CN1782138A - Anti-chlorine ion corrosion Ni-Cr nano composite coating and preparing method and use - Google Patents
Anti-chlorine ion corrosion Ni-Cr nano composite coating and preparing method and use Download PDFInfo
- Publication number
- CN1782138A CN1782138A CN 200410082839 CN200410082839A CN1782138A CN 1782138 A CN1782138 A CN 1782138A CN 200410082839 CN200410082839 CN 200410082839 CN 200410082839 A CN200410082839 A CN 200410082839A CN 1782138 A CN1782138 A CN 1782138A
- Authority
- CN
- China
- Prior art keywords
- nano
- composite plate
- coating
- preparation
- chlorine ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 54
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 54
- 238000005260 corrosion Methods 0.000 title claims abstract description 39
- 230000007797 corrosion Effects 0.000 title claims abstract description 39
- 229910018487 Ni—Cr Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000007747 plating Methods 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000011780 sodium chloride Substances 0.000 claims description 21
- 238000000992 sputter etching Methods 0.000 claims description 19
- 230000036571 hydration Effects 0.000 claims description 11
- 238000006703 hydration reaction Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000013535 sea water Substances 0.000 claims description 2
- 239000011253 protective coating Substances 0.000 claims 1
- 238000009827 uniform distribution Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 25
- 229910045601 alloy Inorganic materials 0.000 abstract description 23
- 239000000956 alloy Substances 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 229910001120 nichrome Inorganic materials 0.000 abstract 1
- 238000002161 passivation Methods 0.000 description 16
- 230000010287 polarization Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
本发明公开一种耐氯离子腐蚀的Ni－Cr纳米复合镀层及制备方法和应用。其成分为纳米尺寸金属Ni及Cr，按质量百分数计，Cr含量为4－15％，余量为Ni。制备：以金属Ni为基材，在基材上采用常规共电沉积技术复合电镀金属Ni和Cr颗粒，制得Ni－Cr纳米复合镀层。用这种方法制备的纳米复合镀层，比相近Cr含量的NiCr合金和复合微米Cr颗粒的Ni－Cr镀层的耐蚀性能明显提高。本发明工艺简单、成熟，易于推广，生产和维修成本低；镀层致密、成分均匀。纳米复合镀层表面在含Cl离子的水溶液中，能够迅速形成水合的含Cr氧化物和氢氧化物，具有良好的耐Cl离子腐蚀性能。The invention discloses a chloride ion corrosion-resistant Ni-Cr nanocomposite coating, a preparation method and an application. Its composition is nano-sized metal Ni and Cr, and the content of Cr is 4-15% by mass percentage, and the balance is Ni. Preparation: Ni-Cr nanocomposite coating is prepared by using metal Ni as the substrate, and using conventional co-electrodeposition technology to composite electroplate metal Ni and Cr particles on the substrate. Compared with NiCr alloy with similar Cr content and Ni-Cr coating with composite micron Cr particles, the corrosion resistance of the nanocomposite coating prepared by this method is obviously improved. The invention has simple and mature technology, is easy to popularize, and has low production and maintenance costs; the plating layer is compact and has uniform composition. The surface of the nanocomposite coating can quickly form hydrated Cr-containing oxides and hydroxides in an aqueous solution containing Cl ions, and has good corrosion resistance to Cl ions.
Description
Technical field
The present invention relates to coating technology, specifically a kind of metal matrix (Ni-Cr) nano-composite plate and preparation method and application of disperse distribution Cr nano particle of anti-Cl ion etching.
Background technology
The metallic substance that uses in containing the Cl ionic medium (for example: be used for associated materials such as marine naval vessels, submarine, oil drilling facility) needs good anti-Cl ion etching ability.Usually, most of military service steel (for example carbon steel and low alloy steel) can not form the hydration passive film of stable, complete protectiveness Cr, thereby anti-Cl ion etching ability are undesirable owing to do not contain Cr or Cr content is low.According to the literature; for ferrite or austenitic stainless steel; the needed Cr content of hydration passive film that forms the Cr of protectiveness is greater than 20% (mass percent), and the content of its requirement is greater than great majority ferrite commonly used or the Cr content in the austenitic stainless steel.Consider that too high Cr content can make steel brittleness increase and affects the mechanical properties.Therefore desire improves the anti-Cl ion etching ability of steel, and applying protective layer at steel surface is one of effective ways.Composite plating is that the seventies begins to be used for the surface-treated processing method, and its feature is that technology is simple, ripe, is easy to promote, and production and maintenance cost are low.Its ultimate principle is to realize a kind of technological process of codeposition at cathode surface by insoluble solid particle and metal or alloy composition.The present invention adopts the metal-method of nano-metal particle coelectrodeposition to prepare the composite deposite of anti-Cl ion etching, does not also report at present.
