28 June 2017, Volume 48 Issue 6

    

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Focuses & Concerns
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  Preparation of porous carriers for wastewater treatment based on supercritical fluid process

  JIANG Jingzhi, MIAO Kai, CUI Haiting, PENG Peiying, GENG Shimin

  Journal of Functional Materials. 2017, 48(6): 6001-6006. https://doi.org/10.3969/j.issn.1001-9731.2017.06.001

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  Biofilm carrier is a key part of the biological membrane method for wastewater treatment. The performance of the carrier has a direct impact on the wastewater treatment by biological membrane method. PMMA porous carrier was prepared by supercritical fluid induced phase separation-cyclic drying process, with PMMA as model material, acetone as solvent and supercritical CO₂ as non-solvent. Carrier interior structure was characterized by scanning electron microscope. The influence of operating conditions, such as PMMA concentration, CO₂ pressure, CO₂ temperature, pressure holding time t₁, drying time t₂ and pressure relief time t₃, on carrier interior structure was studied. The results show that the PMMA wastewater treatment porous carrier with uniform pore size distribution, excellent connectivity and high porosity can be prepared successfully by the process. The optimal preparation conditions of this process in this work are PMMA concentration of 20wt%, CO₂ pressure of 10 MPa, CO₂temperature of 45 ℃, pressure holding time t₁ of 90 min, drying time t₂ of 90 min and pressure relief time t₃ of 90 min.
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  Study on the preparation and near infrared emissivity of La_0.8Ca_0.2Fe_0.5X_0.5O₃ type oxide

  LIU Qingsheng, CHANG Qing, LI Jianglin, GAO Daowu

  Journal of Functional Materials. 2017, 48(6): 6007-6012. https://doi.org/10.3969/j.issn.1001-9731.2017.06.002

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  La_0.8Ca_0.2Fe_0.5X_0.5O₃(X=Fe, Cu, Cr, Mn) oxides were synthesized by solid phase reaction at 1 300 ℃. They were studied and compared in near infrared emissivity and characterized by XRD, XPS and FT-IR.The results show that the synthesized La_0.8Ca_0.2Fe_0.5X_0.5O₃ type oxide sample is single phase. The emissivity of LaFeO₃ in the near infrared band of 200-2 500 nm was increased by more than 60% after dopingand the Ca-Cr＞Ca-Cu＞Ca＞Ca-Mn＞Ca-Cr was not mixed.The dopedFe⁴⁺ impurity level enhanced free carrier concentration and transition band gap. The different doping concentration of Fe³⁺ caused different transition Fe⁴⁺and oxygen vacancies, resulting in different emission rates of different doping elements.La_0.8Ca_0.2Fe_0.5X_0.5O₃ type oxide materials have excellent near infrared radiation properties, which can play a role in the field of high temperature thermal energy conservation.
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  Modification of magnesium silicate and its adsorption of organic matter in heavy oil wastewater

  DU Guoyong, ZHANG Hongming, LI Yan, DENG Chunping, WANG Qian, ZHU Mengxiang

  Journal of Functional Materials. 2017, 48(6): 6013-6017. https://doi.org/10.3969/j.issn.1001-9731.2017.06.003

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  The acidified magnesium silicate was successfully prepared by process of roasting acidifying. The resulting acidified magnesium silicate was characterized by Fourier transform infrared spectrometer (FT-IR), scanning electron microscope (SEM) and fully auto surface area analyzer. Adsorption properties and different factors affecting the adsorption for the organic matter in heavy oil wastewater, i.e. dose of adsorbent, pH, temperature and time were studied. Results showed that the number of micro pores and the specific surface area of magnesium silicate greatly increased with the crystal form changed. The process of roasting acidifying for magnesium silicate enhanced the adsorption of the organic matter in heavy oil wastewater by the virtue of enhancing its COD reduction from 52.94% to 76.12%. Higher COD reduction was achieved at lower temperatures. At 20 ℃, it was favorable for the adsorption under strong acidic or strong alkaline conditions and COD removal efficiency was attained 65.58% by adsorption process in 0.5 h.
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  Effect of molecular weight on the dielectric and energy storage properties of α-phase poly(vinylidene fluoride)

  ZHAO Yuetao, CHEN Yan, ZHOU Yujiu, YANG Wenyao, XU Jianhua

  Journal of Functional Materials. 2017, 48(6): 6018-6022. https://doi.org/10.3969/j.issn.1001-9731.2017.06.004

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  The molecular weight shows great influence on dielectric and energy storage performance of poly(vinylidene fluoride) (PVDF) films and related devices. In this letter, four kinds of PVDF with different molecular weight and corresponding films with predominant α phase were fabricated and the influences of molecular weight on the dielectric and energy storage properties of these PVDF films were studied. It has been found that the low-molecular-weight PVDF film presents a much slimmer polarization-electric field hysteresis loops, higher discharge energy storage efficiency (73.05%), lower leakage current (0.07175 μA) and higher resistivity(22.7 TΩ·m). Under a 1 000 kV/cm electric field, the discharge energy storage efficiency and resistivity of the low-molecular-weight PVDF film are 2.27 and 18.92 times as much as which of the high-molecular-weight PVDF film respectively, while the leakage current of the former is less than 6% of the latter, which means the low-molecular-weight PVDF film is more desirable and promising for high performance pulse discharge capacitor application.
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  Preparation and characterization of functional copolymer with tourmaline modified by methacryloyl chloride

  HU Yingmo, LI Yunhua, LI Mengcan, HOU Chunyan, LIU Quan

  Journal of Functional Materials. 2017, 48(6): 6023-6028. https://doi.org/10.3969/j.issn.1001-9731.2017.06.005

