CN108587449A - A kind of Cr@ZnO@TiO capsule of nano and preparation method thereof and a kind of gel coat high-strength steel - Google Patents
A kind of Cr@ZnO@TiO capsule of nano and preparation method thereof and a kind of gel coat high-strength steel Download PDFInfo
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- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
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- B22F9/00—Making metallic powder or suspensions thereof
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Abstract
The present invention selects Cr, the TiO that can improve metal corrosion resistance as core material, and Cr@ZnO@TiO capsule of nano has been prepared as wall material, using hydrolysis deposition in sacrificed anticathode material ZnO.The Cr of corrosion resistance excellent in Cr@ZnO@TiO capsule of nano provided by the invention, TiO acts synergistically with sacrificed anticathode material ZnO, there is good iris action to corrosion particle, the Cr@ZnO@TiO capsule of nano is modified gel, the gel coat for the gel-forming that gained Cr ZnO TiO capsule of nano is modified and high-strength steel matrix associativity are good, utilize the structure of the excellent corrosion resisting property and gel densification itself of Cr@ZnO@TiO capsule of nano, the gel coat being capable of the high-strength steel matrix of effective protection, make it have excellent mechanical property and corrosion resistance, suitable for the mal-condition under marine environment.
Description
Technical field
The present invention relates to coating for metal surfaces technical fields, and in particular to a kind of Cr@ZnO@TiO capsule of nano and its system
Preparation Method and a kind of gel coat high-strength steel.
Background technology
The important foundation material that high-strength steel develops as naval ship, corrosion resistance are that naval ship is advanced and safe
One of the deciding factor of property.
Currently, the anti-corrosion method of metal mainly has the metal inside institutional framework method that changes, protective coating method, electrochemistry to protect
It defends the doctrine.Sol method in protective coating method by feat of be simple to operate and friendly to environment, it is of low cost the features such as be widely used,
It is under certain conditions, using salting liquid as reaction raw materials, sol solution to be generated by hydrolysis condensation reaction, to be aged certain
After time becomes colloidal sol, colloidal sol is coated on the metallic matrix for needing to protect with certain method, is finally passed through at dry, heat
Reason so that the curing of coatings densification on surface is to have the function that protect matrix.Although the coating that the above method is formed is to a certain degree
On delayed the progress of corrosion, but effect is not obvious.
Invention content
The purpose of the present invention is to provide a kind of Cr@ZnO@TiO capsule of nano and preparation method thereof and a kind of gel to apply
Layer high-strength steel, Cr ZnO TiO capsule of nano provided by the invention have good iris action to corrosion particle.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of preparation method of Cr@ZnO@TiO capsule of nano,
Include the following steps：
The chromium zinc mixture obtained after chromium powder and zinc powder are mixed is as anode material, using DC arc plasma
Prepare Cr@ZnO nano powder presomas；
In argon gas atmosphere, the Cr@ZnO nanos powder presoma is passivated, obtains Cr@ZnO nano powder；
The Cr ZnO nanos powder is mixed with polyvinylpyrrolidone, polyethylene alcohol and water, obtains suspension；
The poly-vinyl alcohol solution of butyl titanate is added into the suspension, deposition is hydrolyzed, obtains Cr@ZnO@
TiO capsule of nano.
Preferably, the mass ratio of the chromium powder and zinc powder is 95：(4.5~5.5).
Preferably, the operating condition of the DC arc plasma is：The volume ratio of argon gas and hydrogen is (2~3)：
1, electric current is 130~160A, and voltage is 20~30V.
Preferably, the time of the passivation is 8~12h.
Preferably, the Cr ZnO nanos powder, polyvinylpyrrolidone, polyethylene alcohol and water mass ratio be (1~3)：
(1~3)：1：(95~105).
Preferably, the mass ratio of butyl titanate and polyvinyl alcohol is (3 in the poly-vinyl alcohol solution of the butyl titanate
~4)：1.
Preferably, the matter of the Cr@ZnO nanos powder and butyl titanate in the poly-vinyl alcohol solution of the butyl titanate
Amount is than being 1：(2~3).
Preferably, the time of the hydrolysis precipitation is 18~22h.
The present invention provides the Cr@ZnO@TiO capsule of nano that preparation method described in above-mentioned technical proposal is prepared.
