Phase evolution of plasma sprayed Al_2O_3-13%TiO_2 coatings derived from nanocrystalline powders

Commercial nanosized alumina and titania particles were selected as raw materials to prepare the blended slurry with composition of A1203-13%TiO2 （mass fraction）, which were reconstituted into micrometer-sized granules by spray drying, subsequently sintering at different temperatures to form nanostructured feedstock for thermal spraying, and then A1203-13%TiO2 nanocoatings were deposited by plasma spraying. The evolution of morphology, microstructure, and phase transformation of the agglomerated powder and as-sprayed coatings were characterized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The results show that A1203 retains the same a phase as the raw material during sintering, while TiO2 changes from anatase to futile. During plasma spraying, some a-A1203 phases solidify to form metastable y-A1203, and the volume fraction of a-A1203 decreases as CPSP increases. However, peaks of the TiO2 phase are not observed from the as-sprayed coatings except for the coatings sprayed at the lower CPSP. As the CPSP increases, nanostructured TiO2 is dissolved easily in y-A1203 or z-A1203＇TiO2 phase. After heat treatment, y-A1203 in the coatings transforms to a-A1203, and rutile is precipitated.

Fabrication and characterization of electrodeposited nanocrystalline Ni-Fe alloys for NiFe_2O_4 spinel coatings

Nanocrystalline Ni-Fe FCC alloy coatings with Fe content of 1.3%-39%（mass fraction） were fabricated on the nickel substrates using a DC electrodeposition technique. The crystal structure, lattice strain, grain size and lattice constant of the Ni-Fe alloy coatings were studied by X-ray diffraction technique. The chemical composition and surface morphology of the FCC Ni-Fe alloy coatings were investigated with the energy dispersive X-ray spectroscopy（EDS） and atomic force microscopy（AFM）. The results show that the Fe content of the Ni-Fe alloy coatings has a great influence on the preferred orientation, grain size, lattice constant and lattice strain. FCC Ni-Fe alloy coatings exhibit preferred orientations of（200） or（200）（111）. With an increase of Fe content, the preferred growth orientation of（200） plane is weakened gradually, while the preferred growth orientation of（111） increases. An increase of the Fe content in the range of 1.3%-25%（mass fraction） results in a significant grain refinement of the coatings. Increasing the Fe content beyond 25% does not decrease the grain size of FCC Ni-Fe alloys further. The lattice strain increases with increasing the Fe content in the FCC Ni-Fe alloys. Since the alloys with Fe content not less than 25% has similar grain size（~11 nm）, the increase in the lattice strain with the increase of Fe content cannot be attributed to the change in the grain size.

Effects of Additive AlCl_3 on Crystal Phase, Particle Size and Microstructural Parameters of Nanocrystalline TiO_2 Prepared by HF-PCVD

Nanocrystalline TiO2 was prepared by high frequency plasma chemical vapor deposition (HF-PCVD). The effects of additive AlCl3 on crystal phase, particle size and microstructurai parameters of TiO2 nanocrystallites were investigated by X-ray diffraction(XRD) and transmission electron microscopy (TEM). The nanocrystallites obtained experimentally are mixture of anatase and rutile, the uniform diameters of particles are about 30 nm. The phase transformation from anatase to rutile was accelerated by AlCl3, and rutile content is increased from 26.7 wt pct to 53.6 wt pct with increasing of addition of AlCl3 from 0.0 wt pct to 5.0 wt pct. The particle size is reduced and the size distribution becomes very narrow. The crystal lattice constants have the trend to decrease, and celi volumes appear as shrinkable.

Fabrication of C@MoxTi1-xO2-δ nanocrystalline with functionalized interface as efficient and robust PtRu catalyst support for methanol electrooxidation

A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of Mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a Mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,Mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.

Grain growth and thermal stability of nanocrystalline Ni-TiO_2 composites

The grain growth and thermal stability of nanocrystalline Ni-TiO2composites were systematically investigated.Thenanocrystalline Ni-TiO2composites with different contents of TiO2were prepared via electroplating method with the variation ofTiO2nano-particles concentration.The effect of TiO2content on the grain size,phase structure and microhardness was investigatedin detail.The corresponding grain growth and diffusion mechanisms during the heating process were also discussed.The optimalmicrohardness of HV50270was achieved for the composite with addition of20g/L TiO2nano-particles after annealing at400°C for90min.The calculation of the activation energy indicated that lattice diffusion dominated at high temperatures for thenanocrystalline Ni-TiO2composites.It was indicated that the increase of TiO2nano-particles content took effect on restricting thegrain growth at high temperatures by increasing the grain growth activation energy.

