30 May 2023, Volume 54 Issue 5

    

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Focuses & Concerns (The Project of Chongqing Press Fund in 2022)
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  Mechanical properties and pore characteristics of magnesium oxychloride cement modified by biomass silicon

  QIAO Hongxia, CAO Feng, ZHAO Ziyan, WEN Chen

  Jorunal of Functional Materials. 2023, 54(5): 5001-5007. https://doi.org/10.3969/j.issn.1001-9731.2023.05.001

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  Highland barley straw ash (HBSA) prepared by calcination and grinding under certain conditions is an active admixture of biomass silicon source, which will affect the mechanical properties of magnesium oxychloride cement (MOC). In order to study the influence of HBSA added into MOC on its mechanical properties, MOC mortar specimens with different HBSA content were tested for flexural and compressive strength under dry and saturated conditions respectively. Strength loss rate and softening coefficient were used to characterize the degree of mechanical property damage of MOC in saturated conditions. The pore structure of MOC mortar specimens was tested and characterized by low field nuclear magnetic resonance technology and gas adsorption method. The results show that MOC with 5% HBSA has the highest flexural and compressive strength in dry and saturated conditions, while MOC with 10% HBSA has the lowest strength loss rate and the highest softening coefficient in saturated conditions. When the content of HBSA is 10%, the proportion of harmful pores and multi harmful pores in the pore structure of MOC is significantly reduced, and the most probable pore diameter is reduced, which optimizes the pore structure of MOC and enhances the mechanical properties in saturated conditions.
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  Preparation of M-type barium ferrite and its application in microwave devices

  WANG Feng, YANG Qinghui, ZHANG Ding, ZHANG Yuanjing, LI Han, YU Jingyan, YANG Shuting, ZHANG Huaiwu

  Jorunal of Functional Materials. 2023, 54(5): 5008-5019. https://doi.org/10.3969/j.issn.1001-9731.2023.05.002

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  M-type barium ferrite (BaFe₁₂O₁₉, BaM) is an excellent hexagonal permanent magnet material with high saturation magnetization, magnetic anisotropy and remanence ratio. It not only plays an important role in promoting the development and manufacture of self-biased circulators, but also makes the miniaturization process of microwave antennas and the development of new band radar easier to achieve in the future. In addition, M-type barium ferrite is also a typical double-dielectric magnetic material with good electromagnetic loss and resonance absorption characteristics. It can be used to fabricate absorbing materials with excellent performance, which can be used for harmful electromagnetic wave shielding in life and stealth technology of military aircraft. Therefore, the development and utilization of M-type barium ferrite materials have far-reaching influence on the future people's livelihood and military technology. In this paper, the common preparation methods of M-type barium ferrite in recent years are discussed and reviewed, especially the preparation of M-type barium ferrite single crystal materials. In addition, the crystal structure of M-type barium ferrite and its application as magnetic element in microwave devices are also introduced.
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  Preparation of hierarchical pore zeolitization ceramsite from solid wastes and its adsorption properties

  CHEN Yuxin, XU Wensheng, WANG Ning, AN Shengli, PENG Jun, PENG Jihua, SONG Xiwen

  Jorunal of Functional Materials. 2023, 54(5): 5020-5028. https://doi.org/10.3969/j.issn.1001-9731.2023.05.003

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  In this study, a green process of high temperature sintering activation-hydrothermal reaction for the synthesis of novel ceramsite loaded with zeolite P from coal fly ash was designed. XRD and SEM were used to study the effect of synthesis conditions on the phase transition and microstructure of zeolitization ceramsites. The adsorption process of ceramsite was described by experiments and various kinetic model and isothermal adsorption model. The results show that the optimum preparation conditions were as follows: Na₂SiO₃ addition content of 6%, sintering temperature at 1 060 ℃, hydrothermal temperature at 160 ℃, NaOH concentration of 2 mol/L and time of 12 h. The sample mainly contained zeolite P and a small amount of unreacted mullite, which was the main reason for the increase of specific surface area from 0.277 m²/g to 16.775 m²/g. The adsorption mechanism of ammonia nitrogen by ceramsite was mainly ion exchange, which also accorded with the structural characteristics of zeolite. The results are highly attractive for many industrial applications due to the simplicity and green of the synthesis procedure and remarkable adsorption properties.
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  Damage model of nano-silica and steel fiber reinforced recycled concrete

  WANG Yonggui, HUANG Xuyang, LI Shuaipeng, FAN Yuhui

  Jorunal of Functional Materials. 2023, 54(5): 5029-5037. https://doi.org/10.3969/j.issn.1001-9731.2023.05.004

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  In order to improve the mechanical properties of recycled concrete, nano-silica and steel fibers were used as external materials to improve recycled concrete. The replacement rate of recycled coarse aggregate, the nano-silica content and steel fiber content are selected as the mix proportion control parameters, and a total of 18 working conditions of recycled concrete are designed. The stress-strain curve of recycled concrete was analyzed through prismatic compression test, a damage constitutive model was established, and the damage evolution mechanism is analyzed. The results show that the stress-strain curve decreases steeply with the increase of nano-silica content, and the stress-strain curve of recycled concrete becomes fuller with the increase of the steel fiber content. The subsection expression can better express the full stress-strain curve equation of recycled concrete. When the steel fiber or nano-silica is single-doped, the peak stress increases and the peak strain decreases with the increase of the nano-silica content, and the peak stress and peak strain increase with the increase of the steel fiber content. When the steel fiber and nano-silica are added together, the peak stress and peak strain increase with the increase of the steel fiber content, and the peak stress and peak strain do not have obvious regularity with the increase of the nano-silica content. The established damage constitutive model can better satisfy the stress-strain relationship of recycled concrete. The damage variable increases in S-shape with the increase of strain, which can better reflect the damage development of recycled concrete in a certain period of time.
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  Application progress on novel lithium ion solid electrolyte