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  The polymerizable tourmaline was prepared by surface modification of tourmaline with methacryloyl chloride and then it was copolymerized with methyl methacrylate and butyl acrylate to synthesize the tourmaline-containing functional copolymer p(TMC/BA/MMA)with the tourmaline introduced into the copolymer. The experimental results showed that surface modification preserved tourmaline’s anion-releasing properties and the modified tourmaline and its copolymer presented excellent anion-releasing and far-infrared radiation characteristics. In addition, the tourmaline dispersedhomogeneously in the copolymer and as a result, the functional copolymer p(TMC/BA/MMA) film presented strong mechanical properties.
Review & Advance
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  Research progress in the Ni-based molecular sieve catalysts for the methanation of carbon dioxide

  ZHOU Ting, GUO Fang, XU Junqiang, CHEN Zhi, LI Jun, LIU Qi

  Journal of Functional Materials. 2017, 48(6): 6029-6033. https://doi.org/10.3969/j.issn.1001-9731.2017.06.006

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  The research progresses in Ni-based molecular sieve catalysts for CO₂ methanation are reviewed. The effects of the different pore structures of molecular sieves on catalytic performance for the CO₂ methanation are summarized. The interactions between the different carrier structures of molecular sieves and active components are discussed. The relationship among particle size, active component nickel dispersion and anti-sintering are systematically analyzed. The structure-activity relationship of different pore structures of molecular sieve catalysts and the mechanisms of anti-sintering and carbon deposition resistance are explained. Finally, the future developments of Ni-based molecular sieve catalysts for the application of CO₂ methanation are previewed.
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  Research progress of measurement for the thermal conductivity of thin films

  ZHANG Wukang, CHEN Xiaoyuan, LI Dongdong, FANG Xiaohong

  Journal of Functional Materials. 2017, 48(6): 6034-6041. https://doi.org/10.3969/j.issn.1001-9731.2017.06.007

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  Thin film materials are indispensable for the fabrication of micro / nano devices, and their thermal conductivity directly limits the heat dissipation performance of micro / nano devices, which affects the performance and reliability of devices. Therefore, the thermo-physical properties of thin films is very important for the design and manufacture of semiconductor devices and integrated circuit design, Here, the thermal conductivity measurement method of thin film materials is reviewed. Based on the analysis of the microstructure model, the feasibility of the thermal conductivity measurement method is analyzed, which provides technical reference for thermal measurement of thin film materials.
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  Dispersion of carbon nanotubes and research progress on mechanical properties of carbon nanotubes cement-based composites

  TANG Qianlan, HUANG Jun, TIAN Guoxin

  Journal of Functional Materials. 2017, 48(6): 6042-6049. https://doi.org/10.3969/j.issn.1001-9731.2017.06.008

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  As a perfect nano-fiber material, carbon nanotube has excellent mechanical, electrical, thermal and other properties. In civil engineering, the carbon nanotubes with uniform and stable dispersion can be used to enhance the cement-based composites, and improve the strength of the composites better. The dispersion of carbon nanotubes is introduced, and the mechanical properties of carbon nanotube cement-based composites are analyzed and summarized with experimental research and numerical analysis. Finally, the mechanical properties of carbon nanotube cement-based composites are assessed and prospected.
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  Growth mechanisms of graphene prepared by CVD on transition metals substrates

  WU Tao, ZHANG Xiaowei, JIANG Yehua

  Journal of Functional Materials. 2017, 48(6): 6050-6056. https://doi.org/10.3969/j.issn.1001-9731.2017.06.009

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  Graphene has become the focus of research recently due to its unique excellent properties. Various methods have been proposed for the synthesis of graphene and chemical vapor deposition (CVD) appears to be the most promising route for synthesizing large-area graphene. For Cu catalyst, the formation of graphene can be explained by the surface growth model, in which carbon aggregates at the surface of Cu to form graphene. Graphene are formed at different mechanism on different crystalline facets for Ru, Ir, Ni and Co. This review discusses the fundamental mechanisms of the synthesis of graphene from various transition metals through a CVD process and concludes the difficulties and challenges involved in large-scale graphene synthesis and the reuse of the catalysts.
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  Construction of durable superhydrophobic surface and its research progress

  ZHANG Yanping, DONG Binghai, WANG Shimin, ZHAO Li, WAN Li, WANG Erjing

  Journal of Functional Materials. 2017, 48(6): 6057-6063. https://doi.org/10.3969/j.issn.1001-9731.2017.06.010

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  Due to its unique properties, the surface of the lotus leaf has a great application prospect in production and life. However, its practical application has been greatly restricted due to its poor durability. This paper mainly introduces the main construction method of super hydrophobic surface, focuses on how to construct the durable super hydrophobic surface, points out the existing problems of the super hydrophobic and looks forward to its future development.
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  Applications of rare earth up/down conversion materials for dye-sensitized solar cells

  GUO Haiyong, ZHAO Li, WANG Shimin, DONG Binghai, WU Yadan, XIA Si

  Journal of Functional Materials. 2017, 48(6): 6064-6068. https://doi.org/10.3969/j.issn.1001-9731.2017.06.011

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  Dye-sensitized solar cells (DSSCs) have attracted extensive interest as an promising alternative to silicon solar cells. However, DSSCs have a maximum absorption in visible light of solar spectrum, which confines the power conversion efficiency. Rare earth up /down conversion materials were used to effectively make up for the shortage via converting ultraviolet and near-infrared radiation to visible emission in the DSSCs. At the same time, the light-scattering effect can reduce the recombination loss effectively and promote the stability of the DSSCs. The up/down conversion mechanism is pointed and recent research progress of applications based on rare earth up/down conversion materials in DSSCs is reviewed.
Research & Development
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  Multiferroic properties of single-phase Bi_0.95La_0.05Fe_1-xCo_xO₃ ceramics

