An infrared spectroscopic investigation of thin alumina films: measurement of acid sites and surface reactivity

The surface chemical activity of an alumina films grown on Mo(100) by oxidation of aluminum evaporated onto the surface and oxidized using water is examined using Auger, X-ray photoelectron and reflection/absorption infrared spectroscopies. The formation of alumina is confirmed using Auger and X-ray photoelectron spectroscopy from the positions and intensities of the aluminum features and using reflection-absorption infrared spectroscopy from the longitudinal optical modes of the Al–O bonds measured at 935 cm⁻¹. The presence of surface hydroxyls is monitored by forming films using D₂O which are evidenced by a feature at 2700 cm⁻¹. Ammonia adsorption on a dehydroxylated surface yields a single peak at 1260 cm⁻¹ due to ammonia adsorbed at a surface Lewis site where the principle symmetry axis of ammonia is oriented perpendicularly to the surface plane. Ammonia also appears to adsorb at Lewis sites on a hydroxylated surface with a slightly different adsorption geometry from that on a dehydroxylated surface. Finally, the chemistry of trimethyl aluminum adsorbed on the planar hydroxylated alumina surface is compared with that found on high-surface-area γ-alumina where the spectra and the chemistry found in both régimes is exactly identical except that the low-frequency methyl bending modes (at 769 and 718 cm⁻¹) are not obscured on the thin film by the intense substrate whereas they are on the high-surface-area support.     

The interaction of Cu and S2 with aluminum and alumina surfaces: a comparative study

The bonding interactions between Cu and Al are much stronger than those between Cu and Al₂O₃. Cu atoms supported on alumina show a narrow 3d band with a centroid shifted 0.35 eV with respect to that of the 3d band in bulk metallic Cu. In contrast, Cu atoms deposited on aluminum exhibit shifts of 1.3–1.6 eV in the centroid of the 3d band. Similar differences are observed when comparing the behavior of Ag and Pt overlayers on alumina and aluminum. The d band shifts on the oxide substrate are in the order of 0.3–0.4 eV, whereas on the metal substrate they vary from 0.8 to 2.0 eV. These trends are explained in terms of a simple model that takes into account changes in the energy of the Al(3s, 3p) bands when going from metallic aluminum to alumina. The sticking coefficient of S₂ on alumina surfaces is at least one order of magnitude smaller than on aluminum, a difference that also reflects variations in the position of the Al(3s,3p) bands. Submonolayer coverages of Cu do not produce significant changes in the electronic properties of Al₂O₃. In contrast, the deposition of small amounts of sulfur (0.1 ML) induces a substantial reduction (0.4–0.5 eV) in the binding energies of the O KVV, O 1s and Al 2p features of alumina. This is consistent with a transfer of electrons from alumina into the S atoms that produces a transformation similar to a change from n-type to p-type semiconductors. The reactivity of Cu/Al₂O₃ surfaces toward sulfur is much larger than that of pure Al₂O₃ surfaces. Cu clusters supported on alumina react with S₂ to form CuS_x compounds that decompose at temperatures between 850 and 1100 K.     

Influence of nitrogen in aluminum droplet combustion

The influence of nitrogen on the aluminum droplet combustion under forced convection conditions has been studied. An aerodynamic levitation technique of millimetric size liquid droplets heated with a CO₂ laser has been adopted to characterize the combustion of aluminum droplets and, in particular, to observe the surface phenomena. The determination of the burning rate and of the droplet temperature in several atmospheres (H₂O/O₂, H₂O/Ar, H₂O/N₂, and air) has shown that they depend only on the nature and concentration of the oxidizers (O₂ and H₂O); a comparison of experiments in nitrogen and in argon containing mixtures demonstrated that N₂ did not influence the gas phase combustion. However, for nitrogen containing atmospheres we observed the formation of solid aluminum nitride (AlN) at the droplet surface after a latency time depending on the nitrogen pressure. AlN first interacts with the oxide cap producing an aluminum oxynitride, then completely covers the droplet, and finally prevents combustion. The existence of a latency time varying with the nitrogen pressure suggests that the AlN formation is controlled by heterogeneous kinetics. The phenomenon of oxide cap regression during combustion was also observed in all gases, and it is attributed to a chemical decomposition process of alumina by aluminum forming gaseous Al_xO_y species. Therefore, nitrogen effects are significant at the droplet surface rather than in the gas phase, and it is suggested that N₂ is probably one of the main species causing the manifestation of unsteady processes during aluminum droplet burning.     

