High-Temperature thermochemical interactions of molten silicates with Yb2Si2O7 and Y2Si2O7 environmental barrier coating materials

The thermochemical behavior of EBC candidate materials yttrium disilicate (Y₂Si₂O₇) and ytterbium disilicate (Yb₂Si₂O₇) was evaluated with three calcium-magnesium-aluminosilicate (CMAS) glasses possessing CaO:SiO₂ ratios relevant to gas turbine systems. Pellet mixtures of 50 mol% EBC powder to 50 mol% CMAS glass powder were heat treated at 1200°C, 1300°C, and 1400°C. The products of these interactions were evaluated using X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. Above glass melting temperatures, exposure of the disilicates primarily resulted in dissolution into the molten glass followed by precipitation of a Ca₂RE₈(SiO₄)₆O₂ (RE = Yb³⁺, Y³⁺) apatite-type silicate and/or rare earth disilicate. In glasses with high CaO concentrations, apatite readily forms while the disilicate material is consumed by the reaction. As CaO content decreases, the disilicate phase becomes the main reaction product. Overall, reactions with yttrium disilicate favored more apatite crystallization than ytterbium disilicate. The viability of using these disilicates in various operating environments is discussed.     

Significantly improved corrosion resistance of high-entropy rare-earth silicate multiphase ceramics against molten CMAS

To improve the ability of rare-earth (RE) silicates to resist molten calcium–magnesium–aluminosilicate (CMAS) at high temperature, a novel high-entropy (4RE_0.25)₂Si₂O₇/(4RE_0.25)₂SiO₅ (RE = Y, Yb, Er, and Sc) multiphase ceramic was prepared by a two-step process. During sintering, (4RE_0.25)₂SiO₅ can react with SiO₂ at the grain boundaries of (4RE_0.25)₂Si₂O₇, which can not only purify the grain boundary but also promote the growth of the original (4RE_0.25)₂Si₂O₇ grains, thereby significantly improving the ability to resist molten CMAS corrosion at high temperature. After corroding at 1500°C for 48 h, the reaction layer of the multiphase ceramic was only 55 μm thick. Our results confirm that the high-entropy RE silicate multiphase ceramics represent an effective way to improve the ability to resist molten CMAS corrosion at high temperature.     

Hot corrosion of RE2SiO5 with different cation substitution under calcium–magnesium–aluminosilicate attack

Rare earth (RE) silicates have been applied as advanced environmental barrier coatings (EBCs) to protect silicon carbide fibers reinforced silicon carbide ceramic matrix from water vapor and molten salt corrosion in engines. This process, however, is limited by volcanic ash corrosion as assessment of ash-induced corrosion is anecdotal and quantitative data are insufficient. In this account, the corrosion behavior of RE monosilicates (RE₂SiO₅, RE = Y, Lu, Yb, Eu, Gd, and La) by calcium–magnesium–aluminosilicate (CMAS), with similar composition as volcanic ash, was comprehensively investigated. Results indicated that RE₂SiO₅ could react with CMAS at 1200 °C at the interface, where the products crystallized in CMAS glass. RE₂Si₂O₇ was formed by the reaction between RE₂SiO₅ and silica (SiO₂) in CMAS, which was followed by corrosion of RE₂Si₂O₇ by CMAS. RE₂SiO₅ with Type B structure showed better resistance toward CMAS than RE₂SiO₅ with Type A structure. Moreover, RE₂SiO₅ with larger radii of RE³⁺ cations led to easy formation of oxyapatite phase; however, RE₂SiO₅ with smaller radii of RE³⁺ cations easily formed garnet phase. Besides, smaller radii RE³⁺ cations induced slower reactions. These findings can contribute to identifying, preventing, and minimizing the damage to matrix components with EBCs caused by volcanic ash.     