The present invention provides a kind of gel coat high-strength steel, including high-strength steel and the gel coated in the high-strength steel surface
Coating, the gel-forming that gel coat Cr@ZnO@TiO capsule of nano described in above-mentioned technical proposal is modified.
The present invention provides a kind of preparation methods of Cr@ZnO@TiO capsule of nano, are obtained after chromium powder and zinc powder are mixed
Chromium zinc mixture as anode material, Cr@ZnO nano powder presomas are prepared using DC arc plasma；In argon gas
In atmosphere, the Cr@ZnO nanos powder presoma is passivated, obtains Cr@ZnO nano powder；By the Cr@ZnO nanos powder with
Polyvinylpyrrolidone, the mixing of polyethylene alcohol and water, obtain suspension；The poly- second of butyl titanate is added into the suspension
Deposition is hydrolyzed in enolate solution, obtains Cr@ZnO@TiO capsule of nano.Present invention selection can improve metal corrosion resistance
TiO nanometers of Cr@ZnO@have been prepared as wall material, using hydrolysis deposition as core material, sacrificed anticathode material ZnO in Cr, TiO
Microcapsules.Cr, TiO and sacrificed anticathode material ZnO of corrosion resistance excellent in Cr@ZnO@TiO capsule of nano provided by the invention
Synergistic effect has excellent iris action to corrosion particle, the Cr@ZnO@TiO capsule of nano changes gel
Property, the gel coat of the gel-forming of gained Cr ZnO TiO capsule of nano modification and high-strength steel matrix associativity are good, profit
With the structure of the excellent corrosion resisting property and gel densification itself of Cr@ZnO@TiO capsule of nano, the gel coat can be effective
High-strength steel matrix is protected, excellent mechanical property and corrosion resistance are made it have, the mal-condition being suitable under marine environment.
Embodiment the experimental results showed that, the roughness of gel coat high-strength steel provided by the invention is 0.275~0.314 μm, micro-
Hardness is 238~253HV, and corrosion electric current density is 5.58~7.13 μ A/cm2, corrosion potential is -0.559~-0.646V.
Description of the drawings
Fig. 1 is Cr@TiO nanometers of micro- glue of ZnO@in the gel that Cr@ZnO@TiO capsule of nano prepared by embodiment 1 is modified
The SEM of capsule schemes.
Specific implementation mode
The present invention provides a kind of preparation methods of Cr@ZnO@TiO capsule of nano, include the following steps：
The chromium zinc mixture obtained after chromium powder and zinc powder are mixed is as anode material, using DC arc plasma
Prepare Cr@ZnO nano powder presomas；
In argon gas atmosphere, the Cr@ZnO nanos powder presoma is passivated, obtains Cr@ZnO nano powder；
The Cr ZnO nanos powder is mixed with polyvinylpyrrolidone, polyethylene alcohol and water, obtains suspension；
The poly-vinyl alcohol solution of butyl titanate is added into the suspension, deposition is hydrolyzed, obtains Cr@ZnO@
TiO capsule of nano.
In the present invention, if without specified otherwise, all raw material components are commercially available quotient well known to those skilled in the art
Product.
The chromium zinc mixture that the present invention obtains after mixing chromium powder and zinc powder as anode material, using direct-current arc etc. from
Daughter method prepares Cr ZnO nano powder presomas.In the present invention, the mass ratio of the chromium powder and zinc powder is preferably 95：(4.5~
5.5), more preferably 95：5.In the present invention, the grain size of the chromium powder is preferably 50~80nm；The grain size of the zinc powder is preferred
For 60~100nm.In the present invention, the chromium powder and zinc powder are preferably analyzed pure.
The present invention is used as anode material after preferably suppressing the chromium zinc mixture.The present invention does not have the compacting
There is special restriction, using the technical solution of compacting well known to those skilled in the art.Present invention preferably employs forcing presses
The chromium zinc mixture is pressed into cylindrical anode material；It is special that the present invention does not have the size of the anode material
It limits, using size well known to those skilled in the art.
