Effect of manganese on the formation of hybrid zirconiumbased conversion coating on low carbon steel surface

This study revealed the effect of Mn on the formation of hybrid zirconium-based conversion coatings(HZCC)on low carbon steel.The XPS results indicated that the Mn compounds on the surface of low carbon steel were mainly MnO and Mn_(2)SiO_(4).Combined with the electrochemical measurements,the corrosion resistance of HZCC showed an increase followed by a decrease with increasing Mn concentration,which was related to the Mn_(2)SiO_(4) and SiO_(2) on the surface of low carbon steel.The excessive Mn concentration resulted in the loss of SiO_(2) and aggregation of Mn_(2)SiO_(4) on the low carbon steel surface,which caused the aggregation of Zr compounds on the surface and reduced the uniformity of the coating.Meanwhile,a moderate amount of Mn addition would be beneficial to increase the adhesion of organic coatings.

Corrosion resistance and electrical conductivity of V/Ce conversion coating on magnesium alloy AZ31B

A V/Ce conversion coating was deposited in the surface of AZ31B magnesium alloy in a solution containing vanadate and cerium nitrate.The coating composition and morphology were examined.The conversion coating appears to consist of a thin and cracked coating with a scattering of spherical particles.The corrosion behavior of the substrate and conversion coating was studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS).Compared with AZ31B magnesium alloy,the corrosion current density of the conversion coating is decreased by two orders of magnitude.The total impedance of the V/Ce conversion coating rise to 1.6×10^(3)Ω·cm^(2)in contrast with2.2×10^(2)Ω·cm^(2)of the bare AZ31B.In addition,the electrical conductivity of the coating was assessed by conductivity meter and Mott-Schottky measurement.The results reveal a high dependence of the conductivity of the coating on the semiconductor properties of the phase compositions.

Review on the phosphate-based conversion coatings of magnesium and its alloys

Magnesium(Mg)and its alloys are lightweight as well as biocompatible and possess a high strength-to-weight ratio,making them suitable for many industries,including aerospace,automobile,and medical.The major challenge is their high susceptibility to corrosion,thereby limiting their usability.The considerably lower reduction potential of Mg compared to other metals makes it vulnerable to galvanic coupling.The oxide layer on Mg offers little corrosion resistance because of its high porosity,inhomogeneity,and fragility.Chemical conversion coatings(CCs)belong to a distinct class because of underlying chemical reactions,which are fundamentally different from other types of coating.Typically,a CC acts as an intermediate sandwich layer between the base metal and an aesthetic paint.Although chromate CCs offer superior performance compared to phosphate CCs,yet still they release carcinogenic hexavalent chromium ions(Cr^(6+));therefore,their use is prohibited in most European nations under the Registration,Evaluation,Authorization and Restriction of Chemicals legislation framework.Phosphate-based CCs are a cost-effective and environment-friendly alternative.Accordingly,this review primarily focuses on different types of phosphate-based CCs,such as zinc,calcium,Mg,vanadium,manganese,and permanganate.It discusses their mechanisms,current status,pretreatment practices,and the influence of various parameters-such as pH,temperature,immersion time,and bath composition-on the coating performance.Some challenges associated with phosphate CCs and future research directions are also elaborated.

CORROSION BEHAVIOR OF A ZIRCONIUM-TITANIUM BASED PHOSPHONIC ACID CONVERSION COATING ON AA6061 ALUMINIUM ALLOY

The conversion coating was formed by dipping AA6061 in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid （ATMP） solution at room temperature. The formation process and the anti-corrosion performance of the conversion coating were investigated using electrochemical test and salt spray test （SST）, respectively. The electrochemical test shows that the Zr/Ti and ATMP coating improves the corrosion resistance of AA6061 as good as the chromate （VI） coating. But the results of SST show that the corrosion resistance of Zr/Ti and ATMP coating is not as good as the chromate （VI） coating. The corrosion area is less than 2% after 72 h.

Preparation and Corrosion Resistance of Rare Earth Conversion Coatings on AZ91 Magnesium Alloy

The feasibility of forming pollution-free and environmentally benign Ce-based rare earth conversion coatings （short for RECCs） on AZ91 magnesium alloy to enhance corrosion resistance was studied. The effect of optimum processing parameters on corrosion resistance of RECCs, such as density of treating solution, temperature and time of coating formation were discussed. Protective performance of conversion coatings on magnesium alloy was evaluated by moisture/heating test, anodic polarization, etc. The results show that Ce-based RECCs under moisture/heating condition can remain intact, with high coverage and no obvious corrosion phenomenon. Corrosion potential increases and passive phenomenon occurs while current density decreases, therefore Ce-based RECCs can improve corrosion resistance of AZ91 magnesium alloy. The morphology of Ce-based RECCs prepared under optimum process through SEM observation is found to be a few particles coherent to the base coating, and the coating has no cracks and exhibits apparent corrosion resistance during corrosion courses of AZ91 magnesium alloy.