Interaction of Gd2Si2O7 with CMAS melts for environmental barrier coatings

Environmental barrier coatings (EBCs) prevent the oxidation of ceramic matrix composites (CMC), which are used as components in gas turbines. However, EBCs deteriorate more rapidly in real environments, molten silicate deposits accelerate the deterioration of EBCs. In this study, high-temperature behavior sintered Gd₂Si₂O₇ with calcia-magnesia-alumina-silica (CMAS) melt at 1400 °C for 0.5, 2, 12, 48, and 100 h was investigated. HT-XRD results showed that at 1300 °C, CMAS and Gd₂Si₂O₇ chemically reacted to form Ca₂Gd₈(SiO₄)₆O₂ (apatite). The reaction layer became thicker as the heat-treatment time increased, and the thickness of the reaction layer has increased following a parabolic curve. With the extension of the reaction time from 0.5 to 100 h, the thickness of the reaction layer increased from approximately 98 to 315 µm. It was confirmed that Ca₂Gd₈(SiO₄)₆O₂ grew vertically on the Gd₂Si₂O₇ surface. Vertical and horizontal cracks were found after reacting at 1400 °C for 100 h, but no interfacial delamination occurred in this study. In addition, the effects of CaO:SiO₂ molar ratios, monosilicates (RE₂SiO₅) and disilicates (RE₂Si₂O₇), heat-treatment time, and cation size were determined and compared with the results of previous studies (Gd₂SiO_5, Yb₂SiO_5, and Er₂Si₂O₇).     

Calcium–magnesium–aluminosilicate corrosion behaviors of rare-earth disilicates at 1400 °C

Environmental barrier coatings (EBCs) are used to prevent oxidation of underlying ceramic matrix composite (CMC) structural components in gas turbines. When the siliceous minerals deposit on the surface of EBCs, a glassy melt of calcium–magnesium–aluminosilicate (CMAS) will be formed, leading to the EBCs degradation. In this study, seven rare-earth disilicates (RE₂Si₂O₇, RE = Yb, Lu, La, Gd, Eu, Sc, and Y) were fabricated to analyze their CMAS corrosion behaviors. The results indicated that the RE₂Si₂O₇ could react with the CMAS in the temperature range of 1250–1350 °C. Reaction zones formed at the interfaces. For the Yb₂Si₂O₇, Lu₂Si₂O₇, La₂Si₂O₇, Eu₂Si₂O₇ and Gd₂Si₂O₇, the reaction zones dissolved into the molten CMAS and separated from the RE₂Si₂O₇. As for the Sc₂Si₂O₇ and Y₂Si₂O₇, the reaction zones could stay at the interface. They could effectively block the molten CMAS to penetrate into the RE₂Si₂O₇ and protect them from CMAS corrosion.     

High-temperature interactions of desert sand CMAS glass with yttrium disilicate environmental barrier coating material

A calcium-magnesium aluminosilicate (CMAS) glass was prepared by melting a sample of desert sand to evaluate the high-temperature interactions between molten CMAS and yttrium disilicate (Y₂Si₂O₇), an environmental barrier coating (EBC) candidate material. Cold-pressed pellets of 80?wt% Y₂Si₂O₇ powder and 20?wt% CMAS glass powder were heat treated at 1200?°C, 1300?°C, 1400?°C and 1500?°C for 20?h in air. The resulting phases were evaluated using powder X-ray diffraction. In the second set of experiments, free standing hot-pressed Y₂Si₂O₇ substrates with cylindrical wells were filled with CMAS powder to a loading of ~35?mg/cm² and heat treated in air at 1200?°C, 1300?°C, 1400?°C and 1500?°C for 20?h. Scanning electron microscopy, energy-dispersive spectroscopy and electron microprobe analysis were used to evaluate the microstructure and phase compositions of specimens after heat treatment. An oxyapatite silicate (Ca₂Y₈(SiO₄)₆O₂) phase was identified in all specimens after CMAS exposure regardless of heat treatment temperature. Apatite appeared to form by dissolution of Y₂Si₂O₇ into molten CMAS, reacting with CaO in the melt according to the reaction 4Y₂Si₂O₇ +?2CaO → Ca₂Y₈(SiO₄)₆O₂ +?2SiO₂, and followed by precipitation of the apatite phase.     

