CN105369223A - Liquid deposition preparing method for anti-corrosion TiO2-ZrO2 coating and anti-corrosion metal with anti-corrosion TiO2-ZrO2 coating - Google Patents
Liquid deposition preparing method for anti-corrosion TiO2-ZrO2 coating and anti-corrosion metal with anti-corrosion TiO2-ZrO2 coating Download PDFInfo
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- CN105369223A CN105369223A CN201510705020.3A CN201510705020A CN105369223A CN 105369223 A CN105369223 A CN 105369223A CN 201510705020 A CN201510705020 A CN 201510705020A CN 105369223 A CN105369223 A CN 105369223A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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Abstract
The invention discloses a liquid deposition preparing method for an anti-corrosion TiO2-ZrO2 coating. (NH4)2TiF6, H3BO3, Zr(SO4)2 and (NH4)2S2O8 serve as raw materials, metal is deposited for 5 h to 48 h under the water bath condition at the temperature ranging from 20 DEG C to 80 DEG C according to a liquid deposition method, the deposited metal is washed through distilled water and aired and is then put in a high-temperature muffle furnace, the temperature is increased to 400 DEG C to 800 DEG C, calcination is kept for 1 to 5 hours, and therefore the TiO2-ZrO2 coating is prepared on the surface of the metal. Through tests, when prepared stainless steel with the TiO2-ZrO2 coating is compared with untreated stainless steel, the corrosion current density of a polarization curve of the stainless steel with the coating in a terrestrial heat aqueous solution is reduced by about one order of magnitude, the polarization resistance of the stainless steel is improved by 15 to 23 times, the annual corrosion rate is increased by 80% to 90%, and the good corrosion resistant effect is achieved.
Description
Technical field
The invention belongs to metal coating techniques field, be specifically related to a kind of anticorrosive TiO
2-ZrO
2the liquid deposition preparation method of coating and the corrosion-resistant metal containing this coating.
Background technology
Owing to there is macro-corrosion composition in GEOTHERMAL WATER, make the e-quipment and pipe surface in geothermal energy utilization process be easy to galvanic corrosion occurs, thus hamper the efficiency utilization of Geothermal energy always.Anti-corrosion measure conventional in underground heat water utilization system has: (1) adds oxygen scavenger and inhibiter in GEOTHERMAL WATER, but it is comparatively large to there is relevant device investment, and the problem of complex process, injection rate is comparatively large simultaneously, causes environmental pollution, and is unfavorable for recharging of GEOTHERMAL WATER.(2) equipment adopted in geothermal system and pipeline are all adopted corrosion resistant material, as titanium alloy etc., but it is expensive, not easily realizes.Metal cheap and easy to get by contrast such as stainless steel is a kind of alternative material preferably, and the etching component existed in GEOTHERMAL WATER is as dissolved oxygen, Cl
-very easily make stainless steel and other metal materials corrode with sulfide etc., this problem limits the use of other metals material as an alternative, if can prepare a corrosion protection coating in metallic surface, will greatly reduce corrosion of metal situation.
Prior art has employing liquid phase deposition to prepare TiO
2the record of coating, on red copper substrate, liquid phase deposition is adopted to prepare the method for the titanium deoxid film of nano thickness as Chinese patent ZL200710060653.9 reports, but in this patent during pre-treatment red copper substrate, use manual finishing method, be difficult to large-scale production and application, and due to red copper non-refractory sintering, coating sintering temperature is lower.Zeng Zhenou etc. (Zeng Zhenou, Xiao Zhengwei, State of Zhao roc. modern coating technology, 2007:45-51) use liquid phase deposition to prepare coating of titanium dioxide on 304 stainless steels.Chinese patent CN101760737A uses liquid phase deposition to prepare nanometer titanium dioxide coating on the stainless steel-based end, find that this coating has enhancement of heat transfer and anti-scaling property, but the antiseptic property of this coating has much room for improvement.
Separately have and prepare ZrO about liquid phase deposition
2patents, CN104359859A report by liquid deposition on long period fiber grating surface the fast zirconium dioxide of controlled synthesis suitable thickness or tantalum pentoxide nano thin-film, improve detection sensitivity.LinJain-Ming etc. (Jian-mingLin, Ming-chiHsu, Kuan-Zongfung, JounralofPowerSources, 159 (2006) 49-54) use liquid phase deposition to prepare ZrO at silicon chip
2film, but do not inquire into ZrO
2the antiseptic property of coating.