Chemical conversion coating on AZ31B magnesium alloy and its corrosion tendency

The morphology change of the magnesium matrix after pre-treatment and the morphology as well as the phase composition of chemical conversion coating formed by phosphate were studied using scanning electron microscope and X-ray diffraction. The corrosion resistance of the coating was studied by salt spray and damp test, and the corrosion tendency during salt immersion test was analyzed. The results show that the phase composition before and after pre-treatment is almost changeless, and the deep microflaw appears between a andβ phases during acidic pickling. The phosphate conversion coating is mainly composed of Mg, MgO, and some amorphous phase, and it can provide a good protection for the AZ31B alloy. Results from corrosive morphology indicate that the growth and the corrosion resistance of the phosphate conversion coating are related to the forming process of the AZ31B matrix.

Cerium Chemical Conversion Coating on a Novel Mg-Li Alloy

A novel Mg-Li alloy was treated in a cerium nitrate solution and cerium chemical conversion coating was obtained on the alloy. Then the forming process, structure and corrosion resistance of the coating were investigated. The influential factors of cerium conversion coating were discussed through orthogonal experiments, and the optimum processing parameters were confirmed. XPS spectra displayed that the conversion coating consisted of cerium compounds, and the major component of the protective layer was a mixture of Ce （IV） oxide and Ce （IV） hydroxide. In addition, XRD pattern illustrated that there was crystalline CeO2 in the conversion coating. Analysis by SEM showed that the cerium conversion coating was uniform with a fiber-like morphology. The thickness of the conversion coating was 12 μm. The results of electrochemical potentiodynamic polarization and hydrogen evolution measurement indicated that the cerium conversion coating provided effective protection to the novel Mg-Li alloy.

Using EIS to evaluate anti-corrosion properties of the SiC_p/5A06 aluminium MMC treated by cerium conversion coatings

This paper evaluated the protection effect of the cerium conversion coatings on the SiCp/5A06 Al composite and the 5A06 Al alloy.Electrochemical impedance spectroscopy(EIS) was employed to examine the variation of the electrochemical variables of the samples treated and immersed in 3.5% NaCl solution at 35 °C for 1 h,which showed the enhancement of charge transfer resistance(Rt) and coating film resistance(Rc),i.e.,the corrosion resistance of the conversion coated samples was improved.The best protection ef...

New design principles for the bath towards chromate-and crack-free conversion coatings on magnesium alloys

Cracking and low thickness are major obstacles to the high corrosion performance of conversion coating on magnesium alloy.In this work,the ratio of total acidity to p H(TA/p H)was applied as an indicator,and new principles regarding the design of conversion bath were proposed.The treatment bath should be composed of species that can be categorized into two groups:the first group of species that react with Mg substrate to increase the local p H at the interface;the second group that precipitate and contributes to the growth of coating.The species belong to second group exists in a supersaturated state and its precipitation process is almost independent on the reactions of the species in first group.By this way,a thick and crack-free two-layered conversion coating is obtained.Moreover,the nature of the adjustment of TA/p H and the roles of the oxidizing agent and catalyst were discussed.

NON-CHROMATE CONVERSION COATING TREATMENT FOR MAGNESIUM ALLOY

A no pollution organic acid based conversion coating solution MIS. No.1 has been examined as to its suitability as possible replacement for chromate containing formulations on magnesium alloys. Investigations have concentrated on the formation of passive film from simple MIS. No.1 solution using immersion. The morphology of passivated surfaces was examined using scanning electron microscopy (SEM). The corrosion resistance of the passivated surfaces and the painted surface was assessed using electrochemical techniques as well as humidity and salt fog tests. It was concluded that the surface treatment magnesium alloy by MIS.No.1 solution is more effective than that by chromate coating treatment, and the MIS.No.1 coating is also suitable for painting's pretreatment.

XPS Analysis of the Cerium Conversion Coating on the Anodized A16061/SiC_p

A method of concentration analysis based on X-ray photoelectron spectroscopy (XPS) results was introduced. The concentration of Ce-rich conversion coating on the anodized Al based metal matrix composites AI6061/SiCp was then studied according to this method. The results revealed that the Ce conversion coating on the anodized AI6061/SiCp consisted of Al oxide, Ce oxide and Ce hydroxide. The state of Ce element exhibited the mixture of Ce3+ and Ce4+. Some of Cell I was oxidized to be CelV in the outer layer coating.