  WANG Chunmei, ZHOU Zhiyuan, ZHANG Yao, GAO Yanfang

  Jorunal of Functional Materials. 2023, 54(5): 5038-5046. https://doi.org/10.3969/j.issn.1001-9731.2023.05.005

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  The traditional liquid electrolyte produce dendrites at the negative pole cycle, which cause short circuit of the battery. In addition, there areflammab, explos leak. Solid electrolyte can well solve the above safety problems, and have good stability, that replacement of liquid electrolyte. solid state electrolyte needs to satisfy the requirements, such as high ionic conductivity, wide electrochemical window, excellent chemical compatibility, simple preparation process, low cost and so on. Therefore, it is necessary to further develop high performance solid electrolyte and electrode/electrolyte interface modification materials to optimize and improve the electrochemical performance of solid state batteries. Metal organic frameworks and covalent organic frameworks compounds are newly developed porous materials with periodic structure, which have been widely used in the battery field. This paper reviews the applications and research progress of metal organic frameworks and covalent organic frameworks compounds in solid state lithium ion batteries. At last, how to improve the electrochemical performance of metal organic frameworks and covalent organic frameworks solid electrolytes give.
Review & Advance
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  Research progress of multicolor mechanochromic polymers

  LAI Yingsheng, CHEN Zhongtao, ZHAO Xiuli

  Jorunal of Functional Materials. 2023, 54(5): 5047-5055. https://doi.org/10.3969/j.issn.1001-9731.2023.05.006

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  Mechanochromic polymers (MCPs), which can change color or fluorescence in response to mechanical stimuli, show applications in stress sensing and damage visualization. However, MCPs usually display only one color or fluorescence change under an external mechanical stimulus, which limits their use in multimodal analysis of stress and destruction sensing. Therefore, MCPs that exhibit multiple color changes at different intensities or under various types of external mechanical forces have become a research focus. In this paper, the research status of multicolor mechanochromic polymers, including the design strategy and mechanism, is introduced and discussed.
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  Research progress of SiO₂ coating on iron-based soft magnetic composites

  LUO Jian, HE Zhengye, AN Jing, MU Xing, XU Lihong, GUO Shihai

  Jorunal of Functional Materials. 2023, 54(5): 5056-5065. https://doi.org/10.3969/j.issn.1001-9731.2023.05.007

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  Soft magnetic composite materials have important applications in many fields. With the development of technology, the performance requirements of soft magnetic composite materials are constantly improving. In order to meet the application requirements of high frequency and high power working conditions, it is necessary to develop soft magnetic composites with low loss and high permeability. SiO₂, as an insulating coating medium, has high resistivity and thermal stability, and can be coated on magnetic particles by a variety of methods, so it has been widely used in the field of developing new soft magnetic composites. This paper summarizes the application of sol-gel method, chemical liquid deposition method, reverse microemulsion method, chemical vapor deposition method, double-layer coating method and modified resin coating method in SiO₂ insulation coating of iron-based soft magnetic composites. The characteristics of various insulating coating method are summarized and classified according to their characteristics. Some problems faced by SiO₂ insulating coating at present are pointed out, and the development prospect of insulating coating methods is prospected.
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  Research progress of heteroatom-doped carbonmaterials in direct methanol fuel cell catalysts

  ZHANG Jun, LIANG Pingjuan, TANG Mue, XU Xinlan, ZHANG Xianming

  Jorunal of Functional Materials. 2023, 54(5): 5066-5074. https://doi.org/10.3969/j.issn.1001-9731.2023.05.008

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  Direct methanol fuel cells (DMFCs) are one of the clean energy sources for solving the problems of energy shortage and environmental pollution. Methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) are important electrode reactions for DMFCs, but their large-scale commercialization is limited by sluggish kinetic processes. In recent years, carbon materials have attracted much attention as promising catalysts for DMFCs due to their low cost, high specific surface area and well-developed pore structure. Especially, heteroatom doping (nitrogen, sulfur, phosphorus, and boron) is not only beneficial for improving the surface inertness of carbon to enhance the electrical conductivity and increase the defect sites, but also boosts the electrochemical activity by strengthening the strong metal-support interactions. Therefore, developing heteroatom-doped carbon materials which specialized for catalyst or support toward DMFCs is significant to promote the commercialization of DMFCs. In this review, the common preparation methods of heteroatom-doped carbon materials and their application in ORR and MOR are summarized. Ultimately, it is expected that the future developing direction of heteroatom doping carbonaceous materials is aimed at multicomponent co-doping, promotion of stability and in-depth analysis on catalytic reaction mechanism.
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  Research progress on aggregation-induced emission organic materials

  LIU Huan, XIE Yulong

  Jorunal of Functional Materials. 2023, 54(5): 5075-5085. https://doi.org/10.3969/j.issn.1001-9731.2023.05.009

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  The aggregation-caused quenching caused by traditional organic materials in solid state or concentrated state limits the development of organic optical functional materials. In recent years, materials with aggregation-induced luminescence properties have been emerging, which have bright application prospects because of their biodegradability, good biocompatibility and adjustable molecular structure. In this review, representative examples are selected according to different stimulus responses, and the results of photoluminescent materials, mechanoluminescent materials, and electroluminescent materials are highlighted. The basic luminescence mechanism is introduced to better understand the process of stimulus response and provide guidance for designing ideal stimuli-responsive materials.
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  Progress of materials on removal of I^- and IO^-₃ from wastewater