TiO
2-ZrO
2pertinent literature and the patent report of compound coating are as follows: as Chinese patent CN201110369778, report a kind of technological method adopting steam hydrolysis organic titanium, zirconium solution, the obtained high nano-TiO carrying titanium amount
2/ ZrO
2matrix material.Chinese patent CN201110279274, reports sol-gel-impregnation method and prepares a kind of efficient nano composite photocatalyst TiO
2-ZrO
2preparation method.Chinese patent CN201110070874, reports sol-gel method and prepares TiO
2-ZrO
2composite oxide film, for ultraviolet detector.Document LipingLiang etc. (LiPingLiang, YonggangSheng, YaoXu, DongWu, YuhanSun, ThinSolidFilms, 2007,515, the 7765-7771) ZrO that used sol-gel method to prepare
2-TiO
2coating, have studied the optical property of this coating.Document Zhang Yandong etc. (Zhang Yandong, Li Huiyuan, Zhang Limin, Wang Zhiliang, Shen Shubao, Zhu Shemin, silicate is circulated a notice of, and 2008,27,894-898) use coprecipitation method to prepare TiO
2-ZrO
2composite oxides, after 500 DEG C of sintering 2h, remain undefined structure, after 600 DEG C of sintering, have occurred ZrTiO
4crystal formation, and draw TiO
2-ZrO
2the thermostability of composite oxides is far longer than single TiO
2and ZrO
2.Document J.Bautista-Ruiz etc. (J.Bautista-Ruiz, W.Aperador, A.Delgado, etal.Int.J.Electrochem.Sci., 2014, the 9:4144-4157) SiO that used sol-gel method to prepare
2-TiO
2-ZrO
2compound coating, be find in the HCl etchant solution of 3% in concentration, Si/Ti/Zr element has best anti-corrosion effects than the coating being 10/70/20.
Comprehensive above patent and periodical literature, can find out that in prior art, chemical liquid deposition does not prepare ZrO
2-TiO
2compound coating preparation technology, and at present also not relevant antiseptic property test is carried out to obtained coating, and the correlative study of the aspect such as corrosion prevention for e-quipment and pipe in geothermal water system.
Summary of the invention
For prior art above shortcomings, technical problem to be solved by this invention is: how to provide a kind of anticorrosive TiO
2-ZrO
2the liquid deposition preparation method of coating and the corrosion-resistant metal containing this coating, make this coating of obtaining and the corrosion-resistant metal containing this coating have good Corrosion Protection.
To achieve these goals, the present invention adopts following technical scheme: a kind of anticorrosive TiO
2-ZrO
2the liquid deposition preparation method of coating, comprises the steps:
1) (the NH that mol ratio is 1:1 ~ 4 is accurately taken
4)
2tiF
6and H
3bO
3, be mixed with (NH respectively
4)
2tiF
6the aqueous solution and H
3bO
3the aqueous solution;
2) by (NH of step 1) preparation
4)
2tiF
6the aqueous solution and H
3bO
3the aqueous solution leaves standstill respectively and filters, and after two kinds of solution mixing after filtration, then filters, obtains the mixed aqueous solution A clarified;
3) Zr (SO that mol ratio is 1:0.5 ~ 6 is accurately taken
4)
24H
2o and (NH
4)
2s
2o
8, be mixed with Zr (SO respectively
4)
2the aqueous solution and (NH
4)
2s
2o
8the aqueous solution; By described Zr (SO
4)
2the aqueous solution and (NH
4)
2s
2o
8mixed aqueous solution B is obtained after aqueous solution;
4) by step 2) the mixed aqueous solution B that obtains of the mixed aqueous solution A that obtains and step 3) mixes, and adds distilled water diluting adjustment, makes (NH in mixed solution
4)
2tiF
6concentration be 0.01 ~ 0.2mol/L, Zr (SO
4)
2concentration be 0.01 ~ 0.1mol/L, obtain deposition mixed solution C;
5) get that metal carries out polishing successively, polishing and ultrasonic cleaning process, the metal after process is dried naturally;
6) metal after step 5) being dried puts into the deposition mixed solution C that step 4) obtains, under 20 ~ 80 DEG C of water bath condition, deposit 5 ~ 48h;
7) the metal distilled water after step 6) depositing treatment cleaned up and after naturally drying, put into high temperature Muffle furnace and be warming up to 400 ~ 800 DEG C of insulation calcinings 1 ~ 5 hour;
8) take out after the metal naturally cooling after step 7) being calcined, obtain described TiO in metallic surface
2-ZrO
2coating.