Summary of the invention
At above-mentioned deficiency, the object of the invention is to provide a kind of have coating densification, the uniform Ni-Cr nano-composite plate of composition and preparation method and application, guarantees good anti-Cl ion etching performance.
Technical scheme of the present invention is as follows:
The metal-base nano-composite cladding material of the disperse distribution Cr nano particle of anti-Cl ion etching, its composition is the combination (Ni crystal grain and Cr particle size are nano level) of sedimentary nanocrystalline metal Ni and Cr nano particle, by mass percentage, the content of Cr is 4-15%, and surplus is Ni.
Its preparation method is to be base material with Ni, adopts routine techniques, realizes the coelectrodeposition of Ni and nanometer Cr powder (median size 39nm), preparation metal Ni-Cr type nano-composite plate.By mass percentage, the content of Cr is 4-15%, and surplus is Ni.The plating bath of Ni-Cr nano-composite plate preparation is low temperature vitriol plating Ni solution (NiSO
4).Keep nano particle to be suspended in the tank liquor during plating, composite plating equipment is plate pump formula electroplanting device.
What the passive film surface of the Ni-Cr nano-composite plate of the present invention preparation easily formed hydration contains Cr oxide compound and oxyhydroxide, has good anti-Cl ion etching performance.The film formed ultimate principle of passivation is as follows: the Ni-Cr nano-composite plate of acquisition; because nanometer Cr powder is evenly distributed in the nanometer crystalline Ni; compare with the composite deposite of the micron-sized Cr that contains same amount; greatly improved the particle number of Cr in the unit surface; coating surface forms more active site like this; has higher surface active energy; principle according to optimum solvation; under the effect of current potential; these Cr active sites can be rapidly and the dissolved oxygen in aqueous medium or OH ion form Cr-O or Cr-OH bonding; formation has oxide compound and the hydroxide film of the hydration Cr of good protection, thereby suppresses the dissolving of Ni.
With traditional composite deposite and alloy phase ratio with metal-micron order metal powder preparation, advantage of the present invention is as follows:
1. the passive film surface energy forms hydrous oxide and the hydroxide film of the Cr with good protection.The present invention adopts the Ni-Cr nano-composite plate of Ni-Cr nano particle coelectrodeposition preparation.Having 1) porosity is low; 2) coating densification; Characteristics such as 3) composition is even.Particularly in containing Cl ionic medium, form the hydrous oxide of Cr and the passive film of oxyhydroxide, have good anti-Cl ion etching performance.
2. improved the coating pitting resistance greatly.Compare with single Ni coating in the prior art, show than breaking up current potential with higher spot corrosion between long passivation region, the Ni-Cr coating and the Ni-Cr alloy phase ratio of close compound micron particles with containing the Cr amount, composite deposite of the present invention shows: can form the hydrous oxide of Cr and the passive film of oxyhydroxide, has splendid corrosion-resistant ability, and the passive film that the Ni-Cr coating of Ni-Cr alloy and compound micron particles forms is mainly hydrous oxide and the oxyhydroxide of Ni, and corrosion resisting property is poor.
3. technique for preparing coating is simple, ripe, cost is low.Because electroplating is sophisticated technology, utilizes existing plating equipment, in tank liquor, add the nanometer Cr powder of aequum, and nano particle is suspended in tank liquor and be uniformly dispersed by certain technology, just can be made into this novel nano composite deposite, investment is not quite.
4. applied widely.Nano-composite plate of the present invention can be used as and the protective layer that contains the military service metallic substance that the Cl ionic medium directly contacts, can be at ocean naval vessels, job platform facility, and aspect such as pipelines and petrochemical pipelines obtains extensively to quote.
Description of drawings
Fig. 1 is the optical photograph of Ni-10.9Cr (mass percent, the as follows) nano-composite plate of one embodiment of the invention.
Fig. 2 is the stereoscan photograph of the Ni-10.9Cr nano-composite plate of one embodiment of the invention.
Fig. 3 is the transmission electron microscope photo of the Ni-10.9Cr nano-composite plate of one embodiment of the invention.
Fig. 4 is the X-ray diffraction result of the Ni-10.9Cr nano-composite plate of one embodiment of the invention.
Fig. 5 is that single Ni coating, Ni-4.5Cr and the Ni-10.9Cr nano-composite plate of one embodiment of the invention is at the molten electrokinetic potential polarization curve comparison diagram in two of 3.5%NaCl.
Fig. 6-1a is Ni-10.9Cr nano-composite plate spot corrosion pattern in 3.5%NaCl solution of one embodiment of the invention.
Fig. 6-1b is that pattern is amplified in Ni-10.9Cr nano-composite plate spot corrosion in 3.5%NaCl solution of one embodiment of the invention.
