Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Amino acid template-synthesis and characterization of three-dimensional metal phosphate/phosphite networks

In this contribution, two novel metal phosphate/phosphate, namely [Zn₂(HPO₃)₂(H₂O)₄]·H₂O (1) and Cd₅(HPO₄)₂(PO₄)₂(H₂O)₄ (2), were obtained by amino acid template-synthesis under mild hydrothermal conditions. X-ray crystallographic studies show that the inorganic network of 1 contains binuclear zinc building units with large 16-ring channels along [1 0 0] directions. The structure of 2 consists of asymmetric pentanuclear chiral motifs. It is notable that two centered pentanuclear cadmium structure motifs form a mesomeric unit, which is linked by bridging oxygen atoms to construct 3D inorganic network.     

Role of rare-earth Y addition on formation and anticorrosion properties of MAO coating on 2024 aviation aluminum alloy

Different ceramic coatings were prepared on the surface of 2024 aviation aluminum alloy using micro-arc oxidation process in silicate based electrolyte combined with the rare earth based compound Y(NO₃)₃·6H₂O. The thickness, hardness of the coating and conductivity of electrolyte were tested using relative devices, morphology and chemical composition were studied by scanning electron microscope and energy dispersive spectroscope, respectively. The phase composition of the coatings was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. Furthermore, the corrosion resistance of the coating was evaluated by an electrochemical workstation. The results showed that the addition of Y(NO₃)₃·6H₂O could improve the thickness and hardness of the coating. The morphological observation of the coating showed that Y(NO₃)₃·6H₂O was successfully incorporated into the ceramic layer and that the coating had the smallest porosity at 1.5 g/L Y(NO₃)₃. The phase composition of the coating was mainly γ-Al₂O₃, α-Al₂O₃, SiO₂, Y₂O₃, and AlPO₄. The corrosion resistance of coating in simulated seawater with the addition of Y(NO₃)₃·6H₂O was significantly improved, and the values of |Z|_0.01 Hz and corrosion rate of the coating reached the maximum and minimum at 1.5 g/L Y(NO₃)₃, which were 5.63 × 10⁵ Ω cm² and 7.444 × 10⁻⁴ mm/a, respectively.     

Development and characterization of silver and zinc doped bioceramic layer on metallic implant materials for orthopedic application

A successful electrodeposition method for preparing silver and zinc modified bioactive calcium phosphate layers onto surgical grade titanium alloy material (Ti6Al4V) was developed. The coatings were deposited on the Ti6Al4V surface by pulse current at 70 °C from an electrolyte containing adequate amounts of calcium nitrate, ammonium dihydrogen phosphate, zinc nitrate and silver nitrate. The corrosion resistivity of the bioceramic coatings was assessed in conventional Ringer׳s solution in a three electrode open cell by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results revealed the pure bioactive calcium phosphate (CaP) coated implant materials to possess the highest resistivity to corrosion, while the silver and zinc doped CaP layer showed at least one order of magnitude lower corrosion resistance. These modified CaP coatings can be further considered as antimicrobial coatings with enhanced biocompatibility. The morphology and structure of the coatings were characterized by Scanning electron microscopy (SEM), Energy-dispersive X-ray Spectroscopy (EDX) and X-ray diffraction (XRD) that confirmed the pulse current deposited CaP layer to consist of a mixture of different calcium phosphate phases such as hydroxyapatite (HAp), monetite (dicalcium phosphate, CaHPO₄) as well as other Ca-containing components, portlandite (Ca(OH)₂) and parascholzite (CaZn₂(PO₄)₂(H₂O)₂).     

