31 March 2019, Volume 50 Issue 3

    

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Focuses& Concerns(TheProjectofChongqingPressFundin 2018)
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  Electrochemical behavior of TiN nanoparticles as the cathode catalyst for lithium-oxygen batteries

  CHEN Mingzhu, WU Aimin, JIN Xiaozhe, QIN Zhenhai, HUANG Hao

  Journal of Functional Materials. 2019, 50(3): 3001-3007. https://doi.org/10.3969/j.issn.1001-9731.2019.03.001

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  The titanium nitride nanoparticles were prepared by DC arc-discharge method and served as the cathode catalyst for lithium-oxygen batteries. Various analytical methods, including X-ray diffraction, Transmission Electron Microscopy and etc., are used to characterize the microstructure and morphology of the TiN nanoparticles. The results show that the TiN nanoparticles had a cubic structure with good crystallinity. Its grain size varied from 30 to 60 nm. The rotating disk electrode (RDE) test shows that the TiN nanoparticles had dual catalytic properties of both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). As the cathode catalyst for the lithium-oxygen batteries, the TiN electrode delivered 3 037 mAh/g discharge specific capacity at a current density of 50 mA/g. The energy efficiency of the battery could maintain in 62% at a limited capacity of 500 mAh/g and a current density of 75 mA/g. Furthermore, XRD and SEM results of the cycled TiN electrode show that the main reaction of lithium-oxygen batteries was the formation and decomposition of lithium peroxide.
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  The study of chitooligomer modified by laccase/TEMPO system and its inhibitory effect on melanin

  ZHEN Xiaoqin, HAO Dongzhao, PEI Jicheng, ZHANG Fangdong, LIU Haitang,

  Journal of Functional Materials. 2019, 50(3): 3008-3013. https://doi.org/10.3969/j.issn.1001-9731.2019.03.002

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  The specific C-6 oxidation by laccase/TEMPO of chitooligomer (COS) and carboxylate chitooligomer (C-COS) was studied to obtain a safe and effective skin-whitening material. Nuclear magnetic resonance (¹³C NMR) was used to detect the C-COS structure. Besides, the inhibitory effects on melanin and tyrosinase inhibition kinetics studies of C-COS were also measured. The results showed that a peak appeared at 181.46×10^-6 in the ¹³C NMR spectrum of C-COS, corresponding to a CO carbon bond, which indicated that the C6 hydroxyl groups of COS were successfully oxidized into carboxyl groups by laccase/TEMPO system. The rate of inhibition of C-COS on melanin increased with increasing concentration of the samples within limits. When the content of carboxyl groups was 0.6451 mmol/g, the inhibitory effect of C-COS on melanin reached 52.92%. The kinetics research denoted that C-COS displayed a competitive inhibitory effect to the tyrosinase, which belonged to one of three reversible inhibition types. In this study, the inhibitory effect and mechanism of C-COS on melanin were explored and it would provide support for C-COS as a skin whitening agent in the future.
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  Effect of temperature and humidity control and the mechanism of new diatomite humidity-controlling materials

  HU Mingyu, LIU Zhangjun, FAN Caijin, LI Ye

  Journal of Functional Materials. 2019, 50(3): 3014-3019. https://doi.org/10.3969/j.issn.1001-9731.2019.03.003

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  The effect of indoortemperature and humidity control of new diatomite humidity-controlling materials was tested experimentally. Based on the absorption/desorption theory of materials, the modified mechanism and the humidity-controlling mechanism of the diatomite humidity-controlling materials were investigated based on the X-ray diffraction and environmental scanning electron microscope.The results show that the maximum moisture absorption of humidity-controlling materials for unit space was 2.51 g/m³ and the maximum moisture desorption was 1.76 g/m³ when the thickness of the inner surface coating was 0.5 mm under the sealed condition. The relative humidity could be maintained at 50%-60%. Under the condition of ventilation with the outside, the effect of the material on the humidity regulation was gradually weakened with the increase of the reserved gap while the temperature had 1-2 ℃ regulation. The diatomite humidity-controlling materials have nanoscale micropore characteristics and the associative hydroxyl effect of the inner wall of micropores. The diatomite humidity-controlling materials have excellent performance of absorption and desorption under the combination of capillary channel, chemical adsorption and surface physical adsorption.
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  Synthesis and properties of multifunctional nanomaterials

  YU Ting, GUANG Shanyi, XU Hongyao

  Journal of Functional Materials. 2019, 50(3): 3020-3023. https://doi.org/10.3969/j.issn.1001-9731.2019.03.004

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  A series of multifunctional nano solid materials including hydroxyl and epoxy groups were prepared by one-step method using AlCl₃ as catalyst through the reaction of epoxide-based silsesquioxane (E-POSS) with different kinds of amines. Its structure and properties are characterized by solid nuclear magnetic, elemental analysis, infrared spectroscopy and thermogravimetric analysis. The results show that the initial decomposition temperature is 271.4 ℃
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  Research on percolation characteristics of AgNWs/PVA conductive composites

  LU Pin, QU Zhaoming, WANG Qingguo, HE Changan, ZHAO Shiyang, CHENG Wei, WANG Yan

  Journal of Functional Materials. 2019, 50(3): 3024-3027. https://doi.org/10.3969/j.issn.1001-9731.2019.03.005

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  Silver nanowires (AgNWs) with aspect ratio of 240 were prepared by polyol method. Conductive composites were prepared with polyvinyl alcohol (PVA) as matrix and silver nanowires as conductive filler. Based on excluded volume theory and geometric phase transition theory, the percolation threshold and conductivity of AgNWs/PVA composites were predicted and analyzed. The results show that the percolation threshold obtained based on the excluded volume theory was 0.5816%, which was smaller than the actual percolation threshold value of AgNWs/PVA composites. The fitting value of percolation threshold was about 1.26%-1.31%, which was consistent with the actual percolation threshold value of AgNWs/PVA composites. The prediction on the conductivity of AgNWs/PVA composites was consistent with the test results. The prediction on the percolation threshold and conductivity of AgNWs/PVA composites are of great significance to the preparation and characterization of composites.
Review & Advance
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  Research progress of zinc manganese as anode electrode materials for lithium ion batteries

