30 October 2019, Volume 50 Issue 10

    

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Focuses & Concerns (The Project of Chongqing Press Fund in 2018)
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  Theoretical modeling and experimental study on ΔE effect of giant magnetostrictive materials

  LI Bo, ZHU Yanchao, SHU Liang, TAO Menglun, YANG Jiabin

  Journal of Functional Materials. 2019, 50(10): 10001-10007. https://doi.org/10.3969/j.issn.1001-9731.2019.10.001

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  In order to research the ΔE effect of giant magnetostrictive materials, a magnetization model considering the effects of dynamic stress and coefficient changes was proposed by combining the Jiles-Atherton model with the magnetoelastic effect. The magnetic field-magnetization relationship and stress-magnetization relationship of giant magnetostrictive materials under external magnetic field and compressive stress were modeled respectively. According to Hooke's law and the second domain-rotation model, the total strain of materials under the combined action of stress and magnetic field were calculated, and the strain-stress loop of materials under different external magnetic fields were obtained. By calculating the slope of the strain-stress curve, the elastic modulus versus stress curve of the magnetostrictive material under different applied magnetic fields was obtained. A stress test device was built to test the magnetization-stress response and strain-stress response of Terfenol-D under different applied magnetic fields. The test results were basically consistent with the model calculation results. The results show that the ΔE effect was the result of the balance of magnetic field energy and stress anisotropy. The maximum elastic modulus variation of Terfenol-D reached 513%. The research results provided theoretical basis and control methods for the design of variable stiffness of new electromechanical systems.
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  Preparation and properties of (1-x)(Na_0.5K_0.5)NbO₃-x(Ba_0.88Ca_0.12Zr_0.12Ti_0.88O₃) lead-free piezoelectric ceramics

  XU Xiangxin, XING Pengfei

  Journal of Functional Materials. 2019, 50(10): 10008-10012. https://doi.org/10.3969/j.issn.1001-9731.2019.10.002

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  Lead-free piezoelectric ceramics (1-x)(Na_0.5K_0.5)NbO₃-x(Ba_0.88Ca_0.12Zr_0.12Ti_0.88O₃) ((1-x)KNN-xBCZT) have been fabricated by a pressureless sintering technique. KNN and BCZT formed a homogeneous solid solution. Addition of BCZT lowered both T_C and the tetragonal-orthorhombic transformation temperature in an approximately linear relation to concentration. Lowering of the tetragonal-orthorhombic transformation temperature improved the electrical properties of the solid solution. The properties of (1-x)KNN-xBCZT reached the best when x=0.055. Use of MnO₂ as a sintering aid resulted in denser ceramics for which phase boundaries shifted to lower temperatures. 0.055BCZT-0.945KNN-0.01MnO₂ exhibited properties: d₃₃=212 pC/N, d₃₁=-75 pC/N, k_p=45%,ε=875, tanδ=0.02, T_C=340 ℃ and T_O-T=127 ℃.
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  Application of CuO-NRs/GNs composite counter electrode in platinum-free dye-sensitized solar cells

  WANG Xiaoyu, LIU Qinglong, ZHAO Liping, JIN Liguo

  Journal of Functional Materials. 2019, 50(10): 10013-10017. https://doi.org/10.3969/j.issn.1001-9731.2019.10.003

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  In this paper, copper oxide nanorods (CuO-NRs) prepared by uniform precipitation method were combined with graphene (GNs) slurry, and CuO-NRs/GNs composite counter electrodes were prepared on FTO conductive glass substrated by electrohydrodynamics (EHD). The XRD phase analysis and SEM, TEM structure characterization indicated that the CuO-NRs/GNs composite film had a porous network structure. It proved that the CuO-NRs/GNs composite counter electrode had high electrocatalytic activity and faster electron transport rate through a series of electrochemical performance tests, and achieved photoelectric conversion efficiency of DSSC assembled by CuO-NRs/GNs composite counter electrodes (2.57%) reached the same level as that of Pt counter electrodes (3.46%).
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  Improving the hydrophobicity of polyimide aerogel via polysiloxane

  LI Xu, PEI Xueliang

  Journal of Functional Materials. 2019, 50(10): 10018-10022. https://doi.org/10.3969/j.issn.1001-9731.2019.10.004

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  Because of the small pore size, high surface area and open-celled structure, aerogel is inclined to absorb water. The existence of water not only affects the property of aerogel but also breaks its structure. In order to obtain polyimide aerogel with low hydrophilicity, in this study, trimethoxysiloxane and polydimethylsiloxane were incorporated into polyimide via the reaction of the polyimide containing acid chloride side groups with 3-aminopropyltrimethoxysilane and 10 wt% bis(aminopropyl)polydimethylsiloxane. With the aid of the hydrolysis and condensation reactions of trimethoxysilane side groups, chemically cross-linked polyimide gel was formed. After freeze-drying, polyimide aerogel with the density of 0.20 g/cm³ and three-dimensional network structure was obtained. The infrared and thermogravimetric results showed that the hydrophobic polydimethylsiloxane was introduced into the polyimide structure, and X-ray photoelectron spectroscopy showed that the polydimethylsiloxane enriched on the surface of the polyimide aerogel skeleton. As a result, compared with pure polyimide aerogel, polyimide aerogel modified by polydimethylsiloxane had much higher hydrophobicity.
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  Synthesis and characterizations of Li-doped (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃ piezoelectric ceramics

  CHEN Xiaoming, ZHOU Wang, XIONG Junhua, TANG Yunsong, YANG Dong, LIU Wanli, LIN Xizhu, LUO Yongmei, LI Guorong

  Journal of Functional Materials. 2019, 50(10): 10023-10026. https://doi.org/10.3969/j.issn.1001-9731.2019.10.005