Complex study of protective Cr3C2–NiAl coatings deposited by vacuum electro-spark alloying,pulsed cathodic arc evaporation,magnetron sputtering,and hybrid technology

Coatings were obtained by vacuum electro-spark alloying (VESA), pulsed cathodic arc evaporation (PCAE), magnetron sputtering (MS) techniques and VESA-PCAE-MS hybrid technology using Cr₃C₂–NiAl electrodes. The structure of the coatings was analyzed using scanning and transmission electron microscopy, X-ray diffraction and energy-dispersive spectroscopy. Mechanical properties were determined by nanoindentation, while tribological properties were assessed using pin-on-disk tribometer. Corrosion resistance was estimated by voltammetry in 1 N H₂SO₄ and 3.5%NaCl solutions. Oxidation resistance tests were performed at 800°С in air. The VESA coating had the highest thickness, low friction coefficient and high wear resistance. PCAE coating demonstrated the highest hardness (24 GPa) and elastic recovery (59%), oxidation resistance and superior corrosion resistance both in 1 N H₂SO₄ (i_corr = 70 μА/cm²) and 3.5%NaCl (i_corr = 0.74 μА/cm²) solutions. The MS coating had average mechanical properties and low corrosion current density (71 μА/cm²) in 1 N H₂SO₄. Deposition of coatings using VESA-PCAE-MS hybrid technology led to an increase in corrosion and oxidation resistance at least by 1.5 times in comparison with the VESA coating.     

Comparative study of the corrosion resistance of thermally sprayed ceramic coatings and their bulk ceramic counterparts

A comparative study of the corrosion properties of thermally sprayed ceramic coatings (Al₂O₃, Al₂O₃–TiO₂ with different ratios, mullite, and ZrSiO₄) and their sintered bulk ceramic counterparts was performed. The coatings were deposited on corrosion-resistant steel substrates using atmospheric plasma spraying (APS) and high velocity oxy-fuel (HVOF) spraying processes. The corrosion properties were investigated in 1 N solutions of NaOH and H₂SO₄ at 85 °C, respectively. The coating microstructures and phase compositions, as well as the corrosive environment were shown to have a strong effect on the corrosion resistance of the coatings. Al₂O₃–coatings were more sensitive to these factors than Al₂O₃–TiO₂ coatings were.The corrosion resistance of the bulk ceramics was superior to that of the thermally sprayed coatings. This is mainly because the coatings exhibited specific microstructure and contained amorphous and/or metastable phases not appearing in the bulk ceramics.     

Calcium-Magnesium-Aluminosilicate (CMAS) corrosion resistance of high entropy rare-earth phosphate (Lu0.2Yb0.2Er0.2Y0.2Gd0.2)PO4: A novel environmental barrier coating candidate

Single phase (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ was synthesized, and its thermal properties and CMAS resistance were investigated to explore its potential as an environmental barrier coating (EBC) candidate. The high entropy phosphate (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ displays a lower thermal conductivity (2.86 W m⁻¹ K⁻¹ at 1250 K) than all the single component xenotime phase rare-earth phosphates. Interaction of (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ pellets with CMAS at 1300 °C led to the formation of a dense and uniformed Ca₈MgRE(PO₄)₇ reaction layer, which halted the CMAS penetration into the bulk pellet. At 1400 and 1500 °C the (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄-CMAS corrosion showed CMAS penetrating beyond the reaction layer into the bulk pellet via the grain boundaries, and SiO₂ precipitates remaining at the pellet surface. The effects of duration, temperature, and compositions on the resistance against CMAS corrosion are discussed within the context of optimizing materials design and performance of high entropy rare-earth phosphates as candidates for advanced EBC applications.     

Effects of glutamic acid shelled PAMAM dendrimers on the crystallization of calcium phosphate in diffusion systems

Second generation poly(amidoamine) (PAMAM) dendrimers were synthesized and peripherally modified with glutamic acid (PAMAM-MG) as a shell. The effect of the dendrimers on the crystallization of different calcium phosphate compounds was investigated in both double and one way diffusion systems. It was found that the crystals of calcium phosphate showed tape-like morphology in the presence of PAMAM-MG, and the crystals’ thickness and width decreased compared to those grown without dendritic molecules. Such a result might be due to the interaction of electric charges between dendritic molecules and octacalcium phosphate (Ca₈H₂(PO₄)₆·5H₂O, OCP), which led to the adsorption of PAMAM-MG in the 100 and 010 surfaces of OCP. Moreover, PAMAM-MG showed an affinity for gelatin, and it could cause the formation of amorphous calcium phosphate (Ca₉(PO₄)₆·nH₂O, ACP) at a concentration of 5 mg/mL of PAMAM-MG. These results suggest that PAMAM-MG could be used for regulating the morphology of OCP and changing the composition of minerals in gels.     

