Structure and properties of polybutylene crystallized from the glassy state. II. Electron microscopy

Electron microscope studies of as-ultraquenched and subsequently crystallized isotactic polybutylene (PB) are described in this paper. Cold shadowing of the as-quenched samples reveals no distinct structure larger than 30 Å in the amorphous PB. When rapidly warmed to room temperature PB crystallizes as microcrystals of size ranging from 100 to 250 Å. The size of the microcrystals can be changed only by annealing at temperatures higher than T_α; in PB this resulted in the growth of short lamellae. However, by warming the quenched samples slowly to room temperature, large morphological units were obtained. The effect of several quenchants on the crystallization process of PB is also discussed.     

Optical transmittance and microgravimetric studies of the oxidation of 〈100〉 single crystal films of copper

Thin single crystal copper films have been grown and oxidized on (100) faces of cleaved sodium chloride discs suspended from a vacuum ultramicrobalance. Optical transmittance measurements between 400–800 nm and electron microscopic investigations were also used to characterize the oxidation process. Polycrystalline copper films grown at room temperature are substantially the same as those grown previously on glass substrates. Single crystalline growth at 325 ° C on rock salt produces a characteristic transmittance curve due to the “island” nature of the films. These curves compare favorably with other previously published results. Single crystal copper films oxidized to CuO_0.67 at temperatures of 117–159°C in 100 Torr of oxygen for films less than 500 A thick. For films 378 to 1000 Å thick, compositions of CuO_0.52 to CuO_0.62 were obtained between 123–176°C. The oxidation to less than CuO_0.67 is attributed to the existence of islands in these films which are thicker than the average film thickness, and require higher temperatures or thinner films to permit oxidation to CuO_0.67 before the nucleation of CuO sets in.     

A CEMS study of surface oxidation of Fe--Ni alloys

A study by Conversion Electron Mössbauer Spectroscopy (CEMS) carried out by using a Parallel Plate Avalanche Counter with samples of Fe--Ni alloys (50 and 65 at.% Fe) is reported. Each sample was analyzed without oxidation and after heating it under an oxygen atmosphere at 200°C. All CEMS measurements were carried out at room temperature. In both samples (50 and 65 at.% Fe), without oxidation and after oxidation, the Mössbauer spectra showed a six line magnetic spectrum according to their ferromagnetic character, with a broad Hyperfine Field Distribution (HFD), according to the disordered character of the alloys. The obtained Mean Hyperfine Field (MHF) for the sample 50 at.% Fe was 30.9 T, meanwhile for the invar composition (65 at.% Fe) was 25.5 T, which is close to values previously reported by Transmission Mössbauer Spectroscopy (TMS). Results from the treated samples (with oxidation at 200°C) showed a difference in the surface composition as a result of this process. In the 50 at.% Fe sample, additionally appeared a doublet that could be assigned to an oxihydroxide of Fe³⁺. Otherwise, the 65 at.% Fe sample (invar) presented ferromagnetic oxides (α-Fe₂O₃ and Fe₃O₄) with a large relative area (82.5%).     

二氧化钒薄膜的低温制备及其性能研究

针对VO₂薄膜在微测辐射热计上的应用，采用射频反应溅射法，在室温下制备氧化钒薄膜；研究了氧分压对薄膜沉积速率、电学性质及成分的影响.通过调节氧分压，先获得成分接近VO₂的非晶化薄膜，再在400℃空气中氧化退火，便可制得高电阻温度系数，低电阻率的VO₂薄膜，电阻温度系数约为-4%/℃，薄膜方块电阻为R_□为100—300kΩ；薄膜在室温下沉积，400℃下退火的制备方法与微机电加工(micro electromechanic 关键词： 二氧化钒 电阻温度系数 氧分压 射频反应溅射法     