  LI Lu, DENG Huiyu, CHEN Qingchun, LUO Qiaoyu, JIN Tianxiang

  Jorunal of Functional Materials. 2023, 54(5): 5086-5094. https://doi.org/10.3969/j.issn.1001-9731.2023.05.010

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  Excessive or radioactive I^- and IO^-₃ in industrial wastewater may cause thyroid lesions and even carcinogenesis. It does harm to the ecological environment. Therefore, it is imperative to remove I^- and IO^-₃ from wastewater. Adsorption, membrane separation and chemical precipitation are the conventional methods. In recent years, in order to improve the removal efficiency and reduce the secondary pollution caused by the regeneration process of adsorbent, electrochemical and photochemical assisted adsorption have attracted attention of most researchers. In this paper, the basic principles of the above methods are introduced, and the progress of materials for treating iodine-containing wastewater such as ion-exchange resins, layered doublehydroxides,metal organic frame compounds, natural mineral materials, biomass materials and membrane materials are emphasized. Finally, the future research directions are prospected.
Research & Development
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  Preparation and catalytic properties of multifunctional electronic information material MoS₂

  LI Cong, TAN Ming, WANG Yaling, LI Hui

  Jorunal of Functional Materials. 2023, 54(5): 5095-5100. https://doi.org/10.3969/j.issn.1001-9731.2023.05.011

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  As a kind of electronic information materials, semiconductor materials have become one of the hot topics because of their wide band gap and high carrier mobility. MoS₂ composites with different mass fractions of Ag doped (0, 1%, 3%, 5%, 7%) were prepared by hydrothermal method. XRD, SEM, UV-Vis, FT-IR, Raman and catalytic performance analysis were used to test and characterize the crystal structure, microscopic morphology, spectral performance and catalytic performance of Ag-doped MoS₂ composite. The results showed that mono-phase hexagonal MoS₂ was synthesized by hydrothermal method, and Ag was successfully doped into MoS₂. The Ag-doped MoS₂ composite was a spherical structure formed by the stacking of nano-sheets. Ag doping increased the diameter of MoS₂ nanosphere with the size between 300 and 350 nm. Ag doping induced the crystal form of MoS₂ to change from 2H-MoS₂ phase structure to 1T-MoS₂ phase structure, and the crystal form content of 1T-MoS₂ phase structure increased. The absorption ability of MoS₂ composites for visible and ultraviolet light was enhanced, and the absorption strength of MoS₂ composites doped with 5 wt% Ag was the highest. The doping of Ag significantly improved the photocatalytic activity of MoS₂. When the light was 120 min, the degradation efficiency of 5 wt% Ag-doped MoS₂ composites for RhB reached the maximum value of 92.79%, which was 129.74% higher than that of pure MoS₂. Ag-doped MoS₂ composite has potential application value in photocatalytic degradation.
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  Study on preparation and thermal conductivity of foam concrete inorganic thermal insulation materials

  WANG Yiyun, ZHAO Jing, SU Wei

  Jorunal of Functional Materials. 2023, 54(5): 5101-5106. https://doi.org/10.3969/j.issn.1001-9731.2023.05.012

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  Prefabricated foam mixing method was used to prepare foam concrete with different content of graphene oxide (GO) (0, 0.02 wt%, 0.04 wt% and 0.06 wt%). The influence of GO content on the performance of foam concrete was studied by XRD, SEM, mechanical property analysis, TGA and thermal conductivity analysis. The results showed that the proper amount of GO doping accelerated the hydration reaction and improved the roundness and sealing of the pores in the concrete, but didn’t produce new hydration products. When the content of GO was 0.04 wt%, the pore distribution of foam concrete was the most uniform, and the diameter distribution range was 500~700 μm. The mechanical properties, thermal stability and thermal insulation properties of foam concrete were improved by adding appropriate amount of GO. With the increase of GO content, the compressive strength of foam concrete first increased and then decreased, the mass loss first decreased and then increased, and the thermal conductivity first decreased and then increased. When the content of GO was 0.04 wt%, the maximum compressive strength of foam concrete was 2.98 MPa, the minimum mass loss at 500 and 1 000 ℃ was 15.8% and 20.8% respectively, and the minimum thermal conductivity was 0.105 W/(m·K). Comprehensive analysis shows that the optimum doping amount of GO is 0.04 wt%.
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  NiSe₂/Ni(OH)₂/TM heterogeneous integrated electrode for promoting alkaline oxygen evolution

  WEI Xueling, GUO Yuchen, JIA Feihong, LI Yan, BAO Weiwei, ZOU Xiangyu

  Jorunal of Functional Materials. 2023, 54(5): 5107-5112. https://doi.org/10.3969/j.issn.1001-9731.2023.05.013

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  Developing low-cost, and efficient and stable electrodes for alkaline water electrolysis is very important. After Ni(OH)₂ precursor was grown in situ on titanium mesh (TM) by hydrothermal method, it was selenided by solid-phase method to prepare NiSe₂/Ni(OH)₂/TM heterogeneous integrated electrode. XRD and XPS were used to characterize the phase and chemical valence of the electrode. The morphology and element distribution of the electrode were analyzed by SEM and TEM. The oxygen evolution reaction (OER) performance was tested in 1 mol/L KOH electrolyte. XRD and SEM analysis confirmed that the morphology of the electrode depended on selenide time. The electrochemical test results show that the morphology of the electrode has a great influence on the catalytic performance. When selenided at 350 ℃ for 2 h, NiSe₂/Ni(OH)₂/TM electrode has the best alkaline oxygen evolution performance. It displays low overpotential of 285 mV at 10 mA/cm², and small Tafel slope about 50 mV/dec. It also has long-term electrochemical durability in alkaline conditions. The current density decaying rate is 16% in 100 h OER test. The rough surface significantly increases the effective active sites, and the coordination between different species on the heterogeneous interface is strengthened, which improves the conversion rate of intermediates and the electron transfer rate. Thus, the electrode shows excellent intrinsic activity and durability.
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  Preparation and dielectric properties of graphite-polyimide composites

