30 June 2020, Volume 51 Issue 6

    

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Focuses & Concerns
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  Study on microstructures and performances of Cu-18Pb-2Sn coating by laser cladding

  DENG Dewei^{1, 2}, ZHENG Haitong¹, MA Yushan³, CHANG Zhandong³, HUANG Zhiye²,

  Journal of Functional Materials. 2020, 51(6): 6001-6006. https://doi.org/10.3969/j.issn.1001-9731.2020.06.001

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  In this work, the microstructure and property improvements of Cu-18Pb-2Sn coatings by laser cladding under different processing parameters were investigated. Dye-penetrant inspection was used to detect the porosity in the cladding layer. Microstructures of the cladding layer were observed by optical microscopy (OM). Field-emission scanning electron microscopy (FE-SEM) was used to inspect the microstructure and component analysis. Microhardness of the cladding layer was measured by Vickers hardness tester. Wear resistance of the cladding layer was tested using high speed reciprocating friction testing machine. The results showed that there were a large number of holes in the copper alloy cladding layer. The number of holes in the cladding layers was relatively reduced with the gradual increase of laser power. It was observed that Pb phase presented reticular and dispersed punctate structures in Cu matrix. The variationof laser power did not have a significant effect on the hardness of the cladding layer, and the maximum average hardness of the cladding layer was around 77 HV. The friction and wear behavior of Cu alloy cladding layer was thepredominant abrasive wear with a small amount of adhesive wear. The average friction factors of the cladding layer were 0.370, 0.369, 0.368, and 0.360, respectively.
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  Influence of the adhesion and dielectric properties on the triboelectric performance of PDMS-xBaTiO₃ composite films

  DENG Chongwang, SUN Na, LIU Panlei, ZHAO Haoye, WANG Xiaoli

  Journal of Functional Materials. 2020, 51(6): 6007-6011. https://doi.org/10.3969/j.issn.1001-9731.2020.06.002

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  Aiming at the problem of limited practical application due to the low output performance of the triboelectricnanogenerator, PDMS-xBaTiO₃ composite films were prepared (x=0%, 10%, 15%, 20% and 30%)by adding different contents (wt.%) of BaTiO₃ nanoparticles to polydimethylsiloxane (PDMS). The influence of the surface adhesion properties and dielectric properties of the composite films on the triboelectric performance of the films was studied with the triboelectricnanogenerator of the contact and separation mode. The results showed that compared with PDMS film, the triboelectric performance of composite film with BaTiO₃was more than doubled. When the weight ratio of BaTiO₃was less than or equal to 15%, the triboelectric performance increased with the increment of the dielectric constant. When the weight ratio of BaTiO₃was 20%, the triboelectric performance of the composite film decreased because the surface adhesion properties reduced. When the weight ratio of BaTiO₃came to 30%, the triboelectric performance of the composite film decreasedfurther due to the agglomeration of BaTiO₃ nanoparticles.
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  N-doped porous carbon structure with NiCo metal particles as excellent dual-functional electrocatalyst for Zn air battery

  JI Zhongjun¹, LI Shengjuan¹, MA Zhanyu¹, CHU Xiaoman¹, LI Shiting¹, WU Mingxia²

  Journal of Functional Materials. 2020, 51(6): 6012-6021. https://doi.org/10.3969/j.issn.1001-9731.2020.06.003

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  An N-doped porous carbon structure supported with transition metal NiCo metal particles was prepared by using gas foaming technology and high-temperature rapid carbonization as an excellent dual-function electrocatalyst for Zn air batteries. SEM, XRD, specific surface area and pore size, and electrochemical workstation were used to characterize the morphology, phase, specific surface area and pore size, and electrochemical performance of the porous carbon loaded with NiCo metal particles, and finally assembled into a full battery for charge and discharge and stability test. The results show that when the mass ratio of nickel source and cobalt source was 1:1 and the carbonization temperature was 1 000 ℃ (Ni_1/2Co_1/2NCF-1000), the sample not only had a large specific surface area (1 023.85 m²/g), but also its ORR half-wave potential (0.24 V) was only 30 mV lower than the half-wave potential (0.21V) of the noble metal catalyst Pt/C, and the OER overpotential was 450mV, which was much smaller than the noble metal catalyst RuO₂ overpotential (480 mV). After the Ni_1/2Co_1/2NCF-1000 sample was assembled into a Zn air battery, its specific capacity and specific energy reach 827 mAh/g and 1013 Wh/kg, respectively, which were much larger than the specific capacity and specific energy of the precious metal catalyst Pt/C+RuO₂ (756 mAh/g and 871 Wh/kg).
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  Preparation and electrochemical performance of TiS₂ nanosheet porous anode material

  LUO Qian, HUANG Hao

  Journal of Functional Materials. 2020, 51(6): 6022-6026. https://doi.org/10.3969/j.issn.1001-9731.2020.06.004

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  In this paper, TiS₂ nanosheet porous structure was prepared via a facile two-step process. The precursor, TiH_1.924 nanoparticles, were prepared by DC arc-discharge plasma method in the mixed atmosphere of H₂ and Ar with titanium bulk as the titanium source, then blended with sublimated sulfur and heated to obtain the TiS₂ nanosheet porous structure. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman and so on. XRD and Raman results showed that the as-synthesized TiS₂ was fully crystallized. TEM and SEM results showed the nanosheet micro-morphology of the as-synthesized TiS₂. The nanosheets grew in any direction to form a porous structure. The TiS₂ nanosheet porous structure was used as the anode material of lithium-ion batteries to study its electrochemical lithium storage performance. The first charge-discharge specific capacities under the current density of 500 mA/g were 816.0 mAh/g and 1193.0 mAh/g, respectively. After 50 cycles, the capacity remained a capacity of 550 mAh/g. Even under a high current density of 5 A/g, it still maintained a capacity of 100 mAh/g, showing excellent cycle stability and charge-discharge reversibility.
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  Preparationof iron carbide/N-doped carbon nanoparticles and its electrochemical hydrogen evolution property

  YANG Sen¹, WANG Bing¹, XIONG Ying², CHEN Zhuo¹, WANG Guoxin¹

  Journal of Functional Materials. 2020, 51(6): 6027-6033. https://doi.org/10.3969/j.issn.1001-9731.2020.06.005

