Oxide Composite Films Research Articles

Corrosion Ferritic Stainless Steel in a Simulated Hydrothermal Liquefaction Bioconversion Aqueous Solution: Effect of Surface Cr Content

Abstract The objective of this study was to determine the effect of surface Cr content on the corrosion of ferritic stainless steels in hot pressurized alkaline water (310 °C at 10 MPa) simulating a hydrothermal liquefaction bioconversion medium. Two methods to increase the Cr surface content were investigated: (i) selecting commercial grades of ferritic stainless steel with an increasing Cr content and (ii) applying a Cr coating (chromizing) to a low-Cr (Type 409) ferritic stainless steel. The observed parabolic-like corrosion kinetics were analyzed and discussed in terms of the structure and composition of the double layered oxide films that formed. The (surface) Cr content is a critical factor affecting corrosion. Corrosion was reduced by 66% (after 20 days exposure) when increasing the Cr content from 9 wt.% (P91) to 21 wt.% (SS443) in the commercial grades of ferritic stainless steel. Moreover, corrosion was reduced by 84% (after 20 days exposure) by chromizing the surface of a low-Cr (Type 409) ferritic stainless steel. Improved corrosion protection was attributed to increased Cr incorporation into the inner (barrier) Fe(Fe1-nCrn)2O4 layer, with the formation of a Cr2O3 layer (resulting from chromizing) being most beneficial.

Flexible Micro‐Supercapacitors with Enhanced Energy Density Utilizing Flash Lamp Annealed Graphene‐Carbon Nanotube Composite Electrodes

AbstractAs demand for micro‐power sources grows, micro‐supercapacitors (MSCs) have become critical for miniaturized devices, offering robust electrochemical energy storage. However, the challenge remains to develop a simple, scalable fabrication method that achieves both high energy and power densities. In this study, we present a refined approach to fabricating MSCs with 3D interconnected graphene/carbon nanotube (CNT) composite electrodes. Our method combines flash lamp annealing (FLA) and laser ablation, where FLA converts graphene oxide (GO) and CNT composite films into 3D‐structured graphene/CNT electrodes, and laser ablation precisely patterns them into interdigitated designs. This dual‐process technique produces MSCs with exceptional electrochemical performance, including an impressive areal capacitance of 26.11 mF/cm2 and a volumetric capacitance of 31.88 F/cm3. These devices also achieve energy densities of 3.72 μWh/cm2 and 4.43 mWh/cm3, maintaining 97 % of their initial capacitance under extreme bending, demonstrating outstanding mechanical flexibility and durability. Furthermore, the scalability of this method was validated by configuring MSCs in series and parallel, achieving enhanced voltage and current outputs without additional interconnections. Overall, the integration of FLA and laser ablation holds significant promise for advancing the performance and scalability of micro‐sized energy storage devices, addressing the growing need for efficient, flexible, and high‐capacity micro‐power sources.

Triboelectric Nanogenerator Based on Tin Doped Zinc Oxide and Polyvinyl Alcohol Composite Thin Film for Energy Harvesting Applications

The triboelectric nanogenerator (TENG) collects mechanical energy from its surroundings and converts it to electrical signals that can be used in sustainable energy harvesting technologies to help maintain the social ecosystem. However, TENG operation with pure triboelectric material may not be sufficient to power a small electronic system without modification. The optimal material capable of producing significant electrical energy with flexible structures remains a major barrier to practical application. In this study, tin-doped zinc oxide (Sn:ZnO) and polyvinyl alcohol (PVA) composite thin films were prepared using a simple solution immersion technique at various Sn atomic percentage (at.%) concentrations for use in TENG devices. The crystalline quality of a composite thin film made of Sn:ZnO and PVA was identified using x-ray diffraction. The microstructure changes of the composite thin film were found to be influenced by Sn doping, as studied using optical microscopy. The TENG with 2.5 at.% Sn:ZnO/PVA composite thin film and Kapton film achieved the highest peak voltage of 8.5 V in open circuit and 90 µW output power at 1 MΩ. The produced electrical output was then used to store energy in capacitors. According to its TENG properties, the Sn:ZnO/PVA composite thin film-based TENG has the potential to be used in low power electronic devices.