Electrochemical deprotonation of phosphate on stainless steel

Voltammetric experiments performed in phosphate buffer at constant pH 8.0 on platinum and stainless steel revealed clear reduction currents, which were correlated to the concentrations of phosphate. On the basis of the reactions proposed previously, a model was elaborated, assuming that both H₂PO₄⁻ and HPO₄²⁻ underwent cathodic deprotonation, and including the acid-base equilibriums. A kinetic model was derived by analogy with the equations generally used for hydrogen evolution. Numerical fitting of the experimental data confirmed that the phosphate species may act as an efficient catalyst of hydrogen evolution via electrochemical deprotonation. This reaction may introduce an unexpected reversible pathway of hydrogen formation in the mechanisms of anaerobic corrosion. The possible new insights offered by the electrochemical deprotonation of phosphate in microbially influenced corrosion was finally discussed.     

Modern concept of acoustic emission (AE) coupled with electrochemical measurements for monitoring the elastomer-coated carbon steel damage in phosphoric acid medium

Elastomer coatings (rubber) are industrially used to protect phosphoric acid storage tanks against corrosion. Rubber constitutes a barrier against the penetration of H₃PO₄ to metallic surface. Coatings damage induces both acid infiltration and steel corrosion. In this concept, acoustic emission (AE) monitoring technique could be used for the detection of coatings damage as well as for steel corrosion under the coating. In the present work AE was coupled to electrochemical measurements (EM) for rubber damage evaluation and steel corrosion on three types of steels (XC48, E20 and A60) at room temperature in concentrated phosphoric acid (30% P₂O₅) contaminated by Cl⁻, F⁻, SO₄²⁻. Electrochemical behaviour of steels was studied and characterized by potentiodynamic curves and polarization resistance measurement. A good correlation between acoustic emission and polarization resistance or corrosion potential measurements was found during stages of coatings damage and steels corrosion. The majority of AE activity recorded during experiments is related to hydrogen bubbles release. The release of hydrogen bubbles gives rise to two populations of signals: one impulsive and another one resonant.     

Electrochemical behavior of AZ91D magnesium alloy in phosphate medium—part I. Effect of pH

The influence of pH on the corrosion behavior of Mg-based AZ91D alloy was investigated in a constant composition phosphate medium using various electrochemical techniques, complemented with surface analysis data. The studied solutions were 0.1 M H₃PO₄, NaH₂PO₄, Na₂HPO₄ and Na₃PO₄ having pH values of 1.8, 4.5, 9.1 and 11.8, respectively. Spontaneous passivation was substantiated from monitoring the continuous positive shift of the open circuit corrosion potential with both immersion time and solution pH. The impedance data indicated more improvement in the insulating properties of the corrosion products formed on the alloy surface with increase in pH. The electrolyte pH plays a determinant influence on surface film properties, as films formed in phosphate solutions with higher pH values are thicker, thus affording better protection for the alloy than those formed in acidic solutions. Good agreement was observed between the results obtained from electrochemical techniques and those from EDX and XRD examinations. The alloy is more susceptible to corrosion in acidic phosphate solutions than in the alkaline ones. Crystalline magnesium (Mg), magnesium hydride (MgH₂) and magnesium oxide (MgO) were found to be the main constituents of the surface film after holding for 2 h in the acidic phosphate medium.     

