Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131916
Y.C. Ma , H.Y. Tang , Y. Zhang , Y. Fang , S. Zhang , Q. Wang , T. Zhang , Y.Z. Gao
As a bone implant material, the stability of the surface product film of magnesium (Mg) alloys and the fretting wear behavior that occurs in vivo are critical factors influencing the functionality and long-term durability of the implant. This study compared the wear performance, surface product film composition, corrosion resistance and electrochemical properties of pure Mg, Mg–2Zn-0.5Nd-0.5Zr and Mg-9Gd-2Nd-0.5Zr-0.5In alloys in simulated body fluid (SBF) at 37 °C. The Mg-9Gd-2Nd-0.5Zr-0.5In alloy showed the best wear resistance in air, followed by Mg–2Zn-0.5Nd-0.5Zr, with pure Mg exhibiting the poorest. In SBF, wear rates were reduced due to the solution's lubricating properties. Mott-Schottky analysis showed that all three materials exhibited n-type semiconductor behavior, with Mg-9Gd-2Nd-0.5Zr-0.5In forming more stable, dense surface films with fewer oxygen vacancies, contributing to reduced wear.
{"title":"Wear performance and corrosion behavior of Mg–2Zn-0.5Nd-0.5Zr and Mg-9Gd-2Nd-0.5Zr-0.5In alloys in simulated body fluid","authors":"Y.C. Ma , H.Y. Tang , Y. Zhang , Y. Fang , S. Zhang , Q. Wang , T. Zhang , Y.Z. Gao","doi":"10.1016/j.matchemphys.2025.131916","DOIUrl":"10.1016/j.matchemphys.2025.131916","url":null,"abstract":"<div><div>As a bone implant material, the stability of the surface product film of magnesium (Mg) alloys and the fretting wear behavior that occurs in vivo are critical factors influencing the functionality and long-term durability of the implant. This study compared the wear performance, surface product film composition, corrosion resistance and electrochemical properties of pure Mg, Mg–2Zn-0.5Nd-0.5Zr and Mg-9Gd-2Nd-0.5Zr-0.5In alloys in simulated body fluid (SBF) at 37 °C. The Mg-9Gd-2Nd-0.5Zr-0.5In alloy showed the best wear resistance in air, followed by Mg–2Zn-0.5Nd-0.5Zr, with pure Mg exhibiting the poorest. In SBF, wear rates were reduced due to the solution's lubricating properties. Mott-Schottky analysis showed that all three materials exhibited n-type semiconductor behavior, with Mg-9Gd-2Nd-0.5Zr-0.5In forming more stable, dense surface films with fewer oxygen vacancies, contributing to reduced wear.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131916"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131923
Mohammad Mirzaei, Shokoufeh Ariavand, Ali Ghaheri Najafabadi, Saied Mehran Nahvi
Electrochemical sensors play a vital role in applications such as clinical diagnostics, medicine, and food safety by enabling the precise detection of biomolecules and DNA. The stability and performance of reference electrodes, particularly Ag/AgCl quasi-reference electrodes, are essential for achieving reliable measurements. However, challenges such as silver chloride film degradation and limited long-term stability hinder their widespread adoption. This study focuses on developing a low-cost, high-performance Ag/AgCl quasi-reference electrode using sputtering and chlorination techniques. The research explores the relationship between the sputtering duration for silver coating on a PET substrate and the immersion time in sodium hypochlorite solution. Electrodes were fabricated with sputtering durations of 15–35 min and chlorination times of 30–300 s. Optimized electrodes (25 min sputtering, 300 s chlorination; Ag thickness ≈860 nm) showed OCP drift <5 mV over 30 min and stable CV peak positions over 50 cycles; glucose sensing experiments (1–5 mM) produced oxidation peak potentials within 10 ± 5 mV of a commercial Ag/AgCl reference (n = 3). Characterization techniques, including X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy, were utilized. Cyclic voltammetry (CV) and open circuit potential (OCP) tests assessed the electrodes' electrochemical performance. The results demonstrate that a silver coating thickness of 860 nm, achieved with a 25-min sputtering duration and a 300-s immersion time, provides optimal stability and reproducibility. Chlorine penetration improved electrode performance while maintaining structural integrity. The optimized Ag/AgCl electrode exhibited comparable accuracy to commercial electrodes in glucose sensing tests, confirming its potential for biosensing applications. This work underscores the importance of controlled fabrication processes for enhancing the stability and reliability of Ag/AgCl quasi-reference electrodes, paving the way for their integration into cost-effective (bio)sensors.