Fig. 6-2a is single Ni coating spot corrosion pattern in 3.5%NaCl solution of one embodiment of the invention.
Fig. 6-2b is that pattern is amplified in single Ni coating spot corrosion in 3.5%NaCl solution of one embodiment of the invention.
Fig. 7 is the Ni-10.9Cr nano-composite plate of one embodiment of the invention and the electrokinetic potential polarization curve comparison diagram of Ni-12.4Cr coating in 3.5%NaCl solution of compound micron particles.
Fig. 8 is the Ni-10.9Cr nano-composite plate of one embodiment of the invention and the constant potential comparison diagram of Ni-12.4Cr coating in 3.5%NaCl solution of compound micron particles.
Fig. 9 is the optical photograph of Ni-12.4Cr coating of the compound micron particles of one embodiment of the invention.
Figure 10 is the scanning electron microscope pattern of Ni-12.4Cr coating of the compound micron particles of one embodiment of the invention.
Figure 11 is the Ni-10.9Cr nano-composite plate and the electrokinetic potential polarization curve comparison diagram of Ni-10Cr alloy in 3.5%NaCl solution of one embodiment of the invention.
Figure 12 is the Ni-10.9Cr nano-composite plate and the constant potential comparison diagram of Ni-10Cr alloy in 3.5%NaCl solution of one embodiment of the invention.
Figure 13 is that the Ni-10.9Cr nano-composite plate of one embodiment of the invention is at-0.1V, the full spectrogram of the XPS of passive film in the 3.5%NaCl solution.
Figure 14 is that the Ni-12.4Cr coating of compound micron particles of one embodiment of the invention is at-0.1V, the full spectrogram of the XPS of passive film in the 3.5%NaCl solution.
Figure 15 is that the Ni-10Cr alloy of one embodiment of the invention is at-0.1V, the full spectrogram of the XPS of passive film in the 3.5%NaCl solution.
The Ni-10.9Cr nano-composite plate that Figure 16 a-Figure 16 c is respectively one embodiment of the invention is at-0.1V, the XPS of the Cr2p of passive film, Ni2p and O1s figure under the 3.5%NaCl solution.
Figure 17 a-Figure 17 c is respectively the Ni-12.4Cr coating of compound micron particles of one embodiment of the invention at-0.1V, the XPS of the Cr2p of passive film, Ni2p and O1s figure under the 3.5%NaCl solution.
The Ni-10Cr alloy that Figure 18 a-Figure 18 c is respectively one embodiment of the invention is at-0.1V, the XPS of the Cr2p of passive film, Ni2p and O1s figure under the 3.5%NaCl solution.
Table 1 is that single Ni coating, Ni-4.5Cr and the Ni-10.9Cr nano-composite plate electrokinetic potential polarization curve parameter fitting in 3.5%NaCl solution of one embodiment of the invention compares.
Table 2 is that Ni-12.4Cr coating and Ni-10Cr alloy electrokinetic potential polarization curve parameter fitting in 3.5%NaCl solution of the Ni-10.9Cr nano-composite plate of one embodiment of the invention, compound micron particles compares.
Table 3 is the Ni-12.4Cr coating of the Ni-10.9Cr nano-composite plate of one embodiment of the invention, compound micron particles and Ni-10Cr alloy at-0.1V, and the XPS quantitative result of element is relatively in the passive film under the 3.5%NaCl solution.
Table 4 is Ni-12.4Cr coating and Ni-10Cr the alloy composition in the passive film and content comparison under 3.5%NaCl solution of the Ni-10.9Cr nano-composite plate of one embodiment of the invention, compound micron particles.
Embodiment
Below in conjunction with accompanying drawing and subordinate list embodiment is described in detail the present invention.
The preparation method of Ni-Cr nano-composite plate adopts conventional coelectrodeposition technology preparation, and its flow process is:
Substrate metal Ni-surface finish is to 800# waterproof abrasive paper-surperficial ultrasonic cleaning-carry out in containing the plating Ni tank liquor of nanometer Cr powder coelectrodeposition-acquisition Ni-Cr nano-composite plate.Keep nano particle to be suspended in the tank liquor when preparation key of nano-deposit of the present invention is plating, have good dispersing property simultaneously.Preparation process of the present invention is specific as follows:
The electrolysis Ni plate of getting purity 99.96% is a base material, is processed into the small sample of 15 * 10 * 2mm size, is milled to 800 through silicon carbide paper
#, ultrasonic cleaning in acetone;
Get particle diameter in the 10nm-80nm scope, mean particle size is that the nanometer Cr powder (in by Beijing Condar Nanosolutions GmbH preparation) of 39nm is immersed in the sodium dodecyl sulfate solution earlier, so that the homodisperse of nano particle is avoided reuniting;
Electroplate liquid adopts the low temperature modification plating bath, and composition is as follows: NiSO
4.7H
2O 150g/l, NH
4Cl 15g/l, H
3BO
315g/l, C
12H
25NaO
4S 0.1g/l; The solution of preparation is placed 24h through fully stirring after-filtration; The solution pH value can use in the 5.4-5.6 scope.
