Degradation of white anodic-oxide coatings in UV irradiation in vacuum

Photostimulated degradation of the reflectivity of white anodic-oxide coatings on Al alloy (Al-AOCs) that are used as thermal-regulating coatings of space vehicles is investigated by spectroscopy of diffuse reflection in the region of 0.5–6 eV. It is established that irradiation in vaccum when λ≤300 nm leads to the appearance in diffuse-reflection spectra of the absorption bands at 4.0 and ∼4.6 eV that are similar to these induced by vacuum heating for T≥350 K. A growth in the absorption bands is accompanied by gas release from the coatings. These processes have a common excitation spectrum, basic kinetic regularities, and a thermoactivated character. UV irradiation in vacuum is assumed to initiate Al-AOC destruction with the formation of color centers. This process is accompanied by the desorption of molecular products. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 801–806, November–December, 1997.     

A study of the optical absorption induced in vacuum thermolysis of aluminum trihydroxide

The diffuse reflection spectroscopy technique was used to investigate the color centers (CC) in the products of thermolysis and photolysis of disperse Al(OH)₃ in a vacuum. The spectra were recorded in situ in the region of 2.5–6.0 eV and 4000–12,000 cm⁻¹. It was found that in thermolysis of Al(OH₃) production of Al is accompanied, by transformation of the IR spectra of the compound and overtone vibrations of OH groups and by the appearance of an absorption band (AB) at 4.0 eV with a shoulder at 4.4 eV. A similar AB is induced by UV irradiation of Al(OH)₃ in a vacuum. In the position of the maximum and shape, the AB at 4.0 eV in aluminum oxide produced by thermolysis of Al(OH)₃ coincides with the AB of CC responsible for light- and temperature-stimulated degradation of white anode oxide coatings on Al(Al-AOC). This suggests that in Al-AOC, CC are formed in decay of structural O_mH_n groups. In Al oxide and in Al-AOC, their nature is discussed with the use of data on optical absorption of radiation-induced defects in Al₂O₃. Research Institute of Physics at St. Petersburg State University, St. Petersburg 1, Ul’yanovskaya St., Petrodvorets St. Petersburg, 198904, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 400–404, May–June, 1998.     

Giant red shift of the absorption edge in La0.9Sr0.1MnO3

The absorption edge of the perovskite La_0.9Sr_0.1MnO₃, determined using the diffuse reflection coefficient spectra, shifts by the giant amount 0.4 eV in the direction of lower energies as the temperature decreases from the Curie point (155 K) to 141 K. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 4, 303–306 (25 August 1999)     

Laser initiation of a mixture of PETN with NiC nanoparticles at elevated temperatures

The temperature dependence of the probability of the explosion of pentaerythritol tetranitrate (PETN) with an admixture of NiC particles (0.3 wt %) initiated by laser pulses (1064 nm, 20 ns) was studied over the temperature range 295–450 K. At 295–350 K, a weak temperature dependence was observed. The determining contribution to explosion initiation was made by the absorption of laser radiation by nanoparticles. The threshold of explosive decomposition at 295 K decreased by ∼40 times compared with samples free of NiC nanoparticles. Over the temperature range 400–450 K, the threshold of the explosive decomposition of samples containing NiC nanoparticles decreased with the activation energy ∼0.4 eV. A decrease in the threshold of explosive decomposition with a ∼0.4 eV activation energy over the temperature range 340–440 K was also observed for laser action on PETN samples not containing NiC. A hypothesis was suggested according to which the absorption of a light quantum caused the transfer of an electron from the valence band of the crystal to a level in the forbidden band with subsequent thermal positive ion dissociation to the carbocation and NO₃ radical.     

Impurity absorption of SrS-Ce3+ phosphors

We investigate the impurity absorption of SrS−Ce phosphors. For this purpose, we measure the spectra of diffuse reflection of powder phosphors. It is established that the introduction of Ce simultaneously with a coactivator gives rise to a strong absorption band at 2.88 eV, and the introduction of a coactivator (NH₄F, NH₄Cl, NH₄Br, NH₄I, LiCl, NaCl or KCl), to an absorption band at about 2.36 eV. We assume that the absorption band at 2.88 eV is caused by that portion of Ce introduced that forms the center of luminescence of Ce³⁺. Tartu University, Estonian, Republic, 18, Yulikooli St., Tartu, EE2400, Estonia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 542–544, July–August, 1997.     