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  Li-doped (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃ (BCTZL-x) lead-free piezoceramics have been prepared by the conventional ceramic process. The influence of a Li⁺-containing additive on the crystal phase, microstructure and electric properties of (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃ ceramics were systematically investigated through all kinds of measurement, such as X-ray diffraction(XRD) and SEM. The X-ray results show that the BCTZL-x ceramics sintered at 1 400 ℃/2 h had pure ABO₃ perovskite structure. The BCTZL-x ceramics went through the phase transition from O phase to T phase with Li⁺ doping increasing. The ceramics became dense when x≥0.3. Additionally, BCTZL-0.3 ceramics showed an excellent performance:d₃₃=456 pC/N, k_p=0.49, ε_r=4 864, tanδ=0.018, Q_m=130.
Review & Advance
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  Research progress of polymer powder materials for SLS forming technology

  GONG Xiaodi, WANG Zhi, YU Ning, GAO Xia, LI Jing

  Journal of Functional Materials. 2019, 50(10): 10027-10039. https://doi.org/10.3969/j.issn.1001-9731.2019.10.006

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  Selective laser sintering (SLS) is one of additive manufacturing techniques that can produce functional and prototype parts with complex structures. Polymer powder material is the key factor of SLS technology. In this paper, the research progress of SLS forming technology was reviewed from three aspects: categories of polymer powder materials, preparation methods of polymer powder materials and SLS forming process. The existing problems of polymer powder materials in the field of SLS forming technology and the future research directions were also prospected.
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  The state-of-the-art flexible electrochromic material

  WU Qiong, ZHANG Guanguang, CHEN Huangxing, JIANG Man, LI Conghao, YAO Rihui, NING Honglong, PENG Junbiao

  Journal of Functional Materials. 2019, 50(10): 10040-10046. https://doi.org/10.3969/j.issn.1001-9731.2019.10.007

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  With the popularity of wearable electronic devices, flexible electronic devices have become a hot topic of current research. Flexible electrochromic devices are characterized by green environmental protection, low cost, large area, adaptability and convenient production and transportation. They are not only used in intelligent windows of green buildings, dimming glass of electric vehicles, military camouflage, infrared radiation control and variable color short circuit warning batteries, but also have great application prospects in medical care and equipment, and are considered as the key technology of wearable energy storage devices and smart textiles in the future. Based on the flexible electrochromic structure, the development of functional layers such as flexible substrates, electrode materials, electrochromic materials and electrolyte materials was discussed. The relationship between device materials and structure was described clearly, and the key of performance promotion was found. Moreover, several personal insights on the existing challenges and future research direction of flexible electronic devices were considered based on current progress.
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  Research progress of element doped cuprous oxide photovoltaic materials

  LIU Xiaobo, YUAN Binxia, XIA Yangchun, CAI Xiaodong, LIU Jianfeng, ZHU Qunzhi, ZHAO Yuwei

  Journal of Functional Materials. 2019, 50(10): 10047-10056. https://doi.org/10.3969/j.issn.1001-9731.2019.10.008

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  Cuprous oxide (Cu₂O) is an oxide semiconductor material with unique properties. The element doping of cuprous oxide is an effective method for improving the optical and electrical property of the film. Doping modification is one of the important ways to improve the material property. Therefore, in this paper, the changes in optical bandgap, resistivity, conductivity type and conversion efficiency of cuprous oxide with metals, non-metals and rare earth elements and elemental IVA elements were reviewed. The effects of elemental doping on the optical properties of Cu₂O were analyzed comprehensively, and the potential of elemental doped cuprous oxide in future photovoltaic research was prospected.
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  Research progress on high temperature oxidation and corrosion behavior of austenitic heat resistant steel Sanicro25

  JIA Jianwen, HOU Lifeng, DU Huayun, WEI Yinghui

  Journal of Functional Materials. 2019, 50(10): 10057-10062. https://doi.org/10.3969/j.issn.1001-9731.2019.10.009

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  Sanicro25 austenitic heat-resistant steel is a candidate material for advanced ultra-supercritical power plants generator superheater and reheater tubes. In this paper, through micro-structure and overview of the high temperatureO₂/H₂O oxidation, sulfur-chlorine corrosion and salt hot corrosion of Sanicro25 austenitic steel, it suggested that the second phase precipitation in the microstructure and long-term performance of typical environmental media should be further completely investigated, so as to reveal the high temperature oxidation-corrosion behavior of the steel.
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  Progress in application of graphene-like two-dimensional materials and photoelectric devices

  WANG Jiayao, SHI Huanchong, JIANG Linhua, LIU Liming

  Journal of Functional Materials. 2019, 50(10): 10063-10073. https://doi.org/10.3969/j.issn.1001-9731.2019.10.010

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  The two-dimensional layered material is a planar material with a single atomic layer or several atomic layer thicknesses. It has special physical and chemical properties and has important application prospects in the fields of photoelectric functional devices, adsorption and separation, and catalysis. It is the frontier of international research and one of the hotspot areas. Among them, graphene is the first two-dimensional material that investigator have paid attention to, and the graphene-like two-dimensional photoelectric functional materials mainly composed of transition metal sulfides have also been widely studied. The discovery of black phosphorus in recent years also has greatly promoted the research and development of two-dimensional optoelectronic materials. In this paper, the research on graphene and graphene-like sulfides in two-dimensional optoelectronic materials and the application status of their optoelectronic functional devices were briefly reviewed, and their application trends were prospected, which provided reference for the research of photovoltaic materials research.
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  Application of oil-soluble catalysts in suspended-bed hydrogenation of inferior oil

  LONG Chuan, XIONG Kun, ZHANG Haidong, CHEN Jia, ZHANG Xianming, LIU Yunqi

  Journal of Functional Materials. 2019, 50(10): 10074-10080. https://doi.org/10.3969/j.issn.1001-9731.2019.10.011