Adopt plate pump formula device to stir plating bath in the electrodeposition process, to guarantee the suspension of nano particle in the plating bath, uniform deposition is at specimen surface; Bath temperature is 30 ℃, current density I=3A/dm
2, stirring velocity is 110rpm.Electroplating time is 3h, and sample mean thickness is 100 μ m.
The compounding quantity of the nanometer Cr powder in the coating increases with the increase of Cr in the plating bath.It is the experimental data of 10.9% Ni-Cr nano-composite plate that present embodiment provides compounding quantity.Fig. 1 is the optical photograph of Ni-Cr nano-composite plate.Can see even particle distribution on the coating, coating combines well with basal body interface.Fig. 2-Fig. 3 is respectively the scanning electron microscope and the transmission electron microscope photo of Ni-Cr nano-composite plate.As can be known, coating densification (no micro-crack and cavity between coating Ni intercrystalline and Ni/ nano particle interface), crystal grain is tiny.Fig. 4 is the X-ray diffraction result of Ni-10.9Cr nano-composite plate, obtains grain fineness number average out to 31nm by Scherrer (Scherrer) formula corrected Calculation.
Present embodiment has compared the corrosion resisting property of the Ni-Cr nano-composite plate (ENNC:Electrodepositednanoparticle-dispersed nanocomposite coating) of different Cr content.
Utilize EG﹠amp; M273 type potentiostat and PAR M352 electro-chemical test system that G company produces carry out the electrochemical corrosion performance test to single Ni coating (ENNC Ni-0Cr), ENNC Ni-4.5Cr and ENNC Ni-10.9Cr (mass percent, as follows) respectively.The three-electrode system of experiment employing standard: sample is that working electrode (WE), platinized platinum are that supporting electrode (AE), saturated calomel electrode (SCE) are reference electrode (RE), and all current potentials are reference with it all.Experimental data is an automatic record under micro computer monitoring, and carries out curve fitting and the kinetic parameter processing with the software that the M352 system wears.Experimental temperature is a room temperature, and corrosive medium is 3.5%NaCl solution (suitable with the salt amount of seawater).The scope of polarization test is relative open circuit potential-0.5V-0.4V, and sweep velocity is 0.5mV/s.The electrokinetic potential polarization curve comparative result of three kinds of samples as shown in Figure 5, the electrochemical parameter of software match is as shown in table 1.As seen, the spot corrosion of ENNC Ni-10.9Cr is broken up between current potential and passivation region greater than ENNC Ni-4.5Cr, and the spot corrosion of ENNC Ni-4.5Cr breaks up between current potential and passivation region greater than ENNC Ni-0Cr, and anti-Cl ion etching performance the best of ENNC Ni-10.9Cr is described; The anti-Cl ion etching performance of ENNCNi-4.5Cr is taken second place, and ENNC Ni-0Cr is the poorest; From the comparison diagram of spot corrosion pattern (Fig. 6-1a, Fig. 6-1b, Fig. 6-2a, Fig. 6-2b) as can be known, the ENNC Ni-10.9Cr surface overwhelming majority does not have spot corrosion to produce, only the defective that might be coating at indivedual some places or when electroplating Cr powder skewness (these phenomenons all can be avoided by regulating electroplating technological parameter) cause point corrosion pit, but point corrosion pit is not dark, and the ENNCNi-0Cr surface produces a large amount of some pits, many and the hole depth of the quantity in hole erodes to matrix, illustrates that the Cl ion etching speed of ENNC Ni-0Cr will be far longer than ENNC Ni-10.9Cr.From the comparative result of above-mentioned three kinds of samples as can be known, the anti-Cl ion etching performance of coating strengthens along with the increase of Cr content.
Present embodiment has compared the corrosion resisting property of the Ni-Cr coating (EMCC:Electrodeposited microparticle-dispersed composite coating) of ENNC Ni-Cr and compound micron particles.