  YUAN Jing, YUAN Sankui

  Jorunal of Functional Materials. 2023, 54(5): 5113-5118. https://doi.org/10.3969/j.issn.1001-9731.2023.05.014

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  Polyimide is widely used in new building materials, microelectronics, aerospace and other fields because of its excellent mechanical properties, good chemical resistance and low water absorption. Graphite oxide was prepared by the improved Hummer chemical method, and then graphite-polyimide composite adhesive and graphite-polyimide composite film with different mass fractions (0, 1%, 2%, 3%, 4%) were prepared by solution blending method. The composite system was characterized by FT-IR, SEM, mechanical property test and thermogravimetric analysis. The results showed that the basic structure of polyimide wasn’t affected by the addition of graphite. After the addition of appropriate amount of graphite, the graphite and polyimide were uniformly combined, and the section roughness and stability of the composite adhesive were increased. With the increase of graphite doping, the shear strength of the composite adhesive increased first and then decreased. When the amount of graphite doping was 3 wt%, the shear strength of the composite adhesive reached the maximum value of 11.67 MPa. The thermal stability and dielectric properties of polyimide could be effectively improved by adding appropriate amount of graphite. With the appropriate amount of graphite doping, the residual amount and dielectric constant of the composite film at 800 ℃ increased, and the dielectric loss decreased. When the doping amount of graphite was 3 wt%, the residual amount of the composite film at 800 ℃ reached the maximum value of 57.74%, the minimum dielectric loss was 0.016, and the corresponding dielectric constant was 12.7. Comprehensive analysis showed that the optimum doping amount of graphite was 3 wt%.
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  Dielectric and piezoelectric properties of leadzirconate titanate-Portland cement composites

  LI Ye, LI Weina, LI Jing, MA Ruiyan, JIA Xiaopan

  Jorunal of Functional Materials. 2023, 54(5): 5119-5123. https://doi.org/10.3969/j.issn.1001-9731.2023.05.015

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  Lead zirconate titanate-Portland cement composites with different volume fractions (30%, 40%, 50%, 60%) were prepared by pressing method with lead zirconate titanate as the functional phase and ordinary Portland cement P.O 42.5 as the matrix material, and the dielectric, piezoelectric and electromechanical coupling properties of the composites were studied. The results show that the doping of lead zirconate titanate with volume content below 50% can increase the probability of contact between lead zirconate titanate and enhance the connectivity, thus promoting the mutual conduction of current between lead zirconate titanate. With the increasing volume of lead zirconate titanate, the dielectric constant of the composite gradually increases, the dielectric loss gradually decreases, the piezoelectric voltage constant and piezoelectric strain constant gradually increase, and the electromechanical coupling coefficient K_t and the mechanical quality factor Q_m first increase and then decrease. When the volume fraction of lead zirconate titanate is 50%, the maximum K_t is 0.15% and the maximum Q_m is 33.09. When the volume fraction of lead zirconate titanate increases to 60%, the distribution uniformity becomes worse and the electromechanical coupling properties of the composites weaken.
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  Construction and characterization of wood aerogel-supported MOF and its composites

  ZHANG Chaoling, ZHU Gang, DENG Shuduan, LI Kaiqian, ZHANG Xunpeng, KANG Kunyong, SUN Hao

  Jorunal of Functional Materials. 2023, 54(5): 5124-5132. https://doi.org/10.3969/j.issn.1001-9731.2023.05.016

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  The shape of metal-organic frame (MOF) is usually in the form of powder, which was associated with poor processibility and recyclability, thus hindering their further practical application. Therefore, it is urgent to find a self-supporting porous carrier material with good processability for supporting MOF. In this work, a series of wood aerogel porous carrier materials were prepared by corresponding chemical pretreatment and freeze-drying. The microstructure, specific surface area and thermal stability of different wood aerogels were investigated. Compared with other wood aerogels, balsa wood aerogels can maintain a complete honeycomb porous skeleton structure, its specific surface area reaches 43.87 m²/g, and shows ultra-light characteristics of low density (0.091 g/cm³) and excellent thermal stability. Herein, a novel ZIF-8@WA balsa wood aerogel adsorbent was successfully fabricated via in situ growth of ZIF-8 nanoparticles on balsa wood aerogel. The results indicated that dodecahedral ZIF-8 nanoparticles were uniformly decorated on the lumen surface within the balsa wood aerogel scaffold, and the introduction of ZIF-8 will significantly improve the adsorption capacity of balsa wood aerogel porous carrier. The composite displays highly removal efficiency up to 99.2% for methylene blue (MB) and the maximum adsorption capacity can reach 198.3 mg/g. The adsorption process accords with the pseudo-second-order kinetic model, which indicated that the adsorption process of ZIF-8@balsa wood aerogel was mainly controlled by the chemical adsorption mechanism. This work offers a new avenues for designing and constructing functionalized MOF@wood-derived composite that may boost its application in the field of environmental remediation.
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  Preparation of cationic resin-based ferromanganese cerium adsorbent and its performance in the removal of lead and chromium from water

  ZHANG Luohong, LIU Jianyu, LIU Caiqin, YANG Qiaoqiao, LI Qing

  Jorunal of Functional Materials. 2023, 54(5): 5133-5140. https://doi.org/10.3969/j.issn.1001-9731.2023.05.017