  ZHANG Tiange, ZHANG Zhuliu, LI Yanwei, YAO Jinhuan

  Journal of Functional Materials. 2019, 50(3): 3028-3032. https://doi.org/10.3969/j.issn.1001-9731.2019.03.006

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  Research progress of zinc manganese (ZnMn₂O₄) as anode materials for lithium ion batteries in recent years were reviewed. Several methods for improving the electrochemical performance of ZnMn₂O₄, such as construction of nanostructured electrode materials, surface coating on electrode materials, and fabricating composites with carbon-based materials were discussed emphatically. In addition, the research development of full batteries based on ZnMn₂O₄ anode was briefly introduced. Finally, the research focus in future was also prospected.
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  Recent advances of lanthanum-based perovskite oxides for supercapacitor: a review

  NAN Haoshan, LIU Miao, LI Yangen, HU Xiaoying, TIAN Hongwei

  Journal of Functional Materials. 2019, 50(3): 3033-3041. https://doi.org/10.3969/j.issn.1001-9731.2019.03.007

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  In this review, the research on perovskite supercapacitors based on oxygen anion intercalation at home and abroad in recent years was generalized and summarized. The anion-intercalation mechanism and the influences on electrochemical performances were summarized through the analysis of the past perovskite supercapacitor researches. Meanwhile the direction of the research of perovskite materials was put forward by combining the practical conditions for the application of supercapacitor to the vehicle power source with the summarization of the previous experimental design ideas, which provided some ideas for the design of perovskite materials of supercapacitors for the vehicle power source.
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  Research progress on the solar cell of copper indium aluminum selenium

  WANG Xiaoxia, XIE Huaqing, WU Zihua, ZHAI Han, ZHANG Jia

  Journal of Functional Materials. 2019, 50(3): 3042-3048. https://doi.org/10.3969/j.issn.1001-9731.2019.03.008

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  With the further improvement of conversion efficiency, the thin film solar cells of copper indium selenium (CIS) with chalcopyrite structure have attracted more and more attention. Compared with CIS material, copper indium aluminum selenium (CIAS) has a higher banding width and can achieve a considerable band gap with a smaller relative concentration than Ga alloy. In addition, it has the advantages of relatively low material price and high theoretical conversion rate, making it become a research hotspot of solar cell material at present. In this paper, the basic characteristics, preparation methods and application of CIAS in solar cells are reviewed, and the existing problems are summarized and analyzed.
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  Research progress of SLM forming nickel-based superalloys and the simulation

  QIU Dachuang, LI Duosheng, YE Yin, JIANG Wugui, KE Liming, QIN Guohua, QIN Qinghua, HE Junjie

  Journal of Functional Materials. 2019, 50(3): 3049-3058. https://doi.org/10.3969/j.issn.1001-9731.2019.03.009

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  Nickel-based superalloys are widely used in the manufacture of aerospace jet engines and the hottest end parts of various industrial gas turbines due to their high strength, good resistance to oxidation and gas corrosion under high temperature and high pressure conditions. In this paper, firstly, the domestic and international research status of 3D printing nickel-base superalloy parts and simulation by selective laser melting forming technology (SLM) were introduced, and then the mechanical properties and microstructure of nickel-base superalloys by SLM technology and the effects of post-treatment on their microstructure and properties were summerized. Secondly, the simulation of the additive manufacturing process was investigated, and its guiding significance to the process was introduced. Finally, the research hotspots in the field of SLM forming nickel-based superalloys and the application of numerical simulation in this field were further introduced.
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  Research status of pore control of porous activated carbon

  LIU Junke, SUN Zhang, FAN Lihua, XU Lijun

  Journal of Functional Materials. 2019, 50(3): 3059-3063. https://doi.org/10.3969/j.issn.1001-9731.2019.03.010

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  With the wide application of activated carbon in various fields, the pore structure is becoming more and more demanding, and the regulation of pore structure has become a research hotspot and a difficult point. The research progress of activated carbon pore size control technology at home and abroad was summarized, the research results of micropore, mesoporous and macroporous pore structure were introduced, and the advantages and disadvantages of different control techniques were pointed out. The template method and physics-the chemical combined activation method and catalytic activation method used to study the pore structure regulation were focused on, and the development of pore size control technology was prospected.
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  Preparation of surface imprinted polymers and its application in drug separation analysis

  HE Hongfang, LI Yanbin, YU Jiazhao, HU Yizhi

  Journal of Functional Materials. 2019, 50(3): 3064-3070. https://doi.org/10.3969/j.issn.1001-9731.2019.03.011

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  The surface molecular imprinting technique is to polymerize and establish the molecular recognition site on the outer layer or surface of the carrier. As a result, the surface molecularly imprinted polymers have the advantages of fast binding speed, strong identification selectivity, high binding capacity and improved efficiency of imprinted materials. In this paper, the principle of surface molecularly imprinted polymers and four preparation methods (sol-gel method, graft copolymerization method, sacrificial carrier method, polymerization plus membrane method, active controllable free radical polymerization) were briefly introduced. Four aspects of drug separation and analysis (traditional Chinese medicine extraction and separation; drug sensors; chiral drug resolution; the application) in drug release was reviewed.
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  Tuning of the catalytic performance of the catalysts for the catalytic combustion of volatile organic compounds with different preparation methods

  HU Yueyue, ZHANG Haidong, XIONG Kun, SHEN Yu, CHEN Jia, KONG Ying, ZHOU Yufeng, TANG Yuantao, LI Xiaojie