In the present invention, the operating condition of the DC arc plasma is preferably：The volume ratio of argon gas and hydrogen
For (2~3)：1, electric current is 130~160A, and voltage is 20~30V.Tool of the present invention for the DC arc plasma
Body operating procedure does not have special restriction, using the operating procedure of DC arc plasma well known to those skilled in the art
；In an embodiment of the present invention, after specifically placing the anode material that chromium zinc mixture is pressed into, purity is utilized
Equipment is simultaneously evacuated to 3 × 10 by 99.9% argon purge equipment pipe-3Pa, the volume ratio for then pressing argon gas and hydrogen is (2
~3)：1 is passed through argon gas and hydrogen, and adjusting electric current is 130~160A, and voltage is 20~30V, prepares Cr@ZnO nano powder forerunners
Body.
In the present invention, ionization generation plasma makes chromium powder and zinc powder melt and forms steaming inside direct-current discharge environment
Vapour, the steam are collided with argon gas or hydrogen, and final solidification forms nano-powder；Since zinc oxide is different from the fusing point of chromium, institute
The nano-powder of cladded type can be formed when stating steam coagulation.
After obtaining Cr@ZnO nano powder presomas, the present invention is in argon gas atmosphere, by the Cr@ZnO nanos powder presoma
It is passivated, obtains Cr@ZnO nano powder.In the present invention, the time of the passivation is preferably 8~12h, more preferably 10h；
The temperature of the passivation is preferably 20~30 DEG C, is specifically as follows room temperature.The present invention does not have the specific method of the passivation
Special restriction, using the technical solution of passivation well known to those skilled in the art.
In the present invention, the grain size of the Cr@ZnO nano powder is preferably 60~80nm.
In the present invention, the Cr@ZnO nanos powder presoma granularity is small, large specific surface area, has sizable surface
Can, skin effect is fairly obvious, belongs to thermodynamic unstable system, is very easy to that particle coagulation, agglomeration occurs, to lose
Go its due physical property and function；The present invention by being passivated to the Cr@ZnO nanos powder presoma in argon gas atmosphere,
The stronger surface energy in its surface can be reduced, solves the agglomeration traits of the Cr@ZnO nanos powder presoma.
After obtaining Cr@ZnO nano powder, the present invention is by the Cr@ZnO nanos powder and polyvinylpyrrolidone, polyvinyl alcohol
It is mixed with water, obtains suspension.In the present invention, the Cr ZnO nanos powder, polyvinylpyrrolidone, polyethylene alcohol and water
Mass ratio is preferably (1~3)：(1~3)：1：(95~105), more preferably 2：2：1：100.In the present invention, the polyethylene
Pyrrolidones and polyvinyl alcohol are water-soluble high-molecular compound, are to have film forming, caking property as emulsifier and adhesive
Cohesion provides bonding protective effect and phase separation for the formation of Cr@ZnO@TiO capsule of nano.
In the present invention, the mixing of the Cr ZnO nanos powder and polyvinylpyrrolidone, polyethylene alcohol and water preferably exists
It is carried out under ultrasound condition.Each material can be mixed and be uniformly dispersed for the not special restriction of the ultrasound by the present invention；
In the present invention, the time of the ultrasound is preferably 50~70min, more preferably 60min.It is each when the present invention is for the mixing
The charging sequence of material does not have special restriction, using charging sequence well known to those skilled in the art；The present invention's
In embodiment, the Cr@ZnO nano powder is mixed with polyvinylpyrrolidone specifically, then gained mixed material is added
Into the aqueous solution of polyvinyl alcohol.
After obtaining suspension, the poly-vinyl alcohol solution of butyl titanate is added into the suspension by the present invention, carries out water
Solution deposition, obtains Cr@ZnO@TiO capsule of nano.After obtaining suspension, the suspension is preferably stirred by the present invention,
Then the poly-vinyl alcohol solution of butyl titanate is added.In the present invention, the rate of the stirring be preferably 2500~
3500rpm, more preferably 3000rpm；The time of the stirring is preferably 2.5~3.5h, more preferably 3h.In the present invention,
The stirring can be such that suspension is preferably mixed with the poly-vinyl alcohol solution of butyl titanate, accelerate hydrolysis precipitation speed and water
The uniformity of solution.
In the present invention, in the poly-vinyl alcohol solution of the butyl titanate butyl titanate and polyvinyl alcohol mass ratio
Preferably (3~4)：1, more preferably 3.5：1.In the present invention, the addition side of the poly-vinyl alcohol solution of the butyl titanate
Formula is preferably added dropwise；The present invention does not have the rate of the dropwise addition special restriction, use well known to those skilled in the art
Drop rate is specifically such as added dropwise.