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  In order to obtain a high-performance adsorbent with high specificity and easy recovery for the removal of heavy metal ions Pb²⁺ and Cr⁶⁺, a resin-based iron-manganese cerium adsorbent (Fe-Mn-Ce@D001) was successfully prepared by loading iron-manganese cerium metal oxides (Fe-Mn-Ce) onto a strongly acidic cationic resin (D001). The performance of the adsorbent on the removal of Pb²⁺ and Cr⁶⁺ from water was investigated. The effects of different factors on the removal rate of Pb²⁺ and Cr⁶⁺ were examined, and the adsorption kinetics as well as the adsorption thermodynamics experiments were carried out to explore the adsorption law. The experimental results showed that the saturation adsorption capacities of Fe-Mn-Ce@D001 for Pb²⁺ and Cr⁶⁺ were 528.06 mg/g and 218.33 mg/g, respectively, at 298 K, pH=5 and 0.01 g dosage, which were better than the original resin D001. The Fe-Mn-Ce@D001 resin had higher adsorption selectivity for Pb²⁺ and Cr⁶⁺ than D001. The adsorption isothermal model of Fe-Mn-Ce@D001 for Pb²⁺ and Cr⁶⁺ is consistent with the Langmuir model. The adsorption kinetic behaviors were in good agreement with the quasi-primary and quasi-secondary kinetics.
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  Preparation of porous carbon materials from waste wood chips and the adsorption performance for methylene blue

  WU Qianfang, HUANG Caiyang, LI Saisai, LI Minghui, CHANG Bing

  Jorunal of Functional Materials. 2023, 54(5): 5141-5147. https://doi.org/10.3969/j.issn.1001-9731.2023.05.018

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  Porous carbon materials were prepared using waste biomass wood chips as carbon source and ferric nitrate nonahydrate (Fe(NO₃)₃·9H₂O) as catalyst precursor, via direct carbonization method, and the dye methylene blue (MB) adsorption performance with various carbonization temperatures and catalyst contents were investigated. XRD, SEM and BET were used to investigate the structure of as-prepared porous carbon materials. The results showed that the specific surface area of as-prepared porous carbon changed from 171.4 m²/g to 435.2 m²/g with the average pore diameter was between 2.197 nm to 10.63 nm. When the carbonization temperature is 800 ℃ and the catalyst dosage is 3 wt%, the sample prepared showed a good adsorption performance. The adsorption capacities of as-prepared porous carbon for methylene blue (MB) was 321.7 mg/g and the adsorption isotherms fit the Langmuir model and the adsorption kinetics follows the pseudo-second-order kinetic model.
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  Deter mination of hydrogen diffusivity inYb-doped CaZrO₃ proton conductor

  LEI Chonggui, ZHANG Fenglong, BAO Jinxiao, RUAN Fei, ZHOU Fen, GAO Jianquan, SONG Xiwen

  Jorunal of Functional Materials. 2023, 54(5): 5148-5153. https://doi.org/10.3969/j.issn.1001-9731.2023.05.019

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  In order to study the physicochemical properties of Yb-doped CaZrO₃ proton conductor, Yb-doped CaZrO₃ electrolyte was prepared by solid phase reaction at 1 873K for 10 h using analytical pure CaCO₃, ZrO₂ and Yb₂O₃ as raw materials. The impedance of the electrolyte in 5%H₂O-95%N₂ and 5%D₂O(heavy water)-95%N₂ atmospheres was measured by electrochemical workstation, and the resistance delay curves were obtained. The chemical diffusivity of hydrogen in electrolyte samples at different temperatures was determined by using self-designed mathematical algorithm and computer program. The results show that the chemical diffusivity of hydrogen in CaZr_0.85Yb_0.15O_3-α electrolyte is in the range of 1.24×10^-6~2.23×10^-6 cm²/s at the temperature of 1 073~1 373 K. However, the chemical diffusion coefficients of hydrogen in CaZr_0.8Yb_0.2O_3-αis between 1.47×10^-6~ 6.67×10^-6 cm²/s. The relationships between hydrogen diffusion coefficient and temperature are D_H=1.60×10^-5$e^{\frac{-22~499}{RT}}$andD_H=1.22×10^-3$e^{\frac{-59~509}{RT}}$, respectively. Moreover, the corresponding diffusion activation energy is 0.62 eV and 0.23 eV, respectively.
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  Preparation of Zr-ATP / HR-ATP composite adsorbent and its effect on simultaneous removal of nitrogen and phosphorus

  ZHANG Jianmin, HOU Dandan, LI Hongji

  Jorunal of Functional Materials. 2023, 54(5): 5154-5159. https://doi.org/10.3969/j.issn.1001-9731.2023.05.020

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  Zr-ATP/HR-ATP composite adsorbent for simultaneous removal of nitrogen and phosphorus was successfully prepared by modifying natural attapulgite with zirconium salt and acid heat treatment. The synthesized materials were characterized by XRD, SEM and FT-IR, and the effects of calcination temperature, the amount of binder and pore-forming agent on the formation of adsorbent were studied. The results show that 12 h Zr-ATP and HR-ATP1:1 was prepared with a composite preparation molding method and calcined at 600 °C for 2 h. The loss rate was 0.46%, compressive strength was 16N/piece, and the saturated adsorption capacity of nitrogen (10 mg/L) and phosphorus (20 mg/L) were 4.20 mg/g and 8.02 mg/g. The X-ray results showed that the phase composition of the adsorbent did not change. SEM images showed that Zr-ATP and HR-ATP adhered tightly and the composites were porous. The composite adsorbent can be applied to simultaneous removal of nitrogen and phosphorus in eutrophic water.
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  Preparation and properties of MWCNTs/SiC nanocomposites with broadband microwave absorption properties by click reaction