  ZHANG Chunmei, RAN Nian, LIU Haifeng, ZHANG Xingquan

  Journal of Functional Materials. 2017, 48(6): 6069-6073. https://doi.org/10.3969/j.issn.1001-9731.2017.06.012

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  Single-phase Bi_0.95La_0.05Fe_1-xCo_xO₃ ceramics with x=0, 0.1 and 0.2 were prepared by high pressure synthesis. The effects of La and Co doping on phase structure and multiferroic properties were investigated. X-ray diffraction patterns demonstrated rhombohedral structure for all samples.La and Co co-doping favors weak ferromagnetism ordering with evident magnetic hysteresis loop and enhances magnetization values at room temperature, which is attributed to the change in the spin structure from a cycloidal space modulated spin structure to a collinear G-type antiferromagnetic structure. The dielectric constant for the Co-doped BiFeO₃ samples at room temperature increases with increasing applied magnetic fields, which is a signature of the magnetoelectric coupling occurring in the samples. The magnetodielectric coefficient of the Bi_0.95La_0.05Fe_0.9Co_0.1O₃ and Bi_0.95La_0.05Fe_0.8Co_0.2O₃ samples reach 1.61% and 1.75% at H=796 kA/m and f=3 kHz, respectively.
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  Electromechanical response and finite element analysis of dielectric polymer with asymmetric electrodes

  CHEN Lumin, WANG Chen, WANG Caidong, SHI Bo, GUO Dongjie

  Journal of Functional Materials. 2017, 48(6): 6074-6079. https://doi.org/10.3969/j.issn.1001-9731.2017.06.013

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  Dielectric elastomers (DE) actuator with asymmetric electrodes is assembled, where DowCorning 186 silicone rubber is acted as the dielectric elastomer substrate, and silicone elastomers of 184 doped by Ag nanoparticles and conductive graphite are used to fabricate the asymmetric electrodes. There exist evident difference between the mechanical and conductive properties, and the corresponding electrode film thicknesses, moduli, surface resistance are 96.8 μm, 26.6 MPa, 8.42 kΩ/cm² and 179.3 μm, 32.6 MPa, 3.87 kΩ/cm², respectively. Under the excitation signal of 4 kV voltage, 2 Hz frequency, and 25% duty cycle, the largest amplitude deviation from the equilibrium position of the asymmetric DE membrane is 3.6 mm, and the deviation angle is 17.4°. The relationship among the excited displacement, driving voltage and the frequency are studied by using a laser displacement sensor. The results show that the excited displacement increases with the driving voltage, and decreases with the increase of frequency. Meanwhile, ANSYS software is used to simulate the outputted stress, power, and flow of the asymmetric DE pump, and the calculation results can provide experimental data and research foundations for developing a new intelligent controllable micropump.
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  Dissolution behavior of higher DP bamboo dissolving pulp fiber in NaOH/ additive aqueous solution

  SHI Yan, ZHANG Kuo, SUN Haitong, ZHU Yatong, HU Zhenxing, ZHENG Quan, YANG Fang

  Journal of Functional Materials. 2017, 48(6): 6080-6085. https://doi.org/10.3969/j.issn.1001-9731.2017.06.014

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  NaOH/additives aqueous solution solvent being able to dissolve cellulose at low temperature widely attracted the focus of many researchers because of its low cost, environmental protection and rapid dissolution. However, this solvent is difficult to be applied in industry due to its limited solubility. Therefore, commercial bamboo dissolving pulp with high degree of polymerization(DP) was selected as experimental materials in this paper, and its dissolution behavior in 7%NaOH/12% urea aqueous solution,9.5%NaOH/4.5% thiourea aqueous solution and 8%NaOH/8% urea /6.5% thiourea aqueous solution at low temperature was investigated by polar microscopy. In addition, the dissolving capacity of three NaOH/ additives aqueous solution systems was compared by viscosity measurement of transparent cellulose solution, determination of dissolving proportion, UV-Vis spectrum analysis, dynamic light scattering (DLS) test and XRD analysis of insoluble residues. The results showed that 8%NaOH/8%urea/6.5%thiourea solvent system displayed a strong capacity of dissolving cellulose, about 60% dissolving proportion, namely, different from pure cellulose and other lower DP chemical wood pulps, better dissolution of high DP bamboo dissolving pulp with rigid fibers in NaOH/ additives solvent system at low temperature need higher concentration of alkali solution and several additives capable of breaking hydrogen bond.
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  Structure and magnetocaloric effects in Gd_1-xHo_xCo₂ compounds

  MAO Yulong, ZHENG Zhigang, TAN Zhucai, YU Hongya, ZENG Dechang

  Journal of Functional Materials. 2017, 48(6): 6086-6090. https://doi.org/10.3969/j.issn.1001-9731.2017.06.015

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  Gd_1-xHo_xCo₂ (x=0, 0.2, 0.4, 0.6) compounds were prepared by vacuum arc melting. The structure and magnetic properties for all samples were investigated using XRD, SEM and VSM. The results show that the Gd_1-xH_xCo₂ series compounds remain pure MgCu₂ type Laves phase structure, but there exist impurity phase GdCo₃ in the sample. With the increase of Ho contents, although the Curie temperature T_C decreases from 399 to 236 K by 67 percent, magnetic entropy change ΔS_M increases slightly from 3.3 to 4.0 J/(kg·K) under 5 T. The measurement results show that the substitution of Ho for Gd is effective methods to tune the Curie temperature while keeping the values of magnetic entropy change. Furthermore, The RC values increase from 158.3 to 254.6 J/kg by 60.8% with increasing of Ho contents under 0-5 T magnetic field. Furthermore, it is discussed about the relationship between the crystal structure and magnetic properties. Thus, it makes these materials more competitive for practical application in wide temperature regions.
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  First principles research on the electronic and magnetic properties of CuZr₂ phase

