
The epoxy resin is 607 resin of epoxy, any one or two kinds of mixing with arbitrary proportion in 609 resin of epoxy
Object；
Finishing coat first component the preparation method comprises the following steps: according to the above content stock up, by etc. quality mixed solvent and epoxy resin be added
In container, it is warming up to reflux state, stirring and dissolving epoxy resin, until continuing stirring 1 hour after being uniformly dissolved, epoxy resin is made
Solution；Sequentially added under stirring into epoxy resin solution dispersing agent, levelling agent, lemon yellow, titanium dioxide, talcum powder,
Kaolin, mica powder and remaining mixed solvent are ground to fineness less than 30 μm, and filtering and discharging is to get first component；
The high density tungsten alloy wet-heat resisting antisepsis finishing paint second component is made of polyisocyanates, catalyst, mixed solvent, each group
Dividing the sum of mass percentage is 100%；
Finishing coat second component the preparation method comprises the following steps: according to the above content stock up, under stirring into polyisocyanates successively plus
Enter catalyst, mixed solvent, is filtered after mixing evenly to get second component.
2. high density tungsten alloy wet-heat resisting anticorrosive paint as described in claim 1, the silicon fluoride is that main chain has 8 or more
The silicon fluoride of carbon atom.
3. high density tungsten alloy wet-heat resisting anticorrosive paint as described in claim 1, the dispersing agent is BYK-110, BYK-
At least one of 104S；The levelling agent is at least one of BYK-310, BYK-320；Mixing in finishing coat first component
Solvent is at least one of cyclohexanone, acetone, butanone.
4. high density tungsten alloy wet-heat resisting anticorrosive paint as described in claim 1, the polyisocyanates is degree of functionality 2
Above isocyanate compound, NCO mass content is 8%~30%；The catalyst be dibutyl tin dilaurate,
At least one of stannous octoate, dibutyltin diacetate；Mixed solvent in finishing coat second component be cyclohexanone, acetone, butanone,
At least one of ethyl acetate, butyl acetate.
5. the preparation method of high density tungsten alloy wet-heat resisting anticorrosive paint, feature exist as described in claim 1-4 any one
In: the coating is made of priming paint and finishing coat,
Based on the gross mass of high density tungsten alloy wet-heat resisting anti-corrosion primer, each component in high density tungsten alloy wet-heat resisting anti-corrosion primer
Content are as follows:
The sum of each component content is 100%；
Priming paint the preparation method comprises the following steps: as described above content stock up, with acetic acid by the mixed liquor of isopropanol and softened water adjust
PH is 5, then heats to 55 DEG C ± 5 DEG C, under stiring, silicon fluoride is slowly added within the used time 1 hour, in this temperature after addition
Lower insulation reaction 8 hours to get high density tungsten alloy wet-heat resisting anti-corrosion primer；
The finishing coat is grouped as by first component and second group,
Based on the gross mass of high density tungsten alloy wet-heat resisting antisepsis finishing paint first component, high density tungsten alloy wet-heat resisting antisepsis finishing paint first
The content of each component in component are as follows:
The sum of each component content is 100%；
The epoxy resin is 607 resin of epoxy, any one or two kinds of mixing with arbitrary proportion in 609 resin of epoxy
Object；
Finishing coat first component the preparation method comprises the following steps: according to the above content stock up, by etc. quality mixed solvent and epoxy resin be added
In container, it is warming up to reflux state, stirring and dissolving epoxy resin, until continuing stirring 1 hour after being uniformly dissolved, epoxy resin is made
Solution；Sequentially added under stirring into epoxy resin solution dispersing agent, levelling agent, lemon yellow, titanium dioxide, talcum powder,
Kaolin, mica powder and remaining mixed solvent are ground to fineness less than 30 μm, and filtering and discharging is to get first component；
The high density tungsten alloy wet-heat resisting antisepsis finishing paint second component is made of polyisocyanates, catalyst, mixed solvent, each group
Dividing the sum of mass percentage is 100%；
Finishing coat second component the preparation method comprises the following steps: according to the above content stock up, under stirring into polyisocyanates successively plus
Enter catalyst, mixed solvent, is filtered after mixing evenly to get second component.
6. high density tungsten alloy wet-heat resisting anticorrosive paint is used for the use of tungsten alloy coating as described in claim 1-4 any one
On the way, it is characterised in that: in use, first tungsten alloy surface is wiped or rinsed with dehydrated alcohol, it is ensured that be coated
Substrate surface is clean, and the tungsten alloy cleaned up is submerged initially in high density tungsten alloy wet-heat resisting anti-corrosion primer, is taken after 30 minutes
It dries out 24 hours, high density tungsten alloy wet-heat resisting the first and second component of antisepsis finishing paint is uniformly mixed, carry out the coating of finishing coat later,
Finishing coat requires coating twice, and coating layer thickness controls between 60-100 microns, wherein the quality of first component and second component in finishing coat
Than for 100:10-20.
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| CN106752933B true CN106752933B (en) | 2019-04-16 |
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| CN102010636A (en) * | 2010-12-15 | 2011-04-13 | 广东电网公司电力科学研究院 | Anti-pollution flashover normal-temperature cured fluorocarbon resin coating and preparation method thereof |
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| CN102010636A (en) * | 2010-12-15 | 2011-04-13 | 广东电网公司电力科学研究院 | Anti-pollution flashover normal-temperature cured fluorocarbon resin coating and preparation method thereof |
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