A novel route to synthesize metal titanium phosphate ceramic pigments: Co,Ni, and Cu-incorporated α-Ti(HPO4)2⋅H2O from ilmenite

Solid-state reaction of α-Ti(HPO₄)₂·H₂O (α-TiP) and acetates of Co, Ni, or Cu at 500 °C and 800 °C produce a number of different metal titanium phosphate (MTiP) inorganic pigments with different colors and shades. At a given metal to α-TiP ratio and calcination temperature, the reaction produces several types of pigments such as phosphates M_0.5TiO(PO₄), M_0.5Ti₂(PO₄)₃, M₂P₂O₇, and M₃(PO₄)₃ (M = Co, Ni, and Cu) with a unique color. α-TiP, an iron free base material was prepared by digestion of high-grade natural ilmenite beach sand (FeTiO₃) with 85 wt% H₃PO₄ at 120 °C. TGA, XRD, SEM/EDX, Diffuse reflectance UV–vis, and Raman spectroscopy techniques were used for characterization. Synthesized MTiP pigments after enameling at a single fire glazing at 1100 °C for 45 min exhibit vivid colors, ranging from purple, yellow, and green with different shades.     

Microstructures,mechanical properties and corrosion resistance of sprayed Ca–P coating for micropatterning carbon/carbon substrate surface

Carbon/carbon (C/C) surface micropatterning is a method of modifying the surface into the complete and regular geometry. In this work, we introduce a positive effect on bonding strength between sprayed Ca–P coating and surface micropatterning C/C substrate. Interestingly, C/C substrate coated by Ca–P coating provides textured surface for a new bone ingrowth. The sprayed Ca–P coating is then subjected to microwave-hydrothermal (MH) treatment with the aim of eliminating surface defects and obtaining a uniform purity phase. These objectives were achieved in our previous study by the MH method. The molar ratio of Ca/P in the coatings is nearly close to 1, which is far below that of Ca/P for hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HA, 1.67). The purpose of this article is to transform the phases in the sprayed Ca–P coating, which owns the better bioactivity and high corrosion resistance. In order to raise the molar ratio of Ca/P, the coatings are treated under high-temperature (around 700 °C). They are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and a fourier transform infrared spectra (FTIR). The bonding strength (coating/substrate), biological activity and corrosion resistance of the coatings are investigated. The resulting coatings own the different microstructures and phase compositions from the original sprayed Ca–P coating. Especially, results show that the shear strength of the sprayed Ca–P coating deposited on surface micropatterning C/C substrate increases by 61% which is more than that of the coating on non-surface micropatterning C/C substrate. Additionally, high-temperature treated coating presents a good biological activity and an excellent corrosion resistance of current density (1.3078 × 10^-6 A/cm²) and potential (−0.17 V_SCE).     

Corrosion behavior of air plasma spraying zirconia-based thermal barrier coatings subject to Calcium–Magnesium–Aluminum-Silicate (CMAS) via burner rig test

Three different kinds of thermal barrier coatings (TBCs) — 8YSZ, 38YSZ and a dual-layered (DL) TBCs with pure Y₂O₃ on the top of 8YSZ were produced on nickel-based superalloy substrate by air plasma spraying (APS). The Calcium–Magnesium–Aluminum-Silicate (CMAS) corrosion resistance of these three kinds of coatings were researched via burner rig test at 1350 °C for different durations. The microstructures and phase compositions of the coatings were characterized by SEM, EDS and XRD. With the increase of Y content, TBCs exhibit better performance against CMAS corrosion. The corrosion resistance against CMAS of different TBCs in descending was 8YSZ + Y₂O₃, 38YSZ and 8YSZ, respectively. YSZ diffused from TBCs into the CMAS, and formed Y-lean ZrO₂ in TBCs because of the higher diffusion rate and solubility of Y³⁺ in CMAS than Zr⁴⁺. At the same time, 38YSZ/8YSZ + Y₂O₃ reacts with CAMS to form Ca₄Y₆(SiO₄)₆O/Y_4·67(SiO₄)₃O with dense structure, which can prevent further infiltration of CMAS. The failure of 8YSZ coatings occurred at the interface between the ceramic coating and the thermally grown oxide scale (TGO)/bond coating. During the burner rig test, the Y₂O₃ layer of the DL TBCs peeled off progressively and the 8YSZ layer exposed gradually. DL coatings keep roughly intact and did not meet the failure criteria after 3 h test. 38YSZ coating was partially ablated, the overall thickness of the coating is thinned simultaneously after 2 h. Therefore, 8YSZ + Y₂O₃ dual-layered coating is expected to be a CMAS corrosion-resistant TBC with practical properties.     