Corrosion of RE2Si2O7 (RE=Y,Yb, and Lu) environmental barrier coating materials by molten calcium-magnesium-alumino-silicate glass at high temperatures

With the increased demand for high operating temperature of gas turbine engines, corrosion by molten calcium-magnesium-alumino-silicate (CMAS) exhibits a significant challenge to the development of durable environmental barrier coatings (EBCs). EBC candidates, γ-Y₂Si₂O₇, β-Yb₂Si₂O₇, and β-Lu₂Si₂O₇ were explored on their corrosion resistance to CMAS melts at 1300 °C and 1500 °C for 50 h. Interaction and degradation mechanisms were investigated and the corrosion behaviors showed different trends at high temperatures. At 1300 °C, RE₂Si₂O₇ dissolves into CMAS melts and apatite phases reprecipitate forming a thick recession layer. However, when the temperature increases to 1500 °C, CMAS melts vigorously penetrate through the grain boundary of RE₂Si₂O₇ and ‘blister’ cracks form throughout the samples. The reduced grain boundary stability at 1500 °C promotes the penetration of CMAS melts in RE₂Si₂O₇. Grain boundary engineering is critically demanded to optimize CMAS corrosion at high temperatures.     

Resistance of pure and mixed rare earth silicates against calcium-magnesium-aluminosilicate (CMAS): A comparative study

Rare earth silicate environmental barrier coatings (EBCs) are state of the art for protecting SiC ceramic matrix composites (CMCs) against corrosive media. The interaction of four pure rare earth silicate EBC materials Yb₂SiO₅, Yb₂Si₂O₇, Y₂SiO₅, Y₂Si₂O₇ and three ytterbium silicate mixtures with molten calcium-magnesium-aluminosilicate (CMAS) were studied at high temperature (1400°C). The samples were characterized by SEM and XRD in order to evaluate the recession of the different materials after a reaction time of 8 hours. Additionally, the coefficient of thermal expansion (CTE) was determined to evaluate the suitability of Yb silicate mixtures as EBC materials for SiC CMCs. Results show that monosilicates exhibit a lower recession in contact with CMAS than their disilicate counterparts. The recession of the ytterbium silicates is far lower than the recession of the yttrium silicates under CMAS attack. Investigation of the ytterbium silicate mixtures exposes their superior resistance to CMAS, which is even higher than the resistance of the pure monosilicate. Also their decreased CTE suggests they will display better performance than the pure monosilicate.     

A promising molten silicate resistant material: Rare-earth oxy-apatite RE9.33(SiO4)6O2 (RE = Gd,Nd or La)

In this work we reported a new class of rare earth oxy-apatite, RE_9.33(SiO₄)₆O₂, with superior molten silicate resistant capability which shows promising application for thermal barrier coatings (TBCs). Three RE elements with different ion radius, i.e., Gd, Nd and La, were selected to prepare RE_9.33(SiO₄)₆O₂ bulk using co-precipitation and pressless-sintering. After 8-h CMAS attack at 1300 °C, the specimens exhibited a dense, continuous reprecipitated layer at RE-apatite/CMAS interface, which is predominantly controlled by a dissolution-reprecipitation mechanism distinguishing from the sacrificial material which is usually with reaction layer being formed. With an increase of ion radius, apatite is easier to crystallize in the melt.     

Variable thermochemical stability of RE2Si2O7 (RE = Sc,Nd, Er,Yb, or Lu) in high-temperature high-velocity steam

Five rare-earth (RE) disilicates (RE₂Si₂O₇, RE = Sc, Nd, Er, Yb, or Lu) were synthesized and exposed to high-velocity steam (up to 235 m/s) for 125 hours at 1400°C. Water vapor reaction products, mass loss, average reaction depths, and product phase microstructural evolution were analyzed for each material after exposure. Similar to steam testing results in the literature, RE₂Si₂O₇ (RE = Er, Yb, Lu) underwent silica depletion producing gaseous silicon hydroxide species, RE₂SiO₅, and RE₂O₃ product phases. Sc₂Si₂O₇ reacted with high-velocity steam to produce only a Sc₂O₃ product layer with no stable Sc₂SiO₅ phase detected by X-ray diffraction or microscopy techniques. Further, Nd₂Si₂O₇ rapidly reacted with steam to produce with no Nd₂SiO₅ or Nd₂O₃ reaction products. All RE₂Si₂O₇ that produced a silicate reaction product (RE = Nd, Er, Yb, Lu) showed densification of the product phase at steam velocities above 150 m/s that resulted in enhanced resistance. The results presented in this work demonstrate that rare-earth silicates show diverse steam reaction products, reaction product microstructures, and total reaction depths after high-temperature high-velocity steam exposure. Of the materials in this study, RE₂Si₂O₇ (RE = Yb, Lu) were most stable in high-temperature high-velocity steam, making them most desirable as environmental barrier coating candidates.     

