The dielectric properties and optical propagation loss of c-axis oriented ZnO thin films deposited by sol–gel process

The c-axis oriented ZnO thin films were prepared on various substrates by sol–gel processes. The stability of solution was examined through solvent and stabilizer. The c-axis orientation and grain size of films were increased with increasing of heat treatment temperature. The optical propogation losses of ZnO films deposited SiO₂/Si(111) substrates were measured using end-coupling method. The losses result in the scattering of the interface of ZnO/SiO₂, and the ZnO grain. Dielectric constant and resistivity of thin films deposited on Pt/SiO₂/Si(111) substrates are, respectively, in the range of 7–13 and 1.7×10⁴9.8×10⁵Ω cm.     

Diamond growth by carbon ion implantation of diamond

Medium energy (5–25 keV) ¹³C⁺ ion implantation into diamond (100) to a fluence ranging from 10¹⁶ cm⁻² to 10¹⁸ cm⁻² was performed for the study of diamond growth via the approach of ion beam implantation. The samples were characterized with Rutherford backscattering/channelling spectroscopy, Raman spectroscopy, X-ray photoemission spectroscopy and Auger electron spectroscopy. Extended defects are formed in the cascade collision volume during bombardment at high temperatures. Carbon incorporation indeed induces a volume growth but the diamond (100) samples receiving a fluence of 4 × 10¹⁷ to 2 × 10¹⁸ at. cm⁻² (with a dose rate of 5 × 10¹⁵ at. cm⁻² s⁻¹ at 5 to 25 keV and 800 °C) showed no He-ion channelling. Common to these samples is that the top surface layer of a few nanometers has a substantial amount of graphite which can be removed by chemical etching. The rest of the grown layer is polycrystalline diamond with a very high density of extended defects.     

Diamond nucleation suppression in chemical vapor deposition process

A systematic study of the effect of different pre-treatments of the Si substrate surface in suppressing diamond nucleation was performed to investigate the nature of the nucleation centers in chemical vapor deposition (CVD) of diamond. The Si substrates were initially scratched with diamond powder and then submitted to one of the following pre-treatments: thermal annealing in high vacuum and in air, deposition of an amorphous silicon film, and ⁸⁴Kr⁺ ion implantation. The pre-treated substrates were used in a hot filament CVD diamond process, and the diamond films obtained were analyzed by different techniques. The results suggest that the observed nucleation reduction under certain pre-treatment conditions is related to modifications induced on the original topographical features of the scratched substrate surface, which would be responsible for the CVD diamond nucleation. The dimensions of these surface features are estimated to be of the order of 5 nm.     

The improvement in oxidation resistance of carbon by a graded SiC/SiO2 coating

A dense functionally gradient SiC/SiO₂ coating has been developed to improve the oxidation resistance of carbon at elevated temperatures. SiC was coated on the surface of a graphite substrate by a reaction between thermally evaporated silicon and carbon at 1400 °C. The SiO₂ layer was deposited by exposing the SiC coated specimens next to a bed of Si powder in a flowing H₂–H₂O gas (P_H2O=2.6×10⁻² atm) at 1400 °C. The formed SiC/SiO₂ layers were dense and had gradient compositions with good adhesion to the carbon substrate. However, as the coating thickness increased, the coating layer became cracked and delaminated from the substrate due to thermal stress. The specimens with the continuous SiC/SiO₂ layer showed a remarkably improved oxidation resistance up to 1200 °C.     

Lithia porcelains as promising breeder candidates - II. Structural changes induced by fast neutron irradiation

The promise of lithia ceramics as candidate breeder materials necessitates investigations on radiation damage induced structural variations. Prepared porcelain systems consisting of β-eucryptite (Li₂O.Al₂O₃.2SiO₂), its solid-solution (Li₂O.Al₂O₃.3SiO₂) and β-spodumene (Li₂O.Al₂O₃4SiO₂), previously characterized, were irradiated by fast neutrons at room temperature. A ²⁵²Cf source (2 MeV) was used to give fluences of 1 × 10⁵, 1 × 10⁸ or 1 × 10¹⁰ n/cm². Samples of each group received fluences in a one-shot technique, i.e. new samples were used for each fluence before being subjected to structural testing. Damage was assessed by X-ray diffraction (XRD) and infrared (IR) spectral analyses. Relevance dilatation changes were followed through coefficient of change with temperature up to 1000 °C. Surface morphologies were examined using scanning electron microscopy (SEM) and selected area electron diffraction (SAED).