Discovery and Analysis of Key Core Technology Topics in Proton Exchange Membrane Fuel Cells Through the BERTopic Model

As a core component of clean energy technology, proton exchange membrane fuel cells (PEMFC) play a crucial role in promoting the evolution of energy structures and realizing sustainable development, representing an environmentally friendly energy conversion strategy. This paper identifies the key core technology themes in the field of the proton exchange membrane fuel cells by constructing patent and paper datasets in the field, applying the BERTopic model for theme identification, and calculating the key core technology scores of each theme using the importance, innovativeness, and high competitiveness barriers to identify the key core technology themes in the field, so as to provide guidance and references for the relevant research and practice. The results of the study show that patent documents and academic papers show obvious differentiation in technical themes: the key core technologies identified in patent texts include ‘battery separator materials’, ‘rubber sealing materials’, and ‘porous carbon fibre materials’. The key core technologies identified in the academic paper of the thesis include ‘palladium-based electrocatalys’, ‘graphene oxide composite film’, and ‘platinum-graphene oxide catalyst’.

Study on the Oxidation Behavior of TiB2-CeO2-Modified (Nb,Mo,Cr,W)Si2 Coating on the Surface of Niobium Alloy.

A novel TiB2-CeO2-modified (Nb,Mo,Cr,W)Si2 coating was prepared on a Nb-5W-2Mo-1Zr alloy substrate using two-step slurry sintering and halide-activated pack cementation to address the limitations of a single NbSi2 coating in meeting the service requirements of niobium alloys at elevated temperatures. At 1700 °C, the static oxidation life of the coating exceeded 20 h, thus indicating excellent high-temperature oxidation resistance. This was due to the formation of a TiO2-SiO2-Cr2O3 composite oxide film on the coating surface, which, due to low oxygen permeability, effectively prevented the inward infiltration of oxygen. Additionally, the dense structure of the composite coating further enhanced this protective effect. The composite coating was able to withstand over 1600 thermal shock cycles from room temperature to 1700 °C, and its excellent thermal shock performance could be attributed to the formation of MoSi2, CrSi2, and WSi2 from elements such as Mo, Cr, and W, which were added during modification. In addition to adjusting the difference in thermal expansion coefficients between the layers of composite coatings to reduce the thermal stress generated by thermal shock cycles, the formation of silicide compounds also improved the overall fracture toughness of the coating and thereby improved its thermal shock resistance.

On the corrosion resistance of the CoCrFeMnNi high entropy alloys in chloride-containing sulfuric acid solutions

The electrochemical reactivity of the high entropy Cantor alloy (CoCrFeMnNi) was investigated via potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and surface analysis as a function of chloride content, in sulfuric acid solutions. The results revealed that corrosion mechanism of the CoCrFeMnNi alloy at the corrosion potential, is a two-step mechanism, involving one adsorbed intermediate, similar to that of pure iron in the H2SO4, and this model provided a good description of the impedance data. X-ray photoelectron spectroscopy (XPS) surface characterization and impedance data fitting revealed that chloride ions do not alter the corrosion mechanism or the thickness of the surface oxide film. Instead, they affect the corrosion resistance by changing the composition of the oxide film. Additionally, this work demonstrated that the corrosion mechanism of the CoCrFeMnNi alloy varies with the applied potential, as evidenced by impedance measurements under potentiostatic polarization. Surface observations using scanning electron microscopy (SEM) and XPS analysis provided insights into the morphology and composition of the surface oxide film at different applied potentials, explaining the observed changes in impedance.

Renewable Nanocellulose/rGO film with a dense brick-and-mortar structure for electromagnetic interference and energy storage

Considering the high requirements for robust and flexible power supplies, the green and sustainable fiber-based supercapacitor is suitable to accommodate the inevitable serious deformation and low radiation issues in wearable electronic energy storage devices due to its easy integration. Compatible natural nanocellulose (NFC) as a framework and the two-dimensional conductive graphene (GO) nanosheets constructed a dense brick-and-mortar structure, which the dispersing effect of NFC avoided GO aggregation. The utilization of the green-reducing agent and the obtained NFC/reduced graphene oxide (rGO) composite film endowed the composite film with a continuous conductive network by the self-assembly behavior of NFC and GO, that the lightweight flexible electrode NFC/50rGO with 13 μm thickness had high conductivity (883.70 S m−1), a total electromagnetic shielding efficiency of 27.1 dB at 8.2 GHz frequency, electrochemical behavior (mass-specific capacitance up to 170.6F g−1), and reversible charge–discharge behavior. Developing a green and portable small electronic device with such a flexible and high-strength electrode symbolizes the critical development direction in the future electronic equipment field.