  XU Zhichao, FENG Zhongxue, SHI Qingnan, YANG Yingxiang, WANG Xiaoqi, QI Huarong

  Journal of Functional Materials. 2017, 48(6): 6091-6096. https://doi.org/10.3969/j.issn.1001-9731.2017.06.016

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  CuZr₂ phase is the main reinforcement in the Mg alloys. By using the first principles method, the electronic and magnetic of CuZr₂ were calculated and analyzed in detail. The calculated lattice parameter were in good agreement with the experimental data. The computing results on the band structure and density of state demonstrate that bonding peak is generated through the interaction of Cus,Cup,Cud and Zrd obrits。The Mulliken population distribution computation illustrates that electric charge transferred from Zr to Cu were 0.34. The electron density distribution of CuZr₂ shows that Cu-Zr bond has an obvious locality. It is regarded that the Cu-Zr bond is polar covalent bond. Furthermore, the studies on the integrated spin density demonstrate that the CuZr₂ phase shows paramagnetic, which stems mainly from Zrd obrit, will make an electromagnetic shielding effect in ZW alloys.
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  Fabrication and property study of elastin-like polypeptide and silk complex scaffold

  CHEN Zhuoyue, WEI Qi, WANG Jinrong, LONG Kaiping, LI Hongmin

  Journal of Functional Materials. 2017, 48(6): 6097-6103. https://doi.org/10.3969/j.issn.1001-9731.2017.06.017

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  Silk microfibers and Elastin-like polypeptide (ELP) were treated with four methods, (1) Dehydrothermal treatment (DHT);(2) mixing with genipin;(3) mixing with proanthocyanidin (PA);(4) mixing with PEG and glutaraldehyde (GA). The resulting materials were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR) and mechanical properties. The fiber reinforcement (Silk-ELP-DHT, Silk-ELP-Genipin and Silk-ELP-PEG-GA) resulted in the development of more mechanically robust constructs compared to silk alone. Meanwhile, the Silk-ELP-DHT and Silk-ELP-Genipin composite scaffolds show higher and more stable mechanical properties and better cytocompatibility.
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  Synthesis of a novel thermosensitive core-shell polymer microspheres and their application

  TANG Jieli, MA Jing

  Journal of Functional Materials. 2017, 48(6): 6104-6108. https://doi.org/10.3969/j.issn.1001-9731.2017.06.018

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  In this article, core-shell microspheres were synthesized by surfactant-free emulsion polymerization and seed polymerization with polystyrene as the core and poly(N-isopropylacrylamide-co-acryloxysuccinimide) as the shell by modified emulsifier-free emulsion polymerization. The structures and properties of the composite were characterized by FT-IR, SEM, TEM and particle size analyzer. The results show that the as-prepared materials exhibited a well monodispersity and clear core-shell structure. The relationship of diameter and temperature was detected, and the result showed that the microspheres have thermo-sensitive property with the lower critical solution temperature(LCST) about 31 ℃. The bromelain was covalently conjugated to the surface of the microsphere through the reaction between primary amino groups and the succinimide ester groups in the shell due to their high reactivity. The influence of pH and temperature on binding rate of the two substances were investigated. It was found that the optimum conditions were pH=6.39, t=4 ℃, and the binding rate reach the maximum in 4 h.
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  Preparation and characterization of anodized aluminum films under high voltage

  REN Yaxuan, XU Qin, SUN Yubao, MA Hongmei, ZHANG Shiyuan, GUO Yuqiang, FU Mingzhu

  Journal of Functional Materials. 2017, 48(6): 6109-6112. https://doi.org/10.3969/j.issn.1001-9731.2017.06.019

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  Porous anodic alumina film can be formed on aluminum substrate in malonic acid and ethylene glycol electrolyte solution by electrochemical method. Effects of concentration of electrolyte on thickness and interpore distances of porous anodic alumina film were discussed. The test results ofthe porous anodic alumina show highly ordered dimple arrays measuring 200-400 nm in interpore distances at the ultra-high voltage of 500 V. Such film shows bright color successfully. The reflection peak shifts gradually with the alumina interpore distances toward longer wavelength. The aluminum specimens were anodized in 1.5 mol/L malonic acid and ethylene glycol electrolytes, and its maximum peak reaches 622 nm at 400 nm in interpore distances.
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  Liquid phase catalytic hydrogenation of tetrabromobisphenol-A over palladium doped on modified graphitic carbon nitride

  LIU Boyan, CHEN Huan, JIANG Fang

  Journal of Functional Materials. 2017, 48(6): 6113-6118. https://doi.org/10.3969/j.issn.1001-9731.2017.06.020

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  Pd doped mesoporous graphitic carbon nitride catalysts (Pd/mpg-C₃N₄) were synthesized via a photo-deposition method. The prepared catalysts were characterized. Characterization results indicated that Pd/mpg-C₃N₄ was synthesized with the structure of mesoporous and higher specific surface area. The Pd particles were well-distributed onto the surface of mpg-C₃N₄. Their catalytic performance was examined by the liquid phase catalytic hydrogenation of tetrabromobisphenol-A (TBBPA). The liquid phase catalytic hydrogenation of tetrabromobisphenol-A over Pd/mpg-C₃N₄ showed high catalytic activity. It turned out that the catalytic activity of Pd/mpg-C₃N₄ is positively associated with Pd²⁺ on the surface of the support. Also, the process of the liquid phase catalytic hydrogenation of TBBPA can be described by the model of Langmuir-Hinshelwood, which indicated that the control procedures of catalytic hydrogenation is the absorption of TBBPA on the surface of the catalysts.
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  Preparation and photocatalytic properties of magnesium phthalocyanine/PHBV films