A kind of corrosion-resistant metal, described metallic surface is covered with the TiO adopting above-mentioned preparation method to obtain
2-ZrO
2coating.
Compared to existing technology, the present invention has following beneficial effect:
1, the present invention has obtained TiO by chemical liquid deposition on the stainless steel-based end
2-ZrO
2coating, and characterized by SEM and find that this coatingsurface is smooth, fine and close, evenly, can the contact at hot-water corrosion medium and the stainless steel-based end effectively isolator; Compared with traditional sol-gel method preparation technology, the preparation of coating of the present invention is without the need to spin-coating equipment or lift equipment, and preparation method is simpler, and can overcome in sol-gel process preparation technology because solvent evaporates the coated porous or problem of Cracking caused.
2, the present invention by obtained with TiO
2-ZrO
2the static corrosion that the stainless steel of coating carries out 50 DEG C of-90 DEG C of GEOTHERMAL WATER soaks after 30 days and finds after electrochemistry Tafel test, compared with the stainless steel without the inventive method process, adopt the inventive method obtained with TiO
2-ZrO
2corrosion electric current density decline about 1 order of magnitude of the polarization curve of stainless steel in GEOTHERMAL WATER solution of coating, stainless steel polarization resistance (Rp) improves 15-23 doubly respectively, and year erosion rate (CR) improves 80-90% respectively, achieves good preservative effect.
3, corrosion-resistant metal surface of the present invention is covered with TiO
2-ZrO
2coating, this coating metal has good preservative effect in usually hot aqueous medium, and the coating planeness of this metal is better, even compact, be combined closely with base metal, and then corrosion-resistant metal of the present invention can be used as anticorrosion GEOTHERMAL WATER pipeline, be expected the etching problem effectively solving heat-exchange equipment and pipeline in China's geothermal energy resources system, there is significant progressive.
Accompanying drawing explanation
Fig. 1 be embodiment 1 obtained there is TiO
2-ZrO
2the stainless steel substrates of coating amplifies the SEM figure of 50000 times;
Fig. 2 be embodiment 1 obtained there is TiO
2-ZrO
2the stainless steel substrates of coating amplifies the SEM figure of 10000 times;
Fig. 3 be embodiment 1 obtained there is TiO
2-ZrO
2the stainless steel substrates EDS power spectrum test zone figure of coating;
Fig. 4 be embodiment 1 obtained there is TiO
2-ZrO
2the stainless steel substrates EDS energy spectrogram of coating;
Fig. 5 be embodiment 2 obtained there is TiO
2-ZrO
2the stainless steel substrates of coating amplifies the SEM figure of 50000 times;
Fig. 6 be embodiment 2 obtained there is TiO
2-ZrO
2the stainless steel substrates of coating amplifies the SEM figure of 5000 times;
Fig. 7 be embodiment 2 obtained there is TiO
2-ZrO
2the stainless steel substrates EDS power spectrum test zone figure of coating;
Fig. 8 be embodiment 2 obtained there is TiO
2-ZrO
2the stainless steel substrates EDS energy spectrogram of coating;
Fig. 9 be embodiment 3 obtained there is TiO
2-ZrO
2the stainless steel substrates of coating amplifies the SEM figure of 50000 times;
Figure 10 be embodiment 3 obtained there is TiO
2-ZrO
2the stainless steel substrates of coating amplifies the SEM figure of 5000 times;
Figure 11 be embodiment 3 obtained there is TiO
2-ZrO
2the stainless steel substrates EDS power spectrum test zone figure of coating;
Figure 12 be embodiment 3 obtained there is TiO
2-ZrO
2the stainless steel substrates EDS energy spectrogram of coating;
Figure 13 is embodiment 1, embodiment 2 and embodiment 3 and the untreated stainless Tafel curve comparison figure that polarizes.
Embodiment
Below in conjunction with specific embodiment and Figure of description, the present invention is described in further detail.The implementation case is implemented under premised on the technology of the present invention, now provide detailed embodiment and concrete operating process, illustrate that the present invention is creative, but protection scope of the present invention is not limited to following embodiment.