XRD patterns revealed various degrees of imperfections that were reflected as shifts in lattice planes. The IR spectral bands suffered shift, especially in the fingerprint region, parallel with the fluence intensity. Coefficient of contraction and/ or expansion evidenced various degree of damage, which upon intense irradiation annealed to the original values. SEM micrographs revealed that large grains comprising either β-eucryptite or β-spodumene bodies are much more affected by fast neutrons compared to smaller grains detected in the body containing the solid-solution. Additional evidence was obtained by the SAED results, where the continuous polycrystalline rings of both β-eucryptite and β-spodumene turned upon irradiation to the amorphous metamict state simulating the initial solidsolution structure. The latter acquired higher crystalline order, as well as polycrystalline habit. The degrees of induced imperfections were found to be dependent on initial crystallinity. The higher sensitivity to fast neutrons of β-eucryptite was related to its higher lithia content rather than its hexagonal spiral structure compared to the tetragonal β-spodumene. Intense irradiation caused annealing of the produced damage observed by fragmentation of the grains and various degree of amorphism.     

Characterization of diamond-like carbon films before and after heavy energetic ion implantations

Hydrogenated diamond-like carbon films were implanted by 110 keV Fe⁺ at doses ranging from 1 × 10¹³ to 5 × 10¹⁶ ions cm⁻². The film resistivities and the infra-red transmittances of the specimens were determined as functions of the implanted doses. Raman spectra and the infra-red transmittances of the film layers were used to characterize the structural changes of the implanted films. It was found that, when the implantation dose was higher than about 5 × 10¹⁴ or 1 × 10¹⁵ ions cm⁻², the film resistivity and the total infra-red transmittance of the specimens decreased significantly. However, when the dose was smaller than this value, the resistivity decreased firstly and then increased with dose and the measured values were higher than those of corresponding as-grown ones. The infra-red transmittance of the specimens was also improved to some extent under the lower dose range. By using structural characterization results, especially the infra-red transmittances of the film layers, we conclude that the electrical and optical property changes at doses higher than about 5 × 10¹⁴ or 1 × 10¹⁵ ions cm⁻² were due to the following changes, i.e., the decrease in the population of both sp² C-H and sp³ C-H bonds (compared with that of sp³ C-H bonds, the decrease in speed of sp² C-H bonds is smaller), the decrease of bond-angle disorder and the increased population of sp² C-C bonds. However, at doses between 1 × 10¹⁴ and 5 × 10¹⁴ or 1 × 10¹⁵ ions cm⁻², the implantation induced increase of C-H bonds was responsible for the observed property changes. Compared with the previous reports, the novelty of the present work is: the IR transmittance curves of the single film layers give us direct evidence for the changes of different C-H bonds with increasing ion dose and thus proved the transformation mechanism proposed previously.     

Pyrylium salt-photosensitised degradation of phenolic contaminants present in olive oil wastewaters with solar light: Part II. Benzoic acid derivatives

Solar light photodegradation, catalysed by a pyrylium salt, of seven benzoic acids present in olive oil mill, has been studied. Significant percentages of photodegradation (20–40%) have been achieved after 6 h of solar exposure for six of the acids, even though they were expected to be difficult to oxidise, due to the presence of an electron-withdrawing carboxylic acid group directly attached to the aromatic ring. Quenching constants for the electron-transfer process between the substrate and the excited catalyst were calculated by means of fluorescence measurements for syringic acid (66×10⁹ M⁻¹ s⁻¹), gallic acid (51×10⁹ M⁻¹ s⁻¹), veratric acid (51×10⁹ M⁻¹ s⁻¹), vanillic acid (48×10⁹ M⁻¹ s⁻¹), protocatechuic acid (37×10⁹ M⁻¹ s⁻¹) and p-hydroxybenzoic acid (15×10⁹ M⁻¹ s⁻¹); no quenching was found for benzoic acid. These photophysical measurements are in good correlation with the yields obtained in the pyrylium salt photocatalysed degradation of those phenolic acids.     