Solvothermal synthesis and enhanced electrochromic properties of coal-based reduced graphene oxide and covalent organic framework electrochromic composite films containing triphenylamine unit

Two-dimension covalent frameworks (2D COFs) with reversible redox units show the potential in the field of photo-electronic functional materials because of their rich electron transport path and reversible redox characteristic. However, the pure organic conjugated system of COF results in poor electrical conductivity and weak cyclic performance. In this work, tris (4-aminophenyl) amine and 4,4-biphenyldiformaldehyde (TABP) COF electrochromic film with triphenylamine (TPA) active unit was synthesized by a solvothermal method in Teflon-lined reactor. And then the TABP-COF/coal-based reduced graphene oxide (C-rGO) film was prepared by the one pot method. C-rGO provides the growth substrate and electron transport path for COF. Taixi anthracite with a high degree of graphitization also contributes to the preparation of GO. The electrochemical and electrochromic properties of TABP-COF and TABP-COF/C-rGO were studied and they could be switched reversibly from yellow and brown. Relative to TABP-COF, the impedance and response time of composite decrease and the contrast of composite increases. Moreover, TABP-COF/C-rGO exhibits the excellent stability, which can remain 80.1 % initial contrast after 5000 s cycle.

Free-Standing Poly(vinyl benzoquinone)/Reduced Graphene Oxide Composite Films as a Cathode for Lithium-Ion Batteries.

Quinones with a rapid reduction-oxidation rate are promising high-capacity cathodes for lithium-ion batteries. However, the high solubility of quinone molecules in polar organic electrolytes results in low cycle stability, while their low electric conductivity causes low utilization of electrode materials. In this article, a new p-benzoquinone derivative, poly(vinyl benzoquinone) (PVBQ), is designed and synthesized, and a solution-based method of preparing free-standing PVBQ/reduced graphene oxide (RGO) composite films is developed. PVBQ has a high theoretical specific capacity (400 mA h g-1) because of its low dead moiety mass. In the produced composite films, PVBQ nanoparticles are uniformly dispersed on RGO sheets, which endows the composite films with high electric conductivity and inhibits the dissolution of PVBQ through strong adsorption. As a result, the composite films show a high active material utilization, high practical specific capacity, and excellent cycling stability. PVBQ in the composite membrane containing 60.2 wt % RGO deliver 244 mA h g-1 capacity after 200 charge-discharge cycles at a current density of 300 mA g-1. At a current density of 1500 mA g-1, the reversible specific capacity is still 170 mA h g-1. This work provides a high-performance cathode material for lithium-ion batteries, and the molecular structure and electrode structure design ideas are also instructive for developing other organic electrode materials.

A New Mechanism for the Inhibition of SA106 Gr.B Carbon Steel Corrosion by Nitrite in Alkaline Water.

The purpose of this study was to investigate the composition of oxide films formed on SA106 Gr.B carbon steel in nitrite solutions at 35 °C for 1000 h. The product of the reduction of nitrite during the corrosion inhibition process was also examined. The X-ray photoelectron spectroscopy results revealed that a thin Fe3O4 film was formed and ammonium ions were adsorbed on the outermost surface of the oxide film. The presence of ammonium ions was also demonstrated by ion chromatography. These results indicate that nitrites are reduced to ammonium ions, which in turn promotes the formation of the protective Fe3O4 film.

Nacre inspired supertough and flame-retardant reduced graphene oxide composite films