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  The suspended bed hydrotreating is considered as an advanced technology for high-efficiency conversion of inferior oil and waste oil with its unique advantages. Since the technology is not yet mature, some research efforts have been devoted to solving the coking problems, developing high activity and high dispersion catalysts. Among them, oil-soluble catalysts exhibit excellent catalytic activity due to their high dispersibility and low coking characteristics. Moreover, it is not necessary for these catalysts to be separated from the oil, avoiding secondary pollutants. However, the cost of catalyst is too high to realize large-scale application. Therefore, developing high-efficiency catalysts with low-cost has become the focus of research. In this paper, the current status of oil-soluble catalysts in recent years was described, focusing on the preparation, catalytic performance and active sites of different oil-soluble catalysts. Finally, the prospects for the challenges and research directions were proposed to shed light on future development of oil-soluble catalysts.
Research & Development
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  Study on the surface treatment of pure titanium and its corrosion resistance and wettability

  ZHANG Mengjiao, OU Feiyang, CHEN Xianchun

  Journal of Functional Materials. 2019, 50(10): 10081-10086. https://doi.org/10.3969/j.issn.1001-9731.2019.10.012

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  The aim of this study is to investigate the effects of different acid etching conditions on the corrosion rate and wettability of pure titanium sheet and the corresponding corrosion mechanism, so as to provide experimental and theoretical basis for the surface modification and clinical application of pure titanium sheet. Firstly, the polished pure titanium sheets were treated by different types of weak acid etching systems, and then video optical contact angle measuring instrument, scanning electron microscope and surface roughness meter were used to investigate the surface properties of the titanium sheet, and the relationship between the surface properties and wettability was analyzed. The results showed that the corrosion rate decreased with increasing contact angle. It suggested that the wettability of pure titanium sheet mainly depended on the special morphology and surface groups formed on the surface, and had no direct relationship with the surface roughness.
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  Study on microstructure of Al/SnPb composite interface

  ZHANG Zhuo, LIU Xinkuan, MA Fengcang, WANG Ziyan, XUE Siyu

  Journal of Functional Materials. 2019, 50(10): 10087-10091. https://doi.org/10.3969/j.issn.1001-9731.2019.10.013

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  The Al/SnPb composite layer was prepared by brushing a layer of SnPb alloy on the surface of Al by mechanical rupture and induction heating. The binding interface was characterized by polarized light microscopy (PM), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and X-ray energy spectroscopy (EDS). The results show that the bonding interface of Al/SnPb composites was good, and the microscopic interface exhibited a distinct transitional state. The bonding interface was jagged and had a small amount of Al-Sn supersaturated solution. The Al matrix was effectively bonded to the Sn-Pb alloy through the transition layer.
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  Structure and magnetism of Mn₉₅Ni₅Fe₁₀₀P₇₇Ge₂₃ compound

  HAN Lei, LI Yingjie, OU Zhiqiang, Hasichaolu, O.Tegus

  Journal of Functional Materials. 2019, 50(10): 10092-10095. https://doi.org/10.3969/j.issn.1001-9731.2019.10.014

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  The Mn₉₅Ni₅Fe₁₀₀P₇₇Ge₂₃ compound was prepared by high energy ball milling and powder sintering techniques. The Mn₉₅Ni₅Fe₁₀₀P₇₇Ge₂₃compound has been investigated by means of X-ray diffraction and magnetic measurements. It crystallized in the Fe₂P type structure with the lattice parameters a=b=0.61357(3) nm and c=0.33537(2) nm at 160 K and underwent a first-order phase transition at the Curie temperature of 284 K. The temperature dependence of X-ray diffraction measurements showed that the compound had a magnetic transition between the paramagnetic and ferromagnetic phases at 280 K. Isothermal magnetization curves of Mn₉₅Ni₅Fe₁₀₀P₇₇Ge₂₃compound near Curie temperature were measured. It was obviously found that magnetization transition phenomena caused by the increase of magnetic field appeared above Curie temperature.
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  Study on properties and yield of hollow glass microsphere prepared from waste glass

  LIU Xiangfeng, YU Hongbo, LI Yang, SU Zhenguo, CHANG Shibo, LIU Kele, DUAN Ting, LI Yajie, WANG Xiuhui, YANG Jinlong

  Journal of Functional Materials. 2019, 50(10): 10096-10103. https://doi.org/10.3969/j.issn.1001-9731.2019.10.015

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  Using waste glass as raw material, hollow glass microspheres were prepared by spray drying. The effects of the types of foaming agents, sintering temperatures, particle size and feeding speed on the surface morphology and yield of hollow glass microspheres were studied. Results show that the particle size distribution was an vital factor limiting beads yield, and using inorganic salt and organic compound as composite foaming agent could increase the decomposition of foaming agent temperature range, which improved the efficiencies of microspheres, body foaming and yield. Furthermore, with the increase of sintering temperature and feed speed, the beads yields increased rapidly and then decreased gradually. In this study, when the quality fraction of foaming agent was 3%, sintering temperature was 850 ℃, and feeding wind speed was 1.6 m/s, the microbeads owned the maximum yield of 91%, the bulk density of 0.26 g/cm³, the true density of 0.55 g/cm³, and the compressive strength of 4 MPa.
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  Effects of La on the wettability, structure and properties of ATO/Cu electrical contact materials

  DING Yi, ZHU Zhixiang, SHAO Wenzhu, LI Weijian, XU Hongyang, CHEN Baoan, ZHANG Qiang, HAN Yu, CHEN Xin, WANG Qiang

  Journal of Functional Materials. 2019, 50(10): 10104-10109. https://doi.org/10.3969/j.issn.1001-9731.2019.10.016