Electrodeposition of SnO_2 nanocrystalline thin film using butyl-rhodamine B as a structure-directing agent

Porous SnO2 nanocrystalline thin films were successfully electrodeposited from an oxygen-saturated acid aqueous solution of SnCl2 containing different concentrations of butyl-rhodamine B（BRhB） at 70℃.BRhB with substitute of amidocyanogen can be dissolved in the acid deposition solution,where HCl was added to suppress hydrolysis of SnCl2.So it was used as a structure-directing agent to promote the crystal growth of SnO_2.The formed porous morphology and tetragonal rutile crystalline structure of the electrodeposited thin films were controlled by the addition of BRhB with different amounts.

Densification Behavior of Nanocrystalline Mg2Si Compact in Hot-pressing

Densification behavior of nanocrystalline Mg2Si （n-Mg2Si） with grain size about 30-50 nm was investigated by hot-pressing at 400℃. The results indicated that the densification process of n-Mg2Si exhibited three linear segments： p〈0.3 GPa, 0.3 GPa〈p〈1.2 GPa, and p〉1.2 GPa determined by Heckel formula, among which the third fast increasing segment in high pressure range p〉1.2 GPa has seldom been reported in conventional coarse-grained polycrystalline materials. Nevertheless, in the whole pressure range （0.125-1.500 GPa） investigated the densification behavior of n-Mg2Si can be well described by a Kawakita formula p/C=（1/a）p＋ 1/（ab） with constant α=0.452 being in good agreement with the initial porosity of the compact.

Interfacial Structure of Nanocrystalline SnO_2 and SiO_2-doped SnO_2

The study of nanocrystalline SnO2 (n-SnO2) and SiO2-doped SnO2 (n-Si-SnO2) samples pre-pared by the sol-gel process showed that SiO2 doping can effectively restrained the growth of nanocrystalline SnO2 grains, thus improving thermal stability of the materials.

Effect of melt spinning on gaseous hydrogen storage characteristics of nanocrystalline and amorphous Nd-added Mg_2Ni-type alloys

Nanocrystalline and amorphous Mg-Nd-Ni-Cu quaternary alloys with a composition of(Mg_(24)Ni_(10)Cu_2)_(100-x)Nd_x(x=0, 5, 10, 15, 20) were prepared by melt spinning technology and their structures as well as gaseous hydrogen storage characteristics were investigated. The XRD, TEM and SEM linked with EDS detections reveal that the as-spun Nd-free alloy holds an entire nanocrystalline structure but a nanocrystalline and amorphous structure for the as-spun Nd-added alloy, implying that the addition of Nd facilitates the glass forming in the Mg_2Ni-type alloy. Furthermore, the degree of amorphization of the as-spun Nd-added alloy and thermal stability of the amorphous structure clearly increase with the spinning rate rising. The melt spinning ameliorates the hydriding and dehydriding kinetics of the alloys dramatically. Specially, the rising of the spinning rate from 0(the as-cast was defined as the spinning rate of 0 m/s) to 40 m/s brings on the hydrogen absorption saturation ratio(R_5~a)(a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity) increasing from 36.9% to 91.5% and the hydrogen desorption ratio(R_(1 0)~d)(a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity) rising from 16.4% to 47.7% for the(x=10) alloy, respectively.

Time-resolved Microwave Conductivity Studies on the Chemical Treatment of the Nanocrystalline Porous TiO2 Films

Effect of Ti(iso-C3H7O)4 treatment on the photoinduced charge carrier kinetics of nanocrystalline porous TiO2 films is studied by time-resolved microwave conductivity measurements. Analysis of the transient photoconductivity decays indicates that Ti(iso-C3H7O)4 treatment leads to an increased concentration of photogenerated charge carriers and a fast interfacial transfer rate of holes via the surface modification of the freshly growing TiO2 nanocrystallites.

Relations among High-frequency Magnetic Properties and Frequency in Nanocrystalline Fe_(72.5)Cu_1Nb_2V_2Si_(13.5)B_9 Alloy

High-frequency magnetic properties, such as core loss, coercivity and amplitude permeabilityof a newly-developed nanocrystalline Fe72.5Cu1Nb2V2Si13.5B9 alloy in the wide ranges of f =20-103 kHz, Bm = 0.01~0.6 T and Bmf = 10~40 (T.kHz) have been measured. A largeamount of experimental data have been fitted by a computer, thus obtaining several expressionsrepresenting the influence of frequency on high-frequency magnetic properties, that are useful inpractical applications.

Hydrogen Absorption and Electrochemical Properties of As-Quenched Nanocrystalline Mg20Ni10 – xCux (x = 0 – 4) Alloys

Nanocrystalline Mg2Ni-type alloys with nominal compositions of Mg20Ni10 – xCux (x = 0, 1, 2, 3, 4) were synthesized by rapid quenching technique. The microstructures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys were measured using an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage performances were tested by an automatic galvanostatic system. The results show that all the as-quenched alloys hold a typical nanocrystalline structure, and the rapid quenching does not change the major phase Mg2Ni. The hydrogen absorption and desorption capacities of the alloys significantly increase with rising quenching rate. Additionally, the rapid quenching significantly improves the electrochemical hydrogen storage capacity of the alloys, but it slightly impairs the cycle stability of the alloys.

Highly Improved Electrochemical Performances of the Nanocrystalline and Amorphous Mg_2Ni-type Alloys by Substituting Ni with M (M=Cu,Co,Mn)

The element Ni in the Mg2Ni alloy is partially substituted by M（M = Cu, Co, Mn） in order to ameliorate the electrochemical hydrogen storage performances of Mg2Ni-type electrode alloys. The nanocrystalline and amorphous Mg20Ni10-xMx（M = None, Cu, Co, Mn; x = 0-4） alloys were prepared by melt spinning. The effects of the M（M = Cu, Co, Mn） content on the structures and electrochemical hydrogen storage characteristics of the as-cast and spun alloys were comparatively studied. The analyses by XRD, SEM and HRTEM reveal that all the as-cast alloys have a major phase of Mg2Ni but the M（M = Co, Mn） substitution brings on the formation of some secondary phases, MgCo2 and Mg for the（M = Co） alloy, and Mn Ni and Mg for the（M = Mn） alloy. Besides, the as-spun（M = None, Cu） alloys display an entirely nanocrystalline structure, whereas the as-spun（M = Co, Mn） alloys hold a nanocrystalline/amorphous structure, suggesting that the substitution of M（M = Co, Mn） for Ni facilitates the glass formation in the Mg2Ni-type alloys. The electrochemical measurements indicate that the variation of M（M = Cu, Co, Mn） content engenders an obvious effect on the electrochemical performances of the as-cast and spun alloys. To be specific, the cyclic stabilities of the alloys augment monotonously with increasing M（M = Cu, Co, Mn） content, and the capacity retaining rate（S20） is in an order of（M = Cu） 〉（M = Co） 〉（M = Mn） 〉（M = None） for x≤1 but changes to（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None） for x≥2. The discharge capacities of the as-cast and spun alloys always grow with the rising of M（M = Co, Mn） content but first mount up and then go down with increasing M（M = Cu） content. Whatever the M content is, the discharge capacities are in sequence：（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None）. The high rate discharge abilities（HRDs） of all the alloys grow clearly with rising M（M = Cu, Co） content except for（M = Mn） alloy, whose HRD has a maximum value with varying M（M = Mn） content. Furthermore, for the as-cast alloys, the HRD is in order of（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None）, while for the as-spun（20 m·s^-1） alloys, it changes from（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None） for x = 1 to（M = Cu） 〉（M = Co） 〉（M = None） 〉（M = Mn） for x = 4.

NaH doped TiO_(2)as a high-performance catalyst for Mg/MgH_(2)cycling stability and room temperature absorption

This paper presents the catalytic effect of NaH doped nanocrystalline TiO_(2)(designated as NaTiOxH)in the improvement of MgH_(2)hydrogen storage properties.The catalyst preparation involves ball milling NaH with TiO_(2)for 3 hr.The addition of 5 wt%NaTiOxH powder into MgH_(2)reduces its operating temperature to∼185℃,which is∼110℃lower than the additive-free as-milled MgH_(2).The composite remarkably desorbs∼7.2 wt%H_(2)within 15 min at∼290℃and reabsorbs∼4.5 wt%H_(2)in 45 min at room temperature under 50 bar H_(2).MgH_(2)dehydrogenation is activated at 57 kJ/mol by the catalyst.More importantly,the addition of 2.5 wt%NaTiOxH catalyst aids MgH_(2)to reversibly produce∼6.1 wt%H_(2)upon 100 cycles within 475 hr at 300℃.Microstructural investigation into the catalyzed MgH_(2)composite reveals a firm contact existing between NaTiOxH and MgH_(2)particles.Meanwhile,the NaTiOxH catalyst consists of catalytically active Ti_(3)O_(5),and“rod-like”Na_(2)Ti_(3)O_(7)species liberated in-situ during preparation;these active species could provide multiple hydrogen diffusion pathways for an improved MgH_(2)sorption process.Furthermore,the elemental characterization identifies the reduced valence states of titanium(Ti<4+)which show some sort of reversibility consistent with H_(2)insertion and removal.This phenomenon is believed to enhance the mobility of Mg/MgH_(2)electrons by the creation and elimination of oxygen vacancies in the defective(TiO_(2-x))catalyst.Our findings have therefore moved MgH_(2)closer to practical applications.

