Synthesis of ferromagnetic nanopowders from iron pentacarbonyl in capacitively coupled RF plasma

Ferromagnetic nanopowders (NP), synthesized with magnetically decoupled cores, may represent interesting raw materials for their further conversion into nanostructured magnetic bulk materials, with properties suitable for their utilization in low and high-frequency applications. Capacitively coupled RF discharges at a pressure of 100-250 Pa, were used for the synthesis of binary iron/carbon NP from iron pentacarbonyl (Fe(CO)₅) vapours, diluted with argon. The properties of the obtained NP products were investigated by TEM, XRD, TGA, FTIR and magnetization measurements. Diamagnetic NP, with ≈4% iron content, were obtained at lower pressures (100-130 Pa), whereas increasing the pressure to 250 Pa resulted in the synthesis of ≈40% iron content NP that demonstrated ferromagnetic properties (M_s ≈ 50 emu/gr). The first type of these NP is formed of carbon/iron rods, being 10-50 nm long and several nm wide, covered by graphitic layers and integrated into an amorphous carbon matrix. The second NP type, ferromagnetic NP, consists of isolated hexagonal shaped 20-60 nm crystals of Fe₇C₃ or Fe₂C₃ carbides, again embedded in an amorphous carbon matrix. Factors for favoring the formation of the ferromagnetic carbide NP at the higher pressure are discussed. These factors include: the lower temperatures presumed in the reaction zone, the shifting of the chemical equilibrium from non-bound Fe and its oxides towards the state of carburization, and the decreasing rate of removal of the Fe oxidation products towards the reactor walls.     

Evaluation of different oxygen carriers for biomass tar reforming (II): Carbon deposition in experiments with methane and other gases

This work is a continuation of a previous paper by the authors [1] which analyzed the suitability of the Chemical Looping technology in biomass tar reforming. Four different oxygen carriers were tested with toluene as tar model compound: 60% NiO/MgAl₂O₄ (Ni60), 40% NiO/NiAl₂O₄ (Ni40), 40% Mn₃O₄/Mg-ZrO₂ (Mn40) and FeTiO₃ (Fe) and their tendency to carbon deposition was analyzed in the temperature range 873-1073 K. In the present paper, the reactivity of these carriers to other compounds in the gasification gas is studied, also with special emphasis on the tendency to carbon deposition. Experiments were carried out in a TGA apparatus and a fixed bed reactor. Ni-based carriers showed a tendency to form carbon in the reaction with CH₄, especially Ni60. The addition of water in H₂O/CH₄ molar ratios of 0.4-2.3 could decrease the carbon deposited, but not in the case of Ni60. Mn-based sample reacted with CH₄ almost completely and with low tendency to carbon deposition, while the Fe-based sample showed low reactivity. Ni40 showed more reactivity to CO than Mn40, although in both cases carbon was deposited, especially at 873 K. When H₂ was present, it reacted rapidly with both carriers, decreasing the amount of carbon deposited. The presence of CO₂ could also decrease the carbon deposited on Ni40 at 1073 K. According to both these and the previous results [1], it can be concluded that Mn40 is the most adequate for minimization of carbon deposition in Chemical Looping Reforming (CLR).     

Synthesis of narrow-diameter carbon nanotubes from acetylene decomposition over an iron-nickel catalyst supported on alumina

Carbon nanotubes (CNTs) were synthesized by the catalytic decomposition of acetylene over 40Fe:60Al₂O₃, 40Ni:60Al₂O₃ and 20Fe:20Ni:60Al₂O₃ catalysts. High density CNTs of 20 nm diameter were grown over the 20Fe:20Ni:60Al₂O₃ catalyst, whereas low growth density CNTs of 40 and 50 nm diameter were found over 40Fe:60Al₂O₃ and 40Ni:60Al₂O₃ catalysts. Smaller catalyst particles enabled the synthesis of highly dense, long and narrow-diameter CNTs. It was found that a homogeneous dispersion of the catalyst was an essential factor in achieving high growth density. The carbon yield and the quality of CNTs increased with increasing temperature. For the 20Fe:20Ni:60Al₂O₃ catalyst, the carbon yield reached 121% after 90 min at 700 °C. The CNTs were grown according to the tip growth mode. Based on reports regarding hydrocarbon adsorption and decomposition over different faces of Ni and Fe, the growth mechanism of CNTs over the 20Fe:20Ni:60Al₂O₃ catalyst are discussed.     

