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.

Influence of solution temperature on corrosion resistance of Zn-Ca phosphate conversion coating on biomedical Mg-Li-Ca alloys

The influence of phosphating bath at different temperatures on the formation and corrosion property of calcium-modified zinc phosphate conversion coating （Zn-Ca-P coating） on Mg-Li-Ca alloy was investigated. The morphologies, elemental distribution and chemical structures of the coatings were examined via SEM, EPMA, EDS, XRD and FT-IR. The corrosion resistance was assessed by hydrogen evolution, potentiodynamic polarization and EIS. The results show that the coating is composed of single element Zn and ZnO at below 45 ℃;whereas the coatings are predominantly characterized by Zn3（PO4）2·4H2O and small amount of element zinc and ZnO at above 50 ℃. Mg-Li-Ca alloy with Zn-Ca-P coatings prepared at 55 ℃ has the highest corrosion resistance. However, the hydrogen evolution rates of the coatings obtained at 40-50 ℃ is accelerated due to the galvanic corrosion between the imperfection of the single element Zn coating and the Mg substrate.

Corrosion resistance of cerium-doped zinc calcium phosphate chemical conversion coatings on AZ31 magnesium alloy

Zinc calcium phosphate （Zn-Ca-P） coating and cerium-doped zinc calcium phosphate （Zn-Ca-Ce-P） coating were prepared on AZ31 magnesium alloy. The chemical compositions, morphologies and corrosion resistance of coatings were investigated through energy-dispersive X-ray spectroscopy （EDS）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, electron probe micro-analysis （EPMA） and scanning electron microscopy （SEM） together with hydrogen volumetric and electrochemical tests. The results indicate that both coatings predominately contain crystalline hopeite （Zn3（PO4）2·4H2O）, Mg3（PO4）2 and Ca3（PO4）2, and traces of non-crystalline MgF2 and CaF2. The Zn-Ca-Ce-P coating is more compact than the Zn-Ca-P coating due to the formation of CePO4, and displays better corrosion resistance than the Zn-Ca-P coating. Both coatings protect the AZ31 Mg substrate only during an initial immersion period. The micro-galvanic corrosion between the coatings and their substrates leads to an increase of hydrogen evolution rate （HER） with extending the immersion time. The addition of Ce promotes the homogenous distribution of Ca and formation of hopeite. The Zn-Ca-Ce-P coating has the potential for the primer coating on magnesium alloys.

Preparation of cerium oxide based environment-friendly chemical conversion coating on magnesium alloy with additives

Ce（SO4）2？H2O2 solution was adopted to prepare a chemical conversion coating on AZ91D magnesium alloy.Additives of Ni（NO3）2 and sodium dodecyl benzene sulfonate were applied to improving the coating formation.SEM,EDS,XRD and GIXD were adopted to study the coating morphology,structure and composition,and the potential change curve in the treating solution was recorded to study the coating growth.Sodium dodecyl benzene sulfonate makes a remarkable improvement in the coating compactness,and shortens the time in the second stage of the coating formation from 5 min to 2 min.Compared to Ni（NO3）2,sodium dodecyl benzene sulfonate makes the more remarkable effect on the corrosion resistance improvement,since it can decrease the current density of corrosion from 7.41×10-5 A/cm2 to 2.20×10-5 A/cm2.The additives of Ni（NO3）2 and sodium dodecyl benzene sulfonate can enhance the Ce content from 18.92% to 22.32% and 25.08% in the coating,respectively.The XRD and GIXD results indicated that all the conversion coating formed in different solutions exhibit amorphous structure.

pH Influence on Performance of Phytic Acid Conversion Coatings on AZ31 Magnesium Alloy in Simulated Body Fluid

Phytic acid （PA） conversion coating on AZ31 magnesium alloy is prepared by a deposition method. pH influences on the formation process, microstructure and properties of the conversion coating are investigated. Electrochemical tests including polarization curve and electrochemical impedance spectroscopy are used to examine the corrosion resistance, and scanning electron microscopy is used to observe the microstructure. The chemical nature of conversion coating is investigated by energy dispersive spectroscopy. And thermodynamic method is used to analyze the optimum pH. The results show that PA conversion coating can improve the corrosion resistance of AZ31 Mg alloy. The maximum efficiency achieves 89.19% when the AZ31 Mg alloy is treated by PA solution with pH=5. It makes the corrosion potential of sample shift positively about 156 mV and corrosion current density is nearly an order of magnitude less than that of the untreated sample. The thermodynamic analysis shows that the corrosion resistance of PA coatings is affected by not only the concentration of PA ion and Mg2＋ but also the release rate of hydrogen.

Enhanced corrosion performance of magnesium phosphate conversion coating on AZ31 magnesium alloy

Magnesium phosphate conversion coating(MPCC)was fabricated on AZ31magnesium alloy for corrosion protection by immersion treatment in a simple MPCC solution containing Mg2+and3PO4?ions.The MPCC on AZ31Mg alloy showed micro-cracks structure and a uniform thickness with the thickness of about2.5μm after20min of phosphating treatment.The composition analyzed by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the coating consisted of magnesium phosphate and magnesium hydroxide/oxide compounds.The MPCC showed a significant protective effect on AZ31Mg alloy.The corrosion current of MPCC was reduced to about3%of that of the uncoated surface and the time for the deterioration process during immersion in0.5mol/L NaCl solution improved from about10min to about24h.

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.

Applications of carbonic acid solution for developing conversion coatings on Mg alloy

Works on exploring an environmentally clean method for producing an Mg,Al-hydrotalcite(Mg6Al2(OH) 16CO3·4H2O) layer and/or calcium carbonate(CaCO3) layer on Mg alloy in a carbonic acid solution system(aqueous HCO3-/CO3 2-or Ca 2+ /HCO3-) at 50℃ were reviewed.Conversion treatment for the Mg,Al-hydrotalcite conversion coating was as follows.Mg alloy was treated first in acidic HCO3-/CO3 2-aqueous for precursor layer formation on Mg alloy surface and then in alkaline HCO3-/CO3 2-aqueous to form a crystallized Mg,Al-hydrotalcite coating.Duration of an Mg,Al-hydrotalcite coating on Mg alloy surface was reduced from 12 h to 4 h by the conversion treatment.On the other hand,for reducing the formation time of CaCO3 coating on Mg alloy,the aqueous Ca 2+ /HCO3-with a saturated Ca 2+ content was employed for developing a CaCO3 coating on Mg alloy.A dense CaCO3 coating could yield on Mg alloy surface in 2 h.Corrosion rate(corrosion current density,Jcorr) of the Mg,Al-hydrotalcite-coated sample and CaCO3-coated AZ91D sample was 7-10μA/cm 2,roughly two orders less than the Jcorr of the as-diecast sample(about 200μA/cm 2) . No corrosion spot on the Mg,Al-hydrotalcite-coated sample and CaCO3-coated sample was observed after 72 h and 192 h salt spray test,respectively.

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.

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.

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.