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  The development of environmental-friendly and low-cost synthesis methods for electrocatalysts of hydrogen evolution reaction (HER) is of great significance to renewable energy technologies. Here, Ferrocene, polyvinylpyrrolidone (PVP) and urea were used as raw materials to prepared iron carbide/nitrogen-doped carbon (Fe₃C/N-C) composite nanoparticles by simple hydrothermal method and annealing treatment at a certain temperature in this paper. The composition and morphology of the powders prepared under different pyrolysis temperature conditions and their electrocatalytic hydrogen evolution properties were emphatically compared. The results show that Fe₃C/N-C obtained under 800 ℃ had excellent electrocatalytic activity with a relatively low overpotential of only 211 mV at acertain current density of 10 mA/cm²and a small Tafel slope of only 137 mV/dec in alkaline electrolyte, which was superior to other contrastive catalysts. Moreover, Fe₃C/N-C also had good catalytic stability in alkaline electrolyte, which kept its activity at least 10 h. This work gives new insights about the regulation of transition metal carbide and nitrogen-doped carboncomplex construction, and provides technical support for the development of non-precious electrocatalysts which are efficient and inexpensive.
Review & Advance
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  Research progress on formation mechanism and inhibition methods of porosity and crack defects in laser cladding layer

  LYU Xiaoren¹, MA Xiaowei^{1, 2}, DONG Lihong², WANG Haidou²

  Journal of Functional Materials. 2020, 51(6): 6034-6043. https://doi.org/10.3969/j.issn.1001-9731.2020.06.006

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  The laser cladding technology used a high energy density laser as a heat source to clad the alloy layer on the surface of the base material to achieve metallurgical bonding between the cladding layer and the metal substrate. Since the laser cladding technology has high control precision, constant output power and no arc contact, the molten pool width and depth have good consistency. Furthermore, laser cladding is a promising metal surface modification technology, becauseof high efficiency, concentrated heat input, and small heat affected zone, etc.However, due to its faster cooling rate, defects are easily generated in the cladding layer. The defects in the cladding layer mainly include cracks, porosity, solid inclusions, unfused, and shape defects. Based on the research on defects in the cladding layer at home and abroad, it is found that cracks and porosity have the greatest influence on the cladding layer. Through simulations and experiments, the researchers discovered the form causes of porosity and cracks, and successfully reduced porosity and crack generation by changing processing techniques and powder types. This paper started from the two defects of porosity and cracks in the laser cladding layer. Firstly, the causes of the formation of porosity and the way of diffusion were summarized. The method of porosity inhibition was summarized from the processing technology and powder materials. Secondly, the causes of cracks were explained, several factors affecting the cracks were described, and the processing techniques for reducing cracks and some auxiliary measures were summarized. Finally, the unsolved problems in the current research of laser cladding defects were pointed out and the future development direction was prospected.
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  Research progress of N-isopropylacrylamide hydrogel nanoparticles in recognition of biomolecule

  KANG Lingling, ZHANG Herong, WANG Zhe, WANG Jialun, MENG Zihui, XUE Min

  Journal of Functional Materials. 2020, 51(6): 6044-6051. https://doi.org/10.3969/j.issn.1001-9731.2020.06.007

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  Hydrogel nanoparticles with a three-dimensional network structure of particle size 1~1 000 nm can be stably dispersed in water to form a colloid system. Due to their stimulus responsiveness, they are often referred to as intelligent hydrogel. Among the numerous types of intelligent hydrogel, N-isopropylacrylamide nanohydrogel with thermosensitivity was further studied both on its properties and its application recently. Based on its good biocompatibility, sensitive temperature response and a volume phase change along with the change of external temperature, it was widely applied in biomedical fields such as drug delivery systems, protein separations, medical diagnostics, biosensors, and biomaterials. In this study, the application research and development prospects of N-isopropylacrylamide-based nanohydrogel microspheres in protein recognition, drug delivery and release, and DNA separation were summarized.
Research & Development
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  Preparation and properties of nano-SiO₂/grapheme flame retardant epoxy resin composites

  TIAN Shikai

  Journal of Functional Materials. 2020, 51(6): 6052-6056. https://doi.org/10.3969/j.issn.1001-9731.2020.06.008

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  A new graphene based hybrid material (r-SGO), based on graphene oxide and nano SiO₂, was prepared by sol-gel and surface modification using epoxy resin (EP) as the base material, and nano SiO₂/ graphene flame retarded epoxy composite (r-SGOn/EP) was further prepared.By means of FT-IR, Raman and SEM, the chemical structure, micro morphology and interface bonding properties of the composite were analyzed.The effects of different content of r-SGO on the mechanical properties, thermal stability and flame retardancy of the composite were studied.The results showed that a large amount of SiO₂ were successfully adsorbed on the GO surface through covalent bond. r-SGO could be evenly dispersed in the epoxy matrixand there was a strong interaction between the epoxy resin and the nano material interface. The introduction of r-SGO increased the crosslinking density of the epoxy resin network, and improved the thermal stability of the composite.With the increased of r-SGO content, the comprehensive properties of r-SGOn/EP composite were improved.The glass transition temperature of r-SGO1.5/EP composite was 199 ℃, the tensile strength was 71 MPa, the thermal conductivity was 0.29 w/(m·K), the initial degradation temperature was 345 ℃, and the maximum degradation temperature was 453 ℃.The maximum mass loss rate of r-SGO1.5/EP was lower than that of r-SGO0.5/EP, and the thermal stability was improved.The LOI of r-SGO1.5/EP composite was 30.5%.r-SGOn/EP composite could be transformed into SiO₂nano sheet with high thermal oxidation stability and high aspect thickness ratio through combustion process.The sheet layer had good adsorption and barrier function, and could effectively play the role of flame retardant of layered structure.
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  Synthesis and characterization of all inorganic perovskite material CsPbX₃

  YU Man, ZHANG Yufan

  Journal of Functional Materials. 2020, 51(6): 6057-6061. https://doi.org/10.3969/j.issn.1001-9731.2020.06.009