Synthesis of carbon nanotubes over nickel–iron catalysts supported on alumina under controlled conditions

Carbon nanotubes (CNTs) were synthesized by catalytic decomposition of acetylene over Fe, Ni and Fe–Ni catalysts supported on alumina. The growth of CNTs was carried out at various reaction conditions. The growth density and diameter of CNTs could be controlled by varying the catalyst composition and the growth parameters. The growth density of CNTs increased with increasing the activation time of catalysts in H₂ atmosphere and/or decreasing acetylene concentration. At 600°C, higher density of CNTs was observed at 60 min for higher Fe containing catalyst, whereas at 90 min for higher Ni containing catalyst. The growth density of CNTs highly increased with increasing reaction time from 30 to 60 min. For all the catalysts, the diameter of CNTs decreased with increasing growth time further mainly due to hydrogen etching. Bimetallic catalysts produced narrower diameter CNTs than single metal catalysts. The growth of CNTs followed the tip growth mode and the CNTs were multi-walled CNTs.     

柠檬酸凝胶法制备Mn-Ni-Fe基负温度系数热敏陶瓷

采用柠檬酸凝胶法制备锰-镍-铁基前驱体,在300℃煅烧干燥的前驱体得到纳米粒度粉末,压制成圆片坯体后在1100～1300℃烧结得到负温度系数(negative temperature coefficient,NTC)热敏陶瓷样品。研究了粉体和烧结样品的相结构、微观形貌、电性能和热敏特性。结果表明:合成粉体的纳米颗粒为单相Mn1/3Ni2/3Fe2O4尖晶石,粉体具有高化学均匀性。烧结的Mn1/3Ni2/3Fe2O4陶瓷样品具有均匀的微观结构,陶瓷样品的烧结密度和材料敏感指数β随着烧结温度的增加而增加。测量温度为50～150℃范围时,1300℃烧结的Mn1/3Ni2/3Fe2O4样品,其β可高达4300K。     

Microwave absorption performance of PDCs-SiCN(Fe) ceramics with negative imaginary permeability

PDCs-SiCN(Fe) ceramics were successfully fabricated with different content of ferric acetylacetonate (FA) by polymer-derived method. The effects of FA on the phase composition, microstructure, resistivity, dielectric properties, magnetic properties and microwave absorption properties of PDCs-SiCN(Fe) ceramics in the range of 2–18?GHz were investigated. The samples presented amorphous structure with a few crystalline phases of α-Fe and free carbon in the gaps, which were expected to be good soft magnetic materials. The average real permittivity and imaginary permittivity of PDCs-SiCN(Fe) ceramics with 50?wt% FA was about 14.1 and 5.3 respectively. Furthermore, the PDCs-SiCN(Fe) ceramics with 50?wt% FA addition content showed the broad absorption bandwidth in the 5.1–8.4?GHz with RL ≤??10?dB (>?90% absorption) at 4?mm.     

不同粒径镍锌铁氧体纳米材料的磁性研究

利用液相催化的方法制备了尖晶石结构的Ni0.5Zn0.5Fe2O4铁氧体纳米颗粒,在反应过程中加入适当的助溶剂制备出了不同粒径的颗粒。XRD、TEM的测量结果表明生成物具有良好的尖晶石结构和结晶度,其粒径大小约为15～60nm。振动样品磁强计（VSM）对样品磁滞回线的测量表明随着磁性颗粒的增大,其饱和磁化强度也单调变大,饱和磁化强度的数值在40～65emu／g。随着磁性颗粒粒径的改变,其升温速率和达到的饱和温度在单畴附近达到最大。     

Photocatalytic Disinfection of Escherichia coli over Titanium (IV) Oxide Supported on Hβ Zeolite

Fe loaded Al-MCM-41, (Si/Al = 25, 50, 75 and 100) catalysts were synthesized by hydrothermal method and characterized by the XRD, BET (surface area), FT-IR, and UV- vis and Mössbauer techniques. The liquid phase hydroxylation of phenol with hydrogen peroxide was studied and exclusive formation of dihydroxybenzene was observed. The phenol conversion was found to be almost same at various reaction temperatures viz 40, 60 and 80 °C, but at room temperature only about 30% conversion was recorded. The activity followed the order Fe/Al-MCM-41 (25) > Fe/Al-MCM-41(50) > Fe/Al-MCM-41 (75) > Fe/Al-MCM-41 (100) which was also the order of acidity. Effects of Fe content in Fe/Al-MCM-41 catalysts, solvent, phenol/H₂O₂ mole ratio on phenol conversion was examined. The reaction was also carried out over 10% iron loaded mordenite and the results are compared.     

