Structure and properties of micro-arc calcium phosphate coatings on pure titanium and Ti-40Nb alloy

The microstructure, physical and mechanical, and chemical properties of micro-arc calcium phosphate （CAP） coatings deposited under different process voltages in the range of 150-400 V on the commercially pure titanium （Ti） and Ti-40%Nb （Ti-40Nb） （mass fraction） alloy were investigated by the SEM, TEM, XRD and EDX methods. The coating thickness, roughness, and sizes of structural elements were measured and showed similar linear character depending on the process voltage for the coatings on both substrates. SEM results showed the porous morphology with spherical shape structural elements and rough surface relief of the coatings. XRD and TEM studies exhibited the amorphous structure of the CaP coating. With increasing the process voltage to 300-400 V, the crystalline phases, such as CaHPO4 and β-Ca2P207, were formed onto the coatings. The annealing leads to the formation of complex poly-phase structure with crystalline phases： CaTi4（PO4）6, β-Ca2P2O7, TiP2O7, TiNb（PO4）3, TiO2, NbO2, and Nb2O5. The applied voltage and process duration in the ranges of 200-250 V and 5-10 min, respectively, revealed the coating formed on Ti and Ti-40Nb with optimal properties： thickness of 40-70μm, porosity of 20%-25%, roughness （Ra） of 2.5-5.0 μm, adhesion strength of 15-30 MPa, and Ca/P mole ratio of 0.5-0.7.

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.

Controlling the rate of degradation of Mg using magnesium fluoride and magnesium fluoride-magnesium phosphate duplex coatings

The thin and porous Fluoride Conversion Coating FCC with many cracks could not offer a significant improvement in corrosion resistance for Mg. Magnesium phosphate coating improves the corrosion resistance of Mg, good bioactivity, promotes cell viability and cyto-compatibility and exhibits antibacterial activity. However, rapid dissolution in Mg in acidic magnesium phosphate containing solutions leads to the development of an inhomogeneous coating. The present study attempts to prevent the excessive dissolution of Mg by forming a fluoride conversion coating as a pre-treatment in the first stage followed by deposition of magnesium phosphate coating in the second stage to develop magnesium fluoride-magnesium phosphate duplex coatings. The morphological features, structural characteristics, nature of functional groups, corrosion behavior in Hanks’ balanced salt solution and bioactivity in simulated body fluid are assessed to ascertain the suitability of the magnesium fluoride-magnesium phosphate duplex coating in controlling the rate of degradation of Mg and improving its bioactivity using uncoated Mg and fluoride conversion coated Mg as reference. The findings of the study reveal that the magnesium fluoride-magnesium phosphate duplex coating could offer an excellent corrosion resistance and improve the bioactivity of Mg.

Self-healing mechanism of composite coatings obtained by phosphating and silicate sol post-sealing

Silicate sol post-treatment was applied to form a complete composite coating on the phosphated zinc layer. The chemical compositions of the coatings were investigated using XPS. The coated samples were firstly scratched and then exposed to the neutral salt spray(NSS) chamber for different time. The microstructure and chemical compositions of the scratches were studied using SEM and EDS. And the non-scratched coated samples were compared. The self-healing mechanism of the composite coatings was discussed. The results show that during corrosion, the self-healing ions in composite coatings dissolve, diffuse and transfer to the scratches or the defects, and then recombine with Zn2+ to form insoluble compound, which deposits and covers the exposed zinc. The corrosion products on the scratches contain silicon, phosphorous, oxygen, chloride and zinc, and they are compact, fine, needle and flake, effectively inhibiting the corrosion formation and expansion of the exposed zinc layer. The composite coatings have good self-healing ability.

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.

Phosphate film free of chromate, fluoride and nitrite on AZ31 magnesium alloy and its corrosion resistance

A phosphate solution free of chromate, fluoride and nitrite was prepared and an environment-friendly film was obtained on AZ31 magnesium alloy surface via the chemical deposition method. The morphology, composition, phase structure and its corrosion resistance were studied. The effects of film-forming temperature and free acid on corrosion resistance, microstructure and electrochemical behavior of the film were discussed. The results indicate that the corrosion resistance of AZ31 with the phosphate film was better than blank AZ31 substrate, which was most attributed to the great inhibitive action on the anodic dissolution and cathodic hydrogen evolution of the film.