  Journal of Functional Materials. 2019, 50(3): 3071-3080. https://doi.org/10.3969/j.issn.1001-9731.2019.03.012

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  Volatile organic compounds (VOCs) can cause great harm to environment and human health. At present, the annual emission of VOCs in China has reached the same level as that of NO_x and SO₂ and already been classified as one of the major atmospheric pollutants. Among various VOCs elimination methods, catalytic combustion is regarded as a highly efficient and green VOCs elimination method because it can transform VOCs moleculars into H₂O and CO₂. Additionally, VOCs catalytic combustion is very fitful for the continous removal of the VOCs with low concentration in a closed space. The structure of active sites of VOCs catalytic combustion catalysts can be dramatically decided by their preparetion methods, and thus the different preparation methods can directly affect the catalytic performance of these catalysts. The preparation methods, such as impregnation method, sol-gel method, co-precipitation method, deposition-precipition, grafting method, hydrothermal synthesis method and microemulsion method, are most commonly used to prepare VOCs catalytic combustion catalysts. In the current paper, the difference among the preparation methods for VOCs catalytic combustion catalysts was focused on, in order to present the applicability of these preparation methods to the adjustment of the active sites structure and their effect on the catalytic performance of VOCs catalytic combustion catalysts. This work would provide a prospect, which was valuable for achieving highly efficient VOCs catalytic combustion catalysts, of the relationship between the different preparation methods and different catalyst structures along with different catalytic performance.
Research & Development
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  Study on magnetic field assisted electrodeposition of Ni-SiC nanocoatings on the surface of automobile cylinder liner

  ZHANG Zhaowei, DU Quanbin

  Journal of Functional Materials. 2019, 50(3): 3081-3084. https://doi.org/10.3969/j.issn.1001-9731.2019.03.013

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  In this paper, Ni-SiC nanocoatings were prepared by magnetic field assisted electrodeposition on the surface of cylinder liner. The surface structure and composition of Ni-SiC nanocoatings were studied by using scanning electron microscope (SEM), atomic force microscope (AFM), transmission electron microscope (TEM) and X-ray diffraction (XRD). When the content of SiC in the plating solution was 6 g/L, the aggregation tendency of SiC nanoparticles was the least, and the surface of the Ni-SiC nanocoating was smooth and compact. In addition, when the content of SiC nanoparticles was 6 g/L, the SiC particle size in the Ni-SiC nanocoating further decreased and distributed uniformly. XRD analysis showed that there were Ni grains and SiC particles in the coatings on the cylinder liner surface. When the content of SiC nanoparticles in the bath was 6 g/L, the average grain sizes of Ni and SiC particles in Ni-SiC nanocoating were 50.62 and 39.32 nm, respectively.
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  Direct synthesis of graphene on GaN surface and its application in GaN-LED

  FAN Xing, GUO Weiling, XIONG Fangzhu, DONG Yibo, WANG Le, FU Yafei, SUN Jie

  Journal of Functional Materials. 2019, 50(3): 3085-3089. https://doi.org/10.3969/j.issn.1001-9731.2019.03.014

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  Graphene features in its excellent photoelectric properties. Therefore, it can replace the traditional ITO material as a transparent conductive layer of GaN-LED. In order to realize the industrial production of the above applications, the direct preparation technology of graphene on GaN surface by hot-wall CVD was studied and the growth mechanism was explained. The results demonstrate that the optimal conditions for direct growth were growth temperature of 800 ℃, growth time of 60 min, and the intrinsic standoff ratio of CH₄ and H₂ are 1.59% and 3.17% respectively. Under this condition, multilayer graphene with obvious 2D peak was obtained. The low temperature growth of graphene on GaN surface was studied by cold-wall CVD. The corresponding GaN-LED was produced and its performance was tested. Through producing and testing of GaN-LEDs, it is found that the performance of the device was significantly reduced when the growth temperature was higher than 700 ℃. This research plays certain significant role in realizing the industrial application of graphene in LED.
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  Preparation of macroporous magnetic polymer carrier and study on immobilized sulfate reducing bacteria

  ZHANG Ting, LI Yun, FENG Xinhui, ZHOU Xiaolong

  Journal of Functional Materials. 2019, 50(3): 3090-3095. https://doi.org/10.3969/j.issn.1001-9731.2019.03.015

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  The oleic acid modified nano-Fe₃O₄ particles were prepared by chemical co-precipitation method. Using styrene as the continuous phase, water as the dispersed phase and Fe₃O₄ as the stabilizer, the magnetic macroporous polymer beads (MPMS) were synthesized by high internal phase emulsion template method, and the morphology, hydrophobicity, structure, thermal stability and magnetic properties of MPMS were characterized. Using the simulate sulfate wastewater, the desulfurization performance of immobilized SRB and free SRB was compared with each other. The results show that the macroporous material MPMS exhibited multi-level pore structure with abundant cells and pores. The saturation magnetization of MPMS was 2.043 A·m²/kg, and the saturation magnetization of MPMS after immobilized SRB was 0.188 A·m²/Kg. The polymer carrier retained a certain magnetic property after loading. SRB was immobilized on MPMS for about one week, and a stable biofilm could be formed. Comparing the desulfurization performance of immobilized SRB and free SRB, it can be concluded that the growth state of immobilized SRB was better than that of free SRB. When the sulfate concentration was 2000 mg/L and the desulfurization rate reached 2597.76 mg/(L·d).
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  Preparation and properties of lanthanum doping TiO₂/modified quartz sand composite photocatalyst

  CHEN Chao, LIU Xinwei, CHEN Yong

  Journal of Functional Materials. 2019, 50(3): 3096-3100. https://doi.org/10.3969/j.issn.1001-9731.2019.03.016