  XU Minhong, WANG Kunyan, PAN Guoxiang, GUO Yuhua, WU Tao

  Journal of Functional Materials. 2017, 48(6): 6119-6123. https://doi.org/10.3969/j.issn.1001-9731.2017.06.021

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  The composite catalytic films MgPc/PHBV are prepared by loading MgPc onto the PHBV. The structures and properties of MgPc/PHBV are characterized by XRD, FT-IR, TG-DTA and UV-Vis DRS. The results indicate that MgPc and PHBV may be combined by physical action. Adding MgPc makes the crystallinity of PHBV decrease. In addition, the degradation temperature of PHBV increased 20 ℃ due to MgPc. Tests based on UV-Vis DRS show that the MgPc/PHBV has visible light catalytic activity. Therefore, photocatalytic degradation of organic pollutants methyl orange (MO) with MgPc/PHBV is studied. It is found that MO can only be effectively photocatalytic degradated when light, MgPc/PHBV and H₂O₂ simultaneously present. The residual rate of MO is 0.0% after 160 min illumination, which means MO is completely degraded. Hydroxyl radicals play a key role in photocatalytic oxidation of MO based on the study of reaction mechanism.
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  Preparation and biological characterization of silk fibroin/bladder acellular matrix /hyaluronic acid electrospun scaffolds

  JIANG Dan, HUANG Jianwen, SHAO Huili, HU Xuechao, SONG Lujie, ZHANG Yaopeng

  Journal of Functional Materials. 2017, 48(6): 6124-6128. https://doi.org/10.3969/j.issn.1001-9731.2017.06.022

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  Regenerated silk fibroin (RSF)/bladder acellular matrix (BAM)/hyaluronic acid (HA) scaffolds were electrospun from aqueous solution. The morphology and biological performances in vitro were characterized by scanning electron microscope, ELISA, MTT and fluorescent microscopy. Results showed that the concentrations of spinning solutions had limited impact on the morphology of the scaffolds. The existence, bioactivity and continuous release behaviors of vascular endothelial growth factor (VEGF), platelet-derived growth factor BB (PDGF-BB), keratinocyte growth factor (KGF) from the scaffolds were confirmed and determined. Due to the bioactivity of the growth factors, the RSF/BAM/HA scaffolds showed better performance for cell growth and proliferation than bare RSF scaffolds.
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  Influence of Dy-doping on thermophyscial properties of Sm₂Ce₂O₇

  TANG An, ZHAO Yongtao

  Journal of Functional Materials. 2017, 48(6): 6129-6133. https://doi.org/10.3969/j.issn.1001-9731.2017.06.023

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  In this paper, the (Sm_1-xDy_x)₂Ce₂O₇ solid solutions were prepared by solid reaction method using Dy₂O₃, Sm₂O₃ and CeO₂ as the reactants. Its phase composition was analyzed by XRD technology, the microstructure was observed by scanning electronic microscope (SEM). Its thermal diffusivity and expansion coefficient were measured by laser-flashing method and pushing-rod technology. Results show that pure (Sm_1-xDy_x)₂Ce₂O₇ solid solutions were synthesized successfully, its microstructure was very dense, and the grain interface was clear. Its thermal conductivity and expansion coefficient decrease gradually with the increasing content of Dy³⁺ ions, while its thermophyscial properties match well with the basic requirement for thermal barrier coatings. The synthesized (Sm_1-xDy_x)₂Ce₂O₇ solid solutions have potentials to be explored as candidates for thermal barrier coatings.
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  Sol-gel auto-combustion synthesis of nanocrystalline spinel AFe₂O₄

  XUE Rui, WANG Yongqiang, ZANG Meng, CHEN Xi, LIU Minmin, ZHAO Chaocheng

  Journal of Functional Materials. 2017, 48(6): 6134-6138. https://doi.org/10.3969/j.issn.1001-9731.2017.06.024

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  A series of nano spinels AFe₂O₄ (A=Cu, Co, Ni, Mg, Zn) were synthesized through sol-gel auto-combustion method. The study was focused on the influence of the different elements of A bit on the spinel materials. The prepared samples were characterized by DTA, XRD, FT-IR, BET, SEM, TEM and XPS techniques. The results showed that the dried gel of AFe₂O₄ auto-burned at 200 ℃. And the spinel structures which were constituted by the tetrahedron and hexahedron sublattices formed at 500 ℃. It was found that the lattices with size of around 40 nm were typical nano structures. Especially, the proportions of Fe, Cu, O in the trans spinel material CuFe₂O₄ were 42%, 39% and 19%. BET, TEM and SEM results showed the spinel materials had obvious lamellar mesoporous structures with specific surface areas of around 20 m²/g. With different elements in A bit, the dried gel of AFe₂O₄ auto-burned at different temperature, and the pore structures and microstructures had great difference.
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  Preparation of SrAl₂O₄:Eu²⁺,Dy³⁺ via EDTA-complex process and its modification

  ZHANG Chunxiang, WU Jia, YANG Kaina, XU Zhibin, ZHANG Xiang

  Journal of Functional Materials. 2017, 48(6): 6139-6143. https://doi.org/10.3969/j.issn.1001-9731.2017.06.025