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  All inorganic perovskite material CsPbX₃ (X=Br, I) was synthesized from pure inorganic substances CsX and PbX₂ (X=Br, I) by a recrystallization method at room temperature supersaturated solution. The optimal reaction conditions for the preparation of CsPbX₃ at room temperature with super-saturated solution recrystallization were determined. The best feeding ratios were CsX: PbX₂ molar ratio of 1∶1 and oleylamine and oleic acid volume ratio of 1∶1, and the best volume ratio of precursor to hexane for synthesis of CsPbBr₃ was 1∶25, while CsPbI₃ was 1∶10. The morphology and structure were characterized by SEM and XRD, respectively. The results of UV absorption spectrum showed that CsPbBr₃ perovskite showed strong absorption at 510 nm~680 nm, and CsPbI₃ absorption redshifted ~770 nm. The characteristic fluorescence emission peaks of CsPbBr₃ and CsPbI₃ were around 600 nm and 750 nm, respectively.
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  A study on the modification of spinel LiMn₂O₄ coated with MnO₂

  TAN Libo, ZHANG Hailang

  Journal of Functional Materials. 2020, 51(6): 6062-6066. https://doi.org/10.3969/j.issn.1001-9731.2020.06.010

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  In this paper, spinel LiMn₂O₄ material coated with MnO₂ was synthesized by a simple process, which had a certain commercial value. And the synthesized materials were analyzed by XRD, SEM and electrochemical performance test. The results show that the coating of MnO₂ could effectively inhibit the dissolution of Mn in Spinel LiMn₂O₄ during charging and discharging, and after 50 cycles at high temperature (55 ℃), the capacity retention was 94.2%, showing excellent cycling performance. In addition, EIS test shows that MnO₂ coating could effectively reduce the charge transfer impedance of the material.
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  Study on the synthesis of g-C₃N₄/BiVO₄ composite photocatalyst and its photocatalytic performances

  LI Jiake, LI Wentao, LIU Xin

  Journal of Functional Materials. 2020, 51(6): 6067-6071. https://doi.org/10.3969/j.issn.1001-9731.2020.06.011

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  g-C₃N₄ was prepared by pyrolysis of melamine, and g-C₃N₄/BiVO₄ composite photocatalyst was synthesized by hydrothermal synthesis using Bi(NO₃)₃·5H₂O, NH₄VO₃, HNO₃ and NH_3.H₂O as the main raw material. Phase composition, microstructure and photocatalytic performances of the synthesized samples were studied by XRD, SEM, BET and UV-Vis, etc. The photocatalytic performances of the synthesized samples were evaluated by degradation of methylene blue solution (10 mg/L). The results show that the photocatalytic performances of the composite photocatalyst g-C₃N₄/BiVO₄ were significantly increased than those of the pure BiVO₄ and g-C₃N₄. The composite photocatalyst g-C₃N₄/BiVO₄had the best photocatalytic activity when prepared under g-C₃N₄:BiVO₄ = 0.4:1 (mass ratio), hydrothermal temperature 140 ℃ and synthetic time 10 h. The degradation efficiency of methylene blue solution (10 mg/L) was 80.8% under high pressure mercury lamp irradiation for 150 min, and it was 47.5% and 22.1% higher than those of the pure BiVO₄ and g-C₃N₄ respectively at the same condition, and photocatalytic reaction accorded with the first order kinetic equation.
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  Mussel inspired interfacial modification of boron nitride/graphene nanoplatelets hybrid fillers for epoxy composites with improved thermal conductivity and electrical insulation properties

  JI Bingqiang^{1, 2}, WU Yeping², ZHU Chunhua², ZHANG Ping¹, ZHAO Xiuli^{1, 2}

  Journal of Functional Materials. 2020, 51(6): 6072-6077. https://doi.org/10.3969/j.issn.1001-9731.2020.06.012

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  With the rapid development of electronic technology, the intrinsic low thermal conductivity of polymer materials can no longer meet the heat dissipation requirements of modern electronic devices. Therefore, it is of great significance to improve the thermal conductivity of polymers and achieve efficient heat transfer. In this paper, a series of epoxy resins (EP/BN/mBN/m(BN/GNP)) thermally conductive insulating composites were prepared. The effects of the type and content of fillers on the thermal and electrical insulation properties of the composites were studied. The results show that BN and GNPs modified by polydopamine could be dispersed uniformly in epoxy resin. When 30 wt% m(BN/GNP)=1∶1 was added, the thermal conductivity of the composite material reached 0.61 W/(m·K), which was 238.9% higher than that of pure epoxy matrix. Meanwhile, the composite still maintained excellent insulation properties.
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  Preparationand photo-catalytic characteristics of the TiO₂/activated carbon composite material

  HU Xiaoyang, YAN Minghan, ZHAN Jianfeng

  Journal of Functional Materials. 2020, 51(6): 6078-6083. https://doi.org/10.3969/j.issn.1001-9731.2020.06.013

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  The objective of this work was to investigate the impact of the sorption and photo-catalytic hybrid mechanisms over the photo catalytic properties of the prepared TiO₂/activated carbon composites. A photo catalytic composite material made from TiO₂ and activated carbon (AC) was prepared based upon high temperature hydrothermal procedures. The TiO₂/ AC composite was characterized by XRD, SEM, EDS and FT-IR. The impacts of hydrothermal reaction temperature over the following composite variables, namely, the crystal phase structure, micro-morphological properties and photo catalytic characteristics for methyl orange solutions under ultraviolet light radiation, were analyzed. As the hydrothermal temperature increased, the powder dimensions of the TiO₂particles deposited on AC surface increased accordingly, making the TiO₂deposition states over the surface well distributed. After the UV radiation for 180 min, the decomposition rates of methyl orange (20 mg/L) triggered by TiO₂/AC composite were well above 80%, indicating that the increasing effectiveness of methyl orange decomposition could be achieved through the TiO₂/AC coordinated absorption-photo catalytic effect.
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  Influences of nanosilica on vulcanization behavior and physical foaming behavior of micro-crosslinked EPDM