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  Metal oxides reinforced copper-based composite is one of the most important developing directions of the silver-saving, due to their low-cost, highelectrical conductivity, thermal conductivity and mechanical properties. However, the poor wettability between the reinforcing phase and copper matrix decreases the stability and reliability of the contact materials, which limits their applicants. In this work, Sb-doped SnO₂ (ATO) was employed as the reinforcing phase and the effects of La on the wettability between ATO and Cu matrix at different temperatures were investigated. The microstructure and properties of ATO/Cu electrical contact materials with different content of La were evaluated. The results show that La could improve the wettability between ATO and Cu particles. Increasing the content of La in the matrix could improve the hardness of the composite, however decrease the electrical conductivity. In addition, the addition of La could effectively decrease the contact resistance of ATO/Cu composite, which may be ascribed to the new phases due to the combination of La and ATO.
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  Study on thermal regeneration technology and regeneration mechanism of old asphalt pavement materials

  SHAN Ke, LI Dandan, LI Qiang, YUAN Qihua, FAN Xue

  Journal of Functional Materials. 2019, 50(10): 10110-10114. https://doi.org/10.3969/j.issn.1001-9731.2019.10.017

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  The recycled asphalt and recycled asphalt mixture were prepared by adding different content of recycling agent to recycle the old asphalt pavement materials. The gross volume relative density, void fraction, stability and flow value of recycled asphalt mixture were studied. The effects of different dosage of recycling agent on penetration, ductility and softening point of recycled asphalt were analyzed. The mechanical properties and recycling mechanism of recycled asphalt were studied by bending test and Fourier transform infrared spectroscopy. The results showed that the penetration, ductility and softening point of recycled asphalt with 3 wt% recycling agent were 44 (0.1 mm), 14.9 cm and 54.5 ℃, respectively, which could meet the standard requirements of Panjin 50# asphalt and the requirements of recycled asphalt for pavement. When 3wt% recycling agent was added, the void fraction of recycled asphalt mixture was 5.9%, the stability was 13.43 kN, and the flow value was 26 (0.1 mm), which met the requirements of high-speed and first-class highways for the use of asphalt. Bending test showed that the mechanical properties of recycled asphalt mixture were good after aging, and its durability wasn’t significantly different from that of ordinary asphalt mixture. FT-IR analysis showed that the components of recycled asphalt were almost the same before and after recycling. The recycling mechanism of recycled asphalt was that the saturated hydrocarbons in recycling agent improved the rheological properties of recycled asphalt by dissolving and dispersing asphaltene, and the aromatic compounds in the regenerant supplied the loss of aromatic small molecules during the long aging process of recycled asphalt.
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  Influence of electro-thermal effect on interfacial property of carbon fiber/epoxy resin

  LI Na, WANG Zhenliang, LU Pengcheng

  Journal of Functional Materials. 2019, 50(10): 10115-10120. https://doi.org/10.3969/j.issn.1001-9731.2019.10.018

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  In order to study the effect mechanism of electro-thermal effect on interfacial properties of carbon fiber/epoxy resin, the interfacial shear strength of carbon fiber monofilament/epoxy resin composites with different current intensities treatment was characterized. The effects of current intensities on the interface properties were analyzed by means of scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), differential scanning calorimeter (DSC). The results show that the interfacial temperature of carbon fiber monofilament/epoxy resin composite treatment increased with the increase of current strength. The interfacial shear strength increased first and then decreased. After loading 2-6 mA DC current for a certain period of time, the surface morphology of carbon fibers did not change significantly, the interfacial components took place post-curing reaction, and the glass transition temperature (T_g) showed an upward trend. When the current intensity continued increasing to 8 mA (200 ℃), the sizing agent on the surface of carbon fibers showed obvious ablation phenomenon, the macromolecular chains of interfacial components broke and gradually aged, and the T_g decreased. It is concluded that the change of the physicochemical properties of the interfacial components caused by Joule heat generated by carbon fiber conduction was the main reason for the change of the IFSS of carbon fiber/epoxy resin.
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  Preparation and CO₂ capture of cyclotriphosphazene-based microporous organic polymer

  XIE Jing, LIU Yaqin, LIU Yijiang, LI Huaming

  Journal of Functional Materials. 2019, 50(10): 10121-10126. https://doi.org/10.3969/j.issn.1001-9731.2019.10.019

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  The dialdehyde-containing cyclotriphosphazene derivative (DHBCPP) was synthesized by successive nucleophilic substitution reaction between hexachlorocyclotriphosphazene, 2,2’-diphenol and 4-hydroxy benzaldehyde. Subsequently, the cyclotriphosphazene-based microporous organic polymer PCPP-TZ was prepared through the condensation reaction between DHBCPP and melamine, which were utilized as constructing block units. The composition and morphology of the as-synthesized polymer PCPP-TZ were fully characterized by FT-IR, solid state NMR, thermogravimetic analysis, SEM and TEM. The N₂ adsorption-desorption isotherms indicated that the polymer PCPP-TZ possessed a specific surface area of 884 m²/g, a total pore volume of 0.419 cm³/g and a micropore volume of 0.343 cm³/g. It was found that the cyclotriphosphazene-based microporous organic polymer PCPP-TZ exhibited an excellent CO₂ capture performance. At 298 K/0.1 MPa, CO₂ capture capacity of PCPP-TZ was calculated to be 3.32 mmol/g, and the highest CO₂ capture capacity was achieved to 4.05 mmol/g under 273 K/0.1 MPa.
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  The effect of modified cellulose nanowhisker on thermal degradation kinetics of poly(lactic acid)

  WANG Xuan, YANG Peng, ZHOU Linxiang, SONG Limei

  Journal of Functional Materials. 2019, 50(10): 10127-10132. https://doi.org/10.3969/j.issn.1001-9731.2019.10.020

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  The silane agent (KH-570, MPS) was adopted to modify the surface of cellulose nanowhisker (CNW) and the solution casting method was used to prepare the M-CNW/PLA composite. The chemical structure, micromorphology, dispersion in PLA matrix and thermal degradation behavior of PLA composites under different heating rate were detected by FT-IR, SEM, and TGA, respectively. The results indicated that the M-CNW was successfully synthesized and the micromorphology of CNW was kept. M-CNW showed a good dispersion state in PLA matrix and improvement in the brittle rupture pattern of PLA. Through the analysis results of CR and IKR models, PLA showed the different thermal degradation mechanism with modified or unmodified CNW.
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  Synergistic antibacterial effect of Zn, Co doped and Co/Zn co-doped titania nano-materials