{"title":"Low-cost fabrication and optimization of Ag/AgCl thin films on PET for electrochemical biosensors","authors":"Mohammad Mirzaei, Shokoufeh Ariavand, Ali Ghaheri Najafabadi, Saied Mehran Nahvi","doi":"10.1016/j.matchemphys.2025.131923","DOIUrl":"10.1016/j.matchemphys.2025.131923","url":null,"abstract":"<div><div>Electrochemical sensors play a vital role in applications such as clinical diagnostics, medicine, and food safety by enabling the precise detection of biomolecules and DNA. The stability and performance of reference electrodes, particularly Ag/AgCl quasi-reference electrodes, are essential for achieving reliable measurements. However, challenges such as silver chloride film degradation and limited long-term stability hinder their widespread adoption. This study focuses on developing a low-cost, high-performance Ag/AgCl quasi-reference electrode using sputtering and chlorination techniques. The research explores the relationship between the sputtering duration for silver coating on a PET substrate and the immersion time in sodium hypochlorite solution. Electrodes were fabricated with sputtering durations of 15–35 min and chlorination times of 30–300 s. Optimized electrodes (25 min sputtering, 300 s chlorination; Ag thickness ≈860 nm) showed OCP drift <5 mV over 30 min and stable CV peak positions over 50 cycles; glucose sensing experiments (1–5 mM) produced oxidation peak potentials within 10 ± 5 mV of a commercial Ag/AgCl reference (n = 3). Characterization techniques, including X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy, were utilized. Cyclic voltammetry (CV) and open circuit potential (OCP) tests assessed the electrodes' electrochemical performance. The results demonstrate that a silver coating thickness of 860 nm, achieved with a 25-min sputtering duration and a 300-s immersion time, provides optimal stability and reproducibility. Chlorine penetration improved electrode performance while maintaining structural integrity. The optimized Ag/AgCl electrode exhibited comparable accuracy to commercial electrodes in glucose sensing tests, confirming its potential for biosensing applications. This work underscores the importance of controlled fabrication processes for enhancing the stability and reliability of Ag/AgCl quasi-reference electrodes, paving the way for their integration into cost-effective (bio)sensors.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131923"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131929
B. Ünal , M.A. Almessiere , A. Baykal , A. Demir Korkmaz , M.A. Gondal , Sagar E. Shirsath , S. Caliskan , Y. Slimani
The lanthanum (La3+) doped Ni–Mn based nanospinel ferrites, Mn0·5Ni0.5LaxFe2-xO4 (x ≤ 0.1) NSFs, were synthesized by sol gel auto-combustion method. In XRD patterns, the presence of high intense (311) diffraction peak, confirmed that all samples are spinel ferrites. According to Scherer method, DXRD (crystallite size) of the products are within the range 10–15 nm. Further, the calculated crystallite size was correlated with Williams's Hall, modified Scherrer and size strain plot (SSP) method. The cubic morphology and chemical composition of samples have been verified by SEM, TEM, HR-TEM and EDX. The electrical and dielectric properties were characterized using impedance spectroscopy over a range of temperatures and frequencies. The analysis of AC and DC conductivity revealed a thermally activated, non-monotonic conduction mechanism dependent on the La3+ doping level. To deconvolve the contributions from bulk and interfacial regions, impedance data was fitted to an equivalent circuit model, allowing for the separation of grain (Rg) and grain boundary (Rgb) resistances4. The corresponding activation energies for grain (Ea,g) and grain boundary (Ea,gb) conduction were determined from Arrhenius plots. The results demonstrate a complex interplay of competing mechanisms: at low doping levels (x ≤ 0.06), La3+-driven charge compensation (i.e., partial reduction of Fe3+ to Fe3+) enhances small-polaron hopping, facilitating carrier transport and reducing the activation energy. Conversely, at higher concentrations (x ≥ 0.08), the segregation of large La3+ ions at intergranular regions leads to the formation of insulating secondary phases, which create significant barriers to charge migration and sharply increase the activation energy. An optimal composition was identified at x = 0.06, which exhibited the minimum activation energies for both grain (Ea,g = 256 meV) and grain boundary (Ea,gb = 303 meV) conduction. The dielectric properties were governed by Maxwell-Wagner interfacial polarization, with the x = 0.06 sample showing the most favorable balance of properties. This work demonstrates that La3+ substitution is an effective method for tuning the electrical and dielectric response of Mn–Ni ferrites by modulating the balance between intragrain charge transport and intergranular barrier effects.