Magnesium monophosphate cements derived from diammonium phosphate solutions

Rapid-setting magnesium monophosphate cementitious materials were prepared by mixing calcined magnesium oxide (MgO) powder with an aqueous solution of diammonium phosphate (ADP) at 24°C. The activation energy for the curing reaction of the cement paste was determined to be 30.29 kcal/mole, and at age 1 hr the compressive strength was ≈900 psi (6.2 MPa). X-ray diffraction studies of the cured cement indicated that the major reaction product was magnesium orthophosphate tetrahydrate [Mg₃(PO₄)₂·4H₂O]. Magnesium ammonium phosphate hexahydrate [MgNH₄PO₄·6H₂O] and Mg(OH)₂ were also detected. Subsequent heating of the cement to 1300°C resulted in the conversion of the three compounds to a single phase of anhydrous magnesium orthophosphate [Mg₃(PO₄)₂]. The resultant product had a compressive strength of 7000 psi (48.23 MPa) and was thermally stable in air at temperatures >1000°C.     

Effect of vanadium additive and phosphating time on anticorrosion,morphology and surface properties of ambient temperature zinc phosphate conversion coatings on mild steel

An attempt has been made to investigate the effect of phosphating time and vanadium additive on the anticorrosion and surface properties of ambient temperature zinc phosphate coatings. Zinc phosphate coatings with different phosphating times and vanadium concentrations were applied to low carbon steel samples. A potentiostatic polarization test in 3.5 wt% NaCl solution was carried out to investigate the electrochemical properties of coated samples. Field emission scanning electron microscopy, energy-dispersive spectroscopy, and atomic force microscopy were utilized to evaluate the microstructure, chemistry and roughness of coatings. Surface properties such as wettability, surface tension, and work of adhesion were measured. Results indicate that the sample which was immersed for 30 min in the phosphating bath exhibits the lowest corrosion current density, one tenth of bare steel, due to formation of a compact coating while having a low number of microcracks. Addition of 500 ppm vanadium to the coating in a secondary bath decreases the corrosion rate of zinc phosphate coating remarkably, by almost 80%. Microstructural results reveal that vanadium-rich precipitates are formed and enhance the coating coverage on the steel substrate. Vanadium addition increases the surface roughness, surface free energy, and work of adhesion of the phosphate coating.     

Corrosion protection of steel and bond durability at polyphenylene sulfide-to-anhydrous zinc phosphate interfaces

To enhance the performance of high-temperature polyphenylene sulfide (PPS) coating in protecting steels from corrosion, the cold-rolled steel surfaces were prepared with anhydrous zinc phosphate (Zn · Ph) conversion coatings containing poly(acid) anhydride as an interfacial tailoring material. The factors contributing to the formation of a good bond at the PPS/Zn · Ph joints were as follows: (1) the chemical reaction of PPS with Fe₂O₃ in the Zn · Ph layers, (2) PPS-to-poly(acid) anhydride interaction, and (3) the mechanical interlocking between PPS and the rough Zn · Ph crystal surfaces. Although such interfacial bond structures provide a superior durability of PPS/Zn · Ph joints against a hot H₂SO₄ solution, the cathodic reaction, H₂O + ½O₂ + 2e^? = 2OH^?, occurring at any defect in the PPS/Zn · Ph joint system when NaCl is present will lead to the delamination of the PPS film from the phosphated steel. This cathodic delamination was due mainly to alkali-induced dissolution of Zn · Ph layers. However, the rate of delamination for the PPS/Zn · Ph systems was considerably lower compared with that for the PPS/steel system in the absence of Zn · Ph.     