In the present invention, the Cr@ZnO nanos powder and butyl titanate in the poly-vinyl alcohol solution of the butyl titanate
Mass ratio be preferably 1：(2~3), more preferably 1:2.5.
In the present invention, the temperature of the hydrolysis precipitation is preferably 20~30 DEG C；The time of the hydrolysis precipitation is preferably
18~22h, more preferably 20h.In the present invention, preferably butyl titanate is added into the suspension in the hydrolysis precipitation
Poly-vinyl alcohol solution after, resulting material is stood.In the present invention, during the hydrolysis precipitation, four fourth of metatitanic acid
Ester hydrolyzes in polyvinyl alcohol generates Ti (OH)4, TiO is formed after dehydration2And TiO, part TiO can be doped into Cr@ZnO nano powder
Inside, it by core material, ZnO of Cr and TiO is the Cr@ZnO@TiO capsule of nano of wall material to be formed.
After completing the hydrolysis precipitation, obtained material is preferably separated by solid-liquid separation by the present invention, by obtained solid material
It is washed and is dried successively, obtain Cr@ZnO@TiO capsule of nano.Concrete mode of the present invention for the separation of solid and liquid
There is no special restriction, it is specific as centrifuged using the technical solution of separation of solid and liquid well known to those skilled in the art.This hair
The bright restriction not special for the washing and drying, using washing well known to those skilled in the art and dry technical side
Case.
The present invention provides the Cr@ZnO@TiO capsule of nano that preparation method described in above-mentioned technical proposal is prepared.
In the present invention, the Cr@ZnO@TiO capsule of nano is wall material by core material, ZnO of Cr and TiO.In the present invention, the Cr@
The average particle size of ZnO@TiO capsule of nano is preferably 5~10 μm.
The present invention provides a kind of gel coat high-strength steel, including high-strength steel and the gel coated in the high-strength steel surface
Coating, the gel-forming that gel coat Cr@ZnO@TiO capsule of nano described in above-mentioned technical proposal is modified.In this hair
In bright, the high-strength steel preferably preferably includes following components：C 0.23wt%, Mn 1.26wt%, Nb 0.003wt%, Si
0.233wt%, Ti 0.035wt%, surplus Fe.In the present invention, the thickness of the gel coat is preferably 50~100 μm,
More preferably 60~90 μm, most preferably 70~80 μm.
In the present invention, the preparation method of the gel coat high-strength steel preferably includes following steps：
Zirconium-n-propylate and ethyl acetoacetate are mixed, the pH value for adjusting gained mixed material is 2~3, and it is molten to obtain first
Glue；
It is hydrolyzed after propyl trimethoxy silicane, normal propyl alcohol and water are mixed, obtains the second colloidal sol；
The first ageing is carried out after first colloidal sol and the second colloidal sol are mixed, and obtains gel；
The second ageing is carried out after the gel is mixed with Cr ZnO TiO capsule of nano, obtains TiO nanometers of Cr ZnO
The gel that microcapsules are modified；
The gel coating that the Cr@ZnO@TiO capsule of nano is modified obtains gel in the surface of high-strength steel, solidification
Coating high-strength steel.
The present invention preferably mixes zirconium-n-propylate and ethyl acetoacetate, and the pH value for adjusting gained mixed material is 2~3,
Obtain the first colloidal sol.In the present invention, the volume ratio of the zirconium-n-propylate and ethyl acetoacetate is preferably 1：(1.4~1.6),
More preferably 1：1.5.In the present invention, reagent is preferably hydrochloric acid used by adjusting the mixed material pH value；The hydrochloric acid
Mass concentration be preferably 0.8~1.2mol/L, more preferably 1mol/L.In the present invention, the pH of gained mixed material is adjusted
Value is 2~3, can speed up sequential hydrolysis reaction, plays the role of hydrolyst, and have dispergation, prevents too early
Precipitation.
In the present invention, the mixing of the zirconium-n-propylate and ethyl acetoacetate preferably carries out under ultrasound condition；It is described
The time of ultrasound is preferably 25~35min.After the pH value for adjusting the mixed material of zirconium-n-propylate and ethyl acetoacetate is 2~3,
Resulting material is preferably continued 25~35min of ultrasound by the present invention, obtains the first colloidal sol.
In the present invention, the zirconium-n-propylate is presoma；The ethyl acetoacetate is chelating agent.