Formation characteristics of sodium calcium silicate compounds based on the solid-state reaction

The formation thermodynamics, phase transition and stability of sodium calcium silicate compounds under different calcination parameters in the Na₂O–CaO–SiO₂ system were studied using XRD, FTIR and SEM-EDS methods. As the Na₂O/SiO₂ ratio increases from 0.3 to 0.7 when the CaO/SiO₂ ratio is 1.0, the formation sequence of sodium calcium silicate compounds is Na₂Ca₃Si₂O₈→Na₆Ca₃Si₆O₁₈→Na₂Ca₂Si₂O₇→Na₂CaSiO₄; as the CaO/SiO₂ ratio increases from 0.3 to 1.2 when the Na₂O/SiO₂ ratio is 0.5, the formation sequence is Na₆Ca₃Si₆O₁₈→Na₂Ca₂Si₂O₇→Na₂Ca₃Si₂O₈. As the most stable sodium calcium silicate compound, Na₆Ca₃Si₆O₁₈ forms by the solid-state reaction of preformed Na₂SiO₃ with CaO and SiO₂, while increasing the calcination temperature and holding time can promote its crystal stability. The decomposition of Na₆Ca₃Si₆O₁₈ in sodium aluminate solution follows the mixed control of the film diffusion and chemical reaction, and the corresponding activation energy is between 40 and 41 kJ/mol.     

CaO-MgO-Al2O3-SiO2 corrosion behavior of air-plasma-sprayed (LaxYb1−x)2Zr2O7

The CaO-MgO-Al₂O₃-SiO₂ (CMAS) corrosion of thermal barrier coatings (TBCs) is a crucial problem for the lifetime of blades and vanes of jet engine and gas turbine at high operating temperature. Although many new alternative materials for TBCs have been developed in recent years, their application is limited by the CMAS corrosion. On the other hand, the composition difference of CMAS between regions makes solving this problem very difficult. Therefore, in this study, the yearly composition changes of sand-dust around Beijing area were investigated. The high-temperature corrosion behavior of air-plasma-sprayed 8YSZ and newly developed (La_xYb_1−x)₂Zr₂O₇ TBCs by the representative sand-dust of Beijing was investigated. In comparison, a universally used CaO-riched composition of simulated silicate deposit was also adopted for the TBCs corrosion test. It is found that the (La_xYb_1−x)₂Zr₂O₇ TBCs performs much better anti-corrosion behavior than that of 8YSZ, both by Beijing sand-dust and simulated one. Particularly, Yb₂Zr₂O₇ TBCs appear to be the optimum material against silicate deposits attack. The mechanism of silicate deposits corrosion has also been discussed.     

CaO-MgO-Al2O3-SiO2 corrosion behavior of SrZrO3-La2Ce2O7 composite ceramics

In this work, the corrosion behavior, interaction products, and the corrosion mechanism of (1-x)SrZrO₃-xLa2Ce2O7(x = 0.3, S7L3; x = 0.5, S5L5; x = 0.7, S3L7) composite bulks after CaO-MgO-Al₂O₃-SiO₂ (CMAS) attack at 1250°C for 1, 4, and 12 h were investigated, respectively. The molten CMAS and the bulks rapidly interacted and generated a dense reaction layer, which mainly composed of La-Ce apatite, Ce₂Zr₂O_7.04, ZrO₂ with some Ce, Ca, Si, Mg, and Al elements preventing CMAS from continuous penetration effectively. The formation of CMAS self-crystallizing products such as Ca₂Al₂SiO₇ gehlenite and Mg-Al spinel with high melting points increased the viscosity of CMAS. The elements in the ceramic also diffused into the molten CMAS and formed Ce₂Zr₂O_7.04 and La₂Ce₂O₇, increasing the melt viscosity and blocking the penetration channel of the molten CMAS. The S5L5 bulk has the best corrosion resistance against CMAS attacks.     