  ZHENG Hao^{1, 2, 3}, ZHAI Wentao³, BAO Jingbiao¹, ZHENG Wenge²

  Journal of Functional Materials. 2020, 51(6): 6084-6090. https://doi.org/10.3969/j.issn.1001-9731.2020.06.014

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  In this study, micro-crosslinked EPDM nanocomposite foams were prepared via a solid state foaming process with using compressed CO₂ as blowing agent. Nano-silica was added as a nucleating agent and BIPB was selected as a crosslink agent. The influences of nanoparticle addition on the vulcanization kinetics and foaming behavior of EPDM were studied. It is observed that nano-silica could accelerate the cross-linking rate but reduced the crosslink degree of EPDM. Moreover, presence of nano-silica improved the foamability of EPDM, characterized by the increased foam expansion up to 10.3 times and increased cell density from 10⁵ to 10⁸ cells/cm³. Meanwhile, presence of nano-silica improved the tensile properties of the as-prepared EPDM foams, characterized by the increased tensile strength from 0.75 MPa to 1.65 MPa and increased elongation at break from 225% to 423%. At higher loading of 5 phr, however, nano-silica presented negative effect on the foaming of EPDM and the tensile properties of the prepared EPDM foam. It was interesting to find that the vulcanized EPDM/SiO₂ nanocomposites possessed the micro-crosslinked structure, and which ensured that the fabricated EPDM/SiO₂ foams could be melt-recycled and could be foamed again by blown with CO₂.
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  The effect of C content on microstructure, hardness and resistivity of interstitial solid solution Cu-C thin films

  FU Yanpeng¹, SHANG Hailong², MA Bingyang², LI Rongbin^{1, 2, 3}, RAN zhun³

  Journal of Functional Materials. 2020, 51(6): 6091-6095. https://doi.org/10.3969/j.issn.1001-9731.2020.06.015

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  A series of Cu-C films with different C contents were prepared by magnetron co-sputtering of Cu and C targets. The microstructure, mechanical properties and resistance of the thin films were characterized through a combination of techniques, including X-ray diffraction, transmission electron microscopy, nano-indentation and four-point probe resistance meter. Results show that the Cu-C films formed supersaturated interstitial solid solution due to high dispersibility of vapor particles and non-equilibrium growth of the film in co-sputtering process. The film grains were refined due to dramatic lattice distortion, which increased the film hardness. The films hardness increased with C content increasing. As the C content was 8.2 at.%, the hardness of Cu-C film increased from 2.8 GPa to 4.3 GPa compared with pure Cu film. The film resistivity increased linearly with the C content. Cu lattice distortion hindered the electron migration with 8.2 at.% Cu-C film, and resistivity of the film increased from 2.0 μΩ·cm to 10.7 μΩ·cm compared to pure Cu-C film. The results show that C atoms had better conductivity compared with the other metal atoms added to the Cu-based film.
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  Experimental study on solid electrolyte MgZrNi_1.5(PO₄)₃ of magnesium ion battery

  ZHANG Yunchen¹, JIANG Jinhe¹, MA Xinxin², LIU Fangwang²

  Journal of Functional Materials. 2020, 51(6): 6096-6099. https://doi.org/10.3969/j.issn.1001-9731.2020.06.016

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  The stable structure liquid-phase electrolyte which is suitable for multiple charge and discharge has not been found so far. The development and application of magnesium ion battery are seriously limited^[1-2]. If there is a good solid electrolyte^[2-3] to replace the limited liquid electrolyte, the development of magnesium ion battery will rise one dimension. In this study, the solid electrolyte MgZrNi_1.5(PO₄)₃ of magnesium ion battery was synthesized by sol-gel method and replacing part of Zr⁴⁺ in MgZrNi_1.5(PO₄)₃ with Ni²⁺. By adding nickel ion, the conductivity and capacity of the original solid electrolyte could be increased. It was proved by experiments that after the sol-gel method and ion substitution were used, the conductivity of the prepared solid electrolyte was higher than that of the original solid electrolyte. The conductivity of the synthesized sample was 6.2×10^-6 S/cm at 810 ℃, and compared with the solid electrolyte Mg_0.5Zr₂(PO₄)₃, the conductivity of MgZrNi_1.5(PO₄)₃ was obviously increased. It provided an important reference for the development of solid electrolyte of magnesium ion battery in the future.
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  Molecular dynamics simulation of density variation in compact region of graphene/polyethylene composites

  WEI Qi¹, HUANG Jun¹, HUANG Lixin^{1, 2}

  Journal of Functional Materials. 2020, 51(6): 6100-6107. https://doi.org/10.3969/j.issn.1001-9731.2020.06.017

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  The properties of graphene reinforced composites are affected by many factors, such as bonding interface, compact region and so on. If these factors are not taken into account, the analysis of graphene reinforced composites may lead to errors in results. Molecular dynamics simulationwas used to analyze the density variationin compact region of graphene/polyethylene composites.The molecular dynamics of polyethylene cell was calculated firstly. The obtained density of polyethylene cell was 0.95 g/cm³and was in agreement with the actual density of polyethylene. And then the procedures of polyethylene’s simulation were applied to the molecular dynamics simulation of graphene/polyethylene composites. The density variationtrend of compact regioncould be obtained by slicing.The simulationresults showed that a compact phenomenon appearedin the polyethylene matrix of graphene/polyethylene composites by the effect of the graphene, so that there were symmetrical compact regions on both sides of graphene. Besides, there wasVan der Waals(vdW)gap between graphene and polyethylene and its thickness was 0.28 nm. In compact region, the density of the polyethylene far away from the graphene was 0.95 g/cm³ and in agreement withthe density of the polyethylene under normal temperature and pressure. The peak density of the polyethylene appeared in the place which wasnear the graphene and its value was 1.5 g/cm³. The peak density was 1.6 times of that of the polyethylene density under normal temperature and pressure.
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  Study on sealant for rail insulation repair

  ZHAO Xizhen^{1, 2}, ZHANG Jicheng³

  Journal of Functional Materials. 2020, 51(6): 6108-6113. https://doi.org/10.3969/j.issn.1001-9731.2020.06.018