Rates of redox reactions in basaltic melts determined by Mössbauer spectroscopy

Mössbauer spectroscopy has been widely used for determining the ferric/ferrous ratio in amorphous rock samples to reveal the oxygen pressure in the melt. In the present investigation, Mössbauer spectroscopy in conjunction with melting experiments at controlled oxygen pressures was used to determine the rates of redox reactions in basaltic melts at 1300°C. The samples were kept at a fixed oxygen pressure long enough to reach equilibrium at a well established ferric/ferrous ratio. Then, the oxygen fugacity in the furnace was changed abruptly and the samples were kept for different lengths of time, from 15 min, to 4 hrs, at the new condition. At the end of each run the samples were quenched and the ferric/ferrous ratio analyzed by Mössbauer spectroscopy. A geological corollary of our results is that natural volcanic glasses, representing quenched melts, retain and reflect the oxidation state in the melt immediately prior to eruption, and hence the oxygen fugacity in the magma.     

Hall mobility of undoped n-type conducting strontium titanate single crystals between 19 K and 1373 K

The Hall mobility of undoped n-type conducting SrTiO₃ single crystals was investigated in a temperature range between 19 and 1373 K. Field calculations were used to estimate the influence of sample shape and electrode geometry on the measured values. Between 19 and 353 K samples, which were quenched under reducing conditions, show an impurity scattering behavior at low temperature and high carrier concentrations and a phonon scattering mechanism at room temperature. In this temperature region, no carrier-density-dependent mobility was found. In conjunction with measurements of the mass difference before and after reoxidation, the oxygen deficiency and the oxygen vacancy concentration could be determined. The oxygen vacancies proved to be singly ionized. Above 873 K, Hall mobility and carrier concentration had been determined as a function of both oxygen partial pressure and temperature for the first time. In this temperature range the mobility does not depend on carrier concentration, but shows aT ^–1.5 dependence.     

Decay of colour centres in natural chalcopyrite

Thermoluminescence (TL) or natural chalcopyrite (CuFeS₂) obtained from Mosabani Copper Mines shows two glow peaks at 198 and 250°C upon X-irradiation at room temperature. But the quenched sample when X-irradiated shows four glow peaks at 86, 136, 198 and 250°C. The emission spectra of all the glow peaks show a prominent band with a maximum at 566 nm. Both thermal and anomalous fading were observed in quenched samples. Tentative explanations for emission spectra and anomalous fading are given.     

Volume and surface oxidation of basalt

Natural, Fe²⁺-rich basalt glass (quenched lava) was heat treated as glass pieces and glass powder in air, in 6.0 Ar and in a 9×10^?6 mbar vacuum below temperatures of significant crystallization to access volume and surface oxidation by ⁵⁷Fe Mössbauer spectroscopy. While no oxidation occurs upon heating in vacuum, the amount of Fe³⁺ formed in powder (surface oxidation) is about 10 times higher than in pieces (volume oxidation), and surface oxidation is of the same order in air and Ar. This effect is assigned to chemisorption of water or CO₂. Crystalline basalt, investigated by wet chemistry, includes five glass pieces treated above T of crystallization in air and in 6.0 Ar, and three lava samples of increasing depth up to 9 cm of lava lobes. The high Fe₂O₃ of all these crystalline samples is explained as a stabilization of Fe³⁺ due to the change of the local electronic environment in the course of crystallization; volume oxidation therefore appears to be independent on the environmental atmosphere.     

Formation of a passive layer in surface oxidation of Gd: A leed and AES study

The surface oxidation of epitaxial and polycrystalline Gd samples grown in ultrahigh vacuum on W(110) substrates has been investigated using Auger-electron spectroscopy (AES) and low energy electron diffraction (LEED). The surface crystallography of clean epitaxial films monitored by LEED is hcp(0001) and remains unchanged even after 300 L oxygen exposure at room temperature. The LEED pattern of bulk Gd₂O₃ in Mn₂O₃ structure is observed only when oxygen is exposed at an elevated substrate temperature of about 500°C. AES clearly reveals various stages of oxidation as a function of the oxygen exposure for epitaxial as well as polycrystalline films. It is found that the oxidation does not proceed beyond one monolayer of the Gd surface.     