Composition and Performance of the Composite Coatings Obtained by Phosphating and Cerium Nitrate Post-Sealing on Galvanized Steel

To improve the corrosion resistance of phosphate coatings, the phosphated hot-dip galvanized (HDG) steel was post-sealed with cerium nitrate solution. The morphology, composition, corrosion resistance of the coatings was investigated by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and neutral salt spray (NSS) tests. The results show that after post-sealing the phosphated HDG samples with cerium nitrate solution, the pores among the zinc phosphate crystals are sealed by the compounds containing phosphorus, oxygen and cerium; the zinc phosphate crystals are covered by the flocculent cerium compounds; and the continuous composite coatings are formed on HDG steel. The corrosion resistance of the composite coatings, which increases with the increase in phosphating time and cerium nitrate post-sealing time, is far higher than that of the single phosphate coatings. The composite coatings with the optimal corrosion resistance are obtained for phosphating 300 s and post-sealing 300 s; and the corrosion resistance is more outstanding than that of the chromate coatings.

Improvement of anticorrosion and adhesion to magnesium alloy by phosphate coating formed at room temperature

A new surface protection process was developed to magnesium alloy against corrosion in aggressive environments.Firstly,a phosphate coating was formed on rinsed magnesium alloy.Then,powder painting was carried out on the phosphated magnesium alloy.Surface morphologies and phase compositions of the phosphate coating were investigated by X-ray diffraction(XRD) and scanning electron microscope(SEM) .The results show that the phosphate coatings formed in bath containing earth additives at room temperature have dense and fine microstructure.The phosphate coating provides excellent paint adhesion to the magnesium alloy. Salt spray tests indicate that the corrosion resistance of the phosphate coating plus paint could meet the demand of magnesium alloy automobile components in aggressive environments.

Self-healing Performance of Composite Coatings Prepared by Phosphating and Cerium Nitrate Post-sealing

The phosphated and cerium nitrate post-sealed galvanized steel was firstly scratched to expose zinc layer and then placed in neutral salt spray （NSS） chamber for different durations. The microstructure and compositions of the scratches were investigated using SEM and EDS. The phases of the corrosion products were examined through XRD. The self-healing mechanism of the composite coatings was discussed. The experimental results show that the composite coatings have an excellent corrosion resistance. The corrosion products increase with corrosion time and finally cover the whole scratch. They contain phosphorous, cerium, oxygen, chloride and zinc, and are fine needle and exceedingly compact. The composite coatings are favorable self-healing. During corrosion, the self-healing ions such as Ce3＋, Ce4＋, PO43-, Zn2＋ in the composite coatings were dissolved, migrated, recombined, and covered the exposed zinc, impeding zinc corrosion. The self-healing process of the scratches on the composite coatings can be divided into three stages, about 2 h, 4 h, and 24 h, respectively.

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.

Calcium phosphate conversion technique:A versatile route to develop corrosion resistant hydroxyapatite coating over Mg/Mg alloys based implants

Globally,vast research interest is emerging towards the development of biodegradable orthopedic implants as it overcomes the toxicity exerted by non-degradable implants when fixed in the human body for a longer period.In this context,magnesium(Mg)plays a major role in the production of biodegradable implants owing to their characteristic degradation nature under the influence of body fluids.Also,Mg is one of the essential nutrients required to perform various metabolic activities by the human cells,and therefore,the degraded Mg products will be readily absorbed by the nearby tissues.Nevertheless,the higher corrosion rate in the biological environment is the primary downside of using Mg implants that liberate H2gas resulting in the formation of cavities.Further,in certain cases,Mg undergoes complete degradation before the healing of damaged bone tissue and cannot serve the purpose of providing mechanical support.So,many studies have been focused on the development of different strategies to improve the corrosion-resistant behavior of Mg according to the requirement.In this regard,the present review focused on the limitations of using pure Mg and Mg alloys for the fabrication of medical implants and how the calcium phosphate conversion coating alters the corrosive tendency through the formation of hydroxyapatite protective films for enhanced performance in medical implant applications.