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  SrAl₂O₄:Eu²⁺, Dy³⁺ was prepared by a complexing process using corresponding metal nitrates as raw materials and ethylene diamine tetraacetic acid (EDTA) as complexing agent. PMMA/SrAl₂O₄:Eu²⁺, Dy³⁺ luminescent materials were synthesized via coupling agent modification and graft polymerization. The effect of calcination temperature on the crystal structure was studied. The thermal decomposition of dry gel, crystallization behavior, structure and luminescent properties before and after coating were characterized by TG-DTA, XRD, FT-IR and photoluminescence. The results indicate that the formation of single phase SrAl₂O₄:Eu²⁺, Dy³⁺can be achieved at a relatively low temperature of 1 000 ℃. The structure and luminescent properties were not changed by coating process. However, the water resistance was improved. This helps to expand the application of luminescent materials in wet or aqueous systems.
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  Study on microstructure and mechanical properties of Al_xCoCrFeNi high entropy alloy thin films prepared by magnetron sputtering

  HUANG Chunke, LI Wei, LIU Ping, ZHANG Ke, MA Fengcang, LIU Xinkuan, CHEN Xiaohong, HE Daihua

  Journal of Functional Materials. 2017, 48(6): 6144-6148. https://doi.org/10.3969/j.issn.1001-9731.2017.06.026

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  The Al_xCoCrFeNi high entropy alloy films with different Al contents (x=0 -20at%) were prepared by DC magnetron sputtering technique in this paper. The effect of Al content on the microstructure and mechanical properties of Al_xCoCrFeNi high entropy alloy films was investigated. The results show that the addition of Al element weakens (200) diffraction peak, and the Al_xCoCrFeNi film is consisted of a uniform fcc-structured solid solution with a (111) preferential growth orientation. Due to the solid solution strengthening effect, the hardness of Al_xCoCrFeNi film is 1-2 GPa higher than that of CoCrFeNi film. When the Al content is 0.8, the Al_xCoCrFeNi film presents the finest columnar crystals. Under the strengthening effect of the Hall-Petch relationship, the hardness of Al_xCoCrFeNi film remarkably improves with the maximum value of 18.7 GPa.
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  Research of strain sensing films based on graphene and polymer emulsion

  LI Miaomiao, ZHANG Dong

  Journal of Functional Materials. 2017, 48(6): 6149-6153. https://doi.org/10.3969/j.issn.1001-9731.2017.06.027

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  Graphene, a novel two-dimensional atomic crystal consisting of a single layer of carbon atoms, has stimulated extensive studies due to its fascinating physical properties such as high transparency, high intrinsic electron mobility, large specific surface area, high thermal conductivity, supreme mechanical strength and excellent flexibility. The unique structure and excellent properties of graphene make it great potential in many fields such as strain sensor and wearable electronic devices. Graphene film, as an important form of graphene materials, can fully demonstrate the excellent properties of graphene. Anovel strain sensing film based on graphene/ polymeremulsion was prepared by spray coating method, which can be integrated with the object to be detected. The effects of spraying quantity of graphene and the thickness of emulsionon the microstructure, electrical conductivity and strain sensing properties of graphene/polymeremulsion composite films were studied.
Process & Technology
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  The effect of imidization process on the performance of PI/nano-Al₂O₃ three-layers composite films

  HE Hongju, LIU Lizhu, WENG Ling

  Journal of Functional Materials. 2017, 48(6): 6154-6157. https://doi.org/10.3969/j.issn.1001-9731.2017.06.028

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  In this paper, polyimide/nano-Al₂O₃ three-layers composite films with different imidization process were perpared by in-situ polymerization with pyromellitic dianhydride (PMDA) and 4,4’- two amino two phenylether (ODA) as monomers and N, N- two dimethyl acetamide (DMAc) as solvent. The doping amount is 12wt%. The FT-IR was used to evaluate the imidization process of the first layer of the composite films and the imidization degree was calculated. The interface structures and bonding conditions of the three layer composite films were characterized by scanning electron microscope. At the same time, the trap states of the composite films were tested by photon-stimulated discharge (PSD). In addition, the electric degradation threshold and the corona resistance time of the composite films prepared by different processes were also tested. The results indicated that the higher of the imidization rate and time, the better of the combination degree between the three-layer composite film layers and the stronger of the composite membrane surface corona resistant abilities. Meanwhile, the electric degradation threshold and the corona resistant time of composite films were also improved with the increase of imidization rate.
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  Preparation and characterization of Co modified Au@CeO₂ core-shell structure

  CHEN Yilu, ZHANG Weining, HE Beibei, WANG Xiaohong, XU Jiaqiang

  Journal of Functional Materials. 2017, 48(6): 6158-6164. https://doi.org/10.3969/j.issn.1001-9731.2017.06.029

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  Two types of Co modified Au@CeO₂ core-shell structure nano catalytic material for carbon monoxide oxidation at low temperature are prepared by glucose hydrothermal method. One is named as m%Co-Au@CeO₂, in which the amount of Au@CeO₂ kept constant and m% is the molar percent of Co. The other is named as 2%Au@CeO₂-Co₃O₄X, in which 2% is the mass percent of Au and X is the molar ratio of Co/Ce. All the samples are characterized by XRD, TEM and SEM methods and the catalytic activity for carbon monoxide oxidation is also tested. The results proved that CeO₂ and Co₃O₄ coexist in m%Co-Au@CeO₂ and the interaction between them can prohibit the particles growth with each other. When the content of Co reaches 40%, the catalytic activity is the highest but still lower than that of pure Au@CeO₂, which indicates that the increase of Co content can’t improve its activity. However, when the mass percent of Au is kept constant, the change of Co/Ce molar ratio can improve the catalytic activity. The particle size of 2%Au@CeO₂-Co₃O₄ 60 is the smallest while its catalytic activity is the highest.
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  Preparation of phosphorus-nitrogen synergistic flame retardant MCA-ADEPH and its effects on flame retardancy of PA6