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  Lanthanum doping TiO₂/modified quartz sand composite photocatalyst was prepared by sol-gel method with quartz sand,Ti(OC₄H₉)₄ and La(NO₃)₃. Under the ultraviolet light the photocatalytic activity of the composite photocatalyst was evaluated by degradation of TNT. The results showed that the photocatalytic activities of lanthanum doping TiO₂/ modified quartz sand composite photocatalysts are superior.The photocatalystic activity of the La-TiO₂/ modified quartz sand composite photocatalyst calcined under 400 ℃ and doped with 1.5% of lanthanum was the best.
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  Synthesis, crystal structures and magnetic properties of rare earth polymers with 2, 5-dihydroxy-1, 4-terephthalic acid as ligand

  GU Xingye, CUI Ruiqi, LYU Wei, YANG Yan, SHE Shixiong

  Journal of Functional Materials. 2019, 50(3): 3101-3106. https://doi.org/10.3969/j.issn.1001-9731.2019.03.017

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  Two new types of complexes, ｛[Ln₂(H₂-DHBDC)₃(DMF)₄]｝_n(Ln=Dy(1),Tb(2)) were obtained by solvothermal reaction using 2,5-dihydroxy-1,4-terephthalic acid (H₄DHBDC) and Ln(NO₃)₃·6H₂O (Ln=Dy, Tb) as raw materials. The complexes were characterized by single crystal X-ray diffraction method, Fourier transform infrared spectroscopy, thermogravimetric analysis and powder X-ray diffraction method. The results show that the two complexes were completely isomorphous compound and crystallized in the triclinic system, space group P-1. The secondary building unit of the two compounds consist of two metal ions, three deprotonated ligands and four N, N-Dimethylformamide molecules. And three dimensional frame structure was further formed through the surrounding carboxylic acid groups with two different carboxylic bridging modes. Studies on the magnetic properties show that the complex exhibited slow magnetic relaxation behaviors.
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  The hydrogen storage property of Mg-Al alloy modified by the addition of the transition metal fluoride

  QING Peilin, LAN Zhiqiang, CAI Fangfang, HUANG Xiantun, LI Liujie

  Journal of Functional Materials. 2019, 50(3): 3107-3111. https://doi.org/10.3969/j.issn.1001-9731.2019.03.018

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  Mg-Al alloy was prepared by heat treatment combined with mechanical alloying, and the effect of transition metal fluoride on hydrogen storage performance of Mg-Al alloy was studied. It was found that the Mg-Al alloy was mainly composed of Mg₁₇Al₁₂, and the hydrogenation products of Mg₁₇Al₁₂ were MgH₂ and Al. Under the catalytic action of transition metal fluoride, the comprehensive hydrogen storage performance of Mg-Al alloy was obviously improved. The initial hydrogen absorption/desorption temperature of Mg-Al alloy was about 180 and 300 ℃. When TiF₃, VF₄ and ZrF₄ was added, those temperatures of the alloy decreased by 80, 30, 30 and 80, 80, 25 ℃, respectively. The results indicate that TiF₃ had the best catalytic effect on hydrogen storage of Mg-Al alloy. In particular, after the addition of TiF₃ to the Mg-Al alloy, the formation enthalpy of hydrogenation/dehydrogenation of the Mg-Al alloy hydride decreased from 59.9 and 84.2 kJ/mol to 45.8 and kJ/mol, respectively.
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  Preparation and structure of gelatin-chitosan-nano SiO₂ composite microcapsules

  HOU Xueyan, ZHAO Wenbo, ZHANG Yuqi, ZHANG Ensheng, WANG Xiangxiang, WANG Jijiang, ZHANG Yaoxia

  Journal of Functional Materials. 2019, 50(3): 3112-3117. https://doi.org/10.3969/j.issn.1001-9731.2019.03.019

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  Gelatin-chitosan nano-SiO₂ composite microcapsules were prepared by using paraffin and chitosan as core material and gelatin as shell materials. The influence of microcapsules on the properties and structure was investigated through the adjustment of oil-water ratio and the introdution of nano-SiO₂ into chitosan and gelatin, respectively. Microstructures such as microcapsule morphology were characterized by optical microscope and scanning electron microscope (SEM). The results showed that when the ratio of oil to water was 3:1, microcapsules were obtained with better properties and structure. Based on this, different sizes of nano-SiO₂ were introduced into chitosan and gelatin, respectively. The results indicated that the microcapsules without nano-SiO₂ had spherical structure and some were multi-core microcapsules. The porous structure of the microcapsule wall material appeared and the sphericity decreased when SiO₂ was introduced into chitosan or gelatin. With the increase of SiO₂ content, the microcapsule shell pore structure and heat loss rate increased. Whether the different size nano-SiO₂ was introduced into chitosan or gelatin, the microcapsule heat loss rates increased with the increasing SiO₂ content. The thermal loss rates of microcapsules after the introduction of larger size nano-SiO₂ were smaller than those of microcapsules with introduction of small size nano-SiO₂.
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  Process optimization of polylactic acid graft starch by in-situ solid phase polymerization

  HE Xiaoyu, XU Bingjie, LI Ping, WU Yiqiang, ZUO Yingfeng

  Journal of Functional Materials. 2019, 50(3): 3118-3122. https://doi.org/10.3969/j.issn.1001-9731.2019.03.020