For further studying the corrosion resisting property of ENNC, adopt above-mentioned same equipment and identical parameters and standard three-electrode system, respectively ENNC Ni-10.9Cr and EMCC Ni-12.4Cr electrokinetic potential polarization curve and constant potential I-t curve are tested, Fig. 7 is an electrokinetic potential polarization curve test result.As can be known, under the close situation of Cr content, the spot corrosion of ENNC Ni-10.9Cr is broken up current potential and passivation interval range greater than EMCC Ni-12.4Cr (table 2), thereby the pitting resistance of ENNC Ni-10.9C is better than EMCC Ni-12.4Cr.Fig. 8 is that two kinds of coating are in the I-t curve of (E=-0.1V) between passivation region.As seen, the anodic current density of ENNCNi-10.9Cr passive film is less than 4 times EMCC Ni-12.4Cr, and anodic current reaches steady state in the short period of time, and the anodic current density fluctuation of EMCC Ni-12.4 surface is bigger, anodic current needs the long relatively time to reach stable state, illustrate that the ENNCNi-10.9Cr passivation ability is stronger than EMCC Ni-12.4, thereby illustrate that also the ENNCNi-10.9C corrosion resisting property is better than EMCC Ni-12.4.Top result why occurring is because the condition of surface of coating influences anti-Cl ion etching performance.For ENNC Ni-10.9Cr, can see that particle distribution is even, crystal grain is tiny, the coating densification (Fig. 1-Fig. 3), the anodic current fluctuation that causes under the current potential effect is little, and under the competent situation of Cr content, reach passive state very soon, passivation current is low, and inactivating performance is good, and the EMCCNi-12.4 surface irregularity, coating is not fine and close, uneven components (Fig. 9,10) causes the fluctuation of bigger anodic current, and through just reaching passive state for a long time, and anodic current is much larger than ENNC Ni-10.9Cr's, inactivating performance is bad, thereby anti-Cl ion etching poor performance.
Present embodiment compares ENNC Ni-Cr and arc melting Ni-Cr corrosion resistance of alloy compares.
Adopt above-mentioned same equipment and identical parameters and standard three-electrode system, ENNC Ni-10.9Cr and Ni-10Cr alloy electrokinetic potential polarization curve are tested, as shown in figure 11.As shown in Table 2, the spot corrosion of ENNC Ni-10.9Cr is broken up between current potential height, passivation region than the length of Ni-10Cr alloy, and anti-pitting performance is better than Ni-10Cr alloy.From the I-t curve ratio of Figure 12 more as can be known: the anodic current of Ni-10Cr alloy is greater than ENNC Ni-10.9Cr, and the needed time of time ratio ENNC Ni-10.9Cr that reaches stable state is long, as seen the ENNC passivation ability obviously is better than the Ni-10Cr alloy, also be anti-Cl ion etching performance and Ni-10Cr alloy phase ratio, very big raising is arranged.This mainly is because the Cr content in the Ni-10Cr alloy is low, is not enough to form complete passive film.
The electrochemical parameter that specifies the ENNC Ni-10.9Cr that table 1 and table 2 provide in the embodiment 2-example 4 is different, may be owing to the fluctuation of room temperature and instrument causes, but the result that each group sample records obtains under same temperature, same state, has comparability.
Present embodiment is analyzed the passive film composition of ENNC Ni-Cr.
Be to determine in detail the composition of passive film, further studied three kinds of samples form passive film under-0.1V constant potential XPS test result.
The VGESCALAB MK II type photoelectron spectrograph that experimental installation adopts Britain VG company to produce.What x-ray source adopted is ALK α linear system, is 50eV by energy.The direction of illumination of specimen surface and linear system is 90 °, and the spectral line of all samples that records all adopts C1s (BE=284.5eV) standard to pollute the peak check and correction.The analysis software that the The data instrument of gained is provided for oneself is analyzed match, compares with the data of standard then, determines the composition and the composition of passive film.
The full spectrogram of XPS of Figure 13-Figure 15 passive film that to be three kinds of samples form under-0.1V constant potential, composition analysis is as shown in table 3.As can be known, all there is a large amount of O to exist in three kinds of specimen surface passive films, simultaneously, has Ni, Cr element to exist, illustrate that the passive film that forms on the two surface is Ni, Cr oxide compound at ENNC and alloy passivation film surface; And the existence of Cr is not detected on EMCC passive film surface, has only Ni, illustrates that the oxide compound that has only Ni on the surface of EMCC passive film exists.In addition, three kinds of sample passive films surface spectral lines all have the C1s peak to exist, and pollutent that hydrocarbon polymer is arranged in the passive film of specimen surface (might be because specimen surface is subjected to pollution cause) be described.Figure 16 (a-c)-Figure 18 (a-c) is three kinds of sample Cr2p, the spectrum test of the feature track of Ni2p and Ols surface-element, and the software of providing for oneself according to test result and instrument has carried out the swarming processing to Ni2p3/2, Cr2p3/2 and the O1s of three kinds of samples.Chemical displacement value that obtains and the contrast of the chemical displacement value of reference material, determine its kind, the area of each material that provides according to swarming software again with the mark of each element on total content that the ratio and the table 2 of entire area provides, is determined the ratio of each material in the passive film.The composition of each material and ratio are provided by table 4 in the passive film.As can be known from the results of Table 4, a large amount of constraint H is all arranged in the passive film of three kinds of specimen surfaces
2O exists, and that is to say that the oxide film in the passive film all exists with the form of hydration.The ENNC surface of passivation is the Cr (OH) with hydration
3Be that main mixing passive film is formed, the Ni-10Cr alloy surface of passivation is the Ni (OH) with hydration
2Be that main hybrid films exists, and the EMCC of passivation is the mixed oxide composition with the Ni of hydration.