Surface Coating of NiTi Shape Memory Alloys with Calcium Phosphates by Dip-coating or Plasma-spraying-biological Characterization Examined by in vitro Testing Methods

The influence of different surface coatings of NiTi shape memory allays was examined using in vitro testing methods. Plates of superelastic nickel-titanium shape memory allay （ NiTi ） were coated with calcium phosphates （ hydroxyapatite ） by high-temperature plasma-spraying or by dip-coating. The biocompatibility was tested in vitro by cultivation of isolated human granulocytes and whole blood cells. As substrates, pure NiTi, plasma-spray-coated NiTi and dip-coated NiTi were used. Isolated granulocytes showed an increased adhesion to both calcium phosphate-coated NiTi samples. Compared to non-coated NiTi or dip-coated NiTi, the number of dead granulocytes adherent to plasma-sprayed surfaces was significantly increased （ p 〈 0.01 ）. Whether the d/f- ferences in apoptosis of granulocytes on dip-coated vs plasma-sprayed coatings observed are due to differences in material surface morphologies has to be analyzed in further studies. Because of the cellular interactions with the coating layers, h is likely that the results obtained are not caused by the underlying NiTi but due to the coating itself.

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.

Calcium Phosphate Coating on Al_2O_3 Ceramics by a Biomimetic Method Using Electric Pulse Technique

The preparation of calcium phosphate （CP） coating on alumina ceramics using electric pulse stimulating methoe has been investigated. The cup-shaped alumina ceramics were soaked in a simulated body fluid （SBF）, and a square pulse potential with frequency of 1 Hz and voltage of 110 V was applied between the inner and outer surfaces of the alumina cup. Surface morphology of CP coatings during different deposition periods was observed by a Philips XL-30 scanning electron microscope （SEM）. Compositional analysis was examined by EDAX. The mechanism of nucleation and growth of CP coating was discussed. SEM result indicates that the coating comprises of a large number of tiny needle-like grains and has a porous microstructure. There is a strong bond between the deposited layer and Al2O3 substrate, which may be due to the gentle growth of the biomimetic method. The EDAX analysis indicates that main composition of the coating is calcium and phosphor. The formation of CP coating may be contributed to the stimulation of electric pulse and the high ions concentration which is 1.5 times of the concentration of SBF solution （1.5SBF solution）. Such surface functionalization method by electric pulse potential can be used to prepare CP coating on various electric-insulating bioinert materials for improving their bioactive character.

In vitro corrosion and biocompatibility of phosphating modified WE43 magnesium alloy

Phospahting coated WE43 magnesium alloy was prepared by an immersion method. The microstructure, corrosion resistance and biocompatibility of the coated alloy were investigated. Scanning electron microscopy （SEM） and X-ray diffraction （XRD） were used to examine the microstructure and the composition of the coated alloy. The corrosion resistance was studied by means of potentiodynamic polarization method and the biocompatibility of the surface modified WE43 alloy was evaluated by （3-（4,5）-Dimethylthiazol-2, yl）-2,5-diphenyltetrazolium bromide （MTT） and hemolysis test. The results show that the phosphating coating can enhance the corrosion resistance of WE43 alloy and can be a good candidate to increase the biocompatibility of WE43 alloy.

Effects of Hydroxylamine Sulfate and Sodium Nitrite on Microstructure and Friction Behavior of Zinc Phosphating Coating on High Carbon Steel

Hydroxylamine sulfate （HAS） and sodium nitrite are used as the accelerators for zinc phos- phate coating on high carbon steel. Phase evolution of phosphate coating was investigated by X-ray diffraction. It is found that the phosphating coatings are mainly composed of hopeite Zn3Fe（PO4）2.4H2O and phosphophyllite Zn2Fe（PO4）2.4H2O. The microstructural changes of the phosphate coating, as a function of phosphating time, were evaluated by scanning elec- tron microscopy. Four-ball friction experiments reveal that hydroxylamine sulfate instead of sodium nitrite can effectively reduce the friction coefficient of lubricated phosphating coat- ing. Therefore, it may be expected that HAS will be widely used as a fast and ECO-friendly accelerator in phosphate industry.