{"title":"Correlating microstructure and electrical properties: The role of lanthanum doping in Mn–Ni nanospinel ferrites","authors":"B. Ünal , M.A. Almessiere , A. Baykal , A. Demir Korkmaz , M.A. Gondal , Sagar E. Shirsath , S. Caliskan , Y. Slimani","doi":"10.1016/j.matchemphys.2025.131929","DOIUrl":"10.1016/j.matchemphys.2025.131929","url":null,"abstract":"<div><div>The lanthanum (La<sup>3+</sup>) doped Ni–Mn based nanospinel ferrites, Mn<sub>0·5</sub>Ni<sub>0.5</sub>La<sub>x</sub>Fe<sub>2-x</sub>O<sub>4</sub> (x ≤ 0.1) NSFs, were synthesized by sol gel auto-combustion method. In XRD patterns, the presence of high intense (311) diffraction peak, confirmed that all samples are spinel ferrites. According to Scherer method, D<sub>XRD</sub> (crystallite size) of the products are within the range 10–15 nm. Further, the calculated crystallite size was correlated with Williams's Hall, modified Scherrer and size strain plot (SSP) method. The cubic morphology and chemical composition of samples have been verified by SEM, TEM, HR-TEM and EDX. The electrical and dielectric properties were characterized using impedance spectroscopy over a range of temperatures and frequencies. The analysis of AC and DC conductivity revealed a thermally activated, non-monotonic conduction mechanism dependent on the La<sup>3+</sup> doping level. To deconvolve the contributions from bulk and interfacial regions, impedance data was fitted to an equivalent circuit model, allowing for the separation of grain (R<sub>g</sub>) and grain boundary (R<sub>gb</sub>) resistances<sup>4</sup>. The corresponding activation energies for grain (E<sub>a,g</sub>) and grain boundary (E<sub>a,gb</sub>) conduction were determined from Arrhenius plots. The results demonstrate a complex interplay of competing mechanisms: at low doping levels (x ≤ 0.06), La<sup>3+</sup>-driven charge compensation (i.e., partial reduction of Fe<sup>3+</sup> to Fe<sup>3+</sup>) enhances small-polaron hopping, facilitating carrier transport and reducing the activation energy. Conversely, at higher concentrations (x ≥ 0.08), the segregation of large La<sup>3+</sup> ions at intergranular regions leads to the formation of insulating secondary phases, which create significant barriers to charge migration and sharply increase the activation energy. An optimal composition was identified at x = 0.06, which exhibited the minimum activation energies for both grain (E<sub>a,g</sub> = 256 meV) and grain boundary (E<sub>a,gb</sub> = 303 meV) conduction. The dielectric properties were governed by Maxwell-Wagner interfacial polarization, with the x = 0.06 sample showing the most favorable balance of properties. This work demonstrates that La<sup>3+</sup> substitution is an effective method for tuning the electrical and dielectric response of Mn–Ni ferrites by modulating the balance between intragrain charge transport and intergranular barrier effects.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131929"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131922
S. Mouchou , Y. Toual , A. Aaouine , A. Ghaleb , M. El Moudane , A. Azouaoui , N. Benzakour
Perovskite materials exhibit promising properties for photovoltaic cell applications. However, the efficiency of these cells remains lower than the theoretical limit for multi-junction photovoltaic cells. This study focuses on ab-initio investigation of anti-perovskite NaOCl. The electronic structure, calculated using PBE functional, reveals a direct band gap of 2.05 eV. The absorption coefficient calculated using the same functional indicates that the anti-perovskite is characterized by higher absorption, exceeding 10 cm−1, for wavelengths with energy higher than the band gap value. These properties make NaOCl suitable for photovoltaic applications. The simulation of the FTOSpiro-MeOTAD solar cell shows that, in the presence of a neutral defect concentration of , the cell can achieve an efficiency of 30% and a fill factor of 78%. These high values are attributed to the large absorption coefficient and the sufficiently wide band gap, that enables the absorption of a wide range of visible wavelengths, from 400 nm to 600 nm.
{"title":"Study of electronic and optical properties of Na3OCl anti-perovskite for photovoltaic applications","authors":"S. Mouchou , Y. Toual , A. Aaouine , A. Ghaleb , M. El Moudane , A. Azouaoui , N. Benzakour","doi":"10.1016/j.matchemphys.2025.131922","DOIUrl":"10.1016/j.matchemphys.2025.131922","url":null,"abstract":"<div><div>Perovskite materials exhibit promising properties for photovoltaic cell applications. However, the efficiency of these cells remains lower than the theoretical limit for multi-junction photovoltaic cells. This study focuses on ab-initio investigation of anti-perovskite Na<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>OCl. The electronic structure, calculated using PBE functional, reveals a direct band gap of 2.05 eV. The absorption coefficient calculated using the same functional indicates that the anti-perovskite is characterized by higher absorption, exceeding 10<span><math><msup><mrow></mrow><mrow><mn>5</mn></mrow></msup></math></span> cm<sup>−1</sup>, for wavelengths with energy higher than the band gap value. These properties make Na<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>OCl suitable for photovoltaic applications. The simulation of the FTO<span><math><mrow><mo>|</mo><msub><mrow><mi>TiO</mi></mrow><mrow><mn>2</mn></mrow></msub><mo>|</mo><msub><mrow><mi>Na</mi></mrow><mrow><mn>3</mn></mrow></msub><mi>OCl</mi><mo>|</mo></mrow></math></span>Spiro-MeOTAD solar cell shows that, in the presence of a neutral defect concentration of <span><math><mrow><mn>1</mn><msup><mrow><mn>0</mn></mrow><mrow><mn>15</mn></mrow></msup><mspace></mspace><msup><mrow><mi>cm</mi></mrow><mrow><mo>−</mo><mn>3</mn></mrow></msup></mrow></math></span>, the cell can achieve an efficiency of 30% and a fill factor of 78%. These high values are attributed to the large absorption coefficient and the sufficiently wide band gap, that enables the absorption of a wide range of visible wavelengths, from 400 nm to 600 nm.