  SHI Dai, YANG He, XUE Xiangxin

  Journal of Functional Materials. 2019, 50(10): 10133-10139. https://doi.org/10.3969/j.issn.1001-9731.2019.10.021

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  Cobalt doped titania (Co-TiO₂), zinc doped titania (Zn-TiO₂) and Co/Zn co-doped titania (Co/Zn-TiO₂) nano-materials were synthesized by a sol-gel method. Using E.coli, S.aureus and C.albicans as target strains, the effects of various doped elements and reaction factors on antibacterial activity under visible light irradiation were studied. Nano-materials were characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), specific surface area analyzer (BET), UV-vis diffuse reflectance spectra (DRS) and FT-IR analysis. The experimental results show that zinc doping could cause changes in the structure of TiO₂, accepting excited electrons on the valence band of TiO₂, and absorbing photons to cause electrons to transition to the conduction band of TiO₂. In addition, Zn/TiO₂ nano-materials contained 27% ZnTiO₃, which had photocatalytic activity and could inhibit the growth of strains. The presence of Co component in the Co/TiO₂ nanomaterial increased the grain size of the TiO₂ by inhibiting the grain growth of the TiO₂, which increased the specific surface area of the crystallite. Co ion introduced the impurity level of Co4f into the TiO₂ energy gap, that is, the valence band of TiO₂ transferred with the 4f electric layer of Co to generate the capture level, which reduced the band gap width and increased the absorption of visible light by Co/TiO₂, thus enhancing the photocatalytic performance of antibacterial agents and improving the antibacterial activity. The antibacterial effect of Co-Zn/TiO₂ nanomaterials was the best. Co-doped of Zn and Co with TiO₂ promoted the dissolution of Zn and Co ions. As Zn and Co ions themselves also had bactericidal effects, they penetrated into the bacterial cell wall and inhibited the enzyme activity, leading to the death of bacteria. However, due to the different targets of microbial attack, when the microorganisms were exposed to Zn and Co ions at the same time, different positions on the cell membrane were attacked, resulting in more effective damage.
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  Research on characteristic function and change rule of thermal capacity on graphene

  CHENG Zhengfu, ZHOU Mingjun, FU Chunping, ZHEN Ruilun, YANG Bangchao

  Journal of Functional Materials. 2019, 50(10): 10140-10144. https://doi.org/10.3969/j.issn.1001-9731.2019.10.022

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  In this paper, considering the non-harmonic oscillation of atoms, the theory and method of solid state physics were used. The dependence of free energy and low temperature heat capacity of graphene on temperature was determined, and the influence of atomic anharmonic vibration on them was discussed. The results show that the free energy of characteristic function of graphene was related to the anharmonic coefficient of atomic vibration. The thermal capacity of graphene was much larger than that of ordinary heat storage materials, and the value of graphene increased non-linearly with the increase of temperature. When the temperature was very low ((4.84±0.44)×10³-(5.30±0.48)×10³ W/(m·K), the change rule obeyed (4.84±0.44)×10³-(5.30±0.48)×10³ W/(m·K). When the temperature was not too high ((4.84±0.44)×10³-(5.30±0.48)×10³ W/(m·K), the change was faster. When the temperature was higher ((4.84±0.44)×10³-(5.30±0.48)×10³ W/(m·K), the change was slower. The influence of the anharmonic effect on the heat capacity of the graphene was increased with the increase of the temperature. The basic rules for the study of anharmonic effect of solid materials presented in this paper were effective to the study of the variation of the thermodynamic properties of graphene with changing temperature.
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  Effects of Au component in Ag alloy bonding wire on bonded strength and bonded reliability

  FAN Junling, ZHU Lixia, CAO Jun, HUA Han

  Journal of Functional Materials. 2019, 50(10): 10145-10148. https://doi.org/10.3969/j.issn.1001-9731.2019.10.023

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  The bonded strength and bonded reliability of Ø0.025 mm Ag-Au alloy bonding wire with different Au component were analyzed by scanning electron microscope and strength tester and the effects of different Au component on bonded strength and bonded reliability were investigated. The results show that the shape of free air ball for Ag alloy bonding wire would become spherical when Au component increased. The bonded strength and bonded reliability would increase, and heat affect zone length would decrease when Au component increased in Ag-Au alloy bonding wire. The ball bonded strength and ball shear strength of Ag-5Au bonding wire were 28.4% and 28.6% higher than those of Ag-1Au bonding wire, and the heat affect zone length was 42.8% shorter. For Ag-5Au alloy bonding wire, the middle broken was 96%, and neck broken was 4%. For Ag-1Au alloy bonding wire, the middle broken was 21%, and neck broken was 79%. For Ag-Au alloy bonding wire, the failure mode was neck broken after cool and hot shock, and the reliability of Ag-5Au bonding wire was better than that of Ag-1Au alloy bonding wire.
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  Effects of malic acid carboxyl-terminated hyperbranched polyester washing agents for heavy metal removal from soil

  GONG Wei, LI Meilan, LI Lulu, WANG Lu, ZHANG Guochun, LIU Bailing

  Journal of Functional Materials. 2019, 50(10): 10149-10155. https://doi.org/10.3969/j.issn.1001-9731.2019.10.024