Nacre-like graphene composite films (GCFs) with high strength have been highly developed. However, the GCFs usually exhibit relatively poor toughness and poor flame resistance, seriously limiting their applications as structural materials. Here, reduced graphene oxide (rGO), halloysite nanotubes (HNTs), and flame-retarding modified lignin (F-lignin) were compounded to fabricate the rGO-HNTs-(F-lignin) film. In the rGO-HNTs-(F-lignin) film, the F-lignin binds the rGO sheets and HNTs, enhancing the entanglement of HNTs and the interactions between HNTs and rGO sheets, and the macromolecular F-lignin also improves the ductility of the rGO-HNTs-(F-lignin) film, while the entangled HNTs conversely reinforce the F-lignin to prevent the F-lignin from fracture when the rGO-HNTs-(F-lignin) film is under stress, further increasing the ductility of the rGO-HNTs-(F-lignin) film. The HNTs and F-lignin promote each other to enhance the strengthening and toughening effect on the rGO-HNTs-(F-lignin)-film, and endowing the rGO-HNTs-(F-lignin)-film with the superior mechanical properties of the tensile strength of 634 ± 38 MPa, tensile fracture strain of 8.17 ± 0.59 %, and toughness of 25.35 ± 2.95 MJ/m3, respectively. The rGO-HNTs-(F-lignin) film also exhibits improved flame-retardant properties due to the high flame retardancy of HNTs and F-lignin. These excellent integrated properties of the rGO-HNTs-(F-lignin) film will promote its potential applications as structural materials.

Structural-phase state and properties of heat and wear resistant cast irons of Cr–Mn–Ni–Ti system additionally alloyed with Al and Nb

The paper presents the data on phase composition and structure forming for the alloys, on distribution of elements among the alloy structural components, on variation of wear resistance, scale resistance, growing stability and mechanical properties of cast iron of Cr–Mn–Ni–Ti–Al–Nb system depending on different aluminium and niobium content and thermal ac-cumulating capacity of a casting mould. Complex carbides (Nb, Ti)C are forming in white cast iron during niobium alloying. Quantitative metallographic analysis of (Nb, Ti)C carbides and (Cr, Fe, Mn)7C3 complex carbides was carried out on the samples with examined composition. Aluminium provides favourable influence on forming of the thin protective spinel-type films with minimal amount of defects; diffusion through such oxide film is very difficult. Joint alloying by aluminium and niobium leads to simultaneous increase of heat resistance and wear resistance. Wear resistance increased as a result of enlargement of the part of primary carbides (Nb, Ti)C with high hardness in the structure of cast iron. Composition of oxide films includes aluminium, which strengthens their protective properties and rises of the alloy scale resistance. It is found for the first time that niobium doping leads to secondary solidification during cooling in the casting mold. Dispersion particles of М7С3 carbides are forming in solid state, thereby no structure degradation occurs during testing at increased temperatures, and growing stability rises. On the basis of the complex of the conducted researches the rational composition of heat and wear resistant cast iron is offered at the following ratio of components, wt. %: 2.1–2.2 C; 4.5–5.0 Mn; 18.0–19.0 Cr; 1.0–1.2 Ni; 0.4–0.6 Ti, 2.0 Nb; 2.0 Al. Wear resistance increased 1.2 times compared to cast irons before the introduction of aluminum and niobium, and scale resistance – 2.4–4.5 times depending on the type of casting mold, the index of growth resistance is equal to zero for cast irons cast in dry SLM

Self-Propagating Fabrication of a 3D Graphite@rGO Film Anode for High-performance Potassium-Ion Batteries.

Graphite, with abundant resources and low cost, is regarded as a promising anode material for potassium-ion batteries (PIBs). However, because of the large size of potassium ions, the intercalation/deintercalation of potassium between the interlayers of graphite results in its huge volume expansion, leading to poor cycling stability and rate performance. Herein, a self-propagating reduction strategy is adopted to fabricate a flexible, self-supporting 3D porous graphite@reduced graphene oxide (3D-G@rGO) composite film for PIBs. The 3D porous network can not only effectively mitigate the volume expansion in graphite but also provide numerous active sites for potassium storage as well as allow for electrolyte penetration and rapid ion migration. Therefore, compared to the pristine graphite anode, the flexible 3D-G@rGO film electrode exhibits greatly improved K-storage performance with a reversible capacity of 452.8 mAh g-1 at 0.1 C and a capacity retention rate of 80.4% after 100 cycles. It also presents excellent rate capability with a high specific capacity of 139.1 and 94.2 mAh g-1 maintained at 2 and 5 C, respectively. The proposed self-propagating reduction strategy to construct a three-dimensional self-supporting structure is a viable route to improve the structural stability and potassium storage performance of graphite anodes.