Study on Phytic Acid Conversion Coating on Mg-Li Alloy

The impact of phytic acid concentration,immersion time and soaking temperature on phytic acid conversion coating of the Mg-Li alloy are studied.The surface morphology and the corrosion of the phytic acid conversion coating are tested by using scanning electron microscopy and the electrochemical analyzer.The results show that phytic acid concentration and immersion time,soaking temperature affects the microstructure and corrosion resistance of the phytic acid conversion coating.There is a passivation interval with a smaller capacitor and larger resistor in the phytic acid conversion coating.The phytic acid conversion coating is made up of white particle and flake film.

Influence of oxidant KMnO_4 on film-forming process of rare earth metal conversion coating on LY12 aluminum alloy

A Cu/Al galvanic couple was established to study the influence of the oxidantKMnO_4 on the film-forming process of rare earth metal (REM) conversion coating on LY12 aluminumalloy. It is found that the galvanic couple simulative experiment accords with the actual immersion,and it can be substantially used to simulate the behavior of LY12 aluminum alloy in thefilm-forming process. It is showed that the formation of the coating is quickened in CeCl_3 solutioncontaining KMnO_4 compared with that not containing KMnO_4. XPS results reveal that the coatingformed on cathode is composed of oxide or hydroxide of Ce and Mn, so the mechanism of formation ofREM conversion coating changes when KMnO4 is added.

Comparison of the effects of pre-activators on morphology and corrosion resistance of phosphate conversion coating on magnesium alloy

In this study, Mg–6.0Zn–3.0Sn–0.5Mn(ZTM630) magnesium alloy was pre-activated by colloidal Ti, oxalic acid, and phosphoric acid,and a phosphate conversion coating(PCC) was prepared on the alloy surface. The morphology and corrosion resistance of the prepared PCCs were investigated. Surface morphology studies showed that the phosphate crystals that formed the coating were the smallest for the sample pre-activated by phosphoric acid. The coating on the colloidal Ti and the phosphoric acid samples had the largest and the smallest thickness and surface roughness, respectively. The reason for the discrepancy was analyzed by comparing the surface morphologies of alloy samples immediately after the pre-activation treatment and various phosphating treatments. X-ray diffraction analysis revealed that all three PCCs contained the same compounds. The corrosion resistance time from the copper sulfate drop test and the electrochemical data from the potentiodynamic polarization curves showed that the coating pre-activated by phosphoric acid had the best corrosion resistance. Finally, the 1500 h neutral salt spray corrosion test confirmed that the phosphating treated magnesium alloy, which was pre-activated by phosphoric acid,exhibited excellent corrosion resistance and behavior.

Improving Corrosion Resistance of C_f/Mg Composites using Rare Earth Conversion Coatings

The surface of carbon fiber reinforced Mg matrix (Cf/Mg) composites was modified by treatment of rare earth conversion coating, and nontoxic, non-pollution Ce conversion coatings were prepared. The effect of the coatings on corrosion behaviors of composites was investigated by electrochemical polarization technology and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. The higher Ecorr and lower icorr were obtained by Ce conversion coatings. EIS results showed that the higher values of R2 were obtained by treatment containing CeCl3, the high corrosion resistance occured in treatment containing CeCl3, the low corrosion resistance in uncoating sample, the coating of treatment containing Ce(NO3)3 was medium. The microstructure of Ce conversion coatings was observed by scanning electron microscopy (SEM), and the elements of corresponding for coatings was characterized by energy dispersive spectrometer (EDS). The micro-cracks and Ce-riched spherical particles were characteristics of these coatings.

Study on Anticorrosive Cerium Conversion Coating of C_f/6061A1 Composite Surface

The optimum chemical passivation process of the rare earth metal (REM) conversion coating on the Cf/6061Al composite surface was introduced in this paper and its polarization curves properties were investigated. Ridge-like coatings were found by scanning electro microscope (SEM) observations, and the Al matrix and carbon fibre reinforcement were both coated with Ce conversion coatings, with some minor cracks. The energy dispersive spectroscopy (EDS) plane scan analysis indicates that the major elements in the coating are Ce, O, Si, Al and the Ce content reaches 47.48% (mass fraction). The Ce conversion coatings increase the corrosion resisting properties of Cf/6061A1 composite, with a higher free corrosion potential (Ecorr) and a lower free corrosion current density (icorr) for the coated composite than those of the bare composite. And the Boehmite-treatment would enhance the corrosion resistance of the REM conversion coating. The ca-thodic polarization and anodic polarization were retarded by REM conversion coating, resulting in an improved corrosion resistance.