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  In order to solve the problem of rail insulation failure caused by the iron scraps adsorbed on the wheel set falling into the rail gap when the train passing through the rail gap insulation causes vibrate, taking the silane-modified polyurethane pre-polymers as base gum and the gas phase method of white carbon black compound nanometer calcium carbonate as a reinforcing filler, by studying the base glue, packing, plasticizer, hydrocarbon remover, coupling agent and the dosage of catalyst on the properties of gel, gel formula was optimized and the preparation of a kind of fast curing silane-modified polyurethane pre-polymers insulating sealant. The best formula was: 100 parts silane-modified polyurethane pre-polymer, 200 parts nanometer calcium carbonate, 20 parts vapor phase silica, 60 parts PPG2000, 3 parts A-171, 3 parts A-1120, 1 part organo-tin catalyst, 1 part antioxidant, and 40 parts diluent. After testing, under 25 ℃, the surface dry time was 5 minutes, the tensile strength of the test piece was 2.6 MPa and the tensile expansion rate was 379%. The film was dense and uniform after gluing, with good thermal stability and weatherability, which metthe technical requirements of rail gap insulation repair.
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  Study on the preparation and performance of cement-based grouting material with quick setting and water resistance

  ZHAO Qing, ZHANG Yixia, ZHAO Jun, LIANG Jiajie

  Journal of Functional Materials. 2020, 51(6): 6114-6119. https://doi.org/10.3969/j.issn.1001-9731.2020.06.019

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  As a grouting material, ordinary Portland cement (PO) has the defects of long gel time, no resistance to water dispersion and low early strength, and can not meet the requirements of grouting.In view of the shortage of ordinary Portland cement (PO), based on the combination ofsulphoaluminate cement (SAC), high efficient binder (hydroxypropyl methylcellulose, HPMC) and water, which were added formodification, a rapid setting and water-resistant dispersive cement-based grouting material was prepared. The fluidity, gel time, compressive strength and water dispersibility of grouting material were studied by means of electronic universal testing machine, SEM and XRD. The results showed that with the increased of HPMC dosage, the fluidity of grouting material decreased, the gel time prolonged, but the water dispersibility increased and the compressive strength decreased. With the increasing of water binder ratio, the fluidity of grouting material increased, gel time prolonged, water dispersion resistance become worse, and compressive strength decreased. The quality ratio of PO and SAC had little effect on the composition and surface morphology of the hydration products of grouting materials. When the mass ratio of PO and SAC was 6∶4, the water cement ratio was 0.45, and the HPMC dosage was 1.5‰ of the grouting material quality, it was the optimal ratio of the grouting material. At this time, the fluidity of the prepared grouting material was 150 mm, and the initial setting and final setting time were 23 and 30 min respectively, which could not only ensure the full diffusion and dense filling of the grouting material within the design grouting range, but also could timely final set, develop strength, play a reinforcing role, and have good water resistance and dispersion performance.
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  Study on electrophoretic deposition of bismuth oxide coatings

  WANG Xiaojing, BIAN Chaoqun

  Journal of Functional Materials. 2020, 51(6): 6120-6126. https://doi.org/10.3969/j.issn.1001-9731.2020.06.020

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  Electrophoretic deposition (EPD), a low cost, one-step and flexible method, has been successfully developed to prepare bismuth oxide (Bi₂O₃) coatings. Therefore, Bi₂O₃ coatings were prepared by cathodic electrophoretic deposition and anodic electrophoretic deposition respectively. The effects of different amounts of dispersant polyethyleneimine (PEI) and dodecyl trimethyl ammonium bromide (DTAB) on the dispersibility of Bi₂O₃ suspension were investigated by UV-visible spectrophotometry. XRD, UV-Vis, SEM and EDS were used to characterize the Bi₂O₃ coating. The deposition mechanism and deposition kinetics of Bi₂O₃ coatings deposited on stainless steel mesh by cathodic EPD and on graphite sheet by anodic EPD were firstly investigated. The stable suspensions with a concentration of 1 g/L of Bi₂O₃ particles consisted of ethanol absolute and PEI, ethanol absolute and DTAB correspondently. The results show that when the amount of PEI was 0.4 mL, DTAB was 0.1 g, the dispersion of Bi₂O₃ suspensions was the best. The addition of surfactants would greatly increase the amount of Bi₂O₃ deposition, and the charged groups or ions ionized by the surfactant were adsorbed on the surface of the Bi₂O₃ particles, which would increase the number of charges on the particles and change the charged state of the particles, thereby changing the electrophoretic deposition behavior of Bi₂O₃ particles.
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  Effect of new coupling agent modified fumed silica on the properties of natural rubber

  MEI Junfei, YU Han, LIAO Jianhe, ZHAO Yanfang, CHEN Yongping

  Journal of Functional Materials. 2020, 51(6): 6127-6132. https://doi.org/10.3969/j.issn.1001-9731.2020.06.021

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  Abstract: Coupling agents KH560-oleamine (KH560-OA), KH560-octadecylamine (KH560-ODA), bis-(γ-triethoxysilylpropyl) tetrasulfide (Si69) and γ-(methacryloyloxy) propyltrimethoxysilane (KH570) modified fumed silica were prepared in ethanol/water solution, and then modified silica/NR composites were prepared with different silane coupling agents via mechanical blending. The effects of various modified silica on various properties of NR were investigated. The research results showed that the modification effect of four coupling agents on silica was obvious, and the vulcanization performance, mechanical performance and processing performance were improved a lot. Comprehensively, the self-made coupling agent KH560-OA had the best modification effect and showed the highest tensile strength (33.34 MPa) and the lowest wear volume (0.203 cm³), and the comprehensive dynamic mechanical performance was best.
Process & Technology
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  Synthesis andcharacterization of dendritic mesoporous silica nanospheres (DMSNs) with enlarged pore size

  HAN Yu¹, WANG Yabin¹, DING Xiuping², ZHANG Yantu¹

  Journal of Functional Materials. 2020, 51(6): 6133-6137. https://doi.org/10.3969/j.issn.1001-9731.2020.06.022