The elastic modulus of the poly(phosphonitrilic chloride) crystal

The Young's modulus for a crystal of poly(phosphonitrilic chloride) (poly-dichlorophosphazene) (NPCl₂)_n has been calculated using force constants derived from spectroscopy. Assuming that the molecule is a uniform helix the value of the modulus is 1.38 × 10⁹ dyne cm⁻² [dyne cm⁻² = 0.1 N m⁻²]; the result is 1.66 × 10¹⁰ dyne cm⁻² if a cis-planar structure is assumed for the molecule. Neither value is close to those obtained experimentally (1.8 × 10⁶ to 6.5 × 10⁶ dyne cm⁻²). This is because experimental values relate to the amorphous polymer whereas the calculated values are those for the crystal. There is good agreement between the values calculated for the (NPCl₂)_n crystal and those for other polymer crystals.     

聚醚砜超临界CO2发泡行为研究

以超临界CO₂为发泡剂,采用间歇发泡法制备了聚醚砜（PES）泡沫。采用旋转流变仪和扫描电子显微镜分析表征了PES发泡的均相成核行为,继而分别以滑石粉和二氧化硅（SiO₂）作为异相成核剂,探究了PES发泡过程中的异相成核行为。结果表明,间歇发泡法制备PES泡沫的发泡区间为200~230 ℃;最佳浸泡压力为20 MPa;最佳浸泡时间为3 h;未改性PES的泡孔直径均可在10 μm以下,泡孔密度在10⁹~10¹⁰ 个/cm³之间,但泡孔壁较厚;SiO₂相对于Talc,表现出更显著的异相成核作用;在210 ℃、3 h、20 MPa的发泡条件下,添加0.9 %（质量分数,下同）的SiO₂,可得到泡孔直径为0.77 μm,泡孔密度为7.14×10¹¹ 个/cm³的PES微孔泡沫。     

Free convection mass transfer at horizontal electrodes

The free convection mass-transfer behaviour of upward-facing horizontal surfaces has been investigated experimentally using an electrochemical technique involving the measurement of limiting currents for the deposition of copper on copper electrodes from acidified cupric sulphate solutions. The data are well correlated by the equations

Sh = 0·64(Sc . Gr)^0·25 for 3 × 10⁴ < ScGr < 2·5 × 10⁷ and

Sh = 0·16(Sc . Gr)^0·33 for 2·5 × 10⁷ < ScGr < 10¹². Electrode diameters varied between 0·1 and 12 cm and cupric sulphate concentrations between 0·01 and 0·3 M.

The data compare favourably with previous experimental results for the corresponding heat-transfer case.     

Interpenetrating polymer networks of poly(dimethylsiloxane): 1. Preparation and characterization

Model networks of ,ω-dihydroxy-poly(dimethylsiloxane) (PDMS) were prepared by tetrafunctional crosslinking agent tetraethyl orthosilicate (TEOS) and the catalyst stannous 2-ethylhexanoate. Hydroxylterminated chains of PDMS having molecular weights 15 × 10³ and 75 × 10³ g mol⁻¹ were used in the crosslinking reaction. Bimodal networks were obtained from a 50% (w/w) mixture of PDMS chains with M_n = 15 × 10³ and 75 × 10³ g mol⁻¹. A sequential interpenetrating network of these PDMS chains was also prepared. Physical properties of the elastomers were determined by stress-strain tests, swelling and extraction experiments, and differential scanning calorimetry measurements.     

Preparation of ultra-high-strength nylon-6 fibre by a multi-step zone-annealing method

A multi-step procedure to improve the zone-annealing method was attempted to prepare a high-modulus and high-strength nylon-6 fibre. By the adoption of this procedure, the dynamic storage modulus at room temperature was markedly increased and reached 15.7 × 10¹⁰ dyne cm⁻² which is 1.5 times that obtained by the previous zone-annealing method. Tensile properties, orientation, crystallinity and mechanical dispersion were also measured. Comparing the multi-step procedure with the previous one-step procedure, the excellent effects of the multi-step procedure on mechanical properties are discussed. Further, in order to prevent selective relaxation of amorphous molecular chains on removing the applied tension after zone-annealing, heat-setting at constant length was subsequently carried out on the as-zone-annealed fibre. The mechanical properties were further improved: for example, the dynamic storage modulus at room temperature of the resulting fibre was raised to 16.9 × 10¹⁰ dyne cm⁻², which was well beyond the highest modulus available in the literature, 14 × 10¹⁰ dyne cm⁻².     