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131922"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131925
Omar G. Morales-Saavedra , Cesar A. Guarin , María E. Hernández-Rojas , Sandro Báez-Pimiento , María del Pilar Carreón-Castro , Adolfo Romero Galarza , Alejandro Islas Jácome , Eduardo González-Zamora , Oscar González-Antonio , Leonardo David Herrera-Zúñiga , Ricardo Corona Sánchez , Gerardo Cedillo-Valverde , Sandra L. Castañón-Alonso
In this work, the Hay's oxidative coupling technique was implemented to synthesize a novel poly((4-((4-nitrophenyl)ethynyl)phenyl)azanediyl)bis(ethane-2,1-diyl) polymer containing 4-nitro-4′-N,N-diethanolaminotolane polar dyes as nonlinear optical (NLO) chromophores. A full description of the synthetic route and detailed elemental analyses are provided. This new conjugated polymer shows an unusual rigidity in its main chain structure and displays a high Tg-value of ∼160 °C while preserving good solubility in common organic solvents. Accordingly, high-quality spin-coated film samples were prepared and electrically poled via the corona-poling technique to obtain oriented molecular layers with order parameters up to ∼0.74. According to the Maker-fringes calibration methodology, organic films were able to display stable off-resonant second-order NLO-effects such as second harmonic generation (SHG). Large and macroscopic SHG-coefficients were estimated within the 141 and 46 pm V−1 range, respectively. The polymer's NLO/SHG effects were also assessed by combining ab initio Density Functional Theory (DFT) and molecular dynamics (MD) calculations. Although polar acetylene-based compounds are well known, there are only a few examples of push-pull polymeric systems containing pendant tolane chromophores in the polymeric side chain as NLO-active compounds. The excellent mechanical, thermal, and chemical properties of this novel polymer, in addition to its large SHG coefficients and cross-linkable properties, make this compound a promising organic material for current organic-based optoelectronic and photonic devices.
本文采用Hay's氧化偶联技术合成了一种新型的聚（4-（（4-硝基苯基）乙基）苯基）氮杂二基)双（乙烷-2,1-二基）聚合物，该聚合物含有4-硝基-4 ' -n， n -二乙醇氨基甲苯极性染料作为非线性光学发色团。对合成路线进行了详细的描述和元素分析。这种新型共轭聚合物的主链结构具有不同寻常的刚性，tg值高达160°C，同时在普通有机溶剂中保持良好的溶解度。因此，制备了高质量的自旋涂层薄膜样品，并通过电晕极化技术进行电极化，获得了有序参数高达0.74的定向分子层。根据maker -条纹校准方法，有机薄膜能够显示稳定的非谐振二阶nlo效应，如二次谐波产生（SHG）。大χzz(2)和χzxx(2)宏观shg系数分别在141和46 pm V−1范围内估计。通过从头算密度泛函理论（DFT）和分子动力学（MD）计算，还评估了聚合物的NLO/SHG效应。虽然以极性乙炔为基础的化合物是众所周知的，但在聚合物侧链中含有垂坠的甲苯发色团的推拉式聚合物体系中，只有少数例子是nlo活性化合物。这种新型聚合物优异的机械、热学和化学性能，以及它的大SHG系数和交联性能，使这种化合物成为当前有机光电和光子器件的有前途的有机材料。
{"title":"Synthesis and characterization of novel polymers containing poly((4-((4-nitrophenyl)ethynyl)phenyl)azanediyl)bis(ethane-2,1-diyl) as main chain and tolanic chromophores in the side chain with strong NLO-activity","authors":"Omar G. Morales-Saavedra , Cesar A. Guarin , María E. Hernández-Rojas , Sandro Báez-Pimiento , María del Pilar Carreón-Castro , Adolfo Romero Galarza , Alejandro Islas Jácome , Eduardo González-Zamora , Oscar González-Antonio , Leonardo David Herrera-Zúñiga , Ricardo Corona Sánchez , Gerardo Cedillo-Valverde , Sandra L. Castañón-Alonso","doi":"10.1016/j.matchemphys.2025.131925","DOIUrl":"10.1016/j.matchemphys.2025.131925","url":null,"abstract":"<div><div>In this work, the Hay's oxidative coupling technique was implemented to synthesize a novel poly((4-((4-nitrophenyl)ethynyl)phenyl)azanediyl)bis(ethane-2,1-diyl) polymer containing 4-nitro-4′-<em>N,N</em>-diethanolaminotolane polar dyes as nonlinear optical (NLO) chromophores. A full description of the synthetic route and detailed elemental analyses are provided. This new conjugated polymer shows an unusual rigidity in its main chain structure and displays a high <em>Tg</em>-value of ∼160 °C while preserving good solubility in common organic solvents. Accordingly, high-quality spin-coated film samples were prepared and electrically poled <em>via</em> the corona-poling technique to obtain oriented molecular layers with order parameters up to ∼0.74. According to the Maker-fringes calibration methodology, organic films were able to display stable off-resonant second-order NLO-effects such as second harmonic generation (SHG). Large <span><math><mrow><msubsup><mi>χ</mi><mrow><mi>z</mi><mi>z</mi><mi>z</mi></mrow><mrow><mo>(</mo><mn>2</mn><mo>)</mo></mrow></msubsup></mrow></math></span> and <span><math><mrow><msubsup><mi>χ</mi><mrow><mi>z</mi><mi>x</mi><mi>x</mi></mrow><mrow><mo>(</mo><mn>2</mn><mo>)</mo></mrow></msubsup></mrow></math></span> macroscopic SHG-coefficients were estimated within the 141 and 46 pm V<sup>−1</sup> range, respectively. The polymer's NLO/SHG effects were also assessed by combining <em>ab initio</em> Density Functional Theory (DFT) and molecular dynamics (MD) calculations. Although polar acetylene-based compounds are well known, there are only a few examples of push-pull polymeric systems containing pendant tolane chromophores in the polymeric side chain as NLO-active compounds. The excellent mechanical, thermal, and chemical properties of this novel polymer, in addition to its large SHG coefficients and cross-linkable properties, make this compound a promising organic material for current organic-based optoelectronic and photonic devices.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131925"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131904