More as can be known, ENNC Ni-10.9Cr is because passive surface forms is oxide compound and the oxyhydroxide with hydration Cr of protectiveness from the result of above-mentioned three kinds of samples, thereby has best pitting resistance.The passive film of this protectiveness form be because: the nanometer Cr powder on ENNC Ni-10.9Cr is evenly distributed in the nanometer crystalline Ni, the compound micron order Cr particulate coating identical with content is compared, greatly improved the particle number of Cr in the unit surface, make the nano-deposit surface have more active site, surface active can be higher, the Cr ion on nano-deposit surface can be rapidly and dissolved oxygen in the water or OH ionic bonding in aqueous medium, form Cr-O or Cr-OH key, generate oxide compound or the oxyhydroxide of Cr; Simultaneously, because coating grain refining, there is a large amount of crystal boundaries, the Cr atom of sublevel constantly along crystal boundary to coating surface/passive film interface rapid diffusion, competent Cr content is being provided at the interface, is forming the enrichment region of Cr, promoting oxide compound or the oxyhydroxide healing rapidly at short notice of Cr, form oxide compound or the hydroxide film of successive hydration Cr, and suppress the generation of NiO film.For the Ni-10Cr alloy, because crystal grain is thick, the Cr content that is diffused into the passive film surface by crystal boundary is low, can only form oxide compound and the oxyhydroxide of Ni, and solidity to corrosion is not as nano-deposit; And for EMCCNi-12.4Cr, then easily there is the tendency that forms the corrosion microbattery in because the defective of coating self (porosity height, coating are not fine and close, uneven components) between crystal grain and hole, oxide compound and the hydroxide film instability of the Ni that forms are so anti-Cl ion etching performance is the poorest.
Table 1
| Corrosion current μ Acm -2 | Corrosion potential mV | Current potential mV is broken up in spot corrosion | MV between passivation region | Tie up blunt electric current μ Acm -2 | |
| Single Ni coating | 0.217 | -196.3 | -10 | 186.3 | 1.04 |
| The Ni-4.5Cr nano-composite plate | 0.095 | -200.5 | 6 | 206.5 | 0.274 |
| The Ni-10.9Cr nano-composite plate | 0.079 | -229.1 | 49 | 278.1 | 0.266 |
Table 2
| Corrosion current μ Acm -2 | Corrosion potential mV | Current potential mV is broken up in spot corrosion | MV between passivation region | Tie up blunt electric current μ Acm -2 | |
| The Ni-10.9Cr nano-composite plate | 0.388 | -245.2 | 231 | 454.9 | 1.449 |
| The Ni-12.4Cr coating of compound micron particles | 5.052 | -247.1 | 14.9 | 32 | 14.690 |
| The Ni-10Cr alloy | 0.064 | -238.8 | 199 | 344.9 | 1.264 |
Table 3
| Ni | Cr | O | |
| The Ni-10.9Cr nano-composite plate | 8.99 | 16.25 | 74.76 |
| The Ni-12.4Cr coating of compound micron particles | 4.39 | - | 95.61 |
| The Ni-10Cr alloy | 11.58 | 7.78 | 80.65 |
Table 4
| Cr 2+ | Cr 2O 3/CrO 2 | Cr(OH) 3 | CrO 3 | Ni(OH) 2 | NiO | H 2O | |
| The Ni-10.9Cr nano-composite plate | 2.02 | 3.10 | 7.15 | 3.98 | 4.79 | 4.20 | 38.94 |
| The Ni-10Cr alloy | - | 1.62 | 1.74 | 4.41 | 8.26 | 3.32 | 60.16 |
| The Ni-12.4Cr coating of compound micron particles | - | - | - | - | 0.97 | 3.42 | 88.06 |
Claims (6)
1, a kind of Ni-Cr nano-composite plate of anti-chlorine ion corrosion is characterized in that: this coating is the combination of nano-scale metal Ni and Cr, and by mass percentage, Cr content is 4-15%, and surplus is Ni.