The present invention is hydrolyzed after preferably mixing propyl trimethoxy silicane, normal propyl alcohol and water, obtains the second colloidal sol.
In the present invention, the molar ratio of the propyl trimethoxy silicane, normal propyl alcohol and water is preferably 1.5：(3.8~4.2)：(2.4~
2.6), more preferably 1.5：4：2.5.In the present invention, the mixing of the propyl trimethoxy silicane, normal propyl alcohol and water preferably exists
It is carried out under ultrasound condition；The time of the ultrasound is preferably 20~30min, more preferable 25min.
In the present invention, the temperature of the hydrolysis is preferably 30~50 DEG C, more preferable 40 DEG C；The time of hydrolysis is preferably 3
~5h, more preferable 4h.
After obtaining the first colloidal sol and the second colloidal sol, the present invention carries out after preferably mixing first colloidal sol and the second colloidal sol
First ageing, obtains gel.In the present invention, the volume ratio of first colloidal sol and the second colloidal sol is preferably 1：(1~2.5),
More preferably 1：2.In the present invention, the mixing of first colloidal sol and the second colloidal sol preferably carries out under ultrasound condition；It is described
The time of ultrasound is preferably 1.5~2.5h.In the present invention, the time of first ageing is preferably 1.5~2.5h, more preferably
For 2h；The present invention does not have special restriction for the temperature of first ageing, specific such as room temperature.
After obtaining gel, it is old that the present invention carries out second after preferably mixing the gel with Cr ZnO TiO capsule of nano
Change, obtains the gel of Cr@ZnO@TiO capsule of nano modification.In the present invention, the gel and Cr@TiO nanometers of micro- glue of ZnO@
The mass ratio of capsule is preferably (3~8)：1, more preferably (4~7)：1, most preferably (5~6)：1.In the present invention, described solidifying
The mixing of glue and Cr@ZnO@TiO capsule of nano preferably carries out under ultrasound condition；The time of the ultrasound is preferably 8~
12min.In the present invention, preferably 60~65 DEG C, more preferably 62~63 DEG C of the temperature of second ageing；Second ageing
Time be preferably 18~for 24 hours, more preferably 20~22h.
In the present invention, Cr@ZnO@TiO capsule of nano tables in the gel that the Cr@ZnO@TiO capsule of nano is modified
Bread is wrapped with the high molecular material formed by the first colloidal sol and the second colloidal sol, and granularity is preferably 20~50 μm.
After obtaining the gel of Cr@ZnO@TiO capsule of nano modification, the present invention is preferably micro- by TiO nanometers of the Cr@ZnO@
The gel coating of encapsulation modification obtains gel coat high-strength steel in the surface of high-strength steel, solidification.In the present invention, described high-strength
Steel is using preceding preferred carry out surface preparation；The present invention does not have the method for the surface preparation special restriction, adopts
With the technical solution of surface preparation well known to those skilled in the art.
The present invention does not have the method for the coating special restriction, using coating side well known to those skilled in the art
Method；Present invention preferably employs dip-coatings.In the present invention, the dip-coating is preferably to immerse the high-strength steel after surface preparation
In the gel being modified to the Cr@ZnO@TiO capsule of nano, then high-strength steel is smoothly lifted with even speed and is come out,
Under viscosity and gravity, the gel that the Cr@ZnO@TiO capsule of nano is modified can form one layer on the surface of high-strength steel
Uniform wet film.The present invention does not have special restriction for the speed for lifting the high-strength steel, ripe using those skilled in the art
The speed known.
In the present invention, the solidification preferably carries out under protective atmosphere；The present invention is for providing the protective atmosphere
The type of protective gas does not have special restriction, specific such as argon gas using protective gas well known to those skilled in the art.