José D.S. Guerra , Ramon G.F. Dornelas , Samuel Lopez-Blanco , Francesc Suñol , Atair C. Silva , Michel Venet , José E. Garcia
The multifunctional behavior of BaTi1–xSnxO3 ceramics was systematically investigated within the compositional range 0.09 ≤ x ≤ 0.20, focusing on their potential for energy-related applications. Structural and dielectric studies revealed a gradual suppression of long-range ferroelectric order and the emergence of diffuse, multiphase regimes with increasing Sn substitution. This compositional evolution strongly influenced the electrical response, leading to slim polarization loops and enhanced functional properties. Notably, the composition with x = 0.15 exhibited a recoverable energy-storage density of approximately 45 mJ/cm3 with an efficiency of around 77 %, whereas the strongest electrocaloric response was observed for x = 0.09, yielding an electrocaloric strength of about 0.40 K mm/kV near room temperature. These results highlight the critical role of phase coexistence and relaxor-like behavior in tailoring the multifunctionality of BaTi1–xSnxO3, positioning this system as a promising lead-free platform for capacitive energy storage and solid-state cooling technologies.
在0.09≤x≤0.20的组分范围内，系统研究了BaTi1-xSnxO3陶瓷的多功能行为，重点研究了其在能源相关领域的应用潜力。结构和介电研究表明，随着Sn取代量的增加，长程铁电序逐渐被抑制，并出现扩散的多相体系。这种成分的演变强烈地影响了电响应，导致了细长的极化回路和增强的功能特性。值得注意的是，当x = 0.15时，组合物的可回收能量存储密度约为45 mJ/cm3，效率约为77%，而当x = 0.09时，观察到最强的电热响应，在室温附近产生约0.40 K mm/kV的电热强度。这些结果强调了相共存和类弛豫行为在调整BaTi1-xSnxO3的多功能性方面的关键作用，将该系统定位为有前途的无铅电容储能和固态冷却技术平台。
{"title":"Electrocaloric and energy storage properties of barium stannate titanate system: A multifunctional approach","authors":"José D.S. Guerra , Ramon G.F. Dornelas , Samuel Lopez-Blanco , Francesc Suñol , Atair C. Silva , Michel Venet , José E. Garcia","doi":"10.1016/j.matchemphys.2025.131904","DOIUrl":"10.1016/j.matchemphys.2025.131904","url":null,"abstract":"<div><div>The multifunctional behavior of BaTi<sub>1–<em>x</em></sub>Sn<sub><em>x</em></sub>O<sub>3</sub> ceramics was systematically investigated within the compositional range 0.09 ≤ <em>x</em> ≤ 0.20, focusing on their potential for energy-related applications. Structural and dielectric studies revealed a gradual suppression of long-range ferroelectric order and the emergence of diffuse, multiphase regimes with increasing Sn substitution. This compositional evolution strongly influenced the electrical response, leading to slim polarization loops and enhanced functional properties. Notably, the composition with <em>x</em> = 0.15 exhibited a recoverable energy-storage density of approximately 45 mJ/cm<sup>3</sup> with an efficiency of around 77 %, whereas the strongest electrocaloric response was observed for <em>x</em> = 0.09, yielding an electrocaloric strength of about 0.40 K mm/kV near room temperature. These results highlight the critical role of phase coexistence and relaxor-like behavior in tailoring the multifunctionality of BaTi<sub>1–<em>x</em></sub>Sn<sub><em>x</em></sub>O<sub>3</sub>, positioning this system as a promising lead-free platform for capacitive energy storage and solid-state cooling technologies.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131904"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131920
Biswarup Pal Choudhury , Tanmay Dagar , Debasish Halder , Ritu Sarkar , Shankhanil Sarkar , Surajit Mondal , Sima Pramanick , Joydeep Chowdhury , Yatramohan Jana , Swati De
In the present work, a simple one-pot synthesis of CuO nanoparticle (CuO NP) embedded rGO composite is presented. The synthesis protocol occurs under relatively mild conditions, is cost effective and shows promise for scaling up. One very important aspect to be highlighted is that this photocatalyst is not limited by the tendency of aerial oxidation of Cu which is often a bottleneck in usage of Cu-based materials. The resultant nanocomposite was characterized by powder X-Ray Diffraction (p-XRD) coupled with Rietveld curve fitting. It was found that the drying temperature of the composite during the synthesis process significantly influenced the crystalline phase of the composite. Further characterization was performed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The band gap (Eg) of the materials could be obtained from optical absorption spectra using the Tauc plot. Raman spectra indicated that embedding CuO NPs onto the rGO framework has a distinct advantage in reducing surface traps which are otherwise inherently found on rGO. Thus, from material science aspect too, the CuO-NP/rGO nanocomposites synthesized here are of better quality as they are more defect free. The specific surface area of the