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  In order to reduce the hydrophilic hydroxyl group in starch molecular chain and improve its interfacial compatibility with polylactic acid (PLA) resin, polylactic acid grafted starch (PLA-g-starch) with hydrophobic properties was prepared by in-situ solid-state polymerization with corn starch as raw material, lactic acid as graft monomer and stannous octoate as catalyst. The effects of monomer ratio, reaction temperature and reaction time on the grafting ratio of PLA-g-starch were studied by orthogonal test. The in-situ solid phase polymerization process was optimized by visual analysis and significance analysis. And the hydrophobicity, molecular weight, distribution and gelatinization viscosity were analyzed. The results showed that the optimum conditions for preparing PLA-g-starch were 25% of monomer ratio, 100 ℃ of reaction temperature and 2 h of reaction time. The grafting rate of PLA-g- starch was 20.78% under this technological condition. After in-situ solid phase grafting modification, the hydrophobic properties of starch were significantly improved, and the number-average molecular weight (M_n), weight-average molecular weight (M_w), Z-average molecular weight (M_z) and distribution index (DI) were increased in varying degrees, and the gelatinization viscosity was also increased accordingly.
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  Preparation and microstructure of TiNiNb alloy tube by hot isostatic pressing

  LIU Jun, LIU Junwei, MASAAKI Otsu, LU Shiqiang, WAN Jun

  Journal of Functional Materials. 2019, 50(3): 3123-3127. https://doi.org/10.3969/j.issn.1001-9731.2019.03.021

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  The TiNiNb prealloyed powder was prepared into a large-sized TiNiNb alloy tube (inner diameter of 15 mm, outer diameter of 35 mm, height of 100 mm) by hot isostatic pressing. The microstructure, mechanical properties and martensitic transformation behavior of the prepared TiNiNb alloy tube were investigated. The results show that when the hot isostatic pressure process parameters were 1 373 K, 110 MPa, holding temperature and pressure for3 h, the large-sized TiNiNb alloy tube with uniform microstructure could be prepared. The microstructure of TiNiNb alloy tube mainly included TiNi matrix phase, β-Nb phase and a small amount of (Ti,Nb)₂Ni phase. The hardness of TiNiNb alloy tubes prepared by hot isostatic pressing was higher than that of forged TiNiNb alloys. The martensitic transformation behaviors of TiNiNb alloy tubes were studied. It was found that the martensite phase transformation of the alloy was a two-step phase transformation, but not obvious.
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  Study on SME and mechanical properties of Ti_54.7Ni_30.7Cu_12.3Co_2.3 shape memory alloy

  JIANG Ye, KOU Shengzhong, YANG Huini, ZHAI Yiyue

  Journal of Functional Materials. 2019, 50(3): 3128-3134. https://doi.org/10.3969/j.issn.1001-9731.2019.03.022

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  Ti_54.7Ni_30.7Cu_12.3Co_2.3 shape memory alloy was rolled to predetermined thickness by two-roll hot -cold rolling mill, and conducted insulation treatment at 200 ℃, above the end temperature of martensite inversion, for 2 h. The recovery rates of samples were tested. The results indicate that the shape memory alloy showed the maximum recovery rate of 88.89% at the recovery temperature of 200 ℃ for 2 h when the pre-deformation amount was set as 4%. The recovery effect of the alloy fell off at this recovery temperature for 2 h when the pre-deformation amount was above 4%, which denoted that the shape memory alloy possessed maximum pre-deformation of roughly 4% at the recovery temperature of 200 ℃ for 2 h, and the alloy could not recover completely at this temperature for 2 h when pre-deformation was beyond limit. The shape memory alloy demonstrated maximum breaking strength (2 475 MPa), higher yield strength (1 586 MPa) and plastic strain rate (13.5%) with insulation heat treatment at the temperature of 465 ℃ for 30 min, which manifested the alloy presented optimal room temperature compression performance, and maximum promotion of microhardness with insulation heat treatment at the temperature of 465 ℃ for 30 min.
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  Preparation of Mn-Ce-Co composite oxide and its catalytic performance for combustion of chlorobenzene

  YAO Lin, LIU Zhiying, ZHU Lei, LI Xi, ZHANG Xiao, XU Yanhua

  Journal of Functional Materials. 2019, 50(3): 3135-3141. https://doi.org/10.3969/j.issn.1001-9731.2019.03.023

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  A series of Mn-Ce-Co composite oxide catalysts with different Mn contents were prepared by sol-gel method. The physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD), Brunauer Emmett Teller(BET), hydrogen temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS). The effect of Mn content and calcination temperature on the catalytic performance of the catalyst for the combustion of chlorobenzene was investigated. The results show that the addition of proper amount of Mn promotes the entry of Co into the CeO₂ cubic fluorite structure to form a Mn-Ce-Co-O ternary solid solution, which increases the specific surface area of the catalyst and the surface active oxygen species, thereby enhancing the oxidizing ability of the catalyst. In addition, a suitable calcination temperature causes the catalyst to change to an amorphous state, further increasing the specific surface area of the catalyst and the dispersion of the active component, thereby increasing the activity of the catalyst.
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  Magnetic study of double perovskite oxide Pr_(2-x)Tb_xCoMnO₆ (x=0.00,0.05,0.10)

  LI Xiaoxin, LIU Jiao, WANG Ting, TIAN Ye, YUN Huiqin, XING Ru, ZHAO Jianjun

  Journal of Functional Materials. 2019, 50(3): 3142-3146. https://doi.org/10.3969/j.issn.1001-9731.2019.03.024

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  A series of polycrystalline samples of perovskite cobalt oxide Pr_(2-x)Tb_xCoMnO₆ (x=0.00,0.05,0.10) were prepared by traditional high-temperature solid-state reaction. The XRD spectra, magnetization curves and variation curve of applied magnetic field (M-T, M-H) with temperature were measured to study the crystal structure and magnetic properties of the sample. The results show that the series of samples Pr_(2-x)Tb_xCoMnO₆ (x=0.00,0.05,0.10) exhibited good single phase. The spatial point group was P2₁/n. Due to the ferromagnetic super-exchange interaction between Co²⁺ and Mn⁴⁺ and a small amount of disordered ferromagnetic super-exchange interaction between Co³⁺ and Mn³⁺, two ferromagnetic transition points appeared in all the three samples. It is observed that there is a Griffiths-like phase in the series of samples. When temperature T was higher than T_G, it showed pure paramagnetic state. When temperature was between T_C2-T_G, it showed paramagnetic-ferromagnetic coexistence state. At low temperature (T＜T_N), the ferromagnetic state and the antiferromagnetic state competed with each other, and the behavior of spin cluster glass appeared. With the doping of Tb, T_C1, T_C2, T_N and T_G both decreased. In the measurement temperature range, with the decrease of temperature, the three samples have experienced the process of pure paramagnetic state, paramagnetic-ferromagnetic coexistence state and ferromagnetic-antiferromagnetic competition.
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  Effect of graphene on the salt water resistance of polyurethane/Al-Sm₂O₃ composite coating