Ferromagnetism in diluted magnetic Zn-Co-doped CeO2−δ

Several oxides doped with transition metals can be used in spintronics devices due to their conductive and magnetic properties at room temperature. In this work, samples of Ce_1−2xZn_xCo_xO_2−δ were obtained by an alternative sol–gel proteic process for x=0.01, 0.05 and 0.1. The structural properties of samples were analyzed by XRD and Raman spectroscopy. Magnetization measurements revealed a ferromagnetic behavior at room temperature probably induced by oxygen vacancies.     

Ammoxidation of carbon materials for CO2 capture

Ammoxidised carbons were produced from three different starting materials: an activated carbon obtained from wood by chemical activation using the phosphoric acid process, a steam activated peat-based carbon, and a char obtained from a low-cost biomass feedstock, olive stones. Nitrogen was successfully incorporated into the carbon matrix of the different materials, the amount of nitrogen uptake being proportional to the oxygen content of the precursor. At room temperature the CO₂ capture capacity of the samples was found to be related to the narrow micropore volume, while at 100 °C other factors such as surface basicity took on more relevance. At 100 °C all the ammoxidised samples presented an enhancement in CO₂ uptake compared to the parent carbons.     

(Co, Zn)O compound obtained from ZnTe vapor deposition on Co/Si substrates

(Co, Zn)O compound has been obtained by a non-expensive synthesis route. ZnTe thin films were obtained by isothermal close space sublimation on the Co thin layer previously sputtered on silicon substrates. After the annealing process in humid ambient cobalt atoms diffusion and Zn oxidation were obtained besides partial Te evaporation. The detailed characterization of the samples by using XRD, RBS, AFM, XPS, VSM and MFM techniques point to the formation of room temperature ferromagnetic Co _x Zn_(1−x)O phase (x<0.15). This ferromagnetic behavior is mainly attributed to Co atoms substituting Zn atoms in the ZnO network.     

Determination of oxygen stoichiometry in the mixed-valent manganites

The possible redox (oxidation reduction) chemical methods for precisely determining the oxygen content in the perovskite manganites including hole-doped La_1−xCa_xMnO_y and electron-doped La_1−xTe_xMnO_y compounds are described. For manganites annealed at different temperatures, the oxygen content of the samples was determined by a redox back titration in which the powder samples taken in a quartz crucible were dissolved in (1+1) sulfuric acid containing an excess of sodium oxalate, and the excess sodium oxalate was titrated with permanganate standard solution. The results indicate that the method is effective and highly reproducible. Moreover, the variation of oxygen content is also reflected in significant change in the electrical transport property of the samples, which is mainly considered to be closely related to the introduction of oxygen vacancies in the Mn–O–Mn network.     

Evolution of the magnesium surface during oxidation studied by Metastable Impact Electron Spectroscopy

The evolution of a polycrystalline magnesium surface during oxidation at room temperature has been studied by Metastable Impact Electron Spectroscopy (MIES). This technique allowed us to follow the metal-to-insulator transformation of the top layer of the surface. An electronic signal corresponding to a metallic behavior of the surface evidences the presence of under-stoichiometric MgO species on the surface. The total covering by oxygen of the Mg surface uppermost layer, obtained at around 10 L of oxygen deposition, does not correspond to a fully insulating surface. An insulating surface is obtained after 30 L of oxygen deposition. Depositions of CO₂ on a clean and a preoxidized polycrystalline Mg surface have been analyzed to give information about the composition of the surface and its evolution. CO₂ adsorption in the form of CO₃²⁻ compounds on preoxidized Mg is more efficient than on clean Mg. Oxygen species, corresponding to chemisorbed oxygen less bounded than oxygen in the MgO lattice, allows the formation of CO₃²⁻. Therefore, it is concluded that during oxygen deposition at room temperature, MgO islands and chemisorbed oxygen species coexist on the surface. Moreover, the larger the oxygen predeposition is, the less CO₃²⁻ compounds are formed, meaning a decrease of available chemisorbed oxygen sites. From oxidation measurements at high temperature (420 K), we show that MgO islands and uncovered Mg domain coexist. Further, no under-stoichiometric compound features have been observed. The high temperature allows the direct formation of oxide MgO species in islands.     