  MA Qianqian, JI Xiaoli, YUAN Haoze, LIANG Yingjie

  Jorunal of Functional Materials. 2023, 54(5): 5160-5169. https://doi.org/10.3969/j.issn.1001-9731.2023.05.021

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  MWCNTs/SiC nanocomposites were prepared by click reaction using resistive microwave absorbent MWCNTs as the matrix material and dielectric microwave absorbent SiC as the loss medium. XRD, XPS, TG, SEM and vector network analyzer were used to characterize the structure and test the microwave absorption performance of the composite. In addition, the influence of different feeding ratio on the microwave absorption properties of the composites was also discussed. The experimental results show that the MWCNTs/SiC binary nanocomposites were successfully prepared by clicking method. When the ratio of MWCNTs to SiC is 1:1, the minimum reflection loss (RL_min) of the MWCNTs/SiC binary nanocomposite at the thickness of 2.0 mm reaches -44.96 dB, and the minimum effective absorption bandwidth (RL_min< -10 dB) up to 5.04 GHz (from 12.66-17.93 GHz, covering 87.8% of the Ku band). MWCNTs/SiC binary nanocomposites can effectively absorb electromagnetic waves in the whole X-band, and the thickness range is 2.0~2.5 mm. Moreover, by adjusting the thickness of the absorption layer, almost all the electromagnetic wave of C, X and Ku bands can be effectively covered. Therefore, the composite materials with covalent bond between MWCNTs and SiC prepared by click reaction is a new method to be used as efficient microwave absorbing materials.
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  Preparation of SiO₂@Co(Ⅲ)-Salen as catalyst for the cycloaddition of CO₂ and propylene oxide

  YANG Jing, Miao Qingshan, ZHI Yunfei, SHAN Shaoyun, SU Hongying

  Jorunal of Functional Materials. 2023, 54(5): 5170-5177. https://doi.org/10.3969/j.issn.1001-9731.2023.05.022

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  CO₂ is inert and difficult to be fixed, recycled and utilized. One of the effective ways to solve this problem is to prepare cyclic carbonate by cycloaddition reaction between CO₂ and epoxides. M(Salen) catalyst is widely used in the cycloaddition reaction because of its simple synthesis and high catalytic activity. However, homogeneous M(Salen) catalyst is difficult to separate, recover and reuse from the product. Therefore, heterogeneous M(Salen) catalyst is an important research direction in this field. In this paper, SiO₂ nanoparticles prepared by sol-gel method was used as an inorganic carrier to immobilize Co(Ⅲ)-Salen complex. The supported catalyst (SiO₂@Co(Ⅲ)-Salen) was characterized by FT-IR, XRD, TGA and SEM, and effects of temperature, pressure, reaction time and catalyst dosage on the cycloaddition reaction of CO₂ and propylene oxide were investigated. The optimal reaction conditions were obtained as follows: reaction temperature of 70°C, reaction pressure of 1.5 MPa, reaction time 6 h, and the molar ratio of catalyst to propylene oxide was 1∶500. The yield of cyclic carbonate can reach to 93%. In addition, recycling experiments indicated that the catalytic efficiency reduces significantly after one cycle, which may be caused by the aggregations of SiO₂@Co(Ⅲ)-Salen nanocomposites during the centrifugation process.
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  Microstructure, crystallization behavior and soft magnetic properties of FeNiCoSiBCuNb alloy

  KANG Shujie, CHEN Zhe, ZHU Qianke, GUAN Libin, ZHANG Kewei

  Jorunal of Functional Materials. 2023, 54(5): 5178-5185. https://doi.org/10.3969/j.issn.1001-9731.2023.05.023

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  FeNi-based amorphous soft magnetic alloys have low coercivity and good magnetic frequency characteristics, and are very promising for applications, but they also face many problems. In this study, in order to improve the amorphous formation ability, thermal stability and soft magnetic properties of FeNi-based amorphous soft magnetic alloys, by partially replacing Ni elements with Co element, the effects of micro-structure, thermal stability, crystallization behavior and soft magnetic properties of (Fe₄₀Ni_40-xCo_xSi_9.5B_9.5Cu₁)_0.97Nb_0.03(x=2, 4, 6, 8) amorphous alloy strips were systematically studied by means of XRD, DSC, VSM, MOKE and other characterization methods. The research shows that FeNiSiBCuNb alloy system shows better amorphous forming ability and thermal stability performance with partial substitution of Co element. When x=4 at the optimal annealing temperature of 713 K, coercivity H_c is as low as 0.44 A/m, and the effective magnetic permeability μ_e (f=1 kHz) is 16290. At this time, the internal stress in the alloy is released, the free volume is reduced, and the structure is more uniform. The magneto crystalline anisotropy is reduced, the magnetic domain pinning point is reduced, a d=122 μm wide and uniform magnetic domain structure is formed. When x=6, the saturation magnetic induction intensity B_s can reach 1.15 T at the annealing temperature of 673 K. At this time, the magnetic exchange coupling between Co element and Fe element optimizes the average atomic magnetic moment of the alloy, showing good soft magnetic properties.
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  Study on thermal conductivity of graphene paperbased on the transient electrical heating technique

  GUO Jingtao, LI Bin, ZHANG Lijun, XU Jinbo, SHEN Fuhua, LIN Huan

  Jorunal of Functional Materials. 2023, 54(5): 5186-5191. https://doi.org/10.3969/j.issn.1001-9731.2023.05.024