  LYU Dandan, CHEN Yongting, ZHENG Jiandong, ZHANG Weigang

  Journal of Functional Materials. 2019, 50(3): 3147-3151. https://doi.org/10.3969/j.issn.1001-9731.2019.03.025

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  Graphene modified polyurethane(PU)/Al-Sm₂O₃ composite coating was prepared by scratch coating method using Al powders, Sm₂O₃, PU and graphene as functional pigments, adhesives and modification agent, respectively. The microstructure, functional properties and mechanical properties of modified and unmodified coatings after salt water corrosion for different time were systematically studied by using scanning electron microscopy, infrared emissivity tester, near-infrared spectroscopy and standard test methods for mechanical properties of coatings, and the causes were analyzed and discussed. The results show that the appearance and surface microstructure of the graphene modified coating after salt water corrosion for different time were basically intact, which showing good stability. Compared with the unmodified coating, the stability of the emissivity and reflectivity at 1.06 μm of the modified coating was significantly improved for the salt water corrosion. After salt water corrosion for 21 d, the emissivity only increased from 0.623 before corrosion to 0.638 after corrosion and the reflectivity at 1.06 μm decreased from 40.8% before corrosion to 31.9% after corrosion. After a long period of salt water corrosion, the modified coating had a lower emissivity and a lower reflectivity at 1.06 μm than the unmodified coating. At the same time, the modified coating could maintain more stable and excellent mechanical properties than the unmodified coating, which could better meet the requirements of practical engineering applications.
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  Adsorption performance of Cu²⁺ by loaded silica on zeolite synthesized from fly ash

  WANG Kai, QIU Guangming, JIA Xiaowei, CAI Jinli, CHEN Weiwei

  Journal of Functional Materials. 2019, 50(3): 3152-3158. https://doi.org/10.3969/j.issn.1001-9731.2019.03.026

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  The fly ash zeolite (FAZ) was prepared by hydrothermal method using fly ash (FA) as raw material. The fly ash zeolite loaded silica (FAZS) modified by Na₂SiO₃ was used as an adsorbent for Cu²⁺ wastewater treatment. FAZS was characterized by means of X-ray diffraction(XRD), scanning electron microscopy (SEM) and pore size distribution measurement by nitrogen adsorption(BET). The effects of Cu²⁺ adsorptions were investigated in different pH, FAZS dosage, adsorption time on the adsorption process when copper ions were used as adsorptive ions. The results showed that the synthesized FAZS had a strong potential for Cu²⁺ removal. Under 298 K, the adsorption on the FAZS reached equilibrium within 80 min, and the process followed pseudo-second-order kinetic. The adsorption of heavy metal ions in aqueous solution belonged to a chemisorption process. The highest adsorption capacity was approximately 127.4 mg/g at 298 K. The adsorption process conformed to Langmuir model. The thermodynamic data showed that the adsorption process was endothermic and spontaneous.
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  Study on preparation and retention and drainage aid performance of cationic carboxymethyl hydroxypropyl guar gum

  LIU Chuanjie, SHEN Ran, LI Nan, CHEN Wei

  Journal of Functional Materials. 2019, 50(3): 3159-3164. https://doi.org/10.3969/j.issn.1001-9731.2019.03.027

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  CCMHPG was prepared innovatively in one step using [AMIM]Ac as the reaction medium, and CTA, sodium chloroacetate and propylene oxide as modifiers. The effects of the three modifiers’ dosage, alkali dosage, reaction temperature and reaction time on the degree of substitution and viscosity of the product were studied to determine the optimum preparation conditions.The results showed that the water solubility of the reaction product was good, the viscosity of 1% aqueous solution was 1 072 mPa·s, the cationic substitution degree was 0.24, the carboxymethyl substitution degree was 0.41 and the hydroxypropyl substitution degree was 0.36. ¹H NMR showed that quaternary ammonium groups, carboxymethyl groups and hydroxypropyl groups were successfully grafted onto guar-gel molecules. SEM showed that wrinkles and scaly cracks were observed on the surface of the particles. The CCMHPG/PAC binary system was used for deinking pulp, the retention rate was 94.3% and the beating degree was 43°SR when adding 0.8% PAC and 0.04% CCMHPG.
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  Effects of sintering temperature on the phase composition and mechanical properties of the reaction sintered ferrosilicon nitride composites

  ZHANG Pengzhan, LIU Fei, ZHANG Jin, CHENG Renxiang, ZHANG Leng, LI Yukui

  Journal of Functional Materials. 2019, 50(3): 3165-3169. https://doi.org/10.3969/j.issn.1001-9731.2019.03.028