The effect of polyaniline phosphate on mechanical and corrosive properties of protective organic coatings containing high amounts of zinc metal particles

The objective of this paper is to reduce the zinc metal content in organic coatings while preserving their high anticorrosive efficiency. The two goals can be achieved by using conductive polymers as components of the protective coating. Polyaniline phosphate (PANI-H₃PO₄) was investigated as the conductive polymer and was also used in surface treatment of steatite talc Mg₃(Si₄O₁₀)(OH)₂. Both PANI-H₃PO₄ and Mg₃(Si₄O₁₀)(OH)₂/PANI-H₃PO₄ were specified using physico-chemical parameters. An epoxy ester resin was used as binder for the organic coatings investigated. Organic coatings were prepared by combining zinc metal with PANI-H₃PO₄ or Mg₃(Si₄O₁₀)(OH)₂/PANI-H₃PO₄. The mechanical resistance of the prepared films was evaluated using the results of mechanical tests. The anticorrosive efficiency of the prepared films was evaluated using the results of direct corrosion tests.     

Structure of the hydroxyapatite plasma-sprayed coatings deposited on pre-heated titanium substrates

Plasma spraying is the most commonly used thermal spray method for the application of hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) coatings. In the present study, the HA coatings were plasma spraying deposited onto plates of titanium pre-heated to 20 °C, 300 °C and 550 °C. The obtained HA coatings were investigated by means of X-ray diffraction and scanning electron microscopy. It is found that the coatings, in addition to HA, contain the tetracalcium phosphate (TTCP, (Ca₄(PO₄)₂O) phase (~10%) and a small amount of CaO (<2%). Crystal structure of HA in the coatings is revealed to be distorted. The PO4 tetrahedrons are deformed (Baur distortion coefficient D1(TO) ~0.2). The distances Ca1-O1 and Ca1-O2 are changed as compared to these in stoichiometric hydroxyapatite. These distortions are considered as a result of internal stresses, which are demonstrated in the broadening of peaks on X-ray diffraction pattern of HA. Microstructure of coatings consisting of flattened splats was formed by fully molten particles. The axial base texture was developed in the coatings. Ultrastructure is columnar with a preferred orientation of c-axes of the crystals parallel to the normal of plane coating n. The heating of substrate has a marked effect on the ultrastructure of coatings: the domain size increases from 790 to 1100 Å, the strain Δ decreases from 1.6·10^-3 to 1,2·10^–3, TTCP content diminishes from 12% to 7%. These results show that the effects due to heating of the substrate may be associated with partial recovery of HA microstructure.     

Preparation and characterization of nanocrystalline Fe–Ni–Cr alloy electrodeposits on Fe substrate

Fe–Ni–Cr alloy layers were prepared by electrodeposition from trivalent chromium plating bath in chloride-sulfate based solution. The influences of bath composition and plating parameters on the alloy electrodeposition process and the properties of deposited alloy were studied. The effects of plating parameters and bath composition such as current density, bath pH, bath temperature, the concentrations of FeSO₄ · 7H₂O and CrCl₃ · 6H₂O on the contents of Fe and Cr in Fe–Ni–Cr alloy layer were investigated. Electrodeposited Fe–Ni–Cr alloy layers on Fe substrate were characterized by X-ray diffraction (XRD), Electronic Differential System (EDS) and a CHI600B electrochemistry workstation. The composition of the Fe–Ni–Cr coatings depends on bath composition and plating conditions including pH, current density, and temperature. The internal structure of the alloy is nanocrystalline, the average grain size is 87 nm, and the corrosion resistance of the alloy layers is better than that of pure nickel layers.