The operating gear of chemical liquid deposition of the present invention comprises: a set of water bath with thermostatic control, deposition hanger, ultrasonic cleaner, electronic balance, retort furnace, polishing machine etc.Required reagent: chemical pure ammonium titanium fluoride, analytically pure boric acid, six aqueous sodium persulfates, zirconium sulfate, ammonium persulphate, dehydrated alcohol and analytically pure acetone etc.
Preparation principle is as follows:
Chemical liquid deposition prepares TiO
2chemical equation as follows:
Boric acid makes reaction move right, and accelerates reaction, and
dehydration forms TiO
2crystal.
Chemical liquid deposition prepares ZrO
2chemical equation as follows:
Zirconium sulfate in the aqueous solution and the interaction between persulfate, finally form ZrO
2crystal.
embodiment 1
a kind of anticorrosive TiO
2
-ZrO
2
the liquid deposition preparation method of coating, comprises the steps:
1) standard measures 200mL distilled water, is divided into four parts, is respectively 20mL, 80mL, 70mL and 30mL, dissolves 4.04g (NH respectively
4)
2tiF
6(mass content 98%), 2.49gH
3bO
3(mass content 99.5%), 5.80gZr (SO
4)
24H
2o(mass content 98%) and 11.18g (NH
4)
2s
2o
8(mass content is 98%).Obtain (NH
4)
2tiF
6the aqueous solution, H
3bO
3the aqueous solution, Zr (SO
4)
2the aqueous solution and (NH
4)
2s
2o
8the aqueous solution; Filter respectively after gained solution left standstill and remove naked eyes visible particle, stand-by.
2) by (NH
4)
2tiF
6the aqueous solution and H
3bO
3after aqueous solution, then filter, obtain settled solution A.
3) by Zr (SO
4)
2the aqueous solution and (NH
4)
2s
2o
8settled solution B is obtained after aqueous solution.
4) by A and B solution mix and blend, obtaining mixed deposit liquid C is 200mL, (NH in mixed deposit liquid C
4)
2tiF
6, H
3bO
3, Zr (SO
4)
2(NH
4)
2s
2o
8volumetric molar concentration is respectively 0.1mol/L, 0.2mol/L, 0.08mol/L and 0.24mol/L.
5) get that steel disc carries out polishing successively, polishing and ultrasonic cleaning process, the steel disc after process is dried naturally; Described polishing uses electric grinding machine, selects boron nitride grinding wheel, flap disc, nylon wheel and rubber wheel to polish to steel disc successively, and steel disc surface, significantly cut and oxide on surface polish off; Described being finished to is contained in wool wheel on electric grinding machine, first polishes after heating up to steel disc surface, then the steel disc surface smear green polishing composition after polishing, uses wool wheel that steel disc is polished to minute surface, then naturally cools to room temperature; Described ultrasonic cleaning comprises washing, alkali cleaning, pickling and alcohol+acetone cleaning; Described washing is the greasy dirt and the rubbing paste that use steel disc clean-out system and washing to remove steel disc left on surfaces after polishing; Described alkali cleaning is use NaOH-Starso mixed ammonium/alkali solutions to carry out ultrasonic cleaning 10min to the steel disc after washing, and wherein, in described mixed ammonium/alkali solutions, the mass concentration of NaOH is 3%, the mass concentration of Starso is 1%; Described pickling to be functional quality concentration be 1% hydrochloric acid soln ultrasonic cleaning 5min is carried out to the steel disc after alkali cleaning; The dehydrated alcohol that described alcohol+acetone cleaning is use volume ratio is 1:1 and the mixing solutions of acetone are to the steel disc ultrasonic cleaning 10min after pickling.After finally using rinsed with deionized water steel disc, naturally dry stand-by.
6) the deposition mixed solution C that step 4) obtains put into by the steel disc after step 5) being dried, and after depositing 15h, takes out, and rinsed well with distilled water, naturally dry under 40 DEG C of water bath condition.
7) print after step 6) being dried is put into high temperature Muffle furnace and is warming up to 600 DEG C of insulation calcinings 2 hours with the temperature rise rate of 3 DEG C/min;
8) take out after the metal naturally cooling after step 7) being calcined, obtain protection against corrosion steel disc, described anticorrosion steel disc surface is described TiO
2-ZrO
2coating.