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  Si₃N₄-Fe₃Si composites were prepared by self-propagation method using ferrosilicon powder, Fe-Si₃N₄ powder and ilmenite powder as raw materials. The Si₃N₄-Fe₃Si composite sample was sintered at 1650, 1700, 1750 and 1800 ℃ under the nitrogen atmosphere. The effects of temperature on the density, porosity, microstructure, phase composition and mechanical properties of Si₃N₄-Fe₃Si composites were investigated by X-ray diffraction, infrared spectroscopy, scanning electron microscopy and Vickers hardness. The combustion process of a ferrosilicon-ilmenite mixture was explored by DSC. The research results showed that sintering temperature had a significant effect on the microstructure and mechanical properties of ferrosilicon nitride composites. With the increase of sintering temperature, the density and Vickers hardness of samples were increased, and the density of Si₃N₄-Fe₃Si was increased. But the flexural strength and fracture toughness increased with higher temperature and reached a maximum at 1 750 ℃. At 1 750 ℃, the density, Vickers hardness, flexural strength and fracture toughness of the samples were 3.33 g/cm³, 9.85 GPa, 331 MPa and 8.5 MPa·m^1/2, respectively. The bending strength was increased by 56%, the fracture toughness was increased by 102%, and good bending strength and fracture toughness were exhibited. At 1 750 ℃, main phases of Si₃N₄ - Fe₃Si sintered sample were the beta Si₃N₄, Y₂Si₂O₇, Fe₃Si and small amounts of Al₂O₃. The α-Si₃N₄ to β-Si₃N₄ disguised completely. Under the condition of high temperature, sintered stability of Fe₃Si was good.
Process& Technology
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  Thermodynamic analysis of chemical vapor deposition process for Co-Re alloy coating

  JING Yu, GONG Wei, WANG Enze

  Journal of Functional Materials. 2019, 50(3): 3170-3173. https://doi.org/10.3969/j.issn.1001-9731.2019.03.029

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  Co-Re alloy coating is a potential high temperature ablative material. In this paper, HSC Chemistry 6.0 software was used to simulate the chemical vapor deposition of Co-Re alloy coating. The results show that within the temperature range of 0-1 000 ℃, the ΔG was less than zero when selected H₂-Re₂(CO)₁₀ and H₂-Co(acac)₂ as reaction system. And, the content of Re and Co increased with the increase of deposition temperature. However, during the deposition process, C simple would produce. The optimum reaction temperature range for the preparation of Co-Re alloy coatings was 400-600 ℃.
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  Microstructure and properties of Ag-15Cu-10Au-2Ni alloy

  DONG Peng, REN Tao, QIN Guoyi, XU Siyong, GUO Jinxin

  Journal of Functional Materials. 2019, 50(3): 3174-3178. https://doi.org/10.3969/j.issn.1001-9731.2019.03.030

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  In this paper, Ag-15Cu-10Au-2Ni alloy has been fabricated by vacuum induction melting, and the plastic deformation and microstructure, mechanical and electrical properties after heat treatment were investigated. The results show that the Ag-15Cu-10Au-2Ni alloy was mainly composed of silver-rich phase and copper-rich phase, as well as Ni mostly existed in copper-rich phase. The significant strengthening effect could be observed obviously, while the hardness was 201 Hv (90 Hv as cast condition) and the tensile strength was 744 MPa for the 95% deformed alloy. For the specimen annealed at 650 ℃ for 1 h, the elongation reached 31.8% and the hardness was close to that of the cast condition. The resistivity of the alloy decreased at first and then increased with the increase of annealing temperature. The alloy annealed at 350 ℃ for 1 h had minimum resistivity (3.98 μΩ·cm) due to the emerge of order phase transition after annealing at low temperature region.
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  The preparation and application of modified sponge for efficient recovery of floating oil from water surface

  WANG Zhen, ZHAO Sulei, REN Ruipeng, LYU Yongkang

  Journal of Functional Materials. 2019, 50(3): 3179-3184. https://doi.org/10.3969/j.issn.1001-9731.2019.03.031

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  Polyurethane-graphene composite aerogel (GO-PUA) was made by introducing graphene to modify polyurethane sponge and characterized by water contact angle, FT-IR, XPS, SEM and adsorption ability. The result shows that GO-PUA had excellent compressibility, hydrophobicity and oil adsorption ability. Its adsorption capacity had not changed after repeating adsorption-extrusion processes 200 times. The recovery rate of adsorbed oil was 92.7% in each cycle. Therefore, it is feasible to efficiently recover oil spill from water through GO-PUA.
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  Preparation of TiO₂ electrochromic films by B³⁺ doping and its properties

  XU Zifang, DAI Yan, MA Jun, XIE Yihan

  Journal of Functional Materials. 2019, 50(3): 3185-3189. https://doi.org/10.3969/j.issn.1001-9731.2019.03.032

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  Using sol-gel method and dipping coating process, tetrabutyl titanate and glacial acetic acid were added to the solvent absolute ethanol, and boric acid, deionized water, nitric acid and other raw materials were added. B³⁺ doped TiO₂ film was successfully prepared on ITO glass. The optical properties and electrochromic properties of B³⁺ doped TiO₂ films were studied by means of TG-DTA, XRD, UV-Vis, SEM, and electrochemical workstation. The results show that the spectral control range of B³⁺ doped TiO₂ film was significantly improved, and as well as the electrochemical cycling stability of the film. When the volume fraction of B³⁺ was 9%, the electrochromic effect was the best.
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  Fabrication of “golf ball-like” porous PS microspheres via direct pore-forming breath figure technique

  ZHU Jiafeng, ZHU Yeming, YING Zhangyu, SUN Wei, YEW Maxine, REN Yong

  Journal of Functional Materials. 2019, 50(3): 3190-3194. https://doi.org/10.3969/j.issn.1001-9731.2019.03.033

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  A new surface pore-forming technique based on the traditional breath figure (BF) method was introduced. By performing such direct pore-forming breath figure technique, porous structure was successfully fabricated on the surface of polymeric microspheres. Facile pore formation on the surface of micro-sized three-dimensional objects was proved to be feasible by reforming the way BF method was performed. Specifically, uniform-sized microspheres of polystyrene (PS) were prepared by microfluidic method, and the “golf ball-like” PS microspheres with porous surface pattern were obtained by applying direct pore-forming breath figure technique with solvents under humid conditions. The pore-forming conditions of microspheres were systematically studied by adjusting the choice of solvents, the applied amount of solvents and the humidity. The direct pore-forming breath figure technique may span the range of geometric limitation on the BF substrate/object.
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  Bulk g-C₃N₄ exfoliated by NaOH under normal pressure and its photocatalytic performance