Synthesis and performances of Ni–SDC cermets for IT-SOFC anode

NiO–SDC (samaria-doped ceria) composite powders were synthesized using a urea-combustion technique. The structure, electrical conducting, thermal expansion and mechanical properties of the Ni–samaria-doped ceria (Ni–SDC) cermets have been investigated with respect to the volume contents of Ni. No chemical reaction product between the two constituents was detected for the cermets sintered at 1200–1300 °C for 4 h in air and reduced at 800 °C for 2 h in a 60%N₂ + 40%H₂ atmosphere. A porous microstructure consisting of homogeneously distributed Ni and SDC phases together with well-connected grains was observed. It was found that the open porosity, electrical conductivity, thermal expansion and bending strength of the cermets are sensitive to the volume content of Ni. The Ni–SDC cermets containing 50–60 vol.% Ni were ascertained to be the optimum composition. These compositions offer sufficient open porosity of more than 30%, superior electrical conductivities of over 1000 S/cm at intermediate temperatures (600–800 °C), a moderate average thermal coefficient of 12.6–13.5 × 10⁻⁶ between 100 and 800 °C and excellent bending strength of around 100 MPa.     

Evaluation of different oxygen carriers for biomass tar reforming (I): Carbon deposition in experiments with toluene

In this work, an innovative method for gas conditioning in biomass gasification is analyzed. The objective is to remove tar by selectively reforming the unwanted hydrocarbons in the product gas with a chemical looping reformer (CLR), while minimizing the carbon formation during the process. Toluene, in a concentration of 600-2000 ppmv, was chosen as a tar model compound. Experiments were performed in a TGA apparatus and a fixed bed reactor. Four oxygen carriers (60% NiO/MgAl₂O₄ (Ni60), 40% NiO/NiAl₂O₄ (Ni40), 40% Mn₃O₄/Mg-ZrO₂ (Mn40) and FeTiO₃ (Fe)) were tested under alternating reducing/oxidizing cycles. Several variables affecting the reducing cycle were analyzed: temperature, time for the reduction step and H₂O/C₇H₈ molar ratio. Ni40 and Mn40 presented interesting characteristics for CLR of biomass tar. Both showed stable reactivity to C₇H₈ after a few cycles. Ni40 showed a high tendency to carbon deposition compared to Mn40, specially at high temperatures. Carbon deposition could be controlled by decreasing the temperature and the time for the reduction step. The addition of water also reduced the amount of carbon deposited, which was completely avoided working with a H₂O/C₇H₈ molar ratio of 26.4.     

Ni包裹SiC对SiC(Ni)/Fe复合材料性能的影响

分别以SiC粉体和Ni包裹的SiC复合粉体为硬质相,采用热压工艺(1000°C,20°C/min,40 MPa和45 min)制备了SiC含量为1 wt%~9 wt%的SiC/Fe复合材料。采用扫描电镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)等研究了复合材料的界面反应物。研究结果表明:Ni过渡层的存在有效避免了SiC颗粒与Fe基体之间的化学反应。随着Ni包裹SiC粉体含量的增加,复合材料的相对密度和抗弯强度先增加后减小,当SiC(Ni)粉体含量为5 wt%时达到最大值。     

Flexural Creep Deformation of ZrB2/SiC Ceramics in Oxidizing Atmosphere

Flexural creep of ZrB₂/0–50 vol% SiC ceramics was characterized in oxidizing atmosphere as a function of temperature (1200°–1500°C), stress (30–180 MPa), and SiC particle size (2 and 10 μm). Creep behavior showed strong dependence on SiC content and particle size, temperature and stress. The rate of creep increased with increasing SiC content, temperature, and stress and with decreasing SiC particle size, especially, at temperatures above 1300°C. The activation energy of creep showed linear dependence on the SiC content increasing from about 130 to 511 kJ/mol for ceramics containing 0 and 50 vol% 2-μm SiC, respectively. The stress exponent was about 2 for ZrB₂ containing 50 vol% SiC regardless of SiC particle size, which is an indication that the leading mechanism of creep for this composition is sliding of grain boundaries. Compared with that, the stress exponent is about 1 for ZrB₂ containing 0–25vol% SiC, which is an indication that diffusional creep has a significant contribution to the mechanism of creep for these compositions. Cracking and grain shifting were observed on the tensile side of the samples containing 25 and 50 vol% SiC. Cracks propagate through the SiC phase confirming the assumption that grain-boundary sliding of the SiC grains is the controlling creep mechanism in the ceramics containing 50 vol% SiC. The presence of stress, both compressive and tensile, in the samples enhanced oxidation.     