Thermal Expansion of Rare‐Earth Pyrosilicates

The use of RE₂Si₂O₇ materials as environmental barrier coatings (EBCs) and in the sintering process of advanced ceramics demands a precise knowledge of the coefficient of thermal expansion of the RE₂Si₂O₇. High‐temperature X‐ray diffraction (HTXRD) patterns were collected on different RE₂Si₂O₇ polymorphs, namely A, G, α, β, γ, and δ, to determine the changes in unit cell dimensions. RE₂Si₂O₇ compounds belonging to the same polymorph showed, qualitatively, very similar unit cell parameters behavior with temperature, whereas the different polymorphs of a given RE₂Si₂O₇ compound exhibited markedly different thermal expansion evolution. The isotropy of thermal expansion was demonstrated for the A‐RE₂Si₂O₇ polymorph while the rest of polymorphs exhibited an anisotropic unit cell expansion with the biggest expansion directed along the REO_x polyhedral chains. The apparent bulk thermal expansion coeficcients (ABCTE) were calculated from the unit cell volume expansion for each RE₂Si₂O₇ compound. All compounds belonging to the same polymorph exhibited similar ABCTE values. However, the ABCTE values differ significantly from one polymorph to the other. The highest ABCTE values correspond to A‐RE₂Si₂O₇ compounds, with an average of 12.1 × 10^?6 K^?1, whereas the lowest values are those of β‐ and γ‐RE₂Si₂O₇, which showed average ABCTE values of ~4.0 × 10^?6 K^?1.     

CaO–MgO–Al2O3–SiO2 (CMAS) corrosion behaviour of LaMgAl11O19/GdPO4 thermal barrier coating materials

CaO–MgO–Al₂O₃–SiO₂ (CMAS) corrosion poses serious hidden dangers for the application of thermal barrier coatings (TBCs). In this study, LaMgAl₁₁O₁₉ (LMA) and GdPO₄ were mixed at molar ratios of 2:1, 1:1 and 1:2 to prepare LMA/GdPO₄ materials, and the CMAS corrosion behaviours of these materials were investigated at 1300°C–1500 °C for 20 h and 40 h. It was demonstrated that temperature was the main factor influencing the corrosion behaviours and products. The materials were damaged at 1300 °C by the crystallization of CMAS melts to form CaAl₂Si₂O₈. In contrast, the materials were corroded by CMAS melts via the reaction between CMAS and GdPO₄ at 1500 °C. These results indicate that the addition of GdPO₄ to LMA can improve the resistance of the LMA material to CMAS corrosion.     

Scandium effect on the luminescence of Er-Sc silicates prepared from multi-nanolayer films

Polycrystalline Er-Sc silicates (Er _x Sc_2-x Si₂O₇ and Er _x Sc_2-x SiO₅) were fabricated using multilayer nanostructured films of Er₂O₃/SiO₂/Sc₂O₃ deposited on SiO₂/Si substrates by RF sputtering and thermal annealing at high temperature. The films were characterized by synchrotron radiation grazing incidence X-ray diffraction, cross-sectional transmission electron microscopy, energy-dispersive X-ray spectroscopy, and micro-photoluminescence measurements. The Er-Sc silicate phase Er _x Sc_2-x Si₂O₇ is the dominant film, and Er and Sc are homogeneously distributed after thermal treatment because of the excess of oxygen from SiO₂ interlayers. The Er concentration of 6.7 × 10²¹ atoms/cm³ was achieved due to the presence of Sc that dilutes the Er concentration and generates concentration quenching. During silicate formation, the erbium diffusion coefficient in the silicate phase is estimated to be 1 × 10^-15 cm²/s at 1,250°C. The dominant Er _x Sc_{2 - x} Si₂O₇ layer shows a room-temperature photoluminescence peak at 1,537 nm with the full width at half maximum (FWHM) of 1.6 nm. The peak emission shift compared to that of the Y-Er silicate (where Y and Er have almost the same ionic radii) and the narrow FWHM are due to the small ionic radii of Sc³⁺ which enhance the crystal field strength affecting the optical properties of Er³⁺ ions located at the well-defined lattice sites of the Sc silicate. The Er-Sc silicate with narrow FWHM opens a promising way to prepare photonic crystal light-emitting devices.     