Alumina fiber/reduced graphene oxide composite films for high-temperature heating and sensing

Reduced graphene oxide (rGO) and its composite films have aroused intense interest in electrical heating and temperature sensing fields, but the working temperature is usually limited because the internal layer-stacked structure is breakable at high temperature. In order to promote structure stability, a series of Al2O3 fiber/rGO composite films were developed. It is found that gaseous products mainly including CO2 and CO during thermal reduction contribute to pores, bulges and intervals in rGO films, while appropriate Al2O3 fiber has an adhesion effect on rGO sheets and tightens them together, in which case defects can hardly form and the layered structure is significantly compacted. Therefore, the degree of stacking order and tensile strength tend to increase, resulting in the improvement of structure stability and decrease of electrical resistivity. However, excess Al2O3 fiber makes the formation of debris and cracks, causing the deterioration of conductivity and mechanical properties. With 20 wt% Al2O3 fiber, the composite films can bear higher heating voltage than pure rGO films and stabilize at 634.65 °C under 36 V, which also keep a good linearity between resistance and temperature from 25 to 600 °C, exhibiting a considerable temperature coefficient of resistance (TCR) with −1.70×10−3 /°C at room temperature.

An Integrated Neural Optrode with Modification of Polymer-Carbon Composite Films for Suppression of the Photoelectric Artifacts.

Optogenetics-based integrated photoelectrodes with high spatiotemporal resolution play an important role in studying complex neural activities. However, the photostimulation artifacts caused by the high level of integration and the high impedance of metal recording electrodes still hinder the application of photoelectrodes for optogenetic studies of neural circuits. In this study, a neural optrode fabricated on sapphire GaN material was proposed, and 4 μLEDs and 14 recording microelectrodes were monolithically integrated on a shank. Poly(3,4-ethylenedioxythiophene)/polystyrenesulfonate and multiwalled carbon nanotubes (PEDOT:PSS-MWCNT) and poly(3,4-ethylenedioxythiophene) and graphene oxide (PEDOT-GO) composite films were deposited on the surface of the recording microelectrode by electrochemical deposition. The results demonstrate that compared with the gold microelectrode, the impedances of both composite films reduced by more than 98%, and the noise amplitudes decreased by 70.73 and 87.15%, respectively, when exposed to light stimulation. Adjusting the high and low levels, we further reduced the noise amplitude by 48.3%. These results indicate that modifying the electrode surface by a polymer composite film can effectively enhance the performance of the microelectrode and further promote the application of the optrode in the field of neuroscience.

Effects of oxygen irradiation on the electrical properties of polyethylene oxide/nickel oxide composite films

This study investigates the impact of the ion beam on the properties of composite PEO/NiO, which was fabricated using the solution casting method and applied in advanced dielectric applications. The samples were exposed to ion beam at different fluencies (5 × 1016, 10 × 1016, and 15 × 1016 ions/cm2) using cold cathode ion source. The structure of the pure and treated PEO/NiO films was studied using the XRD technique, which demonstrated the successful fabrication of the composite PEO/NiO. Moreover, the morphological changes were analyzed by SEM, which indicates the homogeneous distribution of NiO in PEO. Furthermore, the dielectric characteristics of PEO/NiO films were tested at a frequency range of 40–106 Hz. The dielectric constant enhanced from 22.8 for PEO/NiO to 128.5 for the irradiated 15 × 1016 ions/cm2, and the energy density enhanced from 1.1x10−4 to 5.6x10−4 J/m3. The results demonstrate that the irradiated PEO/NiO composite exhibits novel dielectric properties, allowing the use of the irradiated PEO/NiO composite in different devices as super-capacitors and batteries.

Hydrophilicity and Pore Structure Enhancement in Polyurethane/Silk Protein-Bismuth Halide Oxide Composite Films for Photocatalytic Degradation of Dye.

Polyurethane/silk protein-bismuth halide oxide composite films were fabricated using a blending-wet phase transformationin situsynthesis method. The crystal structure, micromorphology, and optical properties were conducted using XRD, SEM, and UV-Vis DRS characterize techniques. The results indicated that loaded silk protein enhanced the hydrophilicity and pore structure of the polyurethane composite films. The active species BiOX were observed to grow as nanosheets with high dispersion on the internal skeleton and silk protein surface of the polyurethane-silk protein film. The photocatalytic efficiency of BiOX/PU-SF composite films was assessed through the degradation of Rhodamine B under visible light irradiation. Among the tested films, the BiOBr/PU-SF composite exhibited the highest removal rate of RhB at 98.9%, surpassing the removal rates of 93.7% for the BiOCl/PU-SF composite and 85.6% for the BiOI/PU-SF composite. Furthermore, an active species capture test indicated that superoxide radical (•O2-) and hole (h+) species played a predominant role in the photodegradation process.