Long-range chemical interaction in solid-state synthesis: Reaction of Ni with Fe in epitaxial Ni(001)/Ag(001)/Fe(001) trilayers

The effect of Ag interlayers 0, 60, 420, and 900 nm thick on the reaction of Ni with Fe in epitaxial Ni(001)/Ag(001)/Fe(001) trilayers has been studied by XRD, volume magnetocrystalline anisotropy, and magnetization measurements. Minor mixing was observed at the interface between Ag(001)/Ni(001) and Ag(001)/Fe(001) bilayers at temperatures above 900 K. When the epitaxial Ni(001)/Ag(001)/Fe(001) trilayer undergoes thermal annealing, a total atomic exchange between Ni and Ag occurs independently of an Ag interlayer thickness. Solid-state synthesis of alloy phases was found to occur in the sequence Fe/Ni → Ni₃Fe NiFe → γ_par (Fe₃Ni-like phase). Temperatures for the formation of Ni₃Fe and NiFe phases slightly increase with increasing interlayer thickness, while the initiation temperature for the γ_par phase remains intact. We suggest some scenarios for the observed atomic exchange in the system under consideration. The results are rationalized in terms of long-range chemical interaction between Ni and Fe via an Ag interlayer. This means that Ni reacts with Fe despite the fact that a separation between the above atoms is greater than the length of normal chemical bond by a factor of about 10⁴. The article is published in the original.     

Carbide phases formed in WC–M (M = Fe/Ni/Cr) systems

The effect of composition in the formation of carbides in the WC–M (M = Fe/Ni/Cr) system has been studied. Three conventional compositions have been prepared with 10 wt.% of metallic binder. Fe as a metallic binder was first studied and its partial substitution by Ni and Cr was also investigated. A WC powder coated with a similar binder (Fe/Ni/Cr) amount was also investigated. The XRD results, after thermal treatment at 1400 °C, reveal that the substitution of half percent of the iron content by Ni stabilized the austenite Fe(γ) formation. The introduction of Cr in the binder composition induces the formation of Cr₂C carbide. With the decrease of Cr amount in the binder composition of the coated powder, Cr₂C carbide was not formed, but instead other carbide, M₆C, was detected. In order to eliminate this carbide a small excess of carbon (3.6 wt.%) was added to the coated powder. The results are discussed in terms of the phases formed, the binder composition and the final carbon content.     

Miscibility studies of sodium carboxymethylcellulose/poly(vinyl alcohol) blend membranes for pervaporation dehydration of isopropyl alcohol

Miscibility studies of sodium carboxymethylcellulose/poly(vinyl alcohol) (NaCMC/PVA) blends of different compositions (100/0, 80 : 20, 60 : 40, 50 : 50, 40 : 60, 20 : 80, and 0 : 100) were investigated using viscometric method. NaCMC, PVA, and their blend membranes were prepared by solution‐casting technique and were then crosslinked with glutaraldehyde (GA). The effect of blend composition on mechanical, swelling, and pervaporation results (flux and selectivity) was also investigated in this study. Attenuated total reflectance–Fourier transform infrared spectroscopy (ATR–FTIR) results showed that the blends are miscible over the entire studied composition range and further confirmed the crosslinking reaction with GA. FTIR studies reveal that the blends containing 50 : 50 (NaCMC/PVA) are an optimum miscible blend. Thermogravimetric analysis confirms that the thermal stability increased with increase in NaCMC content in NaCMC/PVA blend membrane. XRD and DSC showed a corresponding decrease in crystallinity and increase in melting point with increase in NACMC content, respectively. NaCMC/PVA blends of all the composition under study were used for dehydration of isopropyl alcohol at different compositions of IPA/water mixture (90 : 10, 87.5 : 12.5, 85 : 15, and 82.5 : 17.5) at 35°C. Swelling studies and PV results reveal that increase in NaCMC content in the blend leads to an increase in flux of water, whereas selectivity decreases. The optimum flux and selectivity were observed for the blend containing 50 : 50 NaCMC/PVA content at a feed ratio of 87.5 : 12.5 IPA/water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electronic and bonding properties of Fe- and Ni based hydrogenated amorphous carbon thin films by X-ray absorption, valence-band photoemission and Raman spectroscopy

Electronic and bonding properties of Me-based hydrogenated amorphous carbon (a-CH:Me, Me = Fe, Ni) thin films have been studied by X-ray absorption near-edge structure (XANES), valence-band photoemission (VB-PES) and Raman spectroscopy. Raman and XANES results show enhancement of the content of sp³-rich diamond-like carbon (DLC) by doping with Fe and Ni. The VB-PES spectrum of a-CH:Fe shows emergence of a prominent feature due to states of sp³-bonded clusters, indicating that a-CH:Fe induced enhancement of DLC structure. The nano-indentation measurement reveals that a-CH:Fe has a greatly enhanced hardness, while electrical resistance measurement shows that a-CH:Me reduces resistivity.     