2, according to the preparation method of the Ni-Cr nano-composite plate of the described anti-chlorine ion corrosion of claim 1, it is characterized in that: with metal Ni is base material, on base material, adopt conventional coelectrodeposition technology composite plating metallic Ni and Cr coating, the Ni-Cr nano-composite plate of preparation; By mass percentage, the content of Cr is 4-15%, and surplus is Ni; Plating bath is low temperature vitriol plating Ni solution, and Cr powder footpath scope is 10nm-80nm.
3, according to the preparation method of the Ni-Cr nano-composite plate of the described anti-chlorine ion corrosion of claim 2, it is characterized in that: described Cr powder footpath average out to 39nm size.
4, according to the preparation method of the Ni-Cr nano-composite plate of the described anti-chlorine ion corrosion of claim 2, it is characterized in that: keep nano particle to be suspended in the tank liquor uniform distribution during plating.
5, according to the application of the Ni-Cr nano-composite plate of the described anti-chlorine ion corrosion of claim 1, it is characterized in that: described nano-composite plate can be used as the protective coating of anti-Cl ion etching, is used for the corrosive environment of sea water resistance.
6, according to the application of the Ni-Cr nano-composite plate of the described anti-chlorine ion corrosion of claim 5, it is characterized in that: the passive film that in 3.5%NaCl solution, forms be hydration contain Cr oxide compound and oxyhydroxide, have good anti-Cl ion etching performance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100828390A CN100445430C (en) | 2004-12-03 | 2004-12-03 | Application of a Ni-Cr Nanocomposite Coating Resistant to Chloride Ion Corrosion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100828390A CN100445430C (en) | 2004-12-03 | 2004-12-03 | Application of a Ni-Cr Nanocomposite Coating Resistant to Chloride Ion Corrosion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1782138A true CN1782138A (en) | 2006-06-07 |
| CN100445430C CN100445430C (en) | 2008-12-24 |
Family
ID=36772730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100828390A Expired - Fee Related CN100445430C (en) | 2004-12-03 | 2004-12-03 | Application of a Ni-Cr Nanocomposite Coating Resistant to Chloride Ion Corrosion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100445430C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494474C (en) * | 2007-06-14 | 2009-06-03 | 上海交通大学 | Method for Improving the Antibacterial and Antirust Performance of Ordinary Carbon Steel |
| CN101967669A (en) * | 2010-11-15 | 2011-02-09 | 沈阳工业大学 | Wear-resistance Ni-Cr nano composite plating, and preparation method and use thereof |
| CN104109895A (en) * | 2014-07-09 | 2014-10-22 | 哈尔滨工程大学 | Method for forming high-corrosion-resistant nickel and chromium composite coating on steel surface |
| CN104562111A (en) * | 2015-01-04 | 2015-04-29 | 上海交通大学 | Method for improving corrosion resistance of nickel-aluminum bronze |
| CN106087003A (en) * | 2016-06-13 | 2016-11-09 | 中国科学院金属研究所 | A kind of improve the method for Cr nano-particle content in Ni Cr nano-composite plate |
| CN109680313A (en) * | 2019-02-18 | 2019-04-26 | 中国恩菲工程技术有限公司 | Flue, preparation method and flue gas of refuse burning recyclable device |
| CN111286777A (en) * | 2020-03-26 | 2020-06-16 | 中国南方电网有限责任公司超高压输电公司柳州局 | Composite coating and preparation method thereof |
| CN111876801A (en) * | 2020-07-15 | 2020-11-03 | 南昌航空大学 | Crack-free Ni-Cr alloy coating and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389598A (en) * | 2002-07-07 | 2003-01-08 | 余泽玲 | Low-temperature and low-concentration electroplating process to form multilayer nano nickel coating |
| CN1176246C (en) * | 2002-11-21 | 2004-11-17 | 上海交通大学 | The Method of Reducing the Crystallization Temperature of Electroless Nickel Plating Alloy |
| FR2848219B1 (en) * | 2002-12-09 | 2006-12-01 | Centre Nat Rech Scient | COMPOSITE MATERIAL FOR USE AS LUBRICATING COATING |
| EP1616047A1 (en) * | 2003-04-11 | 2006-01-18 | Lynntech, Inc. | Compositions and coatings including quasicrystals |
| CN1291070C (en) * | 2003-07-09 | 2006-12-20 | 中国科学院金属研究所 | Thermal growth Cr203 film type M Cr nano composite plating and producing process and application |
-
2004
- 2004-12-03 CN CNB2004100828390A patent/CN100445430C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494474C (en) * | 2007-06-14 | 2009-06-03 | 上海交通大学 | Method for Improving the Antibacterial and Antirust Performance of Ordinary Carbon Steel |