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  The malic acid carboxyl-terminated hyperbranched polyester (HBP-COOH) was successfully prepared by esterification with trimethylolpropane as core and malic acid as AB₂ monomer. Its structure was characterized by FTIR and ¹H NMR. And the HBP-COOH was applied to remove heavy metal from soil. The effects of HBP-COOH on removal of Zn, Cd and Cu from soil were investigated by batch experiments. The results showed that compared with malic acid, HBP-COOH had better leaching effect on Zn, Cd and Cu from the soil of mining area. Moreover, for HBP-COOH leaching agents, the removal efficiencies of Cu and Zn reached 84.9% and 93.8% at pH=4, liquid-solid ratio=25∶1, t=100 min and the concentration of 1.5wt%, respectively, and the maximum removal efficiency of Cd was 95.2% at pH=3, liquid-solid ratio=25∶1, t=140 min and the concentration of 1.5wt%. And the HBP-COOH had less effects on basic physical-chemical properties of soil.
Process & Technology
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  Preparation and application of heavy metal selective reactive nano-adsorbent

  ZOU Xueyan, CAO Pengle, QIU Kunyan, LI Xiaohong, ZHAO Yanbao, ZHANG Zhijun

  Journal of Functional Materials. 2019, 50(10): 10156-10162. https://doi.org/10.3969/j.issn.1001-9731.2019.10.025

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  With the rapid development of industry, wastewater treatment of heavy metal pollution has become an urgent problem to be solved. In this paper, silica nanoparticles were synthesized under acidic condition (20% H₂SO₄) with sodium silicate as the silicon source at 80 ℃ for 2 h. Subsequently, SiO₂-SH adsorbent were gotten in situ modification method with MPS at 80℃ for 2 h (pH value 8). Then the precipitate was gotten by filtering and part of the precipitate was preserved. To obtain SiO₂-SH adsorbent, we dried part of the precipitate at 60 ℃ for 24 h. In order to study the relationship between the adsorbent and heavy metal ions, the effects of initial concentration, adsorption time, amount of adsorbent, adsorbent state (powder, filter cake and emulsion) and addition methods (one addition and multiple addition) on Pb²⁺/Cd²⁺ ions in solution on the adsorption behavior of thiol-silica (SiO₂-SH) nano-adsorbent were investigated in this paper. The prepared adsorbent showed a high adsorption capacity. Meanwhile, the adsorption amount on target ions was firstly increased and then remained unchanged at 20 min with the increase of reaction time, indicating that the reaction was a fast chemical one. It was found that SiO₂-SH NPs had selective reactivity to Pb²⁺ and Cd²⁺ ions, but had little effect on Ca²⁺ and Mg²⁺ by adsorbing the mixed solution (Pb²⁺,Cd²⁺,Ca²⁺,Mg²⁺). Meanwhile, it is also found that the adsorption capacity of dry powder is better than that of filter cake and emulsion, and the difference of adsorption ability of three kinds of adsorbents became small with the higher the initial ion concentration. By comparing one addition with multiple addition, multiple addition can save adsorbent. Then the adsorption isotherm data were analyzed by the Langmuir and the Freundlich isotherm models, respectively. The results show that the adsorption process follows the Langmuir isotherm model. The Langmuir monolayer maximum adsorption capacities of SiO₂-SH NPs for Pb²⁺,Cd²⁺ ions are 32.07,14.92 mg/g, respectively, which have a high adsorption capacity for the target heavy metal ions.
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  Preparation and properties of nano-ZnO-T resin modified polyethylene film

  CHENG Long, YANG Fuxin, JIANG Yue, SUI Yue, XU Tao, WANG Zhiqiang

  Journal of Functional Materials. 2019, 50(10): 10163-10167. https://doi.org/10.3969/j.issn.1001-9731.2019.10.026

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  The modified T resin and the modified nano ZnO were added to the low density polyethylene as the substrate, and the modified polyethylene film was obtained by melt blending using a twin-screw granulator and a casting machine, and the modified T resin was studied. And the effect of modified nano-ZnO content on the antibacterial effect, water vapor transmission, oxygen permeation, mechanical properties, microstructure, infrared spectrum and UV transmittance of polyethylene film. The results show that when 1.5% modified nano-ZnO was added, the antibacterial property of the film was more significant with the increasing content of modified T resin. The change trend of the ultraviolet transmittance first decreased and then increased. When the mass fraction of the modified nano ZnO was 1.5% and the mass fraction of the modified T resin was 1%, the water vapor transmission amount and the oxygen permeation amount were the smallest, and the tensile strength and the elongation at break were the largest. The film had good barrier effect and antibacterial performance, and could be applied to food packaging to extend the shelf life of the food.
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  Preparation and mechanical properties of alkali-resistant glass fiber reinforced concrete

  DING Diandian

  Journal of Functional Materials. 2019, 50(10): 10168-10172. https://doi.org/10.3969/j.issn.1001-9731.2019.10.027

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  In this paper, alkali-resistant glass fiber reinforced concrete was prepared by replacing some cement with alkali-resistant glass fiber with zirconia content of 13.60 wt% and fly ash and its properties were studied. The effects of different fly ash content, glass fiber content and water-cement ratio on the aging resistance of glass fiber reinforced cement (GRC) were studied. The research shows that the alkali-resistant glass fiber reinforced concrete prepared with W/B=0.35, (FA)/(C+FA)=40% and fiber content of 2 vol% had the best compressive strength, flexural strength and dry shrinkage performance. The compressive strength and bending strength were 59.6 and 8.21 MPa, respectively. Although a large amount of fly ash was added to adjust the hydration pH value of the matrix, the fracture morphology of the compression test showed that the alkali-resistant glass fiber surface was still subjected to corrosion. The self-compacting filler method had high compressive strength and flexural strength of self-compacting concrete with high fly ash content, which had important guiding significance for the preparation of high performance GRC composites.
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  Preparation of TiO₂-based composite photocatalyst and its application in wastewater treatment

  QIU Qingling

  Journal of Functional Materials. 2019, 50(10): 10173-10177. https://doi.org/10.3969/j.issn.1001-9731.2019.10.028