  XIAO Yuanfang, XU Jiayou, DENG Haiming

  Journal of Functional Materials. 2017, 48(6): 6165-6170. https://doi.org/10.3969/j.issn.1001-9731.2017.06.030

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  A phosphorus-nitrogen synergistic flame retardant,MCA-ADEPH,was synthesized through adding ADEPH into the reaction between ME and CA,and its chemical structure was characterized. The halogen-free flame retarded PA6/MCA and PA6/MCA-ADEPH composites were prepared by melt blending of flame retardant and PA6,and their flame retardancy and mechanical properties were studied. The results showed that there is no chemical reaction between MCA and ADEPH,and the addition of ADEPH can make the size of MCA particles become smaller. MCA-ADEPH can improve the flame retardancy of PA6 from both gas and condensed phase. What’s more,the excellent mechanical properties are kept while the flame retardancy is improved.
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  Synthesis of N-doped porous carbon/nickel manganese oxide combined with carbon tubes and its capacitance property

  ZHAO Jie, LI Kanshe, WANG Xiaoqin, YANG Yufei, LI Qiaoqin

  Journal of Functional Materials. 2017, 48(6): 6171-6175. https://doi.org/10.3969/j.issn.1001-9731.2017.06.031

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  With coal/polyaniline composites as carbon and nitrogen source, nickel acetate and nickelocene as catalyst precursor, N-doped porous carbon/nickel manganese oxide and carbon tubes are synthesized synchronously through thestage-pyrolysis process in two-stage furnace and KMnO₄ oxidation process. It’s found that the diameter of most carbon microtubes is between 150 to 400 nm. Most carbon nanotubes are about 60 nm in diameter and about 10 nm in thickness of their walls. Porous carbon is mainly mesoporous with BET specific surface area of 801.59 m²/g, BJH average pore diameter of 47.87 nm. Porous carbon is successfully doped by N element and part of N lists in the state of crystalline CN_x. Nickel manganese oxide mainly exists in the chemical state of NiO andaccompaniesNiMn₂O₄ and α-MnO₂.The compounds were attached to the porous carbon surface or inserted in the pores with the shape of nano sheets.N-doped porous carbon/nickel manganese oxide has the specific capacitance of 387.18 F/g in the current density of 1A/g and maintains the specific capacitance retention of 81.48% in the current density of 5 A/g after 1 000-cycle charging and discharging.
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  Preparation and in vitro evaluation of co-delivery of doxorubicin and

  GUO Qingfa, ZHOU Maoling, CAO Hui

  Journal of Functional Materials. 2017, 48(6): 6176-6182. https://doi.org/10.3969/j.issn.1001-9731.2017.06.032

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  In this paper, a novel biodegradable poly (L-lactide)-polyethylenimine copolymer was successfully prepared from low-molecular-weight polyethylenimine and poly (L-lactide) using isophorone diisocyanate (IPDI) as the coupling agent. W/O/W emulsion-solvent evaporation method was used to make PEA microspheres for co-delivery of doxorubicin(DOX) and curcumin(Cur). The obtained PEA/(DOX+Cur) microspheres were characterized by detection of particle size, morphology study, drug loading, encapsulation efficiency, release study, cytotoxicity, cellular uptake and so on. This study suggested that PEA microspheres delivery system may help in development of co-delivery drugs to tumours and other diseases.
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  Preparation of high-density tantalum carbide coating by high-temperature chemical vapor deposition

  ZHANG Li, QI Haitao, XU Yongkuan, WANG Lijie, SHI Yuezeng, LIU Jinxin

  Journal of Functional Materials. 2017, 48(6): 6183-6186. https://doi.org/10.3969/j.issn.1001-9731.2017.06.033

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  Tantalum carbide (TaC) coating was prepared on high-purity, high-density graphite by high-temperature chemical vapor deposition (CVD). The effects of gasification temperatures, flow rates and deposition temperatures on the surface qualities of TaC coating were investigated. And then, the technical conditions of TaC coating prepared by CVD method were confirmed. Finally, TaC coatings with high densities were obtained.
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  Fabrication of PDMS/PTFE superhydrophobic coating by the method of hybrid curing and its self-cleaning property

  ZHAN Yanlong, LI Wen, LI Hong, HU Liangyun

  Journal of Functional Materials. 2017, 48(6): 6187-6192. https://doi.org/10.3969/j.issn.1001-9731.2017.06.034

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  Superhydrophobic coatings with a certain transparency and self-cleaning performance were obtained by hybrid curing PDMS and PTFE ultrafine powder on slide glass substrate with TEOS as cross-linking agent and DOTDL as catalytic agent. Contact angle measurement instrument, FT-IR and SEM were applied to characterize wettability, morphology and structure of the surfaces of superhydrophobic coatings. The effect of the addition of PTFE ultrafine powders on structure and wettability of superhydrophobic coatings surfaces was discussed, and self-cleaning property of superhydrophobic coatings was investigated. The superhydrophobic coatings with maximum contact angle of 169.83° and water roll angle of about 2-3° have superb superhydrophobicity, ultra-low adhesive force and self-cleaning performance.
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  Preparation and swelling mechanism of fluorescent carboxyl polystyrene microspheres

  WANG Yu, LIU Dandan, ZHANG Jiejie, HAN Guozhi

  Journal of Functional Materials. 2017, 48(6): 6193-6198. https://doi.org/10.3969/j.issn.1001-9731.2017.06.035