To obtained, there is TiO
2-ZrO
2the stainless steel substrates of coating carries out SEM sign, the results are shown in Figure 1 ~ Fig. 2, can find out that coatingsurface is the ZrO of 20-30nm by particle diameter
2and TiO
2particle is formed, and coatingsurface is fine and close, without cracking.
To obtained, there is TiO
2-ZrO
2the stainless steel substrates of coating carries out EDS power spectrum sign, and the results are shown in Figure 3 ~ Fig. 4, in known coating, Ti and Zr constituent content is about 2.27% and 1.97%.
embodiment 2 one kinds of anticorrosive TiO 2 -ZrO 2 the liquid deposition preparation method of coating:
1) standard measures 200mL distilled water, is divided into four parts, is respectively 20mL, 80mL, 70mL and 30mL, dissolves 0.40g (NH respectively
4)
2tiF
6(mass content 98%), 0.12gH
3bO
3(mass content 99.5%), 0.73gZr (SO
4)
24H
2o(mass content 98%) and 0.23g (NH
4)
2s
2o
8(mass content is 98%).Obtain (NH
4)
2tiF
6the aqueous solution, H
3bO
3the aqueous solution, Zr (SO
4)
2the aqueous solution and (NH
4)
2s
2o
8the aqueous solution; Filter respectively after gained solution left standstill and remove naked eyes visible particle, stand-by.
2) by (NH
4)
2tiF
6the aqueous solution and H
3bO
3after aqueous solution, then filter, obtain settled solution A.
3) by Zr (SO
4)
2the aqueous solution and (NH
4)
2s
2o
8settled solution B is obtained after aqueous solution.
4) by A and B solution mix and blend, obtaining mixed deposit liquid C is 200mL, (NH in mixed deposit liquid C
4)
2tiF
6, H
3bO
3, Zr (SO
4)
2(NH
4)
2s
2o
8volumetric molar concentration is respectively 0.01mol/L, 0.01mol/L, 0.01mol/L and 0.005mol/L.
5) get that steel disc carries out polishing successively, polishing and ultrasonic cleaning process, the steel disc after process is dried naturally; Described polishing uses electric grinding machine, selects boron nitride grinding wheel, flap disc, nylon wheel and rubber wheel to polish to steel disc successively, and steel disc surface, significantly cut and oxide on surface polish off; Described being finished to is contained in wool wheel on electric grinding machine, first polishes after heating up to steel disc surface, then the steel disc surface smear green polishing composition after polishing, uses wool wheel that steel disc is polished to minute surface, then naturally cools to room temperature; Described ultrasonic cleaning comprises washing, alkali cleaning, pickling and alcohol+acetone cleaning; Described washing is the greasy dirt and the rubbing paste that use steel disc clean-out system and washing to remove steel disc left on surfaces after polishing; Described alkali cleaning is use NaOH-Starso mixed ammonium/alkali solutions to carry out ultrasonic cleaning 10min to the steel disc after washing, and wherein, in described mixed ammonium/alkali solutions, the mass concentration of NaOH is 3%, the mass concentration of Starso is 1%; Described pickling to be functional quality concentration be 1% hydrochloric acid soln ultrasonic cleaning 5min is carried out to the steel disc after alkali cleaning; The dehydrated alcohol that described alcohol+acetone cleaning is use volume ratio is 1:1 and the mixing solutions of acetone are to the steel disc ultrasonic cleaning 10min after pickling.After finally using rinsed with deionized water steel disc, naturally dry stand-by.
6) the deposition mixed solution C that step 4) obtains put into by the steel disc after step 5) being dried, and after depositing 5h, takes out, and rinsed well with distilled water, naturally dry under 20 DEG C of water bath condition.
7) print after step 6) being dried is put into high temperature Muffle furnace and is warming up to 400 DEG C of insulation calcinings 2 hours with the temperature rise rate of 2 DEG C/min;
8) take out after the metal naturally cooling after step 7) being calcined, obtain protection against corrosion steel disc, described anticorrosion steel disc surface is described TiO
2-ZrO
2coating.
To obtained, there is TiO
2-ZrO
2the stainless steel substrates of coating carries out SEM sign, the results are shown in Figure 5 ~ Fig. 6.Find out that coatingsurface is the ZrO of 20-30nm by particle diameter by Fig. 5 and Fig. 6
2and TiO
2particle is formed, and coatingsurface is fine and close, without cracking.