Statistical mechanical model for the formation of octahedral silicon in phosphosilicate glasses

Unlike ambient pressure silicate glasses, some phosphosilicate glasses contain sixfold-coordinated silicon (Si⁶) units even when prepared at ambient pressure. The variation in the fraction of Si⁶ with composition remains a topic of interest, both for technological applications of phosphosilicate glasses and for fundamental understanding of the glass structure. In this work, we use statistical mechanical modeling to predict the composition–structure relationships in Na₂O–P₂O₅–SiO₂ and CaO–P₂O₅–SiO₂ glasses. This is achieved by accounting for the enthalpic and entropic contributions to the interactions between each pairwise modifier ion and structural unit. The initial enthalpy parameters are obtained based on experimental structural data for binary Na₂O–SiO₂, CaO–SiO₂, Na₂O–P₂O₅, and CaO–P₂O₅ glasses, which can then be transferred to predict the structure of mixed former glasses. This approach has previously been used to predict the short-range structure of borosilicate and aluminoborate glass systems. However, here we show that the formation of Si⁶ must be specifically included to make accurate predictions of the composition–structure relationships in phosphosilicate glasses. After incorporating the formation mechanism of Si⁶ in the statistical mechanics model, we find an excellent agreement between model predictions and experimental structure data for Na₂O–P₂O₅–SiO₂ and CaO–P₂O₅–SiO₂ glasses.     

Plasma sprayed nanostructured GdPO4 thermal barrier coatings: Preparation microstructure and CMAS corrosion resistance

Nanostructured GdPO₄ thermal barrier coatings (TBCs) were prepared by air plasma spraying, and their phase structure evolution and microstructure variation due to calcium–magnesium–alumina–silicate (CMAS) attack have been investigated. The chemical composition of the coating is close to that of the agglomerated particles used for thermal spraying. Nanozones with porous structure are embedded in the coating microstructure, with a percentage of ~30%. CMAS corrosion tests indicated that nanostructured GdPO₄ coating is highly resistant to penetration by molten CMAS at 1250°C. Within 1 hour heat treatment duration, a continuous dense reaction layer forms on the coating surface, which are composed of P–Si apatite based on Ca_2+xGd_8?x(PO₄)_x(SiO₄)_6?xO₂, anorthite and spinel phases. This layer provides effective prevention against CMAS further infiltration into the coating. Prolonged heat treatment densifies the reaction layer but does not change its phase composition.     

Environmental-barrier coating ceramics for resistance against attack by molten calcia-magnesia-aluminosilicate (CMAS) glass: Part II, β-Yb2Si2O7 and β-Sc2Si2O7

The high-temperature (1500?°C) interactions of two promising dense, polycrystalline EBC ceramics, β-Yb₂Si₂O₇ and β-Sc₂Si₂O₇, with a calcia-magnesia-aluminosilicate (CMAS) glass have been explored as part of a model study. Unlike YAlO₃ and γ-Y₂Si₂O₇ in the accompanying Part I paper, little or no reaction is found between the Y-free EBC ceramics and the CMAS. In the case of β-Yb₂Si₂O₇, a small amount of reaction-crystallization product Yb-Ca-Si apatite solid solution (ss) forms, whereas none is detected in the case of β-Sc₂Si₂O₇. The CMAS glass penetrates into the grain boundaries of both EBC ceramics, and they both suffer from a new type of ‘blister’ cracking damage. This is attributed to the through-thickness dilatation-gradient caused by the slow grain-boundary-penetration of the CMAS glass. The success of a ‘blister’-damage-mitigation approach is demonstrated, where 1?vol% CMAS glass is mixed into the β-Yb₂Si₂O₇ powder prior to sintering. The CMAS-glass phase at the grain boundaries promotes rapid CMAS-glass penetration, thereby avoiding the dilatation-gradient.     

Kinetics and Mechanism of the Interaction of Alkali Calcium Silicate Glasses with Salt Melts in the KNO3–Pb(NO3)2 System

The interaction of alkali calcium silicate glasses with salt melts in the KNO₃–Pb(NO₃)₂ system is investigated at temperatures of 420–520°C. The chemical composition of crystalline coatings formed upon treatment contains both components of the initial glass (SiO₂, 9–12 wt %; CaO, 0.8–1.2 wt %) and components of the salt melt (PbO, 82–89 wt %). The treatment temperature is the main factor affecting the structure of the modified surface layer. The mechanism of the interaction of alkali calcium silicate glasses with salt melts is analyzed. According to this mechanism, the interaction involves the ion exchange (with the participation of Na⁺, K⁺, Ca²⁺, and Pb²⁺ ions), crystallization of modified surface layers, and incorporation of Pb _x O _y nanoparticles (formed in the salt melt) into the coating structure.