稀土掺杂P2O5-Al2O3-BaO玻璃的制备及其结构研究

稀土掺杂磷酸盐玻璃具有优异的光学和光谱特性,在激光介质、有色滤光材料等领域中有着重要的应用。在P2O5_Al2O3_BaO_Sm2O3(PABS)玻璃形成能力研究的基础上,借助MAS NMR、红外光谱等分析手段,研究了玻璃的结构、玻璃组成与热处理等对玻璃结构的影响。结果表明:不同组成PAB(S)玻璃的31P MAS NMR谱在-20ppm~-25ppm范围内均存在单一的特征信号峰,对应于磷氧多面体[PO4]的Q2型结构;在18ppm、-12ppm和-36ppm处27Al的MAS NMR谱的三个特征信号峰分别对应于27Al的[AlO5][、AlO6]、[AlO6]配位结构,稀土离子的掺入以及热处理均使得[AlO6]向[AlO5]转变;玻璃的网络结构主要由Q2型[PO4]、[AlO5]和[AlO6]构成,并P_O_P、P_O_Al的形式相连接。玻璃在1383 cm-1处出现的吸收峰可能是玻璃结构中形成了P_O_Sm键所致。     

Characterisation of Interfaces Between Liquid Tin and Alumina in the Presence of Titanium Alloy Additions

Neutron reflection spectroscopy has been used to characterise the composition of interfaces between liquid Sn-Ti alloys and Al₂O₃. The reflectivity profiles for both 1% and 3% Ti alloys are consistent with the presence of a layer approximately 2 nm thick at the liquid/solid interface, showing extensive segregation of Ti. The composition of this layer is not pure Ti but shows a greater Ti content than any known Ti oxide composition. In all interfaces exposed to liquid metals at elevated temperature (including pure Sn) there is a layer of thickness 20–100 nm on the alumina surface with slightly lower neutron scattering length density than pure alumina. This is interpreted as evidence for surface roughening of the Al₂O₃ surface during exposure to the liquid metal.     

Surface properties of mesoporous catalytic supports

The influence of the processing parameters on the properties of zirconia, alumina and silica MCM-41 has been investigated. Digestion of the precursors leads to zirconia, alumina and silica MCM-41 with higher surface area and better thermal stability. The effects of digestion are attributed to increased dehydroxylation, strengthening of the network between primary particles, and to a decrease in the number of surface defects. In the case of zirconia and alumina, digestion also increased the surface acidity. This may be due to the smaller crystallites which expose low-coordinated sites at the surface. Al-MCM-41 prepared by post-synthesis grafting of aluminum is compared with MCM-41 prepared by direct incorporation of aluminum during synthesis. The surface Si/Al ratio was determined using XPS and correlated to the catalytic activity of the Al-MCM-41 for the synthesis of jasminaldehyde.     

丝光沸石催化剂的固体高分辨核磁共振研究

利用²⁹Si MAS NMR及²⁷Al MAS NMR技术研究了丝光沸石催化剂制备过程中的结构变化,并利用Al的四极作用大小来区分重叠在一起的不同的Al物种.     