To obtained, there is TiO
2-ZrO
2the stainless steel substrates of coating carries out EDS power spectrum sign, and the results are shown in Figure 7 ~ Fig. 9, in known coating, Ti and Zr constituent content is about 2.24% and 0.99%.
embodiment 3 one kinds of anticorrosive TiO 2 -ZrO 2 the liquid deposition preparation method of coating:
1) standard measures 200mL distilled water, is divided into four parts, is respectively 20mL, 80mL, 70mL and 30mL, dissolves 8.08g (NH respectively
4)
2tiF
6(mass content 98%), 9.94gH
3bO
3(mass content 99.5%), 7.25gZr (SO
4)
24H
2o(mass content 98%) and 27.94g (NH
4)
2s
2o
8(mass content is 98%).Obtain (NH
4)
2tiF
6the aqueous solution, H
3bO
3the aqueous solution, Zr (SO
4)
2the aqueous solution and (NH
4)
2s
2o
8the aqueous solution; Filter respectively after gained solution left standstill and remove naked eyes visible particle, stand-by.
2) by (NH
4)
2tiF
6the aqueous solution and H
3bO
3after aqueous solution, then filter, obtain settled solution A.
3) by Zr (SO
4)
2the aqueous solution and (NH
4)
2s
2o
8settled solution B is obtained after aqueous solution.
4) by A and B solution mix and blend, obtaining mixed deposit liquid C is 200mL, (NH in mixed deposit liquid C
4)
2tiF
6, H
3bO
3, Zr (SO
4)
2(NH
4)
2s
2o
8volumetric molar concentration is respectively 0.2mol/L, 0.8mol/L, 0.1mol/L and 0.6mol/L.
5) get that steel disc carries out polishing successively, polishing and ultrasonic cleaning process, the steel disc after process is dried naturally; Described polishing uses electric grinding machine, selects boron nitride grinding wheel, flap disc, nylon wheel and rubber wheel to polish to steel disc successively, and steel disc surface, significantly cut and oxide on surface polish off; Described being finished to is contained in wool wheel on electric grinding machine, first polishes after heating up to steel disc surface, then the steel disc surface smear green polishing composition after polishing, uses wool wheel that steel disc is polished to minute surface, then naturally cools to room temperature; Described ultrasonic cleaning comprises washing, alkali cleaning, pickling and alcohol+acetone cleaning; Described washing is the greasy dirt and the rubbing paste that use steel disc clean-out system and washing to remove steel disc left on surfaces after polishing; Described alkali cleaning is use NaOH-Starso mixed ammonium/alkali solutions to carry out ultrasonic cleaning 10min to the steel disc after washing, and wherein, in described mixed ammonium/alkali solutions, the mass concentration of NaOH is 3%, the mass concentration of Starso is 1%; Described pickling to be functional quality concentration be 1% hydrochloric acid soln ultrasonic cleaning 5min is carried out to the steel disc after alkali cleaning; The dehydrated alcohol that described alcohol+acetone cleaning is use volume ratio is 1:1 and the mixing solutions of acetone are to the steel disc ultrasonic cleaning 10min after pickling.After finally using rinsed with deionized water steel disc, naturally dry stand-by.
6) the deposition mixed solution C that step 4) obtains put into by the steel disc after step 5) being dried, and after depositing 48h, takes out, and rinsed well with distilled water, naturally dry under 20 DEG C of water bath condition.
7) print after step 6) being dried is put into high temperature Muffle furnace and is warming up to 400 DEG C of insulation calcinings 2 hours with the temperature rise rate of 5 DEG C/min;
8) take out after the metal naturally cooling after step 7) being calcined, obtain protection against corrosion steel disc, described anticorrosion steel disc surface is described TiO
2-ZrO
2coating.
To obtained, there is TiO
2-ZrO
2the stainless steel substrates of coating carries out SEM sign, the results are shown in Figure 9 ~ Figure 10, can find out that coatingsurface is the ZrO of 20-30nm by particle diameter
2and TiO
2particle is formed, and coatingsurface is fine and close, without cracking.Skewed striped in coating is the polishing scratch of polishing substrate.
To obtained, there is TiO
2-ZrO
2the stainless steel substrates of coating carries out EDS power spectrum sign, and the results are shown in Figure 11 ~ Figure 12, in known coating, Ti and Zr constituent content is about 3.27% and 2.97%.