nanocomposite was determined from the Brunauer-Emmett-Teller (BET) isotherm by analyzing the N2adsorption-desorption steps. The CuO-NP/rGO nanocomposite exhibited excellent photocatalytic activity towards the degradation of methylene blue (MB), a toxic dye commonly found in industrial effluents. The composites also served as efficient substrates for Surface Enhanced Raman Spectroscopy (SERS) for detecting trace levels of the dye Rhodamine 6G (R6G). Detection occurred with remarkably high sensitivity (10−8 M) i.e. about three orders of magnitude better than pristine rGO. Additionally, the photocatalyst could be recycled up to 5 cycles with negligible loss in efficiency. The same composite material could be used to detect ultra-low concentrations of pollutants too. Thus the CuO-NP/rGO nanocomposite conforms to some of the concepts of circular economy in chemistry - reuse and recycle. Moreover the photocatalyst can be used in bulk media under open sunlight conditions as exists in real-life industrial sewage systems in developing countries.
{"title":"Cost-effective production of copper oxide nanoparticle-doped rGO materials under mild conditions-recyclable photocatalytic degradation of toxic dyes and SERS sensing at ultralow concentrations","authors":"Biswarup Pal Choudhury , Tanmay Dagar , Debasish Halder , Ritu Sarkar , Shankhanil Sarkar , Surajit Mondal , Sima Pramanick , Joydeep Chowdhury , Yatramohan Jana , Swati De","doi":"10.1016/j.matchemphys.2025.131920","DOIUrl":"10.1016/j.matchemphys.2025.131920","url":null,"abstract":"<div><div>In the present work, a simple <em>one-pot</em> synthesis of CuO nanoparticle (CuO NP) embedded rGO composite is presented. The synthesis protocol occurs under relatively mild conditions, is cost effective and shows promise for scaling up. One very important aspect to be highlighted is that this photocatalyst is not limited by the tendency of aerial oxidation of Cu which is often a bottleneck in usage of Cu-based materials. The resultant nanocomposite was characterized by powder X-Ray Diffraction (<em>p</em>-XRD) coupled with Rietveld curve fitting. It was found that the drying temperature of the composite during the synthesis process significantly influenced the crystalline phase of the composite. Further characterization was performed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The band gap (E<sub>g</sub>) of the materials could be obtained from optical absorption spectra using the Tauc plot. Raman spectra indicated that embedding CuO NPs onto the rGO framework has a distinct advantage in reducing surface traps which are otherwise inherently found on rGO. Thus, from material science aspect too, the CuO-NP/rGO nanocomposites synthesized here are of better quality as they are more defect free. The specific surface area of the nanocomposite was determined from the Brunauer-Emmett-Teller (BET) isotherm by analyzing the N<sub>2</sub> <em>adsorption-desorption</em> steps. The CuO-NP/rGO nanocomposite exhibited excellent photocatalytic activity towards the degradation of methylene blue (MB), a toxic dye commonly found in industrial effluents. The composites also served as efficient substrates for Surface Enhanced Raman Spectroscopy (SERS) for detecting trace levels of the dye Rhodamine 6G (R6G). Detection occurred with remarkably high sensitivity (10<sup>−8</sup> M) i.e. about three orders of magnitude better than pristine rGO. Additionally, the photocatalyst could be recycled up to 5 cycles with negligible loss in efficiency. The same composite material could be used to detect <em>ultra-low</em> concentrations of pollutants too. Thus the CuO-NP/rGO nanocomposite conforms to some of the concepts of circular economy in chemistry - <em>reuse</em> and <em>recycle</em>. Moreover the photocatalyst can be used in bulk media under open sunlight conditions as exists in real-life industrial sewage systems in developing countries.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131920"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131924
Asuman Koçu , Gökhan Yılmaz , Fatih Mehmet Emen
In this study, lead-free (CH3NH3)Bi2I9 (MA3Bi2I9) perovskite thin films were synthesized using the thermal evaporation method and evaluated as optical absorber layers for photovoltaic applications. Structural characterization by XRD confirmed the formation of a single-phase hexagonal crystal system, while FT-IR analysis revealed strong interactions between MA + cations and BiI3 frameworks. Thermal stability was investigated by TG/DTG/DTA techniques, and the MA3Bi2I9 phase was found to be stable up to 208 °C. A multi-step thermal decomposition mechanism was proposed. A multi-step thermal decomposition mechanism was proposed. Kinetic analysis using Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS) methods indicated two distinct decomposition stages. The second stage exhibited low activation energies (Ea ≈17–18 kJ/mol), negative entropy values, and high Gibbs free energy (ΔG > 120 kJ/mol), suggesting a non-spontaneous, ordered transition state. The third stage showed significantly higher activation energy (Ea ≈195 kJ/mol), indicating a more energy-intensive degradation. These findings demonstrate that thermally evaporated MA3Bi2I9 thin films possess favorable thermal and kinetic properties, making them promising candidates for scalable and environmentally friendly photovoltaic applications.