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  Monodisperse dendritic mesoporous silica nanospheres (DMSNs) with enlarged pore size and diameter were synthesized by stearyltrimethyl ammonium bromide which is a ultra-long carbon chain surfactant and acts as template agent. The as-prepared DMSNs-C₁₈ were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Fourie tansform infrared spectroscopy (FT-IR), N₂ adsorption-desorption isotherms to reveal its morphology, crystal texture, chemical compositions, pore volume and specific surface area. The results indicate that the particle and pore sizes of DMSNs-C₁₈ greatly increase, compared with DMSNs fabricated with conventional cetlytrimethyl ammonium bromide as emplate agent (noted as DMSNs-C₁₆). The reason could be that the mutual repulsive force of surfactant increasea with the growth of carbon chain which affects microemulsion formation, giving rise to structural difference.
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  Preparation and mechanical properties of powder metallurgy Ta-Ru alloy

  GUO Shuaidong^{1, 2, 3}, LU Zhi^{1, 2, 3}, WANG Guangxin^{1, 2, 3}, LI Lei⁴

  Journal of Functional Materials. 2020, 51(6): 6138-6142. https://doi.org/10.3969/j.issn.1001-9731.2020.06.023

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  In this paper, high purity Ta-Ru alloy was prepared by powder metallurgy hot press sintering. Tantalum ruthenium powder with high purity was mixed in different composition ratio on planetary ball mill, and hot pressed for 3 h at 1 700 ℃ and 20 MPa in vacuum hot pressing sintering furnace. The effect of different Ru contents on the phase composition, microstructure and mechanical properties of Ta-Ru alloys were investigated by XRD, SEM, EDS, tensile strength test and other analytical methods. The results show that, with increasing Ru content, several intermetallic compounds such as TaRu, Ta₃Ru, and TaRu₄ were successively formed in the alloy. The density and tensile strength of the alloy increased gradually, and the microhardness increased first and then decreased. The fracture mode changed from cleavage fracture to intergranular fracture and ductile fracture.
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  Study on bond strength of silica fume reinforced hybrid fiber cement based grouting materialand old concrete

  QIAO Qinghao¹, LI Zhihua¹, ZHANG Cong^{1, 2, 3}

  Journal of Functional Materials. 2020, 51(6): 6143-6149. https://doi.org/10.3969/j.issn.1001-9731.2020.06.024

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  Through the four-factor and four-level orthogonal experiment, the bond strengthof silica fume reinforced hybrid fiber cement based grouting material and old concrete was studied. The silica fume content, steel fiber type, steel fiber content and PVA fiber content were selected as the research factors, and the corresponding levels were set. Through the double-sided shear test and splitting tensile testofbonding test blocks, the effects of the above factors and their corresponding levels on the bond strength were analyzed by the range analysis. The results showed that when the content of silica fume was 9%, the content of end-hook steel fiber with a length of 35mm was 1.2%, and the content of PVA fiber was0.5%, the bond strength was remarkable. Based on the results of orthogonal experiment, the effects of fiber on the interfacial shear characteristics and split tension failure patterns of cementbased grouting materialand old concrete were studied through four comparative experiments.The results showed that the shear deformation and splitting tensile strength of bonding test blocks were significantly improved when the mixing content of end-hook steel fiberwith a length of 35mm and PVA fiber was 1.2% and 0.5%respectively, showing strong bond performance.
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  Effect of mineral powder on rheological properties of asphalt mastic and microscopic analysis

  LIN Mei, LI Ping, NIAN Tengfei, CHEN Longjian

  Journal of Functional Materials. 2020, 51(6): 6150-6157. https://doi.org/10.3969/j.issn.1001-9731.2020.06.025

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  In order to explore the influence of mineral powder on the rheological properties of asphalt mastic, the rheological tests of asphalt mastics composed of four kinds of mineral powders were carried out under different loading modes by dynamic shear rheometer. The effects of filler-asphalt ratios, temperatures and loads frequency on the high- and low-temperature rheological parameters of asphalt mastic were analyzed. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to investigate the microscopic morphology of mineral powder and mastic. The results showed that the granite had the strongest synergistic effect on the mastic, and the limestone asphalt mastic had the best high- and low-temperature performance. As the filler-asphalt ratio increased, the complex shear modulus of the asphalt mastic increased, but the phase angle had little changes. The best filler-asphalt ratio for the four types of mastic was recommended to be 1.2. Under the optimal filler-asphalt ratio, the micro-interface bonding of the mastic was the best. The research results could provide technical guidance and theoretical support for the application of different kinds of fillers on asphalt pavement.
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  Study on photocatalytic performance of natural attapulgite and optimization of response surface method

  ZHANG Jianmin, LIU Yuqi, Li Hongji, LI Keli

  Journal of Functional Materials. 2020, 51(6): 6158-6163. https://doi.org/10.3969/j.issn.1001-9731.2020.06.026

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  Natural attapulgite was used to decrease the solution of methylene blue under ultraviolet irradiation to explore its photocatalysis and optimize. The functional group structure of natural attapulgite was characterized by XPS and UV-Vis, and then the decolorization rate of methylene blue solution was taken as the response value. Based on the single-factor experiment, the response surface method was used to further explore the photocatalytic influencing factors of natural attapulgite and determine the best experimental conditions. The experimental results showed that there was a small amount of 6-coordination Ti and anatase TiO₂ on the surface of natural attapulgite, and the photocatalytic performance was significant. Single factor initial concentration and addition amount, secondary term addition amount, interaction term initial concentration and addition amount had significant effect on decolorization rate of methylene blue solution. The optimal process parameters predicted by the model were as follows: initial concentration 18.90 g/mL, photocatalytic time 16.55 min, dosage 0.04 g and decolorization rate up to 98.95%.
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  Construction of g-C₃N₄/MnO₂ composite photocatalyst for degradation of tetracycline under visible light

  TAN Shiyang^{1, 2}, DU Chunyan^{1, 2}, YU Guanlong^{1, 2}, SONG Jiahao^{1, 2},

  Journal of Functional Materials. 2020, 51(6): 6164-6168. https://doi.org/10.3969/j.issn.1001-9731.2020.06.027

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  The g-C₃N₄/MnO₂ composite photocatalyst was synthesized by in-situ growth method for degradation of TC under visible light irradiation. The structural and optical properties of composites were characterized by XRD, FTIR and UV-vis. The introduction of MnO₂ enhanced the absorption of visible light and photocatalytic activity of g-C₃N₄/MnO₂ photocatalyst. The degradation rate of TC reached 77.1% within 90 minutes under visible light irradiation and the recycle experiments shown that the g-C₃N₄/MnO₂ photocatalyst exhibited great stability activity after five reactions. The mechanism shown that ·O^2- played important role in TC degradation progress and a Z-scheme heterojunction was formed between g-C₃N₄ and MnO₂, which promoted the transfer of photogenerated electrons and holes and improved the photocatalytic activity.
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  Synthesis of injectable brushite loaded with cobalt, iron, and copper and its antibacterial property

  ZHANG Kaili¹, PEI Zhengjun¹, LI Guangda¹, LI Xiaoyu², ZHAO Santuan³, MI Liuyang¹

  Journal of Functional Materials. 2020, 51(6): 6169-6176. https://doi.org/10.3969/j.issn.1001-9731.2020.06.028

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  In this study, injectable self-setting brushite bone cement containing Co, Fe, and Cu ions (CFC-Bru) was synthesized by using calcium phosphate powder loaded with Co, Fe, and Cu. The setting time, injectability properties, anti-washable ability, phase composition, chemical groups, surface morphology, degradable properties, antibacterial properties, and cytocompatibility of the composite bone cements were evaluated thoroughly. The results show that the setting time of the composite bone cement was approximately 30 min, and the composite bone cement (CFC-Bru) was anti-washout with an injectable coefficient as high as 90%. The XRD tests reveal that the target product brushite and calcium phosphate monobasic were the main phases of the composite bone cement. Moreover, the surface morphology of the composite bone cement was significantly changed as compared with the pure bone cement. Furthermore, the antibacterial plate experiment show that the composite bone cement was sensitive towards Escherichia coli, staphylococcus aureus and pseudomonas aeruginosa, and the inhibition halo of the composite bone cement to the three types of bacteria reached 11 mm, 15 mm, and 25 mm, respectively. The antibacterial experiment of broth shows that the growth of pseudomonas aeruginosa could be completely inhibited at a composite bone cement concentration of 10 mg/mL. Moreover, the Escherichia coli growth was completely inhibited at a composite bone cement concentration of 20 mg/mL. Furthermore, the staphylococcus aureus growth was completely inhibited at a composite bone cement concentration of 50 mg/mL. Additionally, the in vitro cell experiments show that the composite bone cement had no cytotoxicity to human osteosarcoma MG-63 cells. After the cells and bone cement materials were co-cultured for 3 days and 7 days, it is found that the cells could spread and proliferate on the surface, indicating the good cellular compatibility. The composite bone cement (CFC-Bru) could be potentially used as anti-bacterial bone repair material.
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  Preparation and properties of terpolymer scale inhibitor IA/AA/HEMA

  GUO Yani, LI Luming, SU Haiwen

  Journal of Functional Materials. 2020, 51(6): 6177-6185. https://doi.org/10.3969/j.issn.1001-9731.2020.06.029

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  The scale inhibitor IA-AA-HEMA was prepared through aqueous solution polymerization with IA, AA and HEMA as monomers. The scale inhibition effect was evaluated by scale method with scale inhibition rate as index. The preparation conditions of scale inhibitor were optimized by P-B test and CCD test. The results show that the maximum scale inhibition rate could reach 96.69% under the optimum conditions of 15% IPA, 8% KPS, 1:0.5:0.3 of n_IA∶n_AA:n_HEMA, 86℃ polymerization temperature and 85 min polymerization time. The effect of polymerization temperature and n_IA∶n_AA monomer ratio on the scale inhibition rate was very significant, followed by that of polymerization time and KPS. The infrared spectrum shows that IA-AA-HEMA scale inhibitor was polymerized successfully. The SEM analysis of CaCO₃ scale sample shows that the structure of CaCO₃ scale sample was obviously loose after IA-AA-HEMA was added, and the scale inhibition effect was good.
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  Preparation and performance of red phosphor GdVO₄:Eu³⁺ for white LEDs

  LI Zhao, WU Hongqiang, SHI Bingyao, CAO Jing, WANG Yongfeng, WANG Yanan

  Journal of Functional Materials. 2020, 51(6): 6186-6189. https://doi.org/10.3969/j.issn.1001-9731.2020.06.030

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  GdVO₄:Eu³⁺ red phosphors were prepared by high temperature solid phase method. The phase, morphology and luminescence properties of the samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). The results show that the synthesized GdVO₄:Eu³⁺ red phosphor was tetragonal and the surface was spherical. In the excitation spectrum, the excitation peaks at 382 nm, 395 nm, 418 nm, and 466 nm were assigned to⁷F₀→⁵L₇、⁷F₀→⁵L₆、⁷F₀→⁵D₃ and ⁷F₀→⁵D₂ transitions, respectively. In the emission spectrum, the emission peaks at 593 nm, 625 nm, 654 nm, and 701 nm corresponded to the ⁵D₀→⁷F₁、⁵D₀→⁷F₂、⁵D₀→⁷F₃ and ⁵D₀→⁷F₄ transitions of Eu³⁺. It was a highly efficient red phosphor that was expected to be used in white LEDs.
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  Effect of low temperature on properties and microstructure of ECAP copper

  XUE Haiping, LIU Ping, LIU Xinkuan, CHEN Xiaohong, LI Wei, MA Fengcang, ZHOU Honglei, ZHANG Ke

  Journal of Functional Materials. 2020, 51(6): 6190-6194. https://doi.org/10.3969/j.issn.1001-9731.2020.06.031

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  In this paper, the effect of temperature on the microstructure and properties of copper ECAP was studied, and the similarities and differences between the low temperature and room temperature deformation were compared. The results showed that the hardness of the low-temperature samples was slightly increased compared to that of the room temperature ECAP samples. By comparing the metallographic structure, it was found that the low temperature condition obviously hindered the grain deformation at low passes, and inhibited the dynamic recrystallization phenomenon which often occurred at room temperature and high passes. Annealing was performed after ECAP treatment, and it was found that the hardness of room-temperature ECAP samples decreased significantly at 140 ℃, while the low-temperature ECAP samples appeared abnormal and still maintained high hardness.
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  Preparation and fluorescence temperature sensitivity of nanocomposites CNTs@Y₂O₃:Eu³⁺