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  Graphene materials have become one of the materials widely studied and applied in many fields for their excellent thermal, electrical, and mechanical properties. As the cause of deep space exploration continues to develop, the study of the performance of materials in low-temperature and even ultra-low-temperature environments is becoming increasingly important. In this paper, graphene paper was studied and analyzed in the temperature interval of 290 K~20 K using the transient electrical heating technique, and the effect of high temperature heating by electric current on the thermal conductivity of graphene paper was investigated. The thermal diffusion coefficient, thermal conductivity and volumetric specific heat capacity of graphene paper gradually decrease with decreasing temperature, and the resistance gradually increases with decreasing temperature, exhibiting strong non-metallic properties. After the structure of graphene paper is optimized by high temperature heating by electric current, the thermal conductivity of sample 1 increased from 2.31 W/(m·K) to 5.47 W/(m·K) and the thermal conductivity of sample 2 increased from 6.09 W/(m·K) to 22.21 W/(m·K) at 290 K. The thermal conductivity mechanism of phonon scattering from graphene paper was analyzed, and the Debye temperature and phonon mean free range of graphene paper were calculated using the thermal reffusivity model.
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  Effects of Fe/W co-doping on the structure and electrochemical performance of LiNiO₂ cathode materials

  LIU Xiaojiu, LI Donglin, REN Xunqiang, GAO Jianhang, ZHANG Long, LU Jicheng

  Jorunal of Functional Materials. 2023, 54(5): 5192-5197. https://doi.org/10.3969/j.issn.1001-9731.2023.05.025

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  In this paper, iron and tungsten co-doped lithium nickelate cathode materials (LiNi_0.97Fe_0.02W_0.01O₂) were synthesized by the sol-gel method, and the effect of double cation doping on the electrochemical performance of lithium nickelate cathode materials was studied. The results show that the co-doping of iron and tungsten can significantly reduce the Li/Ni cation mixing, inhibiting the phase transition from H2 to H3, improving cycle stability and reducing the voltage platform decay. At a current density of 200 mA/g, the capacity retention of the LiNi_0.97Fe_0.02W_0.01O₂ material after 100 cycles is 88.1%, while that of the LiNiO₂ material is only 62.9%. In addition, the LiNi_0.97Fe_0.02W_0.01O₂ material also has more excellent rate performance (the discharge specific capacity is 126.3 mAh/g at a current density of 4000 mA/g). Therefore, the double cation doping is beneficial to improve the electrochemical performance of the cobalt-free high nickel layered oxide cathode material.
Process & Technology
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  Preparation and durability of graphene toughened fly ash concrete

  CHEN Hui, CHEN Fangfang

  Jorunal of Functional Materials. 2023, 54(5): 5198-5203. https://doi.org/10.3969/j.issn.1001-9731.2023.05.026

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  In order to improve the low hydration activity and insufficient strength of fly ash concrete, graphene toughened fly ash concrete with excellent mechanical properties and durability was prepared by adding graphene to fly ash concrete. The influence of graphene content on mechanical properties, hydration reaction and wear resistance of fly ash concrete was analyzed. The results showed that the addition of graphene accelerated the hydration reaction, shortens the time of hydration induction period, increased the rate of hydration heat release during the induction period, reduced the time when the rate of hydration heat release reached the peak, increased the amount of hydration products in concrete, and improved the structural compactness of concrete. With the increase of graphene doping, the compressive strength, flexural strength and deflection of concrete increasd first and then decreased. The compressive strength and flexural strength of the concrete with 0.05 wt% of graphene content reached the maximum, which were 44.32 and 5.96 MPa, respectively, which were 12.89% and 10.78% higher than that of pure concrete. The maximum deflection value of 0.05 wt% graphene doped concrete was 7.1 mm, and the deformation resistance was improved. With the increase of graphene doping, the wear amount per unit area of concrete decreased first and then increased slightly, the concrete with 0.05wt% of graphene content had the minimum abrasion loss of 1.13 kg/m², and the abrasion resistance was the best.
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  Preparation of water reducing agent based onisoamylenol polyoxyethylene ether and its influence on concrete

  YUAN Lu, LENG Chaoqun

  Jorunal of Functional Materials. 2023, 54(5): 5204-5209. https://doi.org/10.3969/j.issn.1001-9731.2023.05.027

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  Isopentenol polyoxyethylene ether based polycarboxylate superplasticizer was synthesized by aqueous solution free radical copolymerization. The effects of acid ether ratio, amount of chain transfer agent, amount of reducing agent and dropping time on the dispersion of polycarboxylate superplasticizer were studied. The results showed that the best preparation process was that the acid ether ratio is 4.15, the molar ratio of mercaptopropionic acid and TPEG was 0.19, the molar ratio of VC and TPEG was 0.018, and the dropping time was 50 min. The prepared polycarboxylate superplasticizer could make the cement paste have the highest fluidity of 234 mm. The adaptation experiment of concrete showed that the saturated content of polycarboxylate superplasticizer prepared under the best process conditions was higher. When the content of water reducer was 0.3%, the water reduction rate could reach 32.7% and the compressive strength at 28 d was 55.7 MPa. It has broad application prospects in the configuration of high-strength concrete.
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  Effectof dendritic silver powder and surface treatment on the properties of conductive silver adhesives

  DU Zefan, PAN Mingxi, HUANG Hui, GAO Chao, LI Junpeng, LI wenlin

  Jorunal of Functional Materials. 2023, 54(5): 5210-5216. https://doi.org/10.3969/j.issn.1001-9731.2023.05.028