In the present invention, the cured temperature is preferably 80~100 DEG C, more preferably 85~95 DEG C, most preferably 90 DEG C；It is described solid
The time of change is preferably 2~4h, more preferably 3h.In the present invention, the heating rate for being warming up to the cured temperature is preferred
For 10~15 DEG C/min.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
It will analysis pure chromium powder and zinc powder in mass ratio 95：5 mixing, circle is pressed into using forcing press by gained chromium zinc mixture
Cylindrical anode material, after the anode material is placed, using purity 99.9% argon purge equipment pipe and will set
It is standby to be evacuated to 3 × 10-3Pa, the volume ratio for then pressing argon gas and hydrogen is 2.5：1 is passed through argon gas and hydrogen, adjusts electric current and is
Cr@ZnO nano powder presomas are prepared using DC arc plasma in 145A, voltage 25V；
In argon gas atmosphere, the Cr@ZnO nanos powder presoma is passivated 10h at room temperature, Cr@ZnO is obtained and receives
Rice flour；
It is 1 in mass ratio by the Cr ZnO nanos powder and polyvinylpyrrolidone, polyethylene alcohol and water：1：1：100 is mixed
It closes, ultrasonic 1h obtains suspension；
The suspension is stirred into 3h with the rotating speed of 3000rpm, the polyvinyl alcohol that butyl titanate is then added dropwise is molten
(mass ratio of butyl titanate and polyvinyl alcohol is 3.5 to liquid：1, the mass ratio of butyl titanate and Cr@ZnO nano powder is 2：
1) 20h, is stood at 25 DEG C, resulting material is centrifuged, obtained solid material is washed and dried successively, is obtained
Cr@ZnO@TiO capsule of nano；
By zirconium-n-propylate and ethyl acetoacetate by volume 1：1.5 mixing, ultrasonic 30min, use mass concentration for
The pH value that the hydrochloric acid of 1mol/L adjusts gained mixed material is 2.5, and ultrasonic 30min obtains the first colloidal sol；By propyl trimethoxy
Silane, normal propyl alcohol and water in molar ratio 1.5：4：2.5 mixing, ultrasonic 20min are hydrolyzed 4h at 30 DEG C, it is molten to obtain second
Glue；By first colloidal sol and the second colloidal sol by volume 1：1 mixing, ultrasonic 2h carry out ageing 2h, are coagulated at room temperature
Glue；
By the Cr@ZnO@TiO capsule of nano and gel in mass ratio 1：3 mixing, ultrasonic 10min are old at 60 DEG C
Change 20h, obtains the gel of Cr@ZnO@TiO capsule of nano modification；
By high-strength steel, (group becomes C 0.23wt%, Mn 1.26wt%, Nb 0.003wt%, Si 0.233wt%, Ti
0.035wt%, surplus Fe.) carry out surface preparation after immerse in the gel that the Cr@ZnO@TiO capsule of nano is modified,
Then high-strength steel is smoothly lifted with even speed and is come out, under protection of argon gas, with the heating rate of 10 DEG C/min from room temperature
90 DEG C are risen to, heat preservation carries out solidification 3h, obtains gel coat high-strength steel.
Embodiment 2
Prepare gel coat high-strength steel according to the method for embodiment 1, the difference is that, the Cr@ZnO nanos powder with it is poly-
Vinylpyrrolidone, polyethylene alcohol and water mass ratio be 2：2：1：100, metatitanic acid four in the poly-vinyl alcohol solution of butyl titanate
The mass ratio of butyl ester and polyvinyl alcohol is 3：1, the volume ratio of first colloidal sol and the second colloidal sol is 1：1.5, the gel with
The mass ratio of Cr@ZnO@TiO capsule of nano is 3：1.
Embodiment 3
Prepare gel coat high-strength steel according to the method for embodiment 1, the difference is that, the Cr@ZnO nanos powder with it is poly-
Vinylpyrrolidone, polyethylene alcohol and water mass ratio be 3：3：1：100, the mass ratio of butyl titanate and Cr@ZnO nano powder
It is 3：1, the volume ratio of first colloidal sol and the second colloidal sol is 1：2.5, the gel and Cr@ZnO@TiO capsule of nano
Mass ratio is 4：1.
Embodiment 4
Prepare gel coat high-strength steel according to the method for embodiment 1, the difference is that, the Cr@ZnO nanos powder with it is poly-
Vinylpyrrolidone, polyethylene alcohol and water mass ratio be 3：3：1：100, the mass ratio of butyl titanate and Cr@ZnO nano powder
It is 3:1, the mass ratio of butyl titanate and polyvinyl alcohol is 3 in the poly-vinyl alcohol solution of butyl titanate：1, described first is molten
The volume ratio of glue and the second colloidal sol is 1：2, the mass ratio of the gel and Cr@ZnO@TiO capsule of nano is 5：1.