What obtain above-described embodiment 1 ~ 3 has TiO
2-ZrO
2the antiseptic property of the stainless steel substrates of coating is tested, and result is as shown in Figure 13 and table 1; The polarization Tafel curve of embodiment 1, embodiment 2 and embodiment 3 and untreated stainless steel SS is reflected in Figure 13, ordinate zou Potential in Figure 13, Evs.SCE/V refers to that electrochemical workstation compares the scanning current potential of saturated calomel electrode, X-coordinate Currentdensity, lg (| i|/Acm
2) take the value after logarithm for the sweep current density of electrochemical workstation, Case1 curve be embodiment 1 obtained there is TiO
2-ZrO
2result after the electrochemistry Tafel polarization test after 50 DEG C of GEOTHERMAL WATER soak 30 days of the stainless steel substrates of coating, Case2 curve be embodiment 2 obtained there is TiO
2-ZrO
2result after the electrochemistry Tafel polarization test after 60 DEG C of GEOTHERMAL WATER soak 30 days of the stainless steel substrates of coating, Case3 curve be embodiment 3 obtained there is TiO
2-ZrO
2result after the electrochemistry Tafel polarization test after 90 DEG C of GEOTHERMAL WATER soak 30 days of the stainless steel substrates of coating, SS curve is the result after the electrochemistry Tafel polarization test of untreated stainless steel after 50 DEG C of GEOTHERMAL WATER soak 30 days.
The Tafel curve calculation result drawn in table 1 Figure 13
| Numbering | E vs. SCE /V | β a(V/dec) | β b(V/dec) | I corr/(A/cm 2) | R p/(Ω·cm 2) | CR(mm/a) |
| SS | -0.8115 | 0.3180 | 0.2485 | 4.85E-05 | 1247.720 | 0.369 |
| Example 1 | -0.6601 | 1.5883 | 0.5898 | 7.16E-06 | 26095.216 | 0.054 |
| Example 2 | -0.6430 | 0.7333 | 0.5078 | 4.53E-06 | 28772.275 | 0.034 |
| Example 3 | -0.7895 | 0.4336 | 0.3973 | 4.78E-06 | 18846.419 | 0.036 |
Found out by Figure 13 and table 1, corrosion electric current density decline about 1 order of magnitude of the polarization curve of stainless steel substrates in GEOTHERMAL WATER solution after embodiment 1,2 and 3 processes, polarization resistance (Rp) improves 20.9,23.1 and 15.1 times respectively, year erosion rate (CR) improves 85.%, 90.7% and 90.2% respectively; Illustrate that the inventive method effectively improves the corrosion resistance nature of stainless steel (metal), achieve excellent anticorrosion effect.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. an anticorrosive TiO
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, comprises the steps:
1) (the NH that mol ratio is 1:1 ~ 4 is accurately taken
4)
2tiF
6and H
3bO
3, be mixed with (NH respectively
4)
2tiF
6the aqueous solution and H
3bO
3the aqueous solution;
2) by (NH of step 1) preparation
4)
2tiF
6the aqueous solution and H
3bO
3the aqueous solution leaves standstill respectively and filters, and after two kinds of solution mixing after filtration, then filters, obtains the mixed aqueous solution A clarified;
3) Zr (SO that mol ratio is 1:0.5 ~ 6 is accurately taken
4)
24H
2o and (NH
4)
2s
2o
8, be mixed with Zr (SO respectively
4)
2the aqueous solution and (NH
4)
2s
2o
8the aqueous solution; By described Zr (SO
4)
2the aqueous solution and (NH
4)
2s
2o
8mixed aqueous solution B is obtained after aqueous solution;
4) by step 2) the mixed aqueous solution B that obtains of the mixed aqueous solution A that obtains and step 3) mixes, and adds distilled water diluting adjustment, makes (NH in mixed solution
4)
2tiF
6concentration be 0.01 ~ 0.2mol/L, Zr (SO
4)
2concentration be 0.01 ~ 0.1mol/L, obtain deposition mixed solution C;
5) get that metal carries out polishing successively, polishing and ultrasonic cleaning process, the metal after process is dried naturally;
6) metal after step 5) being dried puts into the deposition mixed solution C that step 4) obtains, under 20 ~ 80 DEG C of water bath condition, deposit 5 ~ 48h;
7) the metal distilled water after step 6) depositing treatment cleaned up and after naturally drying, put into high temperature Muffle furnace and be warming up to 400 ~ 800 DEG C of insulation calcinings 1 ~ 5 hour;
8) take out after the metal naturally cooling after step 7) being calcined, obtain described TiO in metallic surface
2-ZrO
2coating.