Low temperature production of glass ceramics in the anorthite–diopside system via sintering and crystallization of glass powder compacts

The production of glass ceramics (GCs) with theoretical anorthite–diopside (An–Di) weight ratios of 60/40, 50/50 and 45/55 via sintering and crystallization of glass powder compacts was investigated at different temperatures between 800 and 950 °C. The investigated compositions are located in the cross-section of the ternary fluorapatite–An–Di system close to An–Di binary joint, with constant fluorapatite content of 4.8 wt.%. Two different groups of glass powders, with mean particle size of 2 and 10 μm, were used. The experimental results showed that sintering is almost complete at 800 °C, preceding crystallization, which takes place via surface crystallization mechanism. The properties values of the produced GCs, which are the best for the composition close to An–Di eutectic line, are discussed with respect to the evolution of crystalline phases and the microstructure over increasing firing temperature. Under the technology perspective, the investigated processing route is significantly superior in comparison to the attempts reported in earlier studies.     

Electrochemical hydrogen evolution on polypyrrole from alkaline solutions

Thin films of conductive polypyrrole (PPy) were formed electrochemically from aqueous sulfuric acid. The films showed good electrocatalytic properties towards hydrogen evolution (h.e.r) from alkaline solutions on planar and packed-bed iron electrodes. Current–potential relations were measured at various temperatures and KOH concentrations on Fe, Ni and Fe/PPy planar electrodes. The current was found to be constant during 40 h of operation. SEM micrographs showed no difference in the morphology before and after this period. The activation energy for h.e.r. was found to be 50.2, 58.5 and 33.4 kJ mol^–1 for Fe, Ni and Fe/PPy planar electrodes, respectively. The results showed that Fe/PPy can be used to produce hydrogen at both ambient and relatively high temperatures 70 C. The polypyrrole coating on iron screens was found to reduce the potential required to sustain a specific rate of hydrogen generation and, hence, the energy consumed during the process.     

Temperature-dependent piezoelectric strain and resonance performance of Fe2O3-modified BiScO3-PbTiO3-Pb(Nb1/3Mn2/3)O3 ceramics

The piezoelectric strain and resonance performance of 0.37BiScO₃-0.6PbTiO₃-0.03Pb(Mn_1/3Nb_2/3)O₃ (BS-PT-PMN-xFe) ceramics with different amounts of Fe content addition were investigated from room temperature to 200 °C. Both the piezoelectric strain and resonance performance are improved by Fe addition in wide temperature range. Piezoelectric strain of BS-PT-PMN-xFe with 1 mol% Fe is 0.23%, which is comparable to that of BiScO₃-PbTiO₃ (BS-PT) ceramics, while the strain hysteresis is only one-third. At 200 °C, the high-field strain coefficient of BS-PT-PMN-Fe with 1 mol% Fe is as large as 700 pm/V. Variation of piezoelectric strain and hysteresis is clearly reducing by Fe addition. The maximum vibration velocity is enhanced up to approximately 1 m/s in 2 mol% Fe-modified BS-PT-PMnN-xFe ceramics, and the vibration velocity is stable from room temperature to 200 °C when the electric voltage magnitude was below 60 V_pp. These results indicate that BS-PT-PMN-xFe ceramics are potential candidates for high-temperature piezoelectric actuator application.     

Enhanced EMW absorption properties of SiCN/Fe/Ni ceramics modified with Fe/Ni bimetal

The SiCN/Fe/Ni ceramics codoped with iron acetylacetonate (FA) and nickle acetylacetonate (NA) was synthesized by polymer-derived ceramics (PDCs) method in this study. The microstructure, phase composition and electromagnetic wave (EMW) absorption properties of the samples were analyzed. The polarization loss and conduction loss of materials were analyzed by the direct current (DC) multimeter and the contribution rate of polarization loss was more than 94% in the whole frequency band. The results showed that C, SiC, Fe₂Si, Ni₃Si, γ- (Fe, Ni) and CNTs were formed after pyrolysis which provided lots of heterogeneous interface and enhanced the interfacial polarization. Meanwhile, Ni could enter the lattice of Fe and formed a unique electronic configuration, which reinforced the conductivity and stability of Fe. In addition, the in-situ generated Fe₂Si and Ni₃Si provided magnetic loss and conduction loss. The RL_min value of SiCN/Fe/Ni-3 ceramic was ?52.06 dB at 1.54 mm and the effective absorption band (EAB, RL ≤ ?10 dB) reached 4.21 GHz (13.79–18 GHz, 1.43 mm).