A Dye-sensitized Nanocrystalline Solid State Photovoltaic Cell

A new type of dye-sensitized nanocrystalline solid state photovoltaic cell based on the wide band gap n-TiO2/p-CuI heterojunction was fabricated. Tetra-carboxyphenyl porphyrine (TPP-(COOH)(4)), squarylium cyanine derivative (SQ-(CH2),(SO3Py+)-Py-.) and ruthenium bipyridyl complex (RuL2(NCS)(2)) were used as photosensitizers. Larger photocurrents and photovoltages were shown in the cell sensitized by ruthenium bipyridyl complex and can be further increased by intercalation of a TiO2 thin underlayer.

Preparation, Structural Analysis and Luminescence Properties of Nanocrystalline Phosphor Gd_2O_3∶Eu

Nanocrystalline monoclinic and cubic Gd 2O 3∶Eu with different Eu 3+ concentration were prepared using glycine-nitrate combustion synthesis. By changing the ratio of glycine to nitrate and proper heat treatment, pure monoclinic and cubic Gd 2O 3∶Eu with particle size less than 40 nm can be easily formed. Under ultraviolet excitation, main emission of Eu 3+ ( 5D 0→ 7F 2) locates at 624 nm in monoclinic Gd 2O 3∶Eu and 611 nm in cubic sample. In excitation spectrum two broad bands corresponding to the host absorption and charge transfer state (CTS) and f-f transitions of Gd 3+ and Eu 3+ were observed and discussed. The quenching concentration of monoclinic and cubic Gd 2O 3∶Eu is 10% and 15%, respectively, both of which are much higher than that of bulk Gd 2O 3∶Eu.

Synthesis,Characterization and Electromagnetic Studies on Nanocrystalline Co_(0.5)Zn_(0.5)Fe_2O_4 Synthesized by Polyacrylamide Gel

Nanocrystalline Co0.5Zn0.5Fe2O4 ferrite was synthesized by polyacrylamide gel method. The electromagnetic and microwave absorption properties of the ferrite were investigated. The results indicated that calcining temperature of the ferrite had a significant influence on the effective properties of the ferrite. When the calcining temperature was 500, 600 and 700℃, the average size of particles was 10, 30 and 80 nm, respectively. The dielectric loss （ε″） and magnetic loss （μ″） of the ferrite was around 0.65 and 0.29 at 8.2 GHz, respectively. Microwave absorption properties of the ferrites were simultaneously influenced due to the strong correlation between reflection loss and electromagnetic parameters of the ferrite.

Optimization of Gas Sensing Performance of Nanocrystalline SnO_2 Thin Films Synthesized by Magnetron Sputtering

Tin oxide （SnO2） is one of the most promising transparent conducting oxide materials, which is widely used in thin film gas sensors. We investigate the dependence of the deposition time on structural, morphologicaJ and hydrogen gas sensing properties of SnO2 thin films synthesized by dc magnetron sputtering. The deposited samples are characterized by XRD, SEM, AFM, surface area measurements and surface profiler. Also the H2 gas sensing properties of SnO2 deposited samples are performed against a wide range of operating temperature. The XRD analysis demonstrates that the degree of crystallinity of the deposited SnO2 films strongly depends on the deposition time. SEM and AFM analyses reveal that the size of nanoparticles or agglomerates, and both average and rms surface roughness is enhanced with the increasing deposition time. Also gas sensors based on these SnO2 nanolayers show an acceptable response to hydrogen at various operating temperatures.

Sintering of Doped, Nanocrystalline CeO_2 Powders Prepared under Hydrothermal Conditions

Nanocrystalline CeO2 powders (particle size ≈10-15 nm), doped with up to 20 at.-% of Mg,Ca or Y were prepared by chemical precipitation under hydrothermal conditions. The particle size and shape of the powders change slightly with the dopant concentrations. The the of the dopants on the sintering of the compacted powders was investigated during heating at a constant rate of 10℃/min. The elemental composition and the concentration of the dopant has significant efFect on the densification and grain growth. Compared to undoped CeO2, the dopants produce a shift in the densification curve to higher temperatures. For the same dopant concentration and under identical sintering conditions, the Ca doped samples reach nearly full density with the smallest grain size (≈50 nm), however, the Mg doped sample has the lowest density (≈95% of the theoretical) with the largest grain size (≈1 μm)