2. anticorrosive TiO according to claim 1
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, (NH in step 1)
4)
2tiF
6and H
3bO
3mol ratio be 1:2.
3. anticorrosive TiO according to claim 1
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, Zr (SO in step 3)
4)
2(NH
4)
2s
2o
8mol ratio be 1:3.
4. anticorrosive TiO according to claim 1
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, described in step 5), polishing is for select boron nitride grinding wheel, flap disc, nylon wheel and rubber wheel to polish to metal successively, and obvious for metallic surface cut and oxide on surface are polished off.
5. anticorrosive TiO according to claim 1
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, is finished to the metallic surface after polishing and smears green polishing composition described in step 5), and medal polish to minute surface, is then naturally cooled to room temperature by use wool wheel.
6. anticorrosive TiO according to claim 1
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, ultrasonic cleaning described in step 5) comprises washing, alkali cleaning, pickling and alcohol+acetone cleaning; Described washing is the greasy dirt and rubbing paste that after using metal cleaner and washing to go polishing, metallic surface remain; Described alkali cleaning is use NaOH-Starso mixed ammonium/alkali solutions to carry out ultrasonic cleaning 10min to the metal after washing, and wherein, in described mixed ammonium/alkali solutions, the mass concentration of NaOH is 3%, the mass concentration of Starso is 1%; Described pickling to be functional quality concentration be 1% hydrochloric acid soln ultrasonic cleaning 5min is carried out to the metal after alkali cleaning; The dehydrated alcohol that described alcohol+acetone cleaning is use volume ratio is 1:1 and the mixing solutions of acetone are to the metal ultrasonic cleaning 10min after pickling.
7. anticorrosive TiO according to claim 1
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, step 6) deposits 15h under 30 DEG C of water bath condition.
8. anticorrosive TiO according to claim 1
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, retort furnace described in step 7) heats up with the temperature rise rate of 2 ~ 5 DEG C/min.
9. anticorrosive TiO according to claim 1
2-ZrO
2the liquid deposition preparation method of coating, is characterized in that, is warming up to 600 DEG C of insulation calcinings 2 hours in step 7).
10. a corrosion-resistant metal, is characterized in that, described metallic surface is covered with the TiO adopting the arbitrary described preparation method of claim 1 ~ 9 to obtain
2-ZrO
2coating.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835078A (en) * | 2017-01-20 | 2017-06-13 | 陕西科技大学 | A kind of structure of trap Ag/TiO2The preparation method of/Au coatings |
| CN107604220A (en) * | 2017-10-01 | 2018-01-19 | 新沂市中诺新材料科技有限公司 | A kind of high-plasticity aluminum alloy processing technology |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215698A (en) * | 2007-12-28 | 2008-07-09 | 天津大学 | Method for preparing film surface of nanometer-stage thickness on red copper surface |
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|---|---|---|---|---|
| CN101215698A (en) * | 2007-12-28 | 2008-07-09 | 天津大学 | Method for preparing film surface of nanometer-stage thickness on red copper surface |
Non-Patent Citations (2)
| Title |
|---|
| HANY M. ABD EL-LATEEF ET AL.: "Corrosion resistance of ZrO2–TiO2 nanocomposite multilayer thin films coated on carbon steel in hydrochloric acid solution", 《MATERIALS CHARACTERIZATION》 * |
| JAIN-MING LIN ET AL.: "Deposition of ZrO2 film by liquid phase deposition", 《JOURNAL OF POWER SOURCES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835078A (en) * | 2017-01-20 | 2017-06-13 | 陕西科技大学 | A kind of structure of trap Ag/TiO2The preparation method of/Au coatings |
| CN106835078B (en) * | 2017-01-20 | 2019-02-01 | 陕西科技大学 | A kind of structure of trap Ag/TiO2The preparation method of/Au coating |
| CN107604220A (en) * | 2017-10-01 | 2018-01-19 | 新沂市中诺新材料科技有限公司 | A kind of high-plasticity aluminum alloy processing technology |
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