{"title":"Thermal analysis and kinetic decomposition of MA3Bi2I9 perovskite thin film for photovoltaic applications","authors":"Asuman Koçu , Gökhan Yılmaz , Fatih Mehmet Emen","doi":"10.1016/j.matchemphys.2025.131924","DOIUrl":"10.1016/j.matchemphys.2025.131924","url":null,"abstract":"<div><div>In this study, lead-free (CH<sub>3</sub>NH<sub>3</sub>)Bi<sub>2</sub>I<sub>9</sub> (MA<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub>) perovskite thin films were synthesized using the thermal evaporation method and evaluated as optical absorber layers for photovoltaic applications. Structural characterization by XRD confirmed the formation of a single-phase hexagonal crystal system, while FT-IR analysis revealed strong interactions between MA <sup>+</sup> cations and BiI<sub>3</sub> frameworks. Thermal stability was investigated by TG/DTG/DTA techniques, and the MA<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> phase was found to be stable up to 208 °C. A multi-step thermal decomposition mechanism was proposed. A multi-step thermal decomposition mechanism was proposed. Kinetic analysis using Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS) methods indicated two distinct decomposition stages. The second stage exhibited low activation energies (Ea ≈17–18 kJ/mol), negative entropy values, and high Gibbs free energy (ΔG > 120 kJ/mol), suggesting a non-spontaneous, ordered transition state. The third stage showed significantly higher activation energy (Ea ≈195 kJ/mol), indicating a more energy-intensive degradation. These findings demonstrate that thermally evaporated MA<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> thin films possess favorable thermal and kinetic properties, making them promising candidates for scalable and environmentally friendly photovoltaic applications.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131924"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study deals with the influence of milling time and silver content on the structural, morphological, and thermal properties of pyrophyllite/Ag nanocomposites, which were produced using mechanical milling as a green synthesis method. Pyrophyllite was mechanochemically activated with AgNO3 (2, 5, and 10 wt% of silver), while the milling time varied from 20 to 320 min. A detailed kinetic analysis of the dehydroxylation reaction, followed by thorough microstructural and morphological analysis obtained by XRD, FTIR, SEM/EDS, PSD, TGA/DTA, was performed. With the increase in milling time, notable particle size reduction and pronounced agglomeration occurred, including the disruption of pyrophyllite's crystalline structure and its amorphization. The XRD diffraction maximum at 2θ of 38.16°of the sample milled for 20 min with 10 wt% of AgNO3 corresponds to metallic silver. EDS mapping confirmed uniform dispersion of silver throughout the composite surface. The conversion curves were modelled as a linear combination of two Weibull functions. At lower temperatures, the highest value of the rate constant was obtained for the 10Ag80 sample, while the 10Ag20 sample underwent the fastest dehydroxylation. The apparent activation energy values, calculated using the isoconversional method, showed the highest value at the beginning of the dehydroxylation reaction, approximately 210 kJ mol−1. Following a sharp drop to the values of 194 kJ mol−1 (5Ag20 sample), 193 kJ mol−1 (10Ag20 sample), and 187 kJ mol−1 (10Ag80 sample), a re-increase in energy values towards the end of the reaction is seen. The obtained results also indicated that the value of the rate constant is influenced more by the milling time than by the added AgNO3 weight fraction.
{"title":"Impact of mechanochemical activation on the thermal and morphological characteristics of silver-doped pyrophyllite","authors":"Sara Mijaković , Branislav Stanković , Jasmina Grbović Novaković , Nenad Filipović , Ljubisav Stamenić , Nebojša Manić , Ana Vujačić Nikezić","doi":"10.1016/j.matchemphys.2025.131933","DOIUrl":"10.1016/j.matchemphys.2025.131933","url":null,"abstract":"<div><div>This study deals with the influence of milling time and silver content on the structural, morphological, and thermal properties of pyrophyllite/Ag nanocomposites, which were produced using mechanical milling as a green synthesis method. Pyrophyllite was mechanochemically activated with AgNO<sub>3</sub> (2, 5, and 10 wt% of silver), while the milling time varied from 20 to 320 min. A detailed kinetic analysis of the dehydroxylation reaction, followed by thorough microstructural and morphological analysis obtained by XRD, FTIR, SEM/EDS, PSD, TGA/DTA, was performed. With the increase in milling time, notable particle size reduction and pronounced agglomeration occurred, including the disruption of pyrophyllite's crystalline structure and its amorphization. The XRD diffraction maximum at 2θ of 38.16°of the sample milled for 20 min with 10 wt% of AgNO<sub>3</sub> corresponds to metallic silver. EDS mapping confirmed uniform dispersion of silver throughout the composite surface<strong>.</strong> The conversion curves were modelled as a linear combination of two Weibull functions. At lower temperatures, the highest value of the rate constant was obtained for the 10Ag80 sample, while the 10Ag20 sample underwent the fastest dehydroxylation. The apparent activation energy values, calculated using the isoconversional method, showed the highest value at the beginning of the dehydroxylation reaction, approximately 210 kJ mol<sup>−1</sup>. Following a sharp drop to the values of 194 kJ mol<sup>−1</sup> (5Ag20 sample), 193 kJ mol<sup>−1</sup> (10Ag20 sample), and 187 kJ mol<sup>−1</sup> (10Ag80 sample), a re-increase in energy values towards the end of the reaction is seen. The obtained results also indicated that the value of the rate constant is influenced more by the milling time than by the added AgNO<sub>3</sub> weight fraction.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131933"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.matchemphys.2025.131862
Amaliya Rasyida , Indra Carllistya Pramadio , Hosta Ardhyananta , Vuri Ayu Setyowati , Iman Adipurnama , Djoko Kuswanto , Tedy Apriawan , Indri Lakhsmi Putri , Agung Purniawan , Sigit Tri Wicaksono
Cranioplasty requires durable and biocompatible materials to restore cranial defects. This study investigated the influence of powder-to-liquid (P/L) ratio and activator type—N,N-Dimethyl-o-toluidine (DMOT) and N,N-Dimethyl-p-toluidine (DMPT)—on the properties of polymethyl methacrylate (PMMA)-based bone cement containing zirconium dioxide (ZrO2) as a radiopaque agent and Calendula sp. extract as a bioactive additive. The formulations were evaluated for radiopacity (X-ray), microstructure (SEM–EDX), mechanical strength (compressive test), and cytocompatibility. DMOT-based formulations with higher powder content demonstrated superior mechanical stability, achieving compressive strengths of 135.9 MPa and 124.1 MPa after 30 and 60 days of immersion, respectively, in accordance with ASTM F451 standards. In contrast, DMPT-based cements showed faster polymerization, greater porosity, and lower mechanical strength. SEM analysis confirmed pore formation in DMPT systems, while EDX mapping verified uniform Zr dispersion across all samples. Radiopacity increased proportionally with ZrO2 concentration. Qualitative MTT results indicated cell viability above 90 %, confirming cytocompatibility. Overall, the findings emphasize that activator selection and formulation balance are key factors for optimizing the mechanical integrity and biocompatibility of PMMA bone cement for cranioplasty applications.
{"title":"Comparative study of DMOT and DMPT accelerators in PMMA-based bone cement: Implications on polymerization, strength, porosity, and cytocompatibility","authors":"Amaliya Rasyida , Indra Carllistya Pramadio , Hosta Ardhyananta , Vuri Ayu Setyowati , Iman Adipurnama , Djoko Kuswanto , Tedy Apriawan , Indri Lakhsmi Putri , Agung Purniawan , Sigit Tri Wicaksono","doi":"10.1016/j.matchemphys.2025.131862","DOIUrl":"10.1016/j.matchemphys.2025.131862","url":null,"abstract":"<div><div>Cranioplasty requires durable and biocompatible materials to restore cranial defects. This study investigated the influence of powder-to-liquid (P/L) ratio and activator type—N,N-Dimethyl-o-toluidine (DMOT) and N,N-Dimethyl-p-toluidine (DMPT)—on the properties of polymethyl methacrylate (PMMA)-based bone cement containing zirconium dioxide (ZrO<sub>2</sub>) as a radiopaque agent and <em>Calendula sp.</em> extract as a bioactive additive. The formulations were evaluated for radiopacity (X-ray), microstructure (SEM–EDX), mechanical strength (compressive test), and cytocompatibility. DMOT-based formulations with higher powder content demonstrated superior mechanical stability, achieving compressive strengths of 135.9 MPa and 124.1 MPa after 30 and 60 days of immersion, respectively, in accordance with ASTM <span><span>F451</span><svg><path></path></svg></span> standards. In contrast, DMPT-based cements showed faster polymerization, greater porosity, and lower mechanical strength. SEM analysis confirmed pore formation in DMPT systems, while EDX mapping verified uniform Zr dispersion across all samples. Radiopacity increased proportionally with ZrO<sub>2</sub> concentration. Qualitative MTT results indicated cell viability above 90 %, confirming cytocompatibility. Overall, the findings emphasize that activator selection and formulation balance are key factors for optimizing the mechanical integrity and biocompatibility of PMMA bone cement for cranioplasty applications.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"350 ","pages":"Article 131862"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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