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 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 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.

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.

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.

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.

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.

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.

Conversion coatings of Mg-alloy AZ91D using trihexyl(tetradecyl) phosphonium bis(trifluoromethanesulfonyl)amide ionic liquid

This work reveals the performance of a trihexyl(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide ([P6,6,6,14][NTf2]) ionic liquid (IL) conversion coating upon AZ91D. Such conversion coatings represent a novel avenue for chromate replacement. An optimization of coating performance was pursued by careful alloy pretreatment to generate a surface on which the coating performs best, as the AZ91 substrate is distinctly different from pure or dilute Mg alloys. The results reveal that a functional conversion coating can be achieved, retarding anodic dissolution kinetics, causing a significant decrease in corrosion rate. The coating efficacy is closely tied to the pretreatment performed, which dictates both the microstructural and electrochemical heterogeneity of the surface. The resulting coatings were found to contain MgxFx and phosphonium cation related components, the proportions of which were dependent on the pretreatment.

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.

Preparation and characterization of Ce-silane-ZrO_2 composite coatings on 1060 aluminum

In order to improve the property of traditional Ce-based conversion coatings, Ce-silane-ZrO2 composite coatings were successfully prepared on 1060 aluminum. The microstructure, chemical element composition and corrosion resistance of Ce-based conversion coatings and Ce-silane-ZrO2 composite coatings were investigated by SEM, AFM, XPS and EIS analyses. Stacking structure of the composite coating can be observed. The inner layer of the composite coatings mainly consists of oxide and hydroxide of Ce（Ⅲ）, and the silane network is composed of the outer layer together with a small amount of Ce（Ⅳ） hydroxide. By adding silane and ZrO2 nanoparticles into Ce-based conversion coatings, the porosity and the micro cracks of the coatings decrease apparently accompanying with the improvement of the corrosion resistance.

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.

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.

Electric field assisted chemical conversion process of AZ91D magnesium alloy in HCO_3^-/CO_3^(2-) solution

A new method for synthesizing Mg-Al hydrotalcite conversion coating on AZ91D Mg alloy was developed by the application of electric field （EF）. By using EF technique, the formation time of the coating can be significantly reduced. The SEM results indicate that a continuous and compact Mg-Al hydrotalcite coating is formed on the surface of Mg alloy after short time EF treatment. However, a long time treatment would make the coating partially exfoliate. The corrosion current density （Jcor ） of the coated sample （EF1＋1 h） is approximately two orders of magnitude lower than that of Mg alloy substrate. The test of electrochemical impedance spectroscopy （EIS） and immersion corrosion also suggest that the coating can effectively protect Mg alloy against corrosion.

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.

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.

Effect of scratch on corrosion resistance of calcium phosphate conversion coated AZ80 magnesium alloy

In order to analyze the effect of scratch on the corrosion behaviour of a calcium phosphate conversion coating(CPCC)on AZ80,the electrochemical testing,scanning vibrating electrode technique(SVET),immersion test and hydrogen evolution experiment were performed to study the corrosion resistance of AZ80,AZ80 with CPCC and coated AZ80 with scratch.The results show that the coating improves the corrosion resistance of the AZ80 from a current density of(85±4)to(4±1)μA/cm^(2).When the coating was damaged,its protection on substrate would be reduced.The scratch with a length of around 12 mm on the coating reduced the corrosion resistance to a current density of(39±1)μA/cm^(2).In addition,the corrosion occurred initially in the scratch area and the corrosion site first occurred at the junction of the scratch and the coating.Besides,the micro corrosion mechanism of the specimen containing scratch was clarified.