Embodiment 5
Fig. 1 is Cr@TiO nanometers of micro- glue of ZnO@in the gel that Cr@ZnO@TiO capsule of nano prepared by embodiment 1 is modified
The SEM of capsule schemes, wherein Fig. 1 a are the enlarged drawing of Fig. 1 b.As shown in Figure 1, the grain size of the Cr@ZnO@TiO capsule of nano is
20~50 μm.
In 3.5wt.%NaCl environment, the gel coat high-strength steel prepared to Examples 1 to 4 is tested for the property, and
It is specific as follows using the high-strength steel of uncoated gel coat as blank control：
The high-strength steel of gel coat high-strength steel and uncoated gel coat is processed into the sample of 1cm × 1cm × 1cm, surpassed
Sound wave cleans drying for standby after 5min；Sample one end conducting resinl after drying is connect with copper conductor, according to epoxy resin with
Curing agent mass ratio is 3.5：1, epoxy resin is mixed, sealing sample with curing agent, high-strength steel electrode examination is prepared after to be dried
Sample；Electro-chemical test is carried out using Shanghai Chen Hua chi660 electrochemical workstations；
According to GB/T1031-1995 standards to the roughness of the high-strength steel of gel coat high-strength steel and uncoated gel coat
It is tested；
According to ISO6507/1-82 standards to the micro- hard of the high-strength steel of gel coat high-strength steel and uncoated gel coat
Degree is tested；
It the results are shown in Table 1.
The performance test results of gel coat high-strength steel prepared by 1 Examples 1 to 4 of table
As shown in Table 1, in Cr@ZnO@TiO capsule of nano provided by the invention corrosion resistance excellent Cr, TiO and anode
Expendable material ZnO synergistic effects have good iris action, by the Cr@ZnO@TiO capsule of nano pair to corrosion particle
Gel is modified, and the gel coat for the gel-forming that gained Cr ZnO TiO capsule of nano is modified is combined with high-strength steel matrix
Property it is good, using the structure of the excellent corrosion resisting property and gel densification itself of Cr@ZnO@TiO capsule of nano, the gel applies
Layer can the high-strength steel matrix of effective protection, make it have excellent mechanical property and corrosion resistance, be suitable for marine environment under
Mal-condition.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of Cr@ZnO@TiO capsule of nano, includes the following steps：
The chromium zinc mixture obtained after chromium powder and zinc powder are mixed is prepared as anode material using DC arc plasma
Cr@ZnO nano powder presomas；
In argon gas atmosphere, the Cr@ZnO nanos powder presoma is passivated, obtains Cr@ZnO nano powder；
The Cr ZnO nanos powder is mixed with polyvinylpyrrolidone, polyethylene alcohol and water, obtains suspension；
The poly-vinyl alcohol solution of butyl titanate is added into the suspension, deposition is hydrolyzed, obtains Cr@ZnO@TiO and receives
Rice microcapsules.
2. preparation method according to claim 1, which is characterized in that the mass ratio of the chromium powder and zinc powder is 95：(4.5
~5.5).
3. preparation method according to claim 1, which is characterized in that the operating condition of the DC arc plasma
For：The volume ratio of argon gas and hydrogen is (2~3)：1, electric current is 130~160A, and voltage is 20~30V.
4. preparation method according to claim 1, which is characterized in that the time of the passivation is 8~12h.
5. preparation method according to claim 1, which is characterized in that the Cr@ZnO nanos powder, polyvinylpyrrolidone,
The mass ratio of polyethylene alcohol and water is (1~3)：(1~3)：1：(95~105).
6. preparation method according to claim 1, which is characterized in that titanium in the poly-vinyl alcohol solution of the butyl titanate
The mass ratio of sour four butyl esters and polyvinyl alcohol is (3~4)：1.
7. according to the preparation method described in claim 1,5 or 6, which is characterized in that the Cr@ZnO nanos powder and the metatitanic acid
The mass ratio of butyl titanate is 1 in the poly-vinyl alcohol solution of four butyl esters：(2~3).
8. preparation method according to claim 1, which is characterized in that the time of the hydrolysis precipitation is 18~22h.
9. the Cr@ZnO@TiO capsule of nano that any one of claim 1~8 preparation method is prepared.
10. a kind of gel coat high-strength steel, including high-strength steel and the gel coat coated in the high-strength steel surface, the gel
The gel-forming that coating Cr@ZnO@TiO capsule of nano described in claim 9 is modified.
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