FTIR study of the adsorption of single pollutants and mixtures of pollutants onto titanium dioxide in water: oxalic and salicylic acids

The use of ATR–FTIR to probe the adsorption of oxalic and salicylic acids, and of mixtures of both, onto TiO₂ (Degussa P-25) demonstrates the potential of the technique to characterise the evolution of the catalyst with time, including surface poisoning. Under equilibrium dark conditions, three surface species are formed by oxalate, and two by salicylate. Their stabilities, described by conditional Langmuir-type equilibria involving the dissociative, electroneutral adsorption of the acids H₂L, are at pH 3.7, 2.4×10⁶, 3.0×10⁴ and 3.0×10³ mol⁻¹ dm³ for oxalic acid, and 2.9×10⁵ and 9.1×10³ mol⁻¹ dm³ for salicylic acid. The nature of the species is discussed in terms of their spectral features. The displacement of each acid from the surface by addition of the other one was followed also by ATR–FTIR. The results demonstrate that oxalate displaces totally chemisorbed salicylate, whereas salicylate displaces oxalate only partially. These results are explained by assuming competitive chemisorption onto two different surface sites, plus oxalate adsorption onto a site that exhibits negligible affinity for salicylate. Irreversible adsorption by partially oxidised products in the course of photocatalytic processes can therefore be assessed by ATR–FTIR.     

Electrical properties of B-doped homoepitaxial diamond (001) film

Relationship between growth condition and quality of homoepitaxially grown B-doped diamond (001) film has been studied using physical measurements of defect density as a function of doping concentration. In particular, electrical properties of the homoepitaxial diamond film were characterized using measurements of conductivity, carrier concentration and mobility. The highest mobility is found to be about 1000 cm²V⁻¹s⁻¹ at 293 K, indicating that the quality of the CVD diamond film is further improved through optimizing the growth condition. The density of the compensation donor was determined from the temperature-dependent hole concentration. The lowest donor density is found to be 8.4 × 10¹⁵ cm⁻³ in the present work. This is an order of magnitude greater than the lowest value measured in natural IIb diamond. Furthermore, it is also found that the donor density increases with increasing doping concentration during the growth. On the other hand, the mobility decreases rapidly with increasing doping concentration. From these results, we speculate that the compensation donor is an origin of an additional scattering center in diamond, and excessive B-doping makes the quality of the CVD diamond worse.     

Modelling formation and growth of H2SO4-H2O aerosols: Uncertainty analysis and experimental evaluation

An aerosol dynamics model, AERO2, is presented, which describes the formation of H₂SO₄-H₂O aerosol in a smog chamber. The model is used to analyse how the uncertainties on four input parameters are propagated through an aerosol dynamics model. The input parameters are: the rate of the reaction between SO₂ and OH (k₁), the ratio between the nucleation rate used in AERO2 and that derived from classical nucleation theory (t_n), the H₂SO₄ mass accommodation coefficient () and a measure of the turbulence intensity in the reactor (k_e). Uncertainties for these parameters are taken from the literature. One of the results of the analysis is that AERO2 and aerosol dynamics models in general can only predict upper bounds for the total number (N_tot) and total volume (V_tot) concentrations of the particles. The uncertainties on N_tot and V_tot are mainly due to the uncertainties on k₁, and t_n. An uncertainty factor of 20–100 still remains when the uncertainty on k₁, is reduced to ±5%. Aerosol measurements from three smog chamber experiments have therefore been used, in an attempt to reduce the uncertainty on k₁ and t_n. Values for k₁ are obtained in the reduced range 7.8 × 10⁻¹³ to 1.0 × 10⁻¹² cm³ s⁻¹, which is within the range found in the literature. For t_n, values in the range 10⁴–10⁷ are obtained, which is close to the upper bound of the range in literature. These values for t_n are in marked contrast with a recent set of experiments on nucleation in H₂SO₄-H₂O mixtures, which suggests a value for t_n of at most 10⁻⁵.     

Bias-enhanced nucleation of oriented diamonds on cone-like Si

Uniform distribution of bias-enhanced nucleation of diamond has been improved on Si substrate of an area of 1 × 1 cm² by using a dome-shaped Mo counter electrode in a microwave plasma chemical vapor deposition reactor. A nucleation density of 10⁹ cm² can be reached within a few minutes when the bias voltage of − 100 V is applied on the substrates. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that a single-crystalline diamond in a few nanometered size can be deposited on a volcano-shaped cubic SiC which is epitaxially formed on a Si cone. Examination reveals a large fraction of diamond nuclei are oriented along with one side of SiC on each Si cone. The Si cone formed on the Si substrate is due to plasma etching. The diamond nuclei have a shape close to rhombus in TEM. With further growth, secondary nucleation of diamond occurs on top of diamond nuclei and SiC which grows with Si cones. As a result, polycrystalline diamonds are deposited on each Si cone.     

Microwave plasma chemical vapor deposition of cone-like structure of diamond/SiC/Si on Si (100)

Diamond deposition on 1 × 1 cm² Si (100) substrates with bias was carried out by microwave plasma chemical vapor deposition (MPCVD). Distribution of deposited diamonds has been significantly improved in uniformity over all the Si substrate surface area by using a novel designed dome-shaped Mo anode. The deposits were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman analysis. SEM observations show that there is a high density of cone-like particles uniformly deposited on the surface of the substrate in short bias nucleation period. The average diameter, height and density of cone-like structure were increased with methane concentration in the bias stage. TEM reveals that the cone-like structure is actually composed of Si conic crystal covered with diamond. Between Si and diamond, a thin layer of cubic SiC is found in epitaxy with Si. Furthermore, for 3% CH₄ concentration, the range of diameter of cone-like structure was about 20–90 nm and the size of diamond was about 10–60 nm.     

HEAT TRANSFER IN LOW PRESSURE LITHIUM CONDENSATION

This paper presents the results of an experimental investigation into lithium condensation. The objective of the investigation is to find the condensing side heat transfer coefficients of lithium on the vertical flow configuration and to explain the discrepancy between Nusselt's theory and the experimental results. The heat fluxes in these experiments varied from about 1.3 × 10⁴ W/m² at 833 k to 1.3 × 10⁵ W/m2 at 898 k, giving heat transfer coefficients of 4078 W/m² k to 37805 W/m² k. These values appear 0.3% to 3% of those predicted by the Nusselt theory. Condensate film thickness was calculated by the Nusselt theory. Boiling and condensing of lithium at low, less than atmospheric pressure, appears to be an efficient energy transport mechanism that may find use in space applications or cooling of the first wall in fusion reactors.     

Conformation of isotactic polystyrene (IPS) in the bulk crystallized state as revealed by small-angle neutron scattering

Neutron scattering experiments have been performed on isotactic polystyrene (IPS) samples in the bulk crystallized state (T_{crystallization} = 185°C). The determination of the conformation of tagged chains ranging from 2.5 × 10⁵ to 7 × 10⁵ has been undertaken on two different hydrogenated IPS matrices. A matrix of usual molecular weight (M_w = 4 × 10⁵) leads to results which do not agree with Flory's model. In this case, measurements on radius of gyration R_g show on the one hand an important increase of this parameter (40%) with increasing crystallinity for the highest molecular weight tagged chains and on the other hand a variation with molecular weight like M^0.78. These results are interpreted with a schematic model involving a long crystalline sequence incorporated in the monocrystal along the 110 plane and two amorphous wings. Such an assumption is confirmed by the scattering behaviours in the intermediate range. On the other hand, by using an IPSH matrix of very high molecular weight (M_w = 1.75 × 10⁶), and the same tagged chains previously considered, a very weak variation of R_g with increasing crystallinity is observed. This leads to consider in this case Flory's conformation which is corroborated by data obtained in the intermediate range.     

Low temperature synthesis of β-SiC by a metal vapor vacuum arc ion source

β-SiC surface layers were synthesized by implantation of C⁺ into Si substrates at a comparatively low temperature of 400°C with a metal vapour vacuum arc ion source. X-ray diffraction patterns showed that these layers had a strong (111) preferred orientation. The amount of β-SiC formed increased significantly with the rise of the implantation dose, but the crystallinity of the layers formed relied little on the implantation dose. Both the broad X-ray diffraction peaks and the scanning electron microscopy photograph showed that the grain size of the sample with a dose of 7×10¹⁷ cm⁻² is relatively small.