Effect of the Al/O ratio on the Al reaction of aluminized RDX-based explosives

Aluminum(Al) powders are used in composite explosives as a typical reducing agent for improving explosion performance. To understand energy release of aluminum in aluminized RDX-based explosives, a series of thermal measurements and underwater explosion(UNDEX) experiments were conducted. Lithium fluoride(LiF) was added in RDX-based explosives, as a replacement of aluminum, and used in constant temperature calorimeter experiments and UNDEXs. The influence of aluminum powder on explosion heat(Qv) was measured. A rich supply of data about aluminum energy release rate was gained. There are other oxides(CO_2, CO, and H_2O) in detonation products besides alumina when the content of RDX is maintained at the same levels. Aluminum cannot fully combine with oxygen in the detonation products. To study the relationship between the explosive formulation and energy release, pressure and impulse signals in underwater experiments were recorded and analyzed after charges were initiated underwater. The shock wave energy(Esk), bubble energy(Eb), and total energy(Et) monotony increase with the Al/O ratio, while the growth rates of the shock wave energy,bubble energy, and total energy become slow.     

Chemisorbed ordered oxygen overlayer on AL(111): An angular resolved photoemission study

Chemisorbed oxygen atoms on aluminum induce a strong O 2p derived surface resonance. On the (111) crystal face the oxygen atoms form an ordered overlayer of (1x1) symmetry. The O 2p resonance in this system has been studied using angle resolved photoemission. The results indicate one of the threefold centered hollow sites as the probable site of chemisorption. At normal electron emission, the O 2p resonance is sharp and symmetric. Strong dispersion effects are seen at non-normal emission indicating appreciable oxygen-oxygen interaction in the chemisorbed layer.     

LBO晶体上1 064，532 nm倍频增透膜的镀制及性能分析

 用电子束蒸发沉积方法在X切LBO（X-LBO）晶体上镀制了两种不同膜系结构的1 064和532 nm倍频增透膜，其中一种膜系结构为基底/ZrO₂/Y₂O₃/Al₂O₃/SiO₂/空气，另一种为基底/0.5Al₂O₃/ZrO₂/Y₂O₃/Al₂O₃/SiO₂/空气，两种膜系结构的主要差别在于有无氧化铝过渡层。测量了薄膜的反射率光谱曲线，发现两种增透膜在1 064和532 nm处的反射率均小于0.5％，实际镀制结果与理论设计曲线的差异主要是由材料折射率的变化引起的。且对样品在空气环境中进行了温度为473 K的退火处理，结果发现两种膜系结构均表现了较优异的光学性能，氧化铝过渡层的加入使薄膜具有强的热应力性能。     

铝纳米晶的低温导电特性研究

采用真空热压技术将电磁感应加热-自悬浮定向流法制备的铝纳米粉末压制成块体样品.通过X射线衍射、透射电子显微镜、扫描电子显微镜及X射线能谱分析了铝纳米晶的微观结构,并用四探针法测量了不同温度下(8—300 K)样品的电阻率,研究了铝纳米晶的电阻率(ρ)随温度的变化规律.结果表明:由于晶界(非晶氧化铝)对电子的散射以及晶界声子对电子的散射效应,低温(40 K)下,铝纳米晶的本征电阻率随温度变化关系明显不同于粗晶铝,不仅呈现出T~4变化,还表现出显著的T3变化规律.因晶界等缺陷和非晶氧化铝杂质对电子的散射,铝纳米晶残余电阻率比粗晶铝电阻率大5—6个数量级.     

An examination of the shrinking-core model of sub-micron aluminum combustion

We revisit the shrinking-core model of sub-micron aluminum combustion with particular attention to the mass flux balance at the reaction front which necessarily leads to a displacement velocity of the alumina shell surrounding the liquid aluminum. For the planar problem this displacement simply leads to an equal displacement of the entire alumina layer, and therefore a straightforward mathematical framework can be constructed. In this way we are able to construct a single curve which defines the burn time for arbitrary values of the diffusion coefficient of O atoms, the reaction rate, the characteristic length of the combustion field, and the O atom mass concentration within the alumina provided that it is much smaller than the aluminum density. This demonstrates a transition between a ‘d  ²–t’ law for fast chemistry and a ‘d–t’ law for slow chemistry. For the spherical geometry, the one of physical interest, the outward displacement velocity creates not a simple displacement, but a stress field which, when examined within the framework of linear elasticity, strongly suggests the creation of internal cracking. We note that if the molten aluminum is pushed into these cracks by the high internal pressure characteristic of the stress field, its surface, where reaction occurs, could be fractal in nature and affect the fundamental nature of the burning law. Indeed, if this ingredient is added to the planar model, a single curve for the burn time can again be derived, and this describes a transition from a ‘d  ²–t’ law to a ‘d  ^ν–t’ law, where 0<ν<1.     