Zinc phosphating of 6061-Al alloy using REN as additive

Zinc phosphate coating formed on 6061-A1 alloy was studied with the help of electrochemical measurements, Fourier Transform Infrared （FTIR）, and Scanning Electron Microscopy （SEM）, after dipping it in phosphating solutions containing different concentrations of Rare Earth Nitrate （REN）. REN, which acted as an accelerator in the phosphating solution, could catalyze the surface reaction and accelerate the phosphating process. REN mainly enabled the P in the phosphate coating to exist in the form of PO4^3- and promoted the hydrolysis of phosphatic acid in a liquid layer at the cathodes. This resulted in the evolution of H2 at the cathodes, which increased the local pH value and in turn drove the precipitation of the phosphate coating. Additionally, REN was adsorbed on the surface of the aluminum substrates to form a gel during the phosphating process. These gel particles were good crystal seeds, which helped to form phosphate crystal nuclei and possess the function of a nucleation agent that could decrease the phosphate crystal size. The corrosion resistance of the formed zinc phosphate coatings was improved.

Study on phosphating treatment of aluminum alloy:role of yttrium oxide

Zinc phosphate coatings formed on 6061-Al alloy, after dipping in phosphating solutions containing different amounts of Y2O3（yttrium oxide）, were studied by scanning electron microscopy （SEM）, X-ray diffraction （XRD） and electrochemical measurements. Significant variations in the morphology and corrosion resistance afforded by zinc phosphate coating were especially observed as Y2O3 in phosphating solution varied from 0 to 40 mg/L. The addition of Y2O3 changed the initial potential of the interface between aluminum alloy substrate and phosphating solution and increased the number of nucleation sites. The phosphate coating thereby was less porous structure and covered the surface of aluminum alloy completely within short phosphating time. Phosphate coating was mainly composed of Zn3（PO4）2·4H2O （hopeite） and AlPO4（aluminum phosphate）. Y2O3, as an additive of phosphatization, accelerated precipitation and refined the gain size of phosphate coating. The corrosion resistance of zinc phosphate coating in 3% NaCl solution was improved as shown by polarization measurement. In the present research, the optimal amount of Y2O3 was 10-20 mg/L, and the optimal phosphating time was 600 s.

Corrosion resistance of a novel SnO2-doped dicalcium phosphate coating on AZ31 magnesium alloy

A SnO2-doped dicalcium phosphate coating was prepared on AZ31 alloy by means of hydrothermal deposition.The results showed that the coating possessed a globular morphology with a long lamellar crystalline structure and a thickness of approximately 40 mm.The surface of the coating became smooth with an increase additive amount of the SnO2 nanoparticles.The corrosion current density and hydrogen evolution rate of the coating prepared in presence of SnO2 were reduced compared to the coating without SnO2 and the bare AZ31 substrate,indicating an improvement in the corrosion resistance of the SnO2-doped coating.

A moisture-resistant antireflective coating by sol-gel process for neodymium-doped phosphate laser glass

Using methyl triethoxysilicane as precursor, a moisture-resistant coating for neodymium-doped laser glass was developed by the sol-gel process. Colloidal silica was added in coating solution as modifier. The refractive index of this coating varied from 1.31 to 1.42. A porous antireflective （AR） silica coating with the index of 1.27 was coated on the moisture-resistant coating surface. The two-layer coating possessed transmission up to 99.1% at wavelength of 966 nm, surface root-mean-square （RMS） roughaess of 1.245 am, and roughness of average （RA） of 0.961 am. In the case of laser of 1053-nm laser waveleilgth and 1-ns pulse duration, the damage threshold of the two-layer coatings was more than 15 J/cm^2.