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  In order to prepare materials with photocatalytic and adsorptive properties for wastewater treatment, wastewater reuse is realized.TiO₂ photocatalyst was prepared by sol-gel method.TiO₂/fly ash composite photocatalyst was prepared by hydrothermal synthesis using fly ash as adsorbent.The composite photocatalyst was characterized by infrared spectroscopy, scanning electron microscopy and BET specific surface area.Phenol and imidacloprid were used as pollutants to investigate the activity of composite photocatalyst.Photocatalytic experiments were carried out with two solar simulators and outdoor solar pilot plant under different radiation intensities to analyze the photodegradation and mineralization effects of pollutants.The results showed that the degradation of phenol and imidacloprid by photocatalyst was significantly affected by radiation intensity;FT2 had better photocatalytic activity than FT1,and the degradation rates of phenol and imidacloprid by three photocatalysts were in the order of titanium dioxide photocatalyst ＞FT2 ＞FT1.After 150 min of solar radiation in CPC, the degradation rates of phenol and imidacloprid were 52% and 88% respectively, and the mineralization rates were 32% and 35% respectively, which indicated that the degradation of imidacloprid by titanium dioxide/fly ash composite photocatalyst was more significant.In addition, fly ash has good filtration performance in wastewater treatment, so FT2 is expected to become a low-cost, filterable photocatalytic material.
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  Preparation and corrosion resistance characterization of ternary alloy film in choline ChCl-urea

  DU Chan, CHEN Biqing, GAO Lixia, XIONG Tongtong, ZHU Yunna, ZHANG Shimin

  Journal of Functional Materials. 2019, 50(10): 10178-10185. https://doi.org/10.3969/j.issn.1001-9731.2019.10.029

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  To investigate the effect of ChCl-urea eutectic solvent on the content of electrodeposited alloy film and improve the corrosion resistance of binary magnesium alloy, the Eu-Mg-Co alloy film was prepared by constant potential electrolysis in a 353 K ChCl-urea eutectic solvent to optimize the composition and corrosion resistance of Mg alloy. Cyclic voltammetry was used to study the electrochemical behavior of ChCl-urea and the addition of metal elements. The cyclic voltammetry curve on the Pt electrode shows that Co(Ⅱ)+2e→Co(0) was a one-step irreversible reaction, and the transfer coefficient α of Co(Ⅱ) on the Pt electrode and the diffusion coefficient D₀ were calculated. The rare earth element Eu and the metal Mg had a relatively low deposition potential, and it was difficult to separately deposit a single element alloy film, but a co-deposition could be induced by Co(Ⅱ) to obtain a multi-alloy film. The electrodeposition was performed by potentiostatic chronoamperometry in different potentials and different compositions. The alloy film was analyzed and characterized by EDS analysis and SEM. The alloy film was subjected to Tafel test, and the self-corrosion current and potential of the alloy film in NaCl solution were obtained by extrapolation. The results show that the transfer coefficient of Co(Ⅱ) on the Pt electrode was α=0.093, and the diffusion coefficient D₀ was 1.177×10^-5 cm²/s. The EDS results show that the Eu content was the highest in the alloy film when the deposition potential was -1.18 V and the plating solution ratio was 0.04 mol/L CoCl₂+0.04 mol/L MgCl₂+0.03 mol/L Eu(NO₃)₃. Eu-Mg-Co had good corrosion resistance. The Eu-Mg-Co alloy film with fine and uniform coating grain was obtained. The corrosion resistance of the ternary alloy film with rare earth Eu element was better than that of Co-Mg binary alloy film.
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  Preparation of microspheres using pollen as mould and their enzyme-carrying activity

  XING Dajie

  Journal of Functional Materials. 2019, 50(10): 10186-10190. https://doi.org/10.3969/j.issn.1001-9731.2019.10.030

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  In this paper, a new method of preparing microspheres by microcasting using natural pollen as mould is introduced. Three kinds of pollen with different particle size and shape, sunflower pollen, camellia pollen and rose pollen, were selected as moulds to prepare microspheres. In the course of implementation, substances such as internal cells of pollen need to be removed so that pollen forms a hollow structure that can be used as mould. Sodium alginate solution was injected into the treated pollen,then soaked in CaCl₂ solution and solidified. Finally, the pollen wall was removed under the combined action of pectinase and cellulase, then three kinds of sodium alginate microspheres with regular shape and uniform particle size can be obtained. The preparation method has the advantages of no emulsifier, simple equipment, mild conditions and wide application range. In addition, the activity test results of the microspheres containing alkaline protease prepared by this method also showed that retaining the pollen wall structure could make the microspheres more advantageous in activity.
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  Preparation of nanofibers based on perylene diimide for electrical information storage

  LI Mowen, MA Ying, REN Pinqiao, WANG Meng, WANG Zihao

  Journal of Functional Materials. 2019, 50(10): 10191-10194. https://doi.org/10.3969/j.issn.1001-9731.2019.10.031

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  With the continuing increase of information, the research of organic electrical bistable materials and devices is becoming more and more urgent. In this work, a perylene diimide molecule modified with ferrocene (PDI-Bay-Fc) was synthesized firstly, and the phase transfer method was adopted for the self-assembly of one-dimensional nanofibers of PDI, in which dichloromethane was chosen as the good solvent and n-hexane was chosen as the poor solvent. Because of the different polarity of these two solvents, the nanofibers of PDI precipitated slowly at the interface of these two solvents under the condition of n-hexane excess. Through the characterization of UV-Vis spectrophotometer (UV-vis), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), the smooth and long nanofibers were observed. The optimal assembly conditions were determined, and the growth mechanism of the nanofiber was studied. Then the one-dimensional nanofiber information storage device was prepared through composition with Au electrodes. The macroscopic electrical properties of this device were determined through the Keithley 4200 semiconductor system. The results show that the PDI-Bay-Fc functional material possessed excellent electrical bistability performance and could be used for high density data storage.
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  Preparation and filtration performance of porous ceramic with diatomite porous microspheres as the raw materials