Corrosion resistance properties of colored zirconium conversion coating and powder coating on cold-rolled steel

Jiuhe Corporation developed a new surface pretreatment for producing a phosphate-free and colored zirconium conversion coating on cold-rolled steel(CRS).Scanning electron microscopy(SEM)and energy-dispersive spectroscopy(EDS)were applied to study the surface morphology and elemental composition of the golden yellow-colored conversion coating.Elec trochemic al impedance spectroscopy(EIS)was used to investigate the electrochemical performance of the conversion coatings with different colors.The corrosion resistance properties of the powder coatings were characterized using the neutral salt spray test(NSS)and the tape adhesion test.The EIS and NSS results demonstrate that the colored zirconium conversion coatings exhibit excellent corrosion resistance properties compared with the bare CRS.The golden yellow-colored conversion coating has a maximum EIS value(748Ω·cm^(2))and achieves 0 mm degree of corrosion,as stipulated by EN ISO 4628-8.This paper proposes a hypothesis concerning the ZrO_(2)-(β-FeOOH)-polymer conversion reaction to explain the color changes.

Anticorrosion behavior of conversion coatings obtained from unbuffered cerium salts solutions on AA6061-T6

The anticorrosive properties of cerium based conversion coatings deposited on AA6061-T6 alloy by immersion in tmbuffercd cerium chloride and cerium nitrate solutions in the presence of hydrogen peroxide were investigated and characterized by potentiodynamic po- larization （PDP） and electrochemical impedance spectroscopy （EIS） in 0.5 mol/L NaCl aqueous solution. The microstructure and chemical composition of the protective films were examined by scanning electron microscopy （SEM） and energy dispersive X-ray spectroscopy （EDS）. It was found that the best corrosion protection was afforded by the samples treated during 600 s in cerium chloride solution at pH values ~5.5-4, showing higher amounts of cerium and polarization resistance values greater than 10 f~ m2. Moreover, an ennoblement of the corro- sion potential and decreasing of the cathodic and anodic currents were obtained compared with the cerium nitrate solutions application. This behavior was attributed to the influence of the deposition parameters such as type of the salt anion, i.e., chelating effect and chaotropic characteristics, pH fluctuations in the conversion solution and deposition time.

Structure and Corrosion Resistance of a Composite γ-Amino Propyl Triethoxy Silane and γ-Glycidoxy Propyl Trimethoxy Silane Conversion Coating on Galvanized Steel

In an aqueous solution of the mixtures of γ-amino propyl triethoxy silane and γ-glycidoxy propyl trimethoxy silane, a composite silane conversion coating was developed on galvanized steel. FESEM （field emission scanning electron microscope）, XPS （X-ray photoelectron spectroscopy）, ATR FTIR （attenuated total reflection Flourier transform infrared spectroscopy） and SST （salt spray test） were used to characterize the obtained composite silane conversion coating and also the coating formation process was studied. The result showed that the surface of the composite silane conversion coating was complete, consecutive and compact. The coating could endure a neutral salt spray test for 72 h without corrosion. The result of salt spray test indicated that the composite silane conversion coating can provide a better corrosion inhibition than the coating which was composed of the single silane. Based on observation and analysis, it was proposed that the formation process of the silane coating on zinc should consist of three steps： the hydrolysis of the silane molecules, silane chemical adsorption and silane crosslinking condensation. The crosslinking reactions took place between ~＇-amino propyl triethoxy and ＂/-glycidoxy propyl trimethoxy silane during the forming process of the coating, and a high crosslinked density interpenetrating structure network was obtained, so the composite silane conversion coating could keep the corrosive substances from the zinc more effectively.

Electrochemical behaviors of magnesium alloy with phosphate conversion coating in NaCl solutions

A composite conversion coating was prepared on magnesium alloy by the only one-step immersion treatment. The characteristics of the conversion coating were investigated by scanning electron microscopy （SEM） and X-ray photoelectron spectroscopy （XPS）. The results indicate that the composite conversion coating consists of magnesium hydroxide, magnesium phosphate and man- ganese phosphate. The electrochemical behavior of the conversion coating was investigated systematically by electrochemical impedance spectroscopy （EIS） and poten- tiodynamic polarization measurement in different NaC1 solutions. Polarization measurements and EIS results reveal that the magnesium alloy with the conversion coating have better corrosion resistance compared to the bare magnesium alloy in these conditions. And the corro- sion rate of the magnesium alloy with conversion coating increases consistently with the chloride ion concentration. In alkaline conditions, the magnesium alloy with conver- sion coating has superior corrosion resistance by the syn- ergistic effects between Mg（OH）2 film and conversion coating. Moreover, the electrochemical corrosion mechanism of the magnesium alloy was analyzed with respect to the conversion coating in a Cl^- containing environment.