  WANG Sainan, LI Ying, ZHANG Chunming

  Journal of Functional Materials. 2020, 51(6): 6195-6199. https://doi.org/10.3969/j.issn.1001-9731.2020.06.032

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  CNTs@Y₂O₃:Eu³⁺ nanocomposites with one-dimensional structure were successfully prepared by homogeneous precipitation method using surfactant sodium dodecylbenzenesulfonate. In order to investigate the microstructure, thermal stability, crystallinity and fluorescence properties, the obtained materials were characterized by SEM, XRD, TEM-EDS, TGA and PL. The results show that CNTs@Y₂O₃:Eu³⁺ fluorescent composites exhibited strong rare earth Eu³⁺ characteristic fluorescence under UV excitation. Furthermore, the fluorescence intensity of the composite material changed significantly at different calcination temperature ranges of 400 ~ 1000 ℃, showing strong temperature-sensitive characteristics.
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  Effect of ammonia and temperature on GaNnanomaterials synthesized by HCVD

  YU Bin¹, ZHANG Zhe¹, XUE Jinbo^{1, 2}, ZHANG Haixia², YU Chunyan^{1, 2},

  Journal of Functional Materials. 2020, 51(6): 6200-6205. https://doi.org/10.3969/j.issn.1001-9731.2020.06.033

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  In this experiment, gallium trichloride (GaCl₃) was used as the Group III precursor, and self-catalyzed growth of GaN nanomaterials were achieved on Si(111) substrates using a self-made halide chemical vapor deposition (HCVD) device. The effects of different factors, including ammonia (NH₃) flow, the reaction temperature and gradient temperature growth process on GaN nanomaterials synthesized from GaCl₃ were discussed. The samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and photoluminescence (PL). The results show that GaN nanostructures were grown in a cluster mode, which followed gas-liquid-solid (VLS) growth mechanism. Under different growth conditions, there were obvious differences in the morphology, crystal quality and luminous properties for GaN. When NH₃ flow was 60 sccm and the reaction temperature was at 900 ℃, GaN had a regular hexagonal structure and good crystal quality, and no obvious red luminescence band (about 680 nm) was found in the PL spectrum. Multiple structure for GaN was obtained in a gradient temperature (from 800 to 900 ℃) growth process, and surface-to-volume ratios and near-band edge emission peak intensity of GaN were both improved.
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  Evaluation onregeneration effect of multi-scale parameters of reclaimed asphalt mortar

  LI Ping, KANG Xiao, NIAN Tengfei, LIN Mei

  Journal of Functional Materials. 2020, 51(6): 6206-6214. https://doi.org/10.3969/j.issn.1001-9731.2020.06.034

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  Dynamic shear rheology test (DSR) and Fourier transform infrared spectroscopy (FTIR) techniques were used to investigate the regeneration effect of regenerated asphalt mortar and the evolution of characteristic functional groups and nanoscopic morphology under different rejuvenator dosages, as well as their influence on high temperature rheological properties. The rheological property parameters, characteristic functional groups and nanoscopic morphology of KL90 base asphalt and its pressure aging (PAV) asphalt, reclaimed asphalt mortar and regenerated asphalt mortar with rejuvenator dosage of 6%, 9% and 12% were tested in this paper. At the same time, the meso-mechanical parameters of the asphalt mortar were obtained by the method of programming and the relationship between the macro-rheological parameters and the meso-mechanical parameters of the asphalt mortar was derived. The results show that temperature had an important influence on the rheological properties of asphalt mortar. The addition of rejuvenator restored the rheological properties of asphalt mortar and reduced its resistance to rutting. When the dosage of rejuvenator was 9%, the high temperature rheological properties of the recovered asphalt mortar recovered better. The carbonyl index (CI) and sulfoxide index (SI) of PAV aged asphalt and reclaimed asphalt mortar increased compared with KL90 base asphalt. The reclaimed asphalt mortar exhibited characteristic peaks of C-O-C at 1260 /cm and Si-O-Si at 1018 /cm and 1089 /cm. The regenerated asphalt mortar exhibited characteristic peaks of saturated fatty acid ester (C=O) and linear C-C bond at 1744 /cm and 1160 /cm. The meso-mechanical parameters E₁、η₁、E₂、η₂ of the reclaimed asphalt mortar were significantly higher than those of KL90 base asphalt and regenerated asphalt mortar. As the amount of the regenerant increased, E₁、η₁、E₂、η₂ gradually decreased.
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  Effect on water retention performance of MOF-5 doping modified cellulose hydrogel composite materials

  YANG Qiang^{1, 2}, FAN Guodong², ZHOU Chunsheng¹, CUI Xiaowei¹, GONG Wei¹

  Journal of Functional Materials. 2020, 51(6): 6215-6220. https://doi.org/10.3969/j.issn.1001-9731.2020.06.035

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  In this work, cellulose hydrogel was modified with MOF-5. The chemical structure was characterized by FT-IR, XRD and SEM. The effects of contents, pH, salt solution concentration, and temperature on the water retention properties and recyclable properties of composite cellulose hydrogels were studied. The results showed that the active groups on the surface of cellulose hydrogel were beneficial to the binding of MOF-5, and the binding effect became more obvious as the doping amount increasing. Compared with traditional cellulose hydrogel, the water absorption rate was up to 4294.94%, which was an increase of 1725.63%. The water retention experiment found that the best water retention effect was obtained when the MOF-5 doped amount was 20%, pH=12, and 4 m mol/L salt solution. The water retention effect of the composite hydrogel in NaCl and AlCl₃ solutions decreased with increasing concentration. The composite cellulose hydrogel with the optimal doped amount still retained more than 50% of water when left at 40 ℃ for 175 min. Recyclability experiments showed that the retention rate of the composite cellulose hydrogel was still higher than 50% when it was used 3 times. Thus composite hydrogel had potential application value in the field of high-temperature agricultural production.