Patterned growth of ZnO nanofibers

A simple method is adopted to grow ZnO nanofibers laterally among the patterned seeds designed in advance on silicon substrate. The preparation of seed lattices is carried out by lithographing the metal zinc film evaporated on the substrate. A layer of aluminum is covered on the zinc layer to prevent the ZnO nanorods vertically growing on the top surface. After oxidation, the patterned ZnO/Al2O3 spots are formed at the sites for the horizontal growth of ZnO nanofibers by the vapor phase transportation （VPT） method using the zinc powders as source material.     

EXAFS analysis of Er sites in Er–O and Er–F co-doped crystalline Si

We present extended X-ray absorption fine structure (EXAFS) and photoluminescence (PL) analyses of Er–O and Er–F co-doped Si. Samples were prepared by multiple implants at 77 K of Er and co-dopant (O or F) ions resulting in the formation of a2 μm thick amorphous layer uniformly doped with 1×10¹⁹ Er/cm³ and 3×10¹⁹ O/cm³, 1×10²⁰ O/cm³ or 1×10²⁰ F/cm³. EXAFS measurements show that the local environment of the Er sites in the amorphous layers consists of 6 Si first neighbors. After epitaxial regrowth at 620°C for 3 h, Er is fully coordinated with 8 F ions in the Er–F samples, while Si and O ions are concomitantly present in the first shell of O co-doped samples. Post regrowth thermal treatments at 900°C leave the coordination unchanged in the Er+F, while the Er+O (ratio 1 : 10) doped samples present Er sites with a fully O coordinated shell with an average of 5 O atoms and 4 O atoms after 30 s and 12 h, respectively. We have also found that the fine structure and intensity of the high-resolution PL spectra are strongly dependent on the Er-impurity ratio and on thermal process parameters in the Er–O co-doped samples, while this is not observed for the F-doped samples. The most intense PL response at 15 K was obtained for the 1 : 3 E : O ratio, suggesting that an incomplete O shell around Er is particularly suitable for optical excitation.     

Influence of combustion temperature and coal types on alumina crystal phase formation of high-alumina coal ash

The alumina content (more than 40%) of high-alumina coal ash is comparative to the middle content bauxite ores in China. So far, in order to meet the high demand of alumina and the rise of circular economy industrial chain, extracting alumina from coal ash has become a way to comprehensively utilize high-alumina coal ash. However, this process has high requirements on the crystal phase and stability of alumina. Different from most studies, this paper focuses on how to produce coal ash more beneficial to the later refining of aluminum. Therefore, the effects of combustion temperature and coal types by classifying high-alumina coal into dull coal and bright coal on alumina crystal phase formation were studied. Through proximate analysis, ultimate analysis, calorific value analysis, X-ray fluorescence spectroscopy, X-ray diffraction (XRD) and scanning electron microscope (SEM) and other methods, it is found that γ-Al₂O₃ in high-alumina coal ash translated into more stable θ-Al₂O₃ and finally α-Al₂O₃ when combustion temperature is higher than 1000°C. Thus compared with pulverized coal boilers, circulating fluidized bed (CFB) boilers with lower combustion temperature can produce higher quality coal ash. Moreover, at the same combustion temperature, alumina crystal phase in dull coal ash is relatively less stable than that in bright coal ash, which is more suitable to the later refining and electrolysis of aluminum.     

液态氧化铝结构的分子动力学模拟

利用分子动力学模拟液态氧化铝从2663 K到过冷温度2223 K的结构变化,通过总双体分布函数得到的液态氧化铝的原子第一、第二近邻距离与Ansell研究小组的实验结果基本一致.通过配位数和偏角分布函数的分析,液态氧化铝的局域结构主要是由氧的三重铝原子配位和铝原子四重(AlO₄)和五重(AlO₅)氧原子配位组成.没有观察到可能因铝原子高、低配位数氧原子的团簇分离而出现的液-液相变.     