| CN101967669A (en) * | 2010-11-15 | 2011-02-09 | 沈阳工业大学 | Wear-resistance Ni-Cr nano composite plating, and preparation method and use thereof |
| CN104109895A (en) * | 2014-07-09 | 2014-10-22 | 哈尔滨工程大学 | Method for forming high-corrosion-resistant nickel and chromium composite coating on steel surface |
| CN104562111A (en) * | 2015-01-04 | 2015-04-29 | 上海交通大学 | Method for improving corrosion resistance of nickel-aluminum bronze |
| CN106087003A (en) * | 2016-06-13 | 2016-11-09 | 中国科学院金属研究所 | A kind of improve the method for Cr nano-particle content in Ni Cr nano-composite plate |
| CN109680313A (en) * | 2019-02-18 | 2019-04-26 | 中国恩菲工程技术有限公司 | Flue, preparation method and flue gas of refuse burning recyclable device |
| CN111286777A (en) * | 2020-03-26 | 2020-06-16 | 中国南方电网有限责任公司超高压输电公司柳州局 | Composite coating and preparation method thereof |
| CN111876801A (en) * | 2020-07-15 | 2020-11-03 | 南昌航空大学 | Crack-free Ni-Cr alloy coating and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100445430C (en) | 2008-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Beltowska-Lehman et al. | Optimisation of the electrodeposition process of Ni-W/ZrO2 nanocomposites | |
| Yu et al. | A novel strategy to electrodeposit high-quality copper foils using composite additive and pulse superimposed on direct current | |
| ZHANG et al. | Electrodeposition and corrosion resistance of Ni–P–TiN composite coating on AZ91D magnesium alloy | |
| CN103173795B (en) | A kind of electric plating method | |
| Khodaei et al. | SiC nanoparticles incorporation in electroless NiP-Graphene oxide nanocomposite coatings | |
| Li et al. | Graphene-reinforced Zn–Ni alloy composite coating on iron substrates by pulsed reverse electrodeposition and its high corrosion resistance | |
| Karakurkchi et al. | Electrochemical deposition of Fe–Mo–W alloy coatings from citrate electrolyte | |
| Safavi et al. | The positive contribution of Cr2O3 reinforcing nanoparticles to enhanced corrosion and tribomechanical performance of Ni–Mo alloy layers electrodeposited from a citrate-sulfate bath | |
| Gao et al. | Electrochemical characteristics and interfacial contact resistance of Ni-P/TiN/PTFE coatings on Ti bipolar plates | |
| Li et al. | Construction and anti-corrosion behavior study of silanol-modified Ni-WS2 superhydrophobic composite coating | |
| Abdel Hamid et al. | Performance of Ni–Cu–ZrO2 nanocomposite coatings fabricated by electrodeposition technique | |
| Wang et al. | A study on the electrocodeposition processes and properties of Ni–SiC nanocomposite coatings | |
| CN1782138A (en) | Anti-chlorine ion corrosion Ni-Cr nano composite coating and preparing method and use | |
| Rashmi et al. | Electrodeposition of Zn–Ni monolithic coatings, characterization, and corrosion analysis | |
| Dănăilă et al. | Titanium carbide nanoparticles reinforcing nickel matrix for improving nanohardness and fretting wear properties in wet conditions | |
| CN109252147A (en) | Prepare method, chemical plating fluid and the plating liquid and preparation method thereof of copper-graphite alkene composite deposite | |
| Zhang et al. | Effects of graphene oxide and current density on structure and corrosion properties of nanocrystalline nickel coating fabricated by electrodeposition | |
| Mirsaeedghazi et al. | Characteristics and properties of Cu/nano-SiC and Cu/nano-SiC/graphite hybrid composite coatings produced by pulse electrodeposition technique | |
| Zhang et al. | Preparation and investigation of Ni-W/CeO2 composite coating and its structure and anti-corrosion properties with different ceria content and deposition time | |
| Li et al. | Investigation on corrosion resistance of electroless Ni-WP coatings co-deposited with SiO2 nanoparticles | |
| Cui et al. | Influence of electrodeposition parameters on the fabrication of Ni–Co/SiC+ TiN composite films through pulse current electrodeposition | |
| Li et al. | Preparation of Sol‐Enhanced Ni–P–Al2O3 Nanocomposite Coating by Electrodeposition | |
| Benea et al. | Tribological behavior of a Ni matrix hybrid nanocomposite reinforced by titanium carbide nanoparticles during electro-codeposition | |
| Pavlov et al. | Influence of nano-tio2 co-deposition on the morphology, microtopography and crystallinity of ni/nano-tio2 electrosynthesized nanocomposite coatings | |
| CN1291070C (en) | Thermal growth Cr203 film type M Cr nano composite plating and producing process and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081224 Termination date: 20161203 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |