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Mechanical and thermal properties of 3D needled carbon fiber reinforced CaZr4(PO4)6 ceramics prepared by fast hot-pressing sintering 快速热压烧结制备三维针刺碳纤维增强CaZr4(PO4)6陶瓷的力学和热性能
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-30 DOI: 10.1016/j.matchemphys.2026.132159
Ning An , Xiaoli Liu , Kai Jiang , Fang Tian , Ziyi Liu , Zhenjia Bu , Chenxi Pei , Yang Wang , Ruixiang Liu , Changling Zhou , Degang Zhao , Futian Liu
CaZr4(PO4)6 (CZP) ceramics, owing to their unique low thermal expansion and low thermal conductivity, have shown great promise for high-temperature applications such as aerospace. However, their inherently low fracture toughness severely limits practical use. To simultaneously address the challenges of toughening while maintaining low thermal conductivity and low thermal expansion, this study employed slurry infiltration (SI) and fast hot-pressing (FHP) techniques at 1200 °C under 40 MPa for 10 min to fabricate three-dimensional needle-punched carbon fiber reinforced CZP composites (3D-Cf/CZP), using a carbon fiber preform with a bulk density of 0.27 g/cm3. Additionally, a pyrolytic carbon (PyC) interphase with a thickness of approximately 500 nm was introduced to produce 3D-Cf/PyC/CZP composites. The effects of carbon fibers and PyC coating on the microstructure, mechanical properties, and thermal behavior of CZP ceramics were systematically investigated. The results demonstrated excellent chemical compatibility and stable coexistence between the carbon fibers and the CZP matrix. The incorporation of three-dimensional carbon fibers significantly enhanced the fracture toughness of CZP ceramics, increasing from 1.46 ± 0.12 to 4.14 ± 0.35 MPa m1/2, and further to 6.83 ± 0.41 MPa m1/2 with the introduction of a PyC interfacial coating. This improvement is primarily attributed to multiple toughening mechanisms, including crack deflection, fiber pull-out, and interfacial debonding. The Cf/CZP composite retained a low coefficient of thermal expansion (CTE), exhibiting an average CTE of 0.95 × 10−6 °C−1, and the thermal conductivity (0.60–0.70 W m−1 K−1) was lower than that of the CZP matrix (0.85–0.95 W m−1 K−1). In contrast, the PyC coating increased the thermal conductivity of Cf/PyC/CZP composite (1.00–1.10 W m−1 K−1), but resulted in a further reduction in CTE to 0.71 × 10−6 °C−1, indicating a certain trade-off between interfacial toughening and thermal transport properties. This study confirms that the combination of 3D-Cf reinforcement and PyC coating can synergistically enhance the fracture toughness of CZP ceramics while maintaining their low thermal conductivity and low thermal expansion characteristics. However, the increase in thermal conductivity induced by the PyC layer, the stability issues of the material in oxidizing environments, and the still-required improvement in flexural strength are critical challenges that must be addressed synergistically in practical applications. These challenges collectively provide clear guidance for subsequent research directions, including interface optimization, oxidation protection, and mechanical performance enhancement.
CaZr4(PO4)6 (CZP)陶瓷由于其独特的低热膨胀和低导热性,在航空航天等高温应用中显示出巨大的前景。然而,其固有的低断裂韧性严重限制了其实际应用。为了同时解决增韧的挑战,同时保持低导热性和低热膨胀,本研究采用浆液渗透(SI)和快速热压(FHP)技术,在1200°C、40 MPa、10分钟下,使用体积密度为0.27 g/cm3的碳纤维预制体,制造三维针刺碳纤维增强CZP复合材料(3D-Cf/CZP)。此外,还引入了厚度约为500 nm的热解碳(PyC)界面相来制备3D-Cf/PyC/CZP复合材料。系统地研究了碳纤维和PyC涂层对CZP陶瓷显微结构、力学性能和热行为的影响。结果表明,碳纤维与CZP基体具有良好的化学相容性和稳定的共存关系。三维碳纤维的掺入显著提高了CZP陶瓷的断裂韧性,从1.46±0.12增加到4.14±0.35 MPa m1/2,引入PyC界面涂层后进一步增加到6.83±0.41 MPa m1/2。这种改善主要归功于多种增韧机制,包括裂纹挠曲、纤维拉出和界面脱粘。Cf/CZP复合材料保持了较低的热膨胀系数(CTE),平均CTE为0.95 × 10−6°C−1,导热系数(0.60 ~ 0.70 W m−1 K−1)低于CZP基体(0.85 ~ 0.95 W m−1 K−1)。相比之下,PyC涂层提高了Cf/PyC/CZP复合材料的导热系数(1.00-1.10 W m−1 K−1),但导致CTE进一步降低至0.71 × 10−6°C−1,表明界面增韧和热输运性能之间存在一定的权衡。本研究证实了3D-Cf增强剂与PyC涂层的结合可以协同提高CZP陶瓷的断裂韧性,同时保持其低导热系数和低热膨胀特性。然而,PyC层引起的热导率的增加,氧化环境下材料的稳定性问题,以及仍然需要提高的弯曲强度是在实际应用中必须协同解决的关键挑战。这些挑战共同为后续的研究方向提供了明确的指导,包括界面优化,氧化保护和机械性能增强。
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引用次数: 0
Enhancing mechanical properties of WC-5Ni hardmetals via microwave sintering: Role of Mo, Si, Ti, and V additives in microstructure evolution and performance optimization 微波烧结增强WC-5Ni硬质合金的力学性能:Mo、Si、Ti和V添加剂在显微组织演变和性能优化中的作用
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-30 DOI: 10.1016/j.matchemphys.2026.132130
Ehsan Ghasali , Saleem Raza , Andrii Babenko , Li Jie , Touradj Ebadzadeh , Yasin Orooji
In this research, four metallic additives (Mo, Si, Ti, and V) were incorporated into WC-5 wt%Ni hardmetals prepared via a rapid microwave sintering process. Five wt% of each additive was individually mixed with WC and Ni powders using a high-energy mixer mill to ensure a uniform distribution of the starting materials. After achieving homogeneity, bar-shaped green bodies were formed under a uniaxial pressure of 240 MPa. Microwave sintering was conducted at 1400, 1500, and 1600 °C without any holding time. XRD analysis revealed that WC was the dominant crystalline phase, while each system also exhibited reaction products such as carbides and intermetallic phases derived from the additives. SEM images of the polished sample surfaces showed a fine microstructure across all samples. Moreover, increasing the sintering temperature from 1400 to 1600 °C led to improved densification, as confirmed by calculated densities and mechanical property evaluations. The highest bending strength (876 ± 25 MPa), Vickers hardness (1728 ± 37 Hv) and Palmqvist fracture toughness (WK) (8.6 ± 0.2 MN m−3/2) were observed in the sample sintered at 1600 °C with the Ti additive, likely due to the formation of NiTi intermetallics and titanium carbide. In contrast, the sample sintered at 1400 °C with the Mo additive exhibited the lowest mechanical properties, probably because the formation of a Ni3Mo3C complex phase consumed the Ni binder.
在本研究中,四种金属添加剂(Mo, Si, Ti和V)加入到通过快速微波烧结工艺制备的WC-5 wt%Ni硬质合金中。每种添加剂的5 wt%分别与WC和Ni粉末混合,使用高能混合机,以确保起始物料的均匀分布。均匀化后,在单轴压力240 MPa下形成条形绿体。在1400、1500和1600℃下进行微波烧结,不需要保温时间。XRD分析表明,WC为主要晶相,同时各体系中还存在由添加剂产生的碳化物和金属间相等反应产物。抛光样品表面的SEM图像显示所有样品的微观结构都很好。此外,将烧结温度从1400℃提高到1600℃,密度计算和力学性能评估证实了致密性的改善。在1600℃下,Ti添加剂烧结后的试样具有最高的抗弯强度(876±25 MPa)、维氏硬度(1728±37 Hv)和Palmqvist断裂韧性(WK)(8.6±0.2 MN m−3/2),这可能是由于NiTi金属间化合物和碳化钛的形成。相比之下,在1400℃下烧结的样品表现出最低的力学性能,这可能是因为Ni3Mo3C配合物的形成消耗了Ni粘结剂。
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引用次数: 0
Synthesis and characterization of BaO- incorporated bismuth-borate glass for gamma radiation shielding: structural, optical, and functional properties 包合硼酸铋- γ辐射屏蔽玻璃的合成与表征:结构、光学与功能特性
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-29 DOI: 10.1016/j.matchemphys.2026.132147
Issam Saber , Abdelali Talbi , Soumya Ferraa , Rachid Hsissou , Mouhsine Galai , Mustapha Belfaquir , Abdelkarim Chaouiki , Mohamed Salaheddine El youbi , Jawza A. Almutairi , Abeer A. AlObaid
This study investigates the effect of barium oxide (BaO) incorporation on the structural, optical, thermal, and radiation shielding properties of bismuth-borate glasses. Various characterization techniques, including X-ray diffraction (XRD), optical absorption spectroscopy, Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy, were employed to analyze the glasses. The radiation shielding properties, which are crucial for applications in photonics and radiation protection, were also thoroughly assessed. The physical analysis revealed that the addition of BaO resulted in an increase in the glass density (ρ), from 5.712 g/cm3 to 6.121 g/cm3, while the molar volume (Vm) decreased from 130.328 cm3/mol to 44.364 cm3/mol. XRD confirmed the amorphous nature of the samples. Thermal analysis demonstrated that as BaO content increased, both the glass transition temperature (Tg) and crystallization temperature (Tc) also rose. FTIR and Raman spectroscopy revealed absorption bands corresponding to structural units such as [BO4], [Bi–O–Bi], and [BiO6], indicating a depolymerized glass network. Optical analysis showed that the bandgap energy for direct transitions decreased from 2.80 eV to 2.52 eV with increasing BaO content. This change aligns with the observed structural modifications, suggesting the formation of non-bridging oxygen atoms. Radiation shielding properties, evaluated using Phy-X simulations, indicated a significant enhancement in radiation shielding efficiency, particularly at low energies. For instance, at 0.284 MeV, the mass attenuation coefficient (MAC) decreased from 0.430 cm2/g for the base glass to 0.259 cm2/g for the glass containing 0.8 mol of BaO. Additionally, the linear attenuation coefficient (LAC) dropped from 2.456 cm−1 for Ba0 to 1.586 cm−1 for Ba0.8. Scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) analyses revealed that higher BaO concentrations led to greater surface heterogeneity and granular formations. These results suggest that BaO-incorporated bismuth-borate glasses exhibit improved structural, optical, and radiation shielding properties, making them promising candidates for photonic and radiation protection applications.
本研究探讨了氧化钡(BaO)掺入对硼酸铋玻璃的结构、光学、热学和辐射屏蔽性能的影响。利用各种表征技术,包括x射线衍射(XRD)、光学吸收光谱、拉曼光谱和傅里叶变换红外光谱(FTIR)对玻璃进行了分析。对光子学和辐射防护中至关重要的辐射屏蔽性能也进行了全面的评估。物理分析表明,BaO的加入使玻璃密度ρ从5.712 g/cm3增加到6.121 g/cm3,而摩尔体积Vm从130.328 cm3/mol降低到44.364 cm3/mol。XRD证实了样品的无定形性质。热分析表明,随着BaO含量的增加,玻璃化转变温度(Tg)和结晶温度(Tc)也随之升高。FTIR和拉曼光谱显示了与[BO4]、[Bi-O-Bi]和[BiO6]等结构单元相对应的吸收带,表明玻璃网络解聚。光学分析表明,随着BaO含量的增加,直接跃迁的带隙能量从2.80 eV降低到2.52 eV。这一变化与观察到的结构变化一致,表明形成了非桥接氧原子。使用Phy-X模拟评估的辐射屏蔽性能表明,辐射屏蔽效率显着提高,特别是在低能量下。例如,在0.284 MeV下,质量衰减系数(MAC)从基玻璃的0.430 cm2/g下降到含有0.8 mol BaO的玻璃的0.259 cm2/g。线性衰减系数(LAC)从Ba0的2.456 cm−1下降到Ba0.8的1.586 cm−1。扫描电镜(SEM)和能谱分析(EDS)表明,较高的BaO浓度会导致更大的表面非均质性和颗粒形成。这些结果表明,bao掺入的硼酸铋玻璃具有更好的结构、光学和辐射屏蔽性能,使其成为光子和辐射防护应用的有希望的候选者。
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引用次数: 0
Ir4–BSe and Rh4–BSe heterojunction systems as highly efficient sensor platforms for detection of NO2, SO2 and SOCl2 gas molecules: A first principles study Ir4-BSe和Rh4-BSe异质结系统作为检测NO2, SO2和SOCl2气体分子的高效传感器平台:第一性原理研究
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-29 DOI: 10.1016/j.matchemphys.2026.132124
Ali Khelef , Tatyana Orlova , Pinank Patel , Venkadeshwaran K , Bilakshan Purohit , Dhirendra Nath Thatoi , Yashwant Singh Bisht , V.S. Subrahmanyam , Baydaa Abd , Ahmed Mohammed Ahmed
To further expand the gas sensor systems, the Ir4 and Rh4 cluster functionalized BSe monolayers were investigated as effective systems for sensing target gases. Then, the adsorption of SO2, NO2 and SOCl2 gases on the surface of cluster modified BSe monolayers were examined. The structural stability of the heterojunction systems composed of Ir4 and Rh4 clusters and BSe nanosheets was also confirmed by the formation energy calculation. The strong interaction between the Ir or Rh atoms and the Se atoms was illustrated based on the CDD analysis, which exhibits large electron density accumulation among Ir–Se and Rh–Se bonds. The conductivity of BSe system was also enhanced after adsorption of Ir4 and Rh4 cluster, which is beneficial for better sensing purpose. The chemical adsorption of SO2, NO2 and SOCl2 gases on the novel Ir4–BSe heterojunction systems was examined by determining the geometric and electronic properties. Our findings offer useful guidance for the experimentalists to develop novel 2D Ir4 cluster modified BSe systems for gas detection and capturing.
为了进一步扩展气体传感器系统,研究了Ir4和Rh4簇功能化BSe单层作为传感目标气体的有效系统。然后,考察了团簇修饰的BSe单层表面对SO2、NO2和SOCl2气体的吸附性能。形成能的计算也证实了由Ir4和Rh4簇与BSe纳米片组成的异质结体系的结构稳定性。CDD分析表明,Ir或Rh原子与Se原子之间存在强相互作用,Ir - Se键和Rh - Se键之间存在较大的电子密度积累。吸附了Ir4和Rh4簇后,BSe体系的电导率也得到了提高,有利于更好的传感目的。通过几何和电子性质的测定,研究了新型Ir4-BSe异质结体系对SO2、NO2和SOCl2气体的化学吸附。我们的研究结果为实验人员开发用于气体检测和捕获的新型二维Ir4簇修饰的BSe系统提供了有用的指导。
{"title":"Ir4–BSe and Rh4–BSe heterojunction systems as highly efficient sensor platforms for detection of NO2, SO2 and SOCl2 gas molecules: A first principles study","authors":"Ali Khelef ,&nbsp;Tatyana Orlova ,&nbsp;Pinank Patel ,&nbsp;Venkadeshwaran K ,&nbsp;Bilakshan Purohit ,&nbsp;Dhirendra Nath Thatoi ,&nbsp;Yashwant Singh Bisht ,&nbsp;V.S. Subrahmanyam ,&nbsp;Baydaa Abd ,&nbsp;Ahmed Mohammed Ahmed","doi":"10.1016/j.matchemphys.2026.132124","DOIUrl":"10.1016/j.matchemphys.2026.132124","url":null,"abstract":"<div><div>To further expand the gas sensor systems, the Ir<sub>4</sub> and Rh<sub>4</sub> cluster functionalized BSe monolayers were investigated as effective systems for sensing target gases. Then, the adsorption of SO<sub>2</sub>, NO<sub>2</sub> and SOCl<sub>2</sub> gases on the surface of cluster modified BSe monolayers were examined. The structural stability of the heterojunction systems composed of Ir<sub>4</sub> and Rh<sub>4</sub> clusters and BSe nanosheets was also confirmed by the formation energy calculation. The strong interaction between the Ir or Rh atoms and the Se atoms was illustrated based on the CDD analysis, which exhibits large electron density accumulation among Ir–Se and Rh–Se bonds. The conductivity of BSe system was also enhanced after adsorption of Ir<sub>4</sub> and Rh<sub>4</sub> cluster, which is beneficial for better sensing purpose. The chemical adsorption of SO<sub>2</sub>, NO<sub>2</sub> and SOCl<sub>2</sub> gases on the novel Ir<sub>4</sub>–BSe heterojunction systems was examined by determining the geometric and electronic properties. Our findings offer useful guidance for the experimentalists to develop novel 2D Ir<sub>4</sub> cluster modified BSe systems for gas detection and capturing.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"354 ","pages":"Article 132124"},"PeriodicalIF":4.7,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191533","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}
引用次数: 0
Cu-doping improves the cyclic stability of P2-type Na0.67Ni0.33Mn0.67O2 cu的掺杂提高了p2型Na0.67Ni0.33Mn0.67O2的循环稳定性
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-29 DOI: 10.1016/j.matchemphys.2026.132133
Mingxuan Zong , Jiayu Song , Wei Zhang , Yanjiang Zhang , Yueyang Liu , Li Zhao , Changsong Dai
P2-type Na0.67Ni0.33Mn0.67O2 garners significant interest in the research community owing to its impressive electrochemical performance, including a high operating voltage of 3.8 V and a substantial cyclic specific capacity of 173 mAh g−1. Despite its promising electrochemical properties, the operational viability of P2–Na0.67Ni0.33Mn0.67O2 cathodes is significantly constrained by voltage-activated crystalline reconfiguration between P2 and O2 polymorphs. To address this issue, this study prepares a series of Cu-doped cathode materials, Na0.67Ni0.33Mn0.67-xCuxO2 (x = 0, 0.02, 0.04, 0.06, 0.08, 0.10), using a co-precipitation method. X-Ray Diffraction shows that Cu-doping enlarges the unit cell, shortens TM-O but lengthens Na–O bonds. Other material phase characterization indicate that Cu is evenly doped in the material structure. The Na0.67Ni0.33Mn0.61Cu0.06O2 material exhibits higher cyclic stability (while the undoped sample retains only 14.15 % capacity after 200 cycles at 100 mA g−1, the modified material maintains 73.51 % of its initial capacity under identical conditions). Electrochemical characterization through charge-discharge cycling and Cyclic Voltammetry tests reveals that Cu doping stabilizes the structure by hindering the P2→O2 phase change. Meanwhile, Electrochemical Impedance Spectroscopy tests indicate that Cu doping effectively improves the charge exchange kinetics of the material. In-situ XRD demonstrates that Cu substitution kinetically suppresses the voltage-induced polymorphic transformation during electrochemical cycling.
由于其令人印象深刻的电化学性能,包括3.8 V的高工作电压和173 mAh g−1的可观循环比容量,p2型Na0.67Ni0.33Mn0.67O2引起了研究界的极大兴趣。尽管具有良好的电化学性能,但P2 - na0.67 ni0.33 mn0.67 O2阴极的工作可行性受到P2和O2多晶之间的电压激活晶体重构的显著限制。为了解决这一问题,本研究采用共沉淀法制备了一系列cu掺杂正极材料Na0.67Ni0.33Mn0.67-xCuxO2 (x = 0, 0.02, 0.04, 0.06, 0.08, 0.10)。x射线衍射结果表明,cu掺杂使晶胞增大,缩短了TM-O键,延长了Na-O键。其他材料相表征表明,Cu在材料结构中均匀掺杂。na0.67 ni0.33 mn0.61 cu0.060 o2材料表现出更高的循环稳定性(在100 mA g - 1下循环200次后,未掺杂样品仅保留14.15%的容量,而改性材料在相同条件下保持其初始容量的73.51%)。通过充放电循环和循环伏安测试的电化学表征表明,Cu掺杂通过阻碍P2→O2相变来稳定结构。电化学阻抗谱测试表明,Cu的掺杂有效地改善了材料的电荷交换动力学。原位XRD分析表明,Cu取代抑制了电化学循环过程中电压诱导的多晶转变。
{"title":"Cu-doping improves the cyclic stability of P2-type Na0.67Ni0.33Mn0.67O2","authors":"Mingxuan Zong ,&nbsp;Jiayu Song ,&nbsp;Wei Zhang ,&nbsp;Yanjiang Zhang ,&nbsp;Yueyang Liu ,&nbsp;Li Zhao ,&nbsp;Changsong Dai","doi":"10.1016/j.matchemphys.2026.132133","DOIUrl":"10.1016/j.matchemphys.2026.132133","url":null,"abstract":"<div><div>P2-type Na<sub>0.67</sub>Ni<sub>0.33</sub>Mn<sub>0.67</sub>O<sub>2</sub> garners significant interest in the research community owing to its impressive electrochemical performance, including a high operating voltage of 3.8 V and a substantial cyclic specific capacity of 173 mAh g<sup>−1</sup>. Despite its promising electrochemical properties, the operational viability of P2–Na<sub>0.67</sub>Ni<sub>0.33</sub>Mn<sub>0.67</sub>O<sub>2</sub> cathodes is significantly constrained by voltage-activated crystalline reconfiguration between P2 and O2 polymorphs. To address this issue, this study prepares a series of Cu-doped cathode materials, Na<sub>0.67</sub>Ni<sub>0.33</sub>Mn<sub>0.67-x</sub>Cu<sub>x</sub>O<sub>2</sub> (x = 0, 0.02, 0.04, 0.06, 0.08, 0.10), using a co-precipitation method. X-Ray Diffraction shows that Cu-doping enlarges the unit cell, shortens TM-O but lengthens Na–O bonds. Other material phase characterization indicate that Cu is evenly doped in the material structure. The Na<sub>0.67</sub>Ni<sub>0.33</sub>Mn<sub>0.61</sub>Cu<sub>0.06</sub>O<sub>2</sub> material exhibits higher cyclic stability (while the undoped sample retains only 14.15 % capacity after 200 cycles at 100 mA g<sup>−1</sup>, the modified material maintains 73.51 % of its initial capacity under identical conditions). Electrochemical characterization through charge-discharge cycling and Cyclic Voltammetry tests reveals that Cu doping stabilizes the structure by hindering the P2→O2 phase change. Meanwhile, Electrochemical Impedance Spectroscopy tests indicate that Cu doping effectively improves the charge exchange kinetics of the material. In-situ XRD demonstrates that Cu substitution kinetically suppresses the voltage-induced polymorphic transformation during electrochemical cycling.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"353 ","pages":"Article 132133"},"PeriodicalIF":4.7,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146170867","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}
引用次数: 0
Tunable semiconducting organotin(IV) complexes as single-source precursors for controlled α-SnS nanostructure synthesis 可调半导体有机锡配合物作为单源前驱体用于可控α-SnS纳米结构的合成
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-29 DOI: 10.1016/j.matchemphys.2026.132154
Rajesh Pratap, Subrato Bhattacharya
Four organotin(IV) complexes (14) were synthesized by reacting various organotin precursors with the sodium salt of S-thiobenzoylthioglycolate, allowing structural variation through different alkyl or aryl substituents and stoichiometric ratios. Single-crystal X-ray diffraction revealed distinct architectures: complex 1 formed a one-dimensional polymeric chain; complexes 2 and 3 adopted ladder-like structures; and complex 4 exhibited a skew-trapezoidal bipyramidal geometry. Spectroscopic analyses (1H, 13C, 119Sn NMR, and IR) corroborated the crystallographic findings. Impedance spectroscopy was used to investigate the electrical properties of complexes 13. The undoped complexes displayed very low conductivity due to the lack of mobile charge carriers, with complex 3 showing the highest among them. Upon iodine doping, conductivity increased significantly through charge carrier generation by oxidation, with complex 1 exhibiting the highest conductivity in the doped state, likely owing to its retained planar structure. AC conductivity analysis indicated a correlated hopping conduction mechanism. Furthermore, pyrolysis of the complexes under controlled conditions yielded tin sulfide nanomaterials; complexes 24 produced phase-pure α-SnS, whereas complex 1 afforded mixed tin sulfides. The resulting materials were characterized by PXRD, SEM, HRTEM, and complementary techniques. These findings establish clear structure–property correlations and highlight the potential of organotin(IV) complexes as tunable precursors for semiconducting SnS nanomaterials.
通过不同的有机锡前体与s -硫苯甲酰巯基乙酸钠盐反应,合成了四种有机锡配合物(1-4),并通过不同的烷基或芳基取代基和化学计量比实现了结构的变化。单晶x射线衍射显示了不同的结构:配合物1形成一维聚合物链;配合物2和3采用阶梯状结构;复合体4呈斜梯形双锥体几何。光谱分析(1H, 13C, 119Sn NMR和IR)证实了晶体学的发现。阻抗谱法研究了配合物1-3的电学性质。由于缺乏移动电荷载流子,未掺杂的配合物的电导率很低,其中配合物3的电导率最高。碘掺杂后,通过氧化产生电荷载流子,电导率显著提高,其中配合物1在掺杂状态下的电导率最高,可能是由于其保留了平面结构。交流电导率分析表明了相关的跳变传导机制。此外,配合物在受控条件下热解得到硫化锡纳米材料;配合物2 ~ 4产生相纯α-SnS,而配合物1产生混合硫化锡。通过PXRD, SEM, HRTEM和互补技术对所得材料进行了表征。这些发现建立了清晰的结构-性能相关性,并突出了有机锡(IV)配合物作为半导体SnS纳米材料可调前体的潜力。
{"title":"Tunable semiconducting organotin(IV) complexes as single-source precursors for controlled α-SnS nanostructure synthesis","authors":"Rajesh Pratap,&nbsp;Subrato Bhattacharya","doi":"10.1016/j.matchemphys.2026.132154","DOIUrl":"10.1016/j.matchemphys.2026.132154","url":null,"abstract":"<div><div>Four organotin(IV) complexes (<strong>1</strong>–<strong>4</strong>) were synthesized by reacting various organotin precursors with the sodium salt of S-thiobenzoylthioglycolate, allowing structural variation through different alkyl or aryl substituents and stoichiometric ratios. Single-crystal X-ray diffraction revealed distinct architectures: complex 1 formed a one-dimensional polymeric chain; complexes <strong>2</strong> and <strong>3</strong> adopted ladder-like structures; and complex <strong>4</strong> exhibited a skew-trapezoidal bipyramidal geometry. Spectroscopic analyses (<sup>1</sup>H, <sup>13</sup>C, <sup>119</sup>Sn NMR, and IR) corroborated the crystallographic findings. Impedance spectroscopy was used to investigate the electrical properties of complexes <strong>1</strong>–<strong>3.</strong> The undoped complexes displayed very low conductivity due to the lack of mobile charge carriers, with complex <strong>3</strong> showing the highest among them. Upon iodine doping, conductivity increased significantly through charge carrier generation by oxidation, with complex <strong>1</strong> exhibiting the highest conductivity in the doped state, likely owing to its retained planar structure. AC conductivity analysis indicated a correlated hopping conduction mechanism. Furthermore, pyrolysis of the complexes under controlled conditions yielded tin sulfide nanomaterials; complexes <strong>2</strong>–<strong>4</strong> produced phase-pure α-SnS, whereas complex <strong>1</strong> afforded mixed tin sulfides. The resulting materials were characterized by PXRD, SEM, HRTEM, and complementary techniques. These findings establish clear structure–property correlations and highlight the potential of organotin(IV) complexes as tunable precursors for semiconducting SnS nanomaterials.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"354 ","pages":"Article 132154"},"PeriodicalIF":4.7,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191536","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}
引用次数: 0
The effect of the pore structure and N-functional groups of COFs on CO2 adsorption: A simulation study COFs孔结构和n -官能团对CO2吸附的影响:模拟研究
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-29 DOI: 10.1016/j.matchemphys.2026.132153
Zeyu Wang , Jiaxin Wang , Ying Liu , Yunlan Sun , Baozhong Zhu
Direct air capture (DAC) adsorbents of CO2 face the challenges of large adsorption capacity and high adsorption selectivity. Covalent organic frameworks (COFs) are promising for CO2 capture due to high surface area, ordered porous structures, and tunable chemical modification. The CO2 adsorption capacity of COFs in complex atmospheres was systematically investigated using three simulation methods. Firstly, the adsorption isotherms of CO2 on COF-1, COF-5, and TpPa-1 were investigated by using Grand Canonical Monte Carlo (GCMC) simulations. Among them, COF-1 demonstrated the highest CO2 capacity (2.97 mmol/g), followed by COF-5 (0.45 mmol/g) and TpPa-1 (0.37 mmol/g). Secondly, the diffusion rate of CO2 in COFs was compared by Molecular dynamics (MD) simulations. COF-1 had the highest diffusion coefficient of 8.3 × 10−5 cm2/s. This indicated that the adsorption performance and diffusion rate were primarily influenced by the pore structure. Thirdly, the CO2 adsorption features of COF-1 modified with nitrogen-containing groups (-CN, –NH2, –NH) were explored by the density functional theory (DFT) method. COF-1-CN had the highest adsorption capacity, which was 1.19 times larger than that of COF-1. Moreover, the adsorption selectivity of COF-1-CN for the CO2/H2O atmosphere increased by 20% at 101 kPa compared to COF-1. This was because nitrogen groups increased the polarity and electron density of the COF-1-CN, which further enhanced the interactions between CO2 and optimized the pore structure. These findings highlight the role of porous structure and surface properties in designing advanced COF-based CO2 adsorbents.
直接空气捕集(DAC)吸附剂对CO2的吸附面临着大吸附容量和高吸附选择性的挑战。共价有机框架(COFs)由于其高表面积、有序的多孔结构和可调的化学修饰,在二氧化碳捕获方面具有很大的前景。采用三种模拟方法系统地研究了COFs在复杂大气环境中的CO2吸附能力。首先,利用大正则蒙特卡罗(GCMC)模拟研究了CO2在COF-1、COF-5和TpPa-1上的吸附等温线。其中COF-1的CO2容量最高(2.97 mmol/g),其次是COF-5 (0.45 mmol/g)和TpPa-1 (0.37 mmol/g)。其次,通过分子动力学(MD)模拟比较CO2在COFs中的扩散速率。COF-1的扩散系数最高,为8.3 × 10−5 cm2/s。这表明吸附性能和扩散速率主要受孔隙结构的影响。第三,利用密度泛函(DFT)方法研究了含氮基团(-CN、-NH2、-NH)修饰的COF-1对CO2的吸附特性。COF-1- cn的吸附量最高,是COF-1的1.19倍。在101 kPa条件下,COF-1- cn对CO2/H2O气氛的吸附选择性比COF-1提高了20%。这是因为氮基团增加了COF-1-CN的极性和电子密度,进一步增强了CO2之间的相互作用,优化了孔结构。这些发现强调了多孔结构和表面特性在设计先进的cof基CO2吸附剂中的作用。
{"title":"The effect of the pore structure and N-functional groups of COFs on CO2 adsorption: A simulation study","authors":"Zeyu Wang ,&nbsp;Jiaxin Wang ,&nbsp;Ying Liu ,&nbsp;Yunlan Sun ,&nbsp;Baozhong Zhu","doi":"10.1016/j.matchemphys.2026.132153","DOIUrl":"10.1016/j.matchemphys.2026.132153","url":null,"abstract":"<div><div>Direct air capture (DAC) adsorbents of CO<sub>2</sub> face the challenges of large adsorption capacity and high adsorption selectivity. Covalent organic frameworks (COFs) are promising for CO<sub>2</sub> capture due to high surface area, ordered porous structures, and tunable chemical modification. The CO<sub>2</sub> adsorption capacity of COFs in complex atmospheres was systematically investigated using three simulation methods. Firstly, the adsorption isotherms of CO<sub>2</sub> on COF-1, COF-5, and TpPa-1 were investigated by using Grand Canonical Monte Carlo (GCMC) simulations. Among them, COF-1 demonstrated the highest CO<sub>2</sub> capacity (2.97 mmol/g), followed by COF-5 (0.45 mmol/g) and TpPa-1 (0.37 mmol/g). Secondly, the diffusion rate of CO<sub>2</sub> in COFs was compared by Molecular dynamics (MD) simulations. COF-1 had the highest diffusion coefficient of 8.3 × 10<sup>−5</sup> cm<sup>2</sup>/s. This indicated that the adsorption performance and diffusion rate were primarily influenced by the pore structure. Thirdly, the CO<sub>2</sub> adsorption features of COF-1 modified with nitrogen-containing groups (-CN, –NH<sub>2</sub>, –NH) were explored by the density functional theory (DFT) method. COF-1-CN had the highest adsorption capacity, which was 1.19 times larger than that of COF-1. Moreover, the adsorption selectivity of COF-1-CN for the CO<sub>2</sub>/H<sub>2</sub>O atmosphere increased by 20% at 101 kPa compared to COF-1. This was because nitrogen groups increased the polarity and electron density of the COF-1-CN, which further enhanced the interactions between CO<sub>2</sub> and optimized the pore structure. These findings highlight the role of porous structure and surface properties in designing advanced COF-based CO<sub>2</sub> adsorbents.</div></div>","PeriodicalId":18227,"journal":{"name":"Materials Chemistry and Physics","volume":"353 ","pages":"Article 132153"},"PeriodicalIF":4.7,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146080218","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}
引用次数: 0
Correlation between heat treatment, microstructure, and mechanical properties of selective laser melted Co–Cr–Mo–W alloy 选择性激光熔化Co-Cr-Mo-W合金热处理、显微组织与力学性能的关系
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-29 DOI: 10.1016/j.matchemphys.2026.132139
Alireza Derakhshi , Farhad Emdadi Derabi , Mostafa Aghazadeh Ghomi , Md Saad Patel , Faseeulla Khan Mohammad , Akbar Heidarzadeh
Selective laser melting (SLM) facilitates the production of Co–Cr–Mo–W alloys with intricate geometries. However, the rapid solidification characteristic of the method results in microstructural heterogeneity that limits its mechanical and tribological reliability. This study systematically examines the impact of various post-processing heat treatments on phase evolution, carbide precipitation, and the performance of an SLM fabricated Co–Cr–Mo–W alloy. Solution treatment, single-stage aging, double-stage aging, and direct aging were utilized to alter solute redistribution and precipitate morphology. The as fabricated alloy, distinguished by a refined cellular microstructure with elements segregation displayed a strength of 1228 MPa with a ductility of 17.5 % and poor wear resistance. Heat treatment modified the equilibrium between γ and ε phases and facilitated the development of M6C and M23C6 carbides, resulting in significant alterations in microstructure and wear performance. The direct aging at 980 °C resulted in a dense array of fine, well anchored precipitates that displayed a hardness of 557 HV and tensile strength of 1424 ± 28.48 MPa, while preserving acceptable ductility (7.9 ± 0.15 %), and concurrently achieved the lowest coefficient of friction of about 0.17. Conversely, multi-stage aging improved chemical homogeneity but produced relatively coarser precipitates, diminishing strengthening efficacy and facilitating particle pull out during wear. The findings establish a distinct structure-property correlation, indicating that heat treatment provides a streamlined and efficient method to enhance the mechanical integrity and surface durability of SLM Co–Cr–Mo–W alloys for diverse applications.
选择性激光熔化(SLM)有利于生产具有复杂几何形状的Co-Cr-Mo-W合金。然而,该方法的快速凝固特性导致微观组织不均匀性,限制了其机械和摩擦学可靠性。本研究系统地研究了各种后处理热处理对SLM制备的Co-Cr-Mo-W合金的相演化、碳化物析出和性能的影响。固溶处理、单段时效、双段时效和直接时效改变了溶质再分布和析出相形态。制备的合金具有细化的胞状组织和元素偏析,强度为1228 MPa,延展性为17.5%,耐磨性较差。热处理改变了γ相和ε相之间的平衡,促进了M6C和M23C6碳化物的形成,导致组织和磨损性能发生了显著变化。在980°C下直接时效,形成了密集的细小、锚定良好的析出相,其硬度为557 HV,抗拉强度为1424±28.48 MPa,同时保持了可接受的延性(7.9±0.15%),同时获得了最低的摩擦系数约0.17。相反,多级时效改善了合金的化学均匀性,但产生了相对较粗的析出相,降低了强化效果,并在磨损过程中促进了颗粒的拔出。研究结果建立了明显的组织-性能相关性,表明热处理为提高SLM Co-Cr-Mo-W合金的机械完整性和表面耐久性提供了一种简化和有效的方法,适用于各种应用。
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引用次数: 0
Structure-activity relationship of modified montmorillonite for treating polluted water 改性蒙脱土处理污水的构效关系
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-29 DOI: 10.1016/j.matchemphys.2026.132155
Di Liu , Chao Niu , Ke Wang , Zhuo Zhang , Tianfeng Zhao , Chunting Wu , Yongchun Guo , Yao Ma , Fei Chen
With the intensification of water pollution and the growing demand for freshwater resources, the development of efficient and environmentally friendly adsorbent materials has become increasingly urgent. Owing to its unique structure and low-cost availability, montmorillonite has emerged as one of the most widely studied adsorbents in wastewater treatment. This paper reviews the current applications of modified montmorillonite in the field of water pollution control, systematically explores the various mechanisms by which modified montmorillonite adsorbs pollutants, and elaborates on the structure–activity relationship between its microstructure and adsorption performance. Furthermore, this review establishes clear links between different modification strategies and the dominant adsorption mechanisms they enhance, while also addressing their applicability to different pollutant classes. An innovative green modification technology based on a 532 nm ps laser is proposed. The results show that at an optimal energy density of 0.75 J/cm2, laser treatment can increase the specific surface area of montmorillonite by approximately 116.06 % and expand the total pore volume by about 100.31 %. This technology provides a novel approach for the green development of modified montmorillonite and offers a highly promising strategy for water pollution control.
随着水污染的加剧和对淡水资源需求的不断增长,开发高效环保的吸附材料已日益迫切。由于其独特的结构和低成本的可用性,蒙脱土已成为污水处理中研究最广泛的吸附剂之一。本文综述了改性蒙脱土在水污染治理领域的应用现状,系统探讨了改性蒙脱土吸附污染物的各种机理,阐述了改性蒙脱土的微观结构与吸附性能的构效关系。此外,本综述建立了不同改性策略与它们增强的主要吸附机制之间的明确联系,同时也解决了它们对不同污染物类别的适用性。提出了一种基于532 nm ps激光器的新型绿色改性技术。结果表明,在0.75 J/cm2的最佳能量密度下,激光处理可使蒙脱土的比表面积增加约116.06%,总孔容增加约100.31%;该技术为改性蒙脱土的绿色发展提供了一条新途径,为水污染治理提供了一种极具前景的策略。
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引用次数: 0
Star-shaped donor-acceptor arylsilanes as 3D ambipolar materials for optoelectronic and bioelectronic applications 星形给受体芳基硅烷作为光电和生物电子应用的三维双极性材料
IF 4.7 3区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-01-29 DOI: 10.1016/j.matchemphys.2026.132152
Dmitry O. Balakirev , Elena A. Kleymyuk , Evgenia A. Svidchenko , Nikolay M. Surin , Sergey A. Pisarev , Artem V. Bakirov , Yulia A. Isaeva , Michael D. Khitrov , Artur L. Mannanov , Svetlana M. Peregudova , Anastasia A. Vetyugova , Askold A. Trul , Olga A. Maloshitskaya , Sergei A. Ponomarenko , Yuriy N. Luponosov
Novel donor-acceptor arylsilane molecules, Si(PP-DCV)4 and Si(PT-DCV)4, featuring three-dimensional star-shaped geometries, were synthesized and investigated in comparison to model compounds. These compounds, comprising a tetraphenylsilane core linked to terminal phenyldicyanovinyl groups through phenylene or thienyl π-spacers, exhibit a range of promising physicochemical properties, including high thermal stability (up to 490 °C), deep-lying HOMO energy levels (up to −6.4 eV), ambipolar charge carrier mobility, efficient light absorption, and high crystallinity. A comprehensive experimental and theoretical investigation, in comparison to model compounds, revealed the nonordinal optical properties of these compounds, elucidating the nature of electronic transitions and fluorescence efficiency. Substitution of the phenylene spacer with a thiophene spacer led to significant changes, including a red shift in the absorption spectrum, an increased extinction coefficient, lower HOMO energy levels, enhanced crystallinity, and improved ambipolar charge carrier mobility in films. Additionally, the polar and amphiphilic nature of these donor-acceptor molecules enabled the formation of stable nanoparticles (50–110 nm) in aqueous solutions without surfactants. These findings highlight the potential of these materials for applications in optoelectronic and biological applications.
合成了具有三维星形结构的新型芳基硅烷分子Si(PP-DCV)4和Si(PT-DCV)4,并与模型化合物进行了对比研究。这些化合物由四苯基硅烷核心组成,通过苯基或噻吩基π间隔剂连接到末端苯基二氰乙烯基,表现出一系列有希望的物理化学性质,包括高热稳定性(高达490°C),深层HOMO能级(高达- 6.4 eV),双极性载流子迁移率,高效的光吸收和高结晶度。综合实验和理论研究,与模型化合物比较,揭示了这些化合物的非序数光学性质,阐明了电子跃迁和荧光效率的本质。用噻吩取代苯基间隔剂导致了显著的变化,包括吸收光谱的红移、消光系数的增加、HOMO能级的降低、结晶度的增强以及薄膜中双极性载流子迁移率的提高。此外,这些供体-受体分子的极性和两亲性使得在没有表面活性剂的水溶液中形成稳定的纳米颗粒(50-110 nm)。这些发现突出了这些材料在光电和生物应用方面的潜力。
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引用次数: 0
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