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  To tackle the low conductivity, unstable contact resistance, poor impact strength of conductive adhesive, this paper studies dendritic silver powders as conductive filler on the properties of conductive adhesive. The results show that compared with flake silver powder preparation of conductive adhesive, doping dendritic conductive silver glue show better electrical conductivity, whose volume resistivity decreased 0.8×10^-3 Ω·cm. On this basis, the effects of surface treatments such as oleic acid and KI on the electrical conductivity and mechanical properties of the conductive adhesive were explored, and the mechanism of improving the conductive property of the conductive adhesive was analyzed. The results showed that the types of surface treatment agents had a selective effect on the properties of conductive adhesives. The conductive adhesives treated with KI had better conductive properties, and the conductive adhesives with dendritic silver powder as filler showed the lowest resistance (0.9 Ω). The conductive adhesive treated with oleic acid showed better mechanical properties, and the conductive adhesive with flake silver powder as filler had better shear force (570 N), which provided technical support for the research and development of conductive adhesive products.
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  Preparation and properties of medium and low temperature dual-stage phase change polyurethane rigid foam

  GAO Ning, ZHANG Weili, TANG Ting, DU Jiaoli, SUN Bocun, LI Youbing, XIA Tian

  Jorunal of Functional Materials. 2023, 54(5): 5217-5222. https://doi.org/10.3969/j.issn.1001-9731.2023.05.029

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  Octadecane/expanded graphite and paraffin/expanded graphite shape-set phase change material precursors were prepared by vacuum adsorption. The medium and low-temperature dual-stage phase change polyurethane rigid foam was prepared by a one-step foa ming method. Cell structure, mechanical properties, phase change properties, thermal stability and temperature regulation capability of polyurethane rigid foams were investigated by SEM, DSC, TGA, universal testing machine and other test methods. The results showed that when the dual-stage phase change material was 95 wt%, the melting enthalpy and crystallization enthalpy of the medium-low temperature dual-stage phase-change polyurethane rigid foam reached 58.29 J/g and 53.69 J/g, respectively. Tow constant temperature platforms appeared at 26 ℃ and 60 ℃, respectively in the process of uniform heating and cooling, showing excellent temperature regulation and control ability.
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  Study on mechanical properties and frost resistance of recycled fly ash concrete for construction

  BU Narui, LIU Rui, FANG Wei, ZHAO HuiBin, BAI Runshan

  Jorunal of Functional Materials. 2023, 54(5): 5223-5229. https://doi.org/10.3969/j.issn.1001-9731.2023.05.030

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  Taking recycled concrete as the research object, fly ash was selected to replace cement. By adjusting the proportion of fly ash, high performance fly ash recycled concrete with different replacement rates (0, 10%, 30%, 50% and 70%) was prepared. The effects of different replacement rates of fly ash on the micro morphology, mechanical properties, flexural toughness and frost resistance of recycled concrete were studied. The results showed that there wasn't new hydration product after adding fly ash, but the hydration reaction rate was accelerated, the diffraction peak strength of Ca (OH)₂ was increased, and the fly ash particles were more closely combined with the hydration product gel, which enhanced the compactness of recycled concrete. When the replacement rate of fly ash was 50%, the structure of recycled concrete was the most dense. With the increase of replacement rate of fly ash, the compressive strength and flexural strength of recycled concrete increased first and then decreased. When the replacement rate of fly ash was 50%, the compressive strength and flexural strength at 28 d reached the maximum value, 44.2 and 5.96 MPa, respectively, and the deflection reached the maximum value of 7.7 mm, with the strongest deformation resistance. With the increase of freeze-thaw cycles, the surface peeling phenomenon of recycled concrete intensified. With the increase of replacement rate of fly ash, the mass loss of recycled concrete decreased first and then increased, and the relative dynamic elastic modulus increased first and then decreased. When the freeze-thaw cycle was 100 times and the replacement rate of fly ash was 50%, the minimum mass loss rate of recycled concrete was -0.09%, the maximum relative dynamic modulus of elasticity was 94.52%, and the frost resistance was the best.
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  Effect of fluoro-aluminum doping on crystal transition and equilibrium phase composition of C₂S

  HAO Shuai, LUO Guoping, LU Yuanyuan, CHAI Yifan, AN Shengli, ZHANG Bokang

  Jorunal of Functional Materials. 2023, 54(5): 5230-5236. https://doi.org/10.3969/j.issn.1001-9731.2023.05.031

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  In order to explore the influence of CaF₂ single mixing and CaF₂ and Al₂O₃ double mixing on the crystal transition of C₂S and the composition of the equilibrium phase, FactSage7.1 thermodynamic software was used to analyze the composition of the equilibrium phase at different temperatures. X-ray diffractometry (XRD) was used to detect the main mineral composition of C₂S sintered with CaF₂ and CaF₂ and Al₂O₃. The results show that the doping of CaF₂ can inhibit the transformation of C₂S crystal form from β-C₂S to γ-C₂S, and the inhibition effect is obvious when the doping amount of CaF₂ exceeds 2.5%. The addition of Al₂O₃ and 3%CaF₂ to C₂S can not only improve the kinetic conditions of the sample at high temperature, promote the solution of CaF₂ into C₂S, and inhibit the transformation of C₂S crystal form. It can also reduce the content of free calcium oxide (f-CaO) in the phase and improve the stability of the sample. At the same time, the generated CaAl₂O₄ phase, with nanocrystalline whisker, has a good bridging effect in aluminate cement, is helpful to enhance the toughness and tensile strength of the castable, and the generated Ca₂Al₂SiO₇, C₂AS) can be used as the main raw materials of glass and ceramics. Thermodynamic analysis shows that the initial synthesis temperature of C₂S is 840 ℃, and the doping of Al₂O₃ can improve the stable synthesis temperature of C₂S and promote the formation of C₂AS. Moreover, the stable temperature range of C₂AS phase and 2-C₂S-CAF₂ phase are determined, which are 700～1 420 ℃ and 700～830 ℃, respectively.