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  Via soap-free emulsion polymerization, carboxyl monodispersed polystyrene microspheres with different carboxyl density were firstly synthesized. Then using hydrophobic fluorescent dye NBD and hydrophilic fluorescent dye ICG as raw materials, two kinds of fluorescent polystyrene microspheres were prepared through swelling method. Analyses of SEM, along with DLS and fluorescence spectroscopy were used to study morphology and properties of the fluorescence polystyrene microspheres. On the basis, the effect of carboxyl content on the two kinds of fluorescent microspheres was investigated and corresponding swelling mechanism was further proposed. The experimental results indicated that the carboxyl density of microsphere surface has quite different impact on the swelling behavior of two fluorescent molecules.
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  Oxygen-vacancy formation and packaging technology of β-SiC/SiO_xC_y/C_free nanocomposite films as heat dissipation substrate

  YANG Min, MAO Yu, CHEN Fen, ZHOU Rui, LIAO Liang, CHEN Zeng, LIU Leyu, YAO Rongqian

  Journal of Functional Materials. 2017, 48(6): 6199-6202. https://doi.org/10.3969/j.issn.1001-9731.2017.06.036

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  Main phases of freestanding β-SiC/SiO_xC_y/C_free nanocomposite films are SiO_xC_y, and β-SiC nano-crystals are embedded within amorphous SiO_xC_y and free carbon clusters. Formation of oxygen vacancy in the samples sintered at 900-1 200 ℃ was investigated by electron paramagnetic resonance (EPR) spectroscopy. The films can be silk-screened by high temperature silver paste electrode with good conductivity and used as heat dissipation substrate for high-power LED devices via the technology of Chip On Board (COB). Morphology and package structure analysis were characterized by scanning electron microscope (SEM) and optical microscope. Junction temperature of LED devices was measured by thermal transient tester. The results show that the proportion of oxygen vacancy increases with increasing pyrolysis temperatures, and resonance lines with g-factor close to the free-electron value (2.0023) is attributed to an unpaired electron trapped on an oxygen vacancy site. Junction temperature of LED devices based on the sample substrate sintered at 1 200 ℃ with high heat transfer capability and good insulation is 33.7 ℃ far below the limit of 120 ℃. The obtained results are expected to have applications in high-power LED devices.
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  The hydrolysis property of aluminum-tin composites for hydrogen production

  GUAN Xu, LUO Ping, DONG Shijie, XIONG Can

  Journal of Functional Materials. 2017, 48(6): 6203-6209. https://doi.org/10.3969/j.issn.1001-9731.2017.06.037

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  The hydrogen production of aluminum-tin(Al-Sn) composites in pure water was studied in this paper. The aluminum-tin(Al-Sn) composites mentioned in this paper were made by mechanical alloying. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for the phase composition and microstructure. The result shows that the hydrogen production and hydrogen generation rate of Al-Sn composites can be improved by increasing the Sn content, improving the initial water temperature, adding grinding aid (NaCl) and low melting point (Bi, In etc.) by improving the activity of Al-Sn composites. The optimized percentage(wt%) Al-6%Sn-2%Bi-2%In composite by adjusting the types and contents of additives shows higher hydrogen production and hydrogen production rate, which reaches 785.6 mL/g and 175 mL/(min·g) in the pure water at 25 ℃.
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  Synthesis and properties of PMN hybrid TPU-EP/SPU composites

  MA Chi, YAN Liling, FANG Qinghong, GUO Zhuo, AN Ranran, LI Jiaxi

  Journal of Functional Materials. 2017, 48(6): 6210-6214. https://doi.org/10.3969/j.issn.1001-9731.2017.06.038

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  A series of lead magnesio-niobate (PMN) hybrid ester-ether type polyurethane damping composites were prepared by solution blending and the influence of PMN on the damping properties, piezoelectric properties, compression heat build-up and mechanical properties were explored. The results indicate that damping properties can be effectively improved by adding PMN to polymer mixture, and the temperature elevation of material resulted from damping effect can be reduced. Meanwhile, piezoelectric properties of composite also can be improved as the content of PMN increases.
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  Preparation of fluorine-containing sulfonated poly(aryl ether ketone)s for VBFR application

  KONG Lingtao, CHEN Juan, CUI Qingqing, CHEN Qingsong, HUANG Xuehong, DING Fuchuan

  Journal of Functional Materials. 2017, 48(6): 6215-6220. https://doi.org/10.3969/j.issn.1001-9731.2017.06.039

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  Proton exchange membrane is a key part of vanadium redox flow battery (VRFB). Three type of fluorine-containing sulfonated poly(fluorenyl ether ketone)s (SPEEK-6Fs) with different ion exchange capacity (IEC) were synthesized from sulfonated-4, 4′-difluorobenzophenone (SDFBP), 4, 4′-difluorobenzophenone (DFBP) and hexafluoro bisphenol A(6FBPA) by changing the molar ratio of the SDFBP and DFBP. The SPEEK-6Fs were fabricated into membranes by solution cast using DMSO as solvent. The structure of the synthesized SPEEK-6F was verified by characterization of FT-IR, NMR and ion exchange content. The results show that the structure of the synthesized SPEEK-6F was as same as the desired product's. The prepared membrane has best H⁺ selectivity when the molar ratio of the monomer SDFBP and DFBP is 1:1. The membrane made from SPEEK-6F50 has better comprehensive performance of single VRFB than Nafion117 with 95% of coulombic efficiency, 78% of voltage efficiency and 74% of energy efficiency, when the charge-discharge current is 50 mA/cm².