  CHANG Shibo, XU Xingxing, SU Zhenguo, LIU Xiangfeng, DUAN Ting, LIU Kele, LI Yajie, REN Bo, WANG Xiuhui, YANG Jinlong

  Journal of Functional Materials. 2019, 50(10): 10195-10201. https://doi.org/10.3969/j.issn.1001-9731.2019.10.032

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  The porous ceramic was prepared by dry pressing with diatomite porous microspheres and glass powder porous microspheres as raw materials. The effect of sintering temperature on its open porosity, specific surface area, median pore diameter, compressive strength and crystal phase was studied, and its filtration performance including total bacterial removal efficiency, turbidity and chroma was studied. The research showed that the porous ceramics calcined at 800 ℃ had a compressive strength of (1.91±0.09) MPa, a median pore diameter of 7.4 μm, a specific surface area of 2.91 m²/g, and an open porosity of 75%, which was beneficial to the improvement of water flux. The removal efficiency of more than 99% for the total number of colonies was achieved in this experiment using the filtration of the porous ceramics. The turbidity and chroma of the filtered water met the hygienic standard of drinking water. It was expected to be applied to the advanced treatment process of the water plant and the coarse filters in the terminal water treatment equipment, and had a good application prospect.
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  Preparation of starch-based magnetic composites and their use for adsorption of heavy metal ions

  HOU Chengmin, LI Na, ZHANG Xiaolin, CAO Congjun, XIA Weimin, KOU Yanping, WANG Mei, ZHANG Wei

  Journal of Functional Materials. 2019, 50(10): 10202-10207. https://doi.org/10.3969/j.issn.1001-9731.2019.10.033

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  With the rapid development of social and industrial processes, heavy metal ions in water have serious harm to the environment and human health. People pay more and more attention to the treatment of wastewater containing heavy metal ions. In this paper, a variety of Fe₃O₄ nanoparticles were prepared by co-precipitation method and changing reaction conditions (the starch-iron ion ratio, the iron ion-sodium hydroxide ratio, reaction time and reaction temperature) with starch as template. The influence of various absorption conditions, like the adsorption time, pH value, temperature, and concentration of Cu²⁺ on the adsorption performance of Cu²⁺ were investigated. The results show that the adsorption effect on the Cu²⁺ of wastewater was the best when the adsorption time was 1 h, the pH value was 11, the temperature was 50 ℃, and the concentration of Cu²⁺ was 0.338 mmol/mL. And the absorption efficiency was reaching 90%.
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  Preparation of DOPO-based sodium salt functionalized LDH and its application in flame retarding epoxy resins

  LUO Qinqin, SUN Yulin

  Journal of Functional Materials. 2019, 50(10): 10208-10213. https://doi.org/10.3969/j.issn.1001-9731.2019.10.034

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  DOPO-based sodium salt (DOPO-ONa) was successfully synthesized from 9, 10-dihydro-9-oxa-10-phosphorphenanthrene-10-oxide (DOPO), aqueous hydrogen peroxide solution and anhydrous sodium carbonate. Then, DOPO-based sodium salt functionalized LDH (R-D-LDH) was successfully prepared by the high temperature roasting of LDH, DOPO-ONa- modification and reconstruction in water, and its structure was characterized by XRD, UV-Vis and TG. The epoxy resins containing R-D-LDH was prepared, and its flame-retardant and thermal properties were studied by using UL-94 vertical burning, LOI, cone calorimeter, TG and DSC. The results indicated that the flame-retardant efficiency of LDH was improved after functionalization by DOPO-based sodium salt. Compared with the epoxy resins containing LDH, the epoxy resins containing R-D-LDH showed the reduced burning degree and had the higher LOI values. The combustion intensity and smoke production of epoxy resin were decreased by the incorporation of R-D-LDH. When 6 wt% R-D-LDH was introduced into epoxy resin, the LOI value of epoxy resin was increased from 23.7% to 24.6%. And during combustion, its PHRR, THR and THR were decreased by 211 kW/m², 13 MJ/m² and 1 229 m²/m², respectively, and its increase range of the residue was 58%. Moreover, its T_gwas 160.6 ℃, which was same as the pure epoxy resin, and its T_5% was as high as 365.7 ℃.
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  Experimental study on the protection of BNC coating to reinforcement in magnesium cement concrete

  QIAO Hongxia, HONG Fen, WANG Penghui, GONG Wei

  Journal of Functional Materials. 2019, 50(10): 10214-10220. https://doi.org/10.3969/j.issn.1001-9731.2019.10.035

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  Aiming at the corrosion problem of chloride ion contained in magnesium cement concrete to steel bar, a coating protection method was proposed to improve its service life. In the test, Bei Naishi (BNC) coating was used to protect the steel bar from corrosion. CS350 electrochemical workstation was used to conduct electrochemical tests on magnesium cement reinforced concrete in humid environment and chlorine salt environment. The corrosion protection effect of Bei Naishi (BNC) coating on the steel bar was analyzed through corrosion current density, open circuit potential method and corrosion rate. The results show that the corrosion current density of double corrosion-resistant coated reinforced concrete in humid environment was 1/2-1/5 of that of bare reinforced concrete, and the corrosion rate of double corrosion-resistant coated reinforced concrete was 1/16-1/40 of that of bare reinforced concrete. The open circuit potential method kept a positive moving trend and corrosion was difficult to occur. The corrosion current density of reinforced concrete with double corrosion-resistant coating in chloride environment was 1/4-1/16 of that of bare reinforced concrete, and the corrosion rate of reinforced concrete with double corrosion-resistant coating was 1/36-1/184 of that of bare reinforced concrete. The positive movement trend of open circuit potential method was obvious. Therefore, it was concluded that Bei Naishi (BNC) coating had good protection effect on reinforcement in wet and chloride environment, and the protection effect of Bei Naishi (BNC) coating in chloride environment was more obvious than that in wet environment.