Evolution mechanism of alumina coating layer on rutile TiO2 powders and the pigmentary properties

The evolution of alumina coating layers on rutile TiO₂ particle surfaces was investigated starting from aluminum sulfate by a chemical liquid deposition method. The morphology of the alumina coating layers was determined by transmission electron microscopy. The chemical structure and the evolution mechanism of the alumina coating layers on TiO₂ surfaces were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and powder X-ray diffraction techniques. The dispersibility of the alumina-coated TiO₂ powders was determined by dynamic laser scattering (DLS) mode. The alumina coating layers existed in boehmite phase, AlOOH, and anchored at the surfaces of TiO₂ via Ti-O-Al bond. The formation of alumina coating layers on TiO₂ surfaces depended on the pH value of the deposition solution and the alumina loading. After coated by alumina layer, the dispersibility, whiteness, brightness, and light scattering index of the resultant samples were promoted.     

Electric field gradients in PrBa2 Cu 3 O 7 : LSDA+U results and comparison with experiment

Electric-field gradient (EFG) and asymmetry parameter (η) at all oxygen and copper sites of nonsuperconducting PrBa₂Cu₃O₇ (Pr123) compound were calculated using the full-potential (linearized)-augmented-plane-wave plus local orbitals method. Exchange and correlation effects were treated by LSDA+U for Cu(3d) and Pr(4f) electrons. The effects of changing screened Coulomb parameters U_Pr, U_Cu1, and U_Cu2 on the results were individually studied. The calculated EFG of O2 site is close to the EFG of O3 site at variance with the experimental result. It was shown that by increasing superconducting holes in O2 and O3 sites the EFG at these sites increase and vice versa. The most famous theories which have been proposed to explain the suppression of superconductivity in perfect (without any mis-substitution or other defects) Pr123 compound are not consistent with the experimental EFG at O2 and O3 sites. By replacing one Pr atom at the Ba site on unit cell of Pr123 (Pr_Ba), it was shown that Pr_Ba mis-substitution reduces the superconducting holes in both O2 and O3 sites and could be responsible for the suppuration of superconductivity in Pr123 samples. It is very probable that the unusual behaviors of experimental EFG at O2 and O3 sites of Pr123 are related to oxygen defects which are produced with Pr_Ba mis-substitution.     

Effect of the current density on the volume expansion of the deposited thin films of aluminum during porous oxide formation

The effect of the anodic current density, temperature and concentration of the oxalic acid on the volume expansion of porous alumina films formed from 1.8 μm thick aluminum films has been investigated. The volume expansion of the aluminum during oxidation was determined by the step height between the aluminum surface and the porous alumina surface at the edge of the anodized region, which was measured with a mechanical profiler with computer signal processing. Experiments showed, that the volume expansion factor as well as the cell dimensions is proportional to the anodizing voltage. The dependence of the volume expansion factor (k) on the anodizing voltage (U) has the linear nature. The volume expansion factor in the 4% solution of oxalic acid can be defined by the following equation: k=1.092+0.007U. It was established, that the dependence of the logarithm of the ion current density on the inverse volume expansion factor of porous alumina has the linear nature.     

硅酸盐玻璃中的Na,Mg K-边XANES谱研究

本文利用同步辐射的NaK 边X 射线近边结构 (XANES)谱研究了含Na玻璃 (Na2 O SiO2 P2 O5和Na2 O SiO2 )的NaK 边的特征 ,同时建立了含磷 (P)的钠玻璃中NaK 边的能量 ,其能量位置随着P的含量增加 ,而增大其能量位置。CaMgSi2 O6(Di) NaAlSi3 O8(Ab)玻璃中MgK 边XANES的能量和Mg—O的键长有关系。在Di Ab玻璃中的Mg—O键距是 2± 0 0 4 。表明本方法可以作为研究含Mg玻璃的配位与局部结构新方法