Advanced Molecular Layer Deposition of SixZnyOz Thin Film Coatings for Improved Electrochemical Performance of NMC811

AbstractThe practical realization of Nickel‐rich layered oxide cathode materials such as LiNi0.8Mn0.1Co0.1O2 (NMC811) is hampered by several structural and interfacial instabilities over prolonged cycling. Several reports have proposed surface passivation via an artificial cathode electrolyte interphase (ACEI) as a promising method for mitigating the parasitic reactions affecting NMC811 while simultaneously improving its electrochemical performance over prolonged cycling. Herein, we report an in‐house designed (tBuMe2Si)2Zn single source precursor for developing SixZnyOz ternary CEI thin films on NMC811 via molecular layer deposition (MLD) in combination with O3 or H2O as oxidizing agent. We demonstrate that the single precursor (tBuMe2Si)2Zn avoids the need for two different precursors (Si & Zn). In‐depth spectroscopic studies reveal the mechanism of the formation of organosiloxane/zinc‐oxide composite thin film, via intermediates of unprecedented organo‐silicon‐zinc compounds. Understanding the reaction mechanism paved the path for a successful deposition of ACEI on NMC811. Rate capability studies shows the ACEI protected cathodes exhibit higher discharge capacity at 4 C than pristine NMC811. Furthermore, studies on full cells with graphite anode were conducted to evaluate the practical viability of SixZnyOz ACEI thin films on NMC811. After prolonged cycling the ACEI‐coated NMC811 full cells significantly improved the electrochemical performance than pristine NMC811 by ~12%.

Palladium enhanced electrochemical supercapacitive performance of chromium oxide thin films synthesized by sputtering process

Recently, the use of transition metal oxide electrodes for supercapacitor applications has increased due to the possibility of variable mixed valence states. The present study has established the use of Pd-Cr2O3 composite thin films as a working electrode for high-performance supercapacitors. The reactive dc magnetron co-sputtering method has been used for the fabrication of thin film of Cr2O3 and Pd-Cr2O3 on SS-304 substrate. X-ray diffraction and X-ray photoemission spectroscopy techniques were used to examine the surface chemistry and phase purity of chromium oxide and Pd-Cr2O3 composite thin films. The incorporation of Pd in Cr2O3 delivers a drastic change in the surface morphology. Due to the modified morphology and electronic properties, a noticeable improvement in the electrochemical properties of Pd-Cr2O3 electrode is observed. The obtained value of specific capacitance for this electrode is 401 Fg−1 at 0.1 mAcm−2 scan rate and within the potential window range 0 to +1.2 V. This value of specific capacitance is almost twice in comparison to the Cr2O3 based electrode. The Pd-Cr2O3 composite thin film shows a good cycle retention capability of 8000 cycles with 87.5 % retention. The obtained value of energy density and power density for Pd-Cr2O3 electrode was 80.2 Whkg−1 and 3.23 kWkg−1, respectively at 0.1 mAcm−2. Consequently, this composite material electrode can be seen as a promising advancement for electrodes in supercapacitor devices.

Effects and mechanisms of rare earth and calcium on the flame retardancy of magnesium alloys

This paper focuses on the effects and mechanisms of rare earth and calcium on the flame retardancy of magnesium alloys. Rare earth elements form dense composite oxide films on the surface of the melt, effectively inhibiting the progress of oxidation reactions and significantly increasing the ignition temperature of magnesium alloys. The mechanisms and optimal compositional ranges of different rare earth elements on the flame retardancy of magnesium alloys. Calcium form CaO-rich oxide films in magnesium alloys, which can effectively prevent oxygen diffusion and enhance the flame-retardant resistance of the alloy. When rare earth elements are compounded with calcium, a notable flame-retardant effect is observed. Composite application can maximize the flame-retardant effect of alloy elements while balancing the influence on various properties. Additionally, the authors illustrate through their own research that precise compositional optimization design is required to efficiently exploit the synergistic effects of RE and Ca and mitigate their adverse impacts.