  LIU Xiaoyu, YANG Lirong, WU Xinyi, LI Mengchen, LIU Zhigang, FENG Xiaoxin

  Journal of Functional Materials. 2019, 50(3): 3195-3200. https://doi.org/10.3969/j.issn.1001-9731.2019.03.034

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  In order to obtain loose porous g-C₃N₄ with large specific surface area, bulk g-C₃N₄ was prepared by thermal polymerization and treated with different concentrations of NaOH solution under normal pressure. The samples were characterized by XRD, SEM, TEM, BET, PL, FT-IR and UV-Vis spectra, and the photocatalytic performance of degraded rhodamine B was tested. The results showed that the looseness of g-C₃N₄ increased with the increase of alkali concentration. The hydrogen bond between the layers of g-C₃N₄ treated with 0.3 mol/L NaOH was destroyed, and the structure in the layer was also damaged to some extent. The specific surface area increased significantly, which was 5.5 times that of bulk g-C₃N₄. The larger specific surface area effectively increased the adsorption performance of rhodamine B, while the recombination rate electrons and holes in g-C₃N₄ treated by 0.3 mol/L NaOH were reduced. The synergistic effect of adsorption and photocatalysis made the efficiency of photocatalytic degradation of rhodamine B by 0.3 mol/L NaOH treated g-C₃N₄ improve significantly compared to bulk g-C₃N₄.
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  Study on high and low temperature performance of SDYK modified rubber asphalt under aging effect

  ZHANG Qi, CHANG Chunqing, WANG Lan

  Journal of Functional Materials. 2019, 50(3): 3201-3206. https://doi.org/10.3969/j.issn.1001-9731.2019.03.035

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  The high temperature and low temperature performance of rubber modified asphalts with different SDYK (0.4%, 0.6%, 0.8%) before and after aging were studied by means of dynamic shear rheological test(DSR) and bending beam rheometer test(BBR). The results of DSR indicate that the SDYK improved the high temperature performances of rubber modified asphalts, in which the complex modulus G^* and modification rutting factor G^*/sin⁹δ increased and the phase angle δ decreased, and its high temperature rheological performance increased gradually with the increase of SDYK. The high temperature rheological performance of rubber modified asphalt of SDYK blending agent was 0.6%. The results of BBR indicate that SDYK reduced the low temperature performances of rubber modified asphalts, in which stiffness modulus S increased, creep speed m and the optimization decreased, and its low temperature rheological performance decreased gradually with the increase of SDYK. Comprehensively considering of the high and the low temperature performance, the mass fraction of 0.6% SDYK blending agent was the best blending amount.
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  Preparation and properties of starch expanded graphite phase change composites

  REN Wanwan, ZHANG Dong

  Journal of Functional Materials. 2019, 50(3): 3207-3214. https://doi.org/10.3969/j.issn.1001-9731.2019.03.036

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  In this paper, a method for preparing starch expanded graphite phase change composites using emulsification mechanism was described. Starch expanded graphite phase change composites were prepared by using paraffin, expanded graphite (EG) and starch as raw materials, and their properties were studied. The infrared spectrum showed that there was a physical bond among paraffin, EG and starch, and no new substances formed. The heat storage capacity of the composite phase change material decreased as the phase change material decreased. When the EG content was less than 8.4 ms%, the phase change heat gradually decreased, and when the EG amount was more than 8.4 ms%, the phase change heat sharply decreased. The thermal conductivity of the phase change composite increased with the increase of EG. When the EG content was less than 8.4 ms%, the thermal conductivity gradually increased. When the EG content was more than 8.4 ms%, the thermal conductivity increased less. When the amount of EG were 8.4 ms% and 11 ms%, scanning electron microscopy showed that the starch expanded graphite phase change composite consisted of many tiny capsule particles. The phase change material was stably encapsulated in the microcapsules to prevent leakage during the phase change. Considering its heat storage, thermal conductivity and stability, the optimum amount of EG in the composite phase change material was 8.4 ms%.
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  Phase regulation of annealing products by chemically prepared Nd-Fe-B particles

  GUAN Wei, GUO Yaozu, YOU Junhua, QU Yingdong, ZHOU Jifeng, YU Qiuci

  Journal of Functional Materials. 2019, 50(3): 3215-3220. https://doi.org/10.3969/j.issn.1001-9731.2019.03.037

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  Aiming to prepare Nd-Fe-B particles with excellent properties, based on the previous research on isochronous temperature annealing and isothermal annealing, the effects of temperature and time on the composition and percentage of Nd-Fe-B oxides were studied, respectively. Accordingly, the physical phase was adjusted. As a result, the optimal annealing temperature and time were determined. Nd-Fe-B nano particles with Nd₂Fe₁₄B as the main phase were prepared. Furthermore, the phase transition and magnetic properties were analyzed by X-ray diffractometer (XRD), Rietveld refinement fitting, scanning electron microscope (SEM), transmission electron microscope (TEM) and vibration sample magnetometer (VSM) detection. The results show that the Nd-Fe-B oxide mainly consisted of FeNdO₃, NdBO₃ and α-Fe. 750 ℃ and 5 h have been found to be the optimal annealing temperature and time, respectively. The Nd-Fe-B oxide obtained included 54.619%, FeNdO₃, 19.901% α-Fe, and 11.760% NdBO₃. Then this oxide was used to prepare Nd-Fe-B nanoparticles containing 88.457% of Nd₂Fe₁₄B and 11.543% of Fe₃B nanoparticles with the coercivity of 206.96 kA/m.