Fast redox kinetics of a perovskite oxygen carrier measured using micro-fluidized bed thermogravimetric analysis

Redox kinetics of oxygen carrier in chemical looping combustion (CLC) is important for reactor design and its oxidation enthalpy is important in order to establish auto thermal demonstration. Most published redox kinetics of oxygen carrier has been measured by thermogravimetric analysis (TGA) which can include additional diffusion limitations and thus underestimate the overall kinetics. In this study, the redox kinetics of a new perovskite oxygen carrier (CaMn_0.375Ti_0.5Fe_0.125O_3-δ) was measured by a novel micro-fluidized bed thermogravimetric analysis (MFB-TGA) method which can achieve real-time weight measurement of oxygen carrier in a fluidizing state with similar mass and heat transfer characteristics as in a CLC reactor. The experimental data from MFB-TGA were analyzed with a reactor model. The redox kinetics was described by a two-stage model of gas-solid reaction. The effect of temperature, O₂ concentrations and reducing gas type (H₂ and CH₄) on the redox kinetics in MFB-TGA was investigated and compared with other oxygen carriers such as natural manganese ore and ilmenite. It is observed that the oxidation of both manganese ore and ilmenite can be divided into two stages, a fast initial stage followed by a second slower stage, resulting in slower total oxidation rates. A very interesting finding is that there is only the fast initial stage for the oxygen carrier of CaMn_0.375Ti_0.5Fe_0.125O_3-δ, and the full oxidation of CaMn_0.375Ti_0.5Fe_0.125O_3-δ can be finished within ～4 s which is ～7.5 and ～30 times faster than that of manganese ore and ilmenite. The reduction kinetics of CaMn_0.375Ti_0.5Fe_0.125O_3-δ by H₂ is also ～5 and ～2.2 times faster than that of manganese ore and ilmenite, respectively. The kinetic parameters of three oxygen carriers were compared and the redox mechanism of CaMn_0.375Ti_0.5Fe_0.125O_3-δ was discussed.     

Catalytic action of gold atoms on the oxidation of Si(111) surfaces

Auger spectroscopy, electron energy loss spectroscopy and ion depth profiling techniques, under ultra high vacuum conditions, have been used in a comparative study of the oxidation of clean and gold precovered silicon (111) surfaces. Exposure of a Si surface covered by a few Au monolayers to an oxygen partial pressure induces the formation of SiO₄ tetrahedra even at room temperature. In contrast, oxidation under the same conditions of a clean Si(111) surface leads to the well known formation of a chemisorbed oxygen monolayer. In the case of the Au covered surfaces, the enhancement of the oxide growth is attributed to the presence of an AuSi alloy where the hybridization state of silicon atoms is modified as compared to bulk silicon. This Au catalytic action has been investigated with various parameters as the substrate temperature, oxygen partial pressure and Au coverage. The conclusions are two fold. At low temperature (T < 400°C), gold atoms enhance considerably the oxidation process. SiO₄ tetrahedra are readily formed even at room temperature. Nevertheless, the SiO₂ thickness saturates at about one monolayer, this effect being attributed to the lack of Si atoms alloyed with gold in the reaction area. By increasing the temperature (from 20°C to ～400°C), silicon diffusion towards the surface is promoted and a thicker SiO₂ layer can be grown on top of the substrate. In the case of the oxidation performed at temperature higher than 400°C, the results are similar to the one obtained on a clean surface. At these temperatures, the metallic film agglomerates into tridimensional crystallites on top of a very thin AuSi alloyed layer. The fact that the latter has no influence on the oxidation is attributed to the different local arrangement of atoms at the sample surface.     

57Fe ion implantation studies on superconducting oxides

Ion implantation of⁵⁷Fe in YBaCuO pellets with different oxygen contents was tested for three parameters: total fluence, energy of the Fe ions and target temperature. The CEMS spectra obtained at room temperature are complex and we present here the analysis obtained for distinct symmetric doublets. The results are discussed on the basis of iron species present in sintered Fe: YBaCuO samples and spurious phases like Y₂BaCuO₅.     

Characterization of LaMnAl11O19 by FT-IR spectroscopy of adsorbed NO and NO/O2

The nature of the NO_x species produced during the adsorption of NO at room temperature and during its coadsorption with oxygen on LaMnAl₁₁O₁₉ sample with magnetoplumbite structure obtained by a sol-gel process has been investigated by means of in situ FT-IR spectroscopy. The adsorption of NO leads to formation of anionic nitrosyls and/or cis-hyponitrite ions and reveals the presence of coordinatively unsaturated Mn³⁺ ions. Upon NO/O₂ adsorption at room temperature various nitro-nitrato structures are observed. The nitro-nitrato species produced with the participation of electrophilic oxygen species decompose at 350 °C directly to N₂ and O₂. No NO decomposition is observed in absence of molecular oxygen. The adsorbed nitro-nitrato species are inert towards the interaction with methane and block the active sites (Mn³⁺ ions) for its oxidation. Noticeable oxidation of the methane on the NOx⁻-precovered sample is observed at temperatures higher than 350 °C due to the liberation of the active sites as a result of decomposition of the surface nitro-nitrato species. Mechanism explaining the promoting effect of the molecular oxygen in the NO decomposition is proposed.     

Interactions of water vapor with polycrystalline uranium surfaces - The low temperature regime

The initial interaction of water vapor with polycrystalline uranium surfaces at low temperatures (LT, 200 K), was studied by combined measurements utilizing Direct Recoil Spectrometry (DRS), Auger electron Spectroscopy (AES) and X-ray Photoelectron Spectroscopy (XPS). Three stages of water dissociation and adsorption can be observed: Stage (1) 0-0.6 oxygen monolayer coverage: full (H₂O → O + 2H) dissociation is dominant, coexisting with partial dissociation (H₂O → OH + H). In contrast to room temperature, where the adsorption is of a Langmuir type, in the present low temperature case it is a precursor-state type - the oxygen accumulation is linear, indicating that a constant fraction of the water molecules impinging on the surface diffuses to a dissociation and adsorption site. Only minor oxidation of the uranium occurs. Stage (2) 0.6-full oxygen coverage: only partial dissociation occurs. Still only minor oxidation of uranium takes place. Stage (3) buildup of a second hydroxyl layer, concurrent with slow continuous oxidation of uranium. Subsequent heating of the sample after the described exposure was accompanied by additional continuous oxidation. Above ∼230 K, the main process seems to be OH decomposition and desorption. A comparison is made to the dissociation and adsorption processes at room temperature.     

Saturation magnetization of MnBi films with different thicknesses and composition

The saturation magnetization of MnBi films in the low-temperature phase and the quenched high-temperature phase was measured at room temperature by a new method recently described. The measurements were performed with samples of varying thickness and composition (ratio Mn:Bi). The results obtained show no dependence either on film thickness or on composition. Hence, the different magnetization values given in the literature for bulk and thin film samples of the quenched high-temperature phase must not be attributed to a thickness dependence of the samples or to stoichiometric variations. This work has been supported by the data processing program of the Federal Department of Research and Technology of the FRG. The authors alone are responsible for the contents.