Synthesis and structures of Al–Ti nanoparticles by hydrogen plasma-metal reaction

Three kinds of Al–Ti nanoparticles (7.7, 27.8, and 42.6 at.% Ti) have been prepared from Al–65, Al–85, and Al–88 at.% Ti master alloys by hydrogen plasma-metal reaction, with average particle sizes of 30, 25, and 80 nm, respectively. The higher evaporation rate of Al than Ti resulted in the low Ti contents in the nanoparticles than those in the master alloys. Microscopy observation revealed that the primary nanoparticles are spherical in shape, and occur as chain aggregates of several individual nanoparticles due to the faster collision rate than the coalescence rate. All the Al–Ti nanoparticles contain amorphous alumina layers of about 2–3 nm in thickness surrounding the crystalline core. AlTi intermetallic nanoparticles were successfully produced for Al–27.8 at.% Ti, with a single crystal of AlTi in one chain aggregate. The composite nanoparticles of Al together with some Al₃Ti phases are prepared for Al–7.7 at.% Ti, with each phase in the individual particle of one chain aggregate. The composite nanoparticles of AlTi with some AlTi₃ were produced for Al–42.6 at.% Ti, with each phase in the individual particle of one chain aggregate. The formation mechanism of Al–Ti nanoparticles was interpreted in terms of phase transition and the effect of hydrogen.     

Exciton absorption spectrum of thin CsPbI<Subscript>3</Subscript> and Cs<Subscript>4</Subscript>PbI<Subscript>6</Subscript> films

A method for preparing thin films of CsPbI₃ and Cs₄PbI₆ complex compounds has been developed. Their absorption spectrum is investigated in the energy range of 2–6 eV at temperatures from 90 to 500 K. It is found that the CsPbI₃ compound is unstable and passes to the Cs₄PbI₆ phase upon heating at T ≥ 400 K.     

Absorption bands of intrinsic point defects in irradiated zinc oxide

A program has been developed for separating the spectrum of radiation-induced absorption in powdered zinc oxide and reflective coatings based on it into individual components which includes calculations of the parameters of the bands arising from intrinsic point defects, bands from chemisorbed gases, and nonelective absorption by free electrons. Experimental results on the changes in the diffuse reflection spectra of ZnO powder and reflective coatings after the action of various forms of radiation have been found. The experimental spectra have been decomposed into individual components. Tomsk Polytechnic University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 106–112, September, 1997.     

Multiplication of electron excitations and the creation of stable radiation-induced defects in ionic crystals

The paper discusses the phenomenon of electron-excitation multiplication that arises when alkali halide crystals are exposed to 12–32 eV photons, with absorption of one photon followed at 8 K by the appearance of two or three electron excitations. Measurement of the spectrum of F-center generation by 6.5–32 eV photons showed that at 200–300 K, when vacancies and interstitials are mobile, the formation of stable defects is especially efficient when radiation creates a mixture of electron-hole pairs and excitons. Certain mechanisms of creation and stabilization of defects at various stages in electron-excitation multiplication are discussed. Institute of Physics of Estonia. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 30–44, November, 1996.     

Effect of coimplantation of iron and chromium ions on the optical properties of aluminum oxide

The optical absorption of leucosapphire and polycrystalline corundum (polycor) upon coimplantation of iron and chromium ions and subsequent annealing in vacuum is studied. The structure of the states localized in the band gap induced by radiation defects exhibits a higher stability to annealing as compared to implantation of other types of ions into aluminum oxide and to separate irradiation with iron and chromium ions. The governing contribution to the exponential and interband absorption is made by substitutional defects of either type, their clusters, and impurity-vacancy complexes. The effect of incorporated iron ions on the population of levels of chromium-containing defect clusters, on their recharge, and on interaction with intrinsic radiation and biographical defects is revealed. Mixed clusters of substitutional defects are optically active in a spectral range of 2.0–4.0 eV after annealing at a temperature of 1300–1600 K.     

Diffuse reflectance spectra of aluminum oxide micropowders,modified powders,and nanopowders and their changes upon electron irradiation

Comparative analysis of the diffuse reflectance spectra (300–2100 nm) and of the integrated absorption factor of coatings based on micropowders, nanopowders, and micropowders modified with Al₂O₃ nanopowders has been performed. In addition, the changes in the spectra resulting from electron irradiation of the powders with energies of 30 keV at a fluence of up to 3∙16 cm^–2 have been analyzed. It has been found that the diffuse reflectance decreases in order of coatings based on micro-powders, nano-powders and modified powders, while radiation resistance increases in order of coatings based on nano-powders, modified and micropowders.     

Thermodynamics and surface properties of liquid Al–Ga and Al–Ge alloys

The surface properties of Al–Ga and Al–Ge liquid alloys have been theoretically investigated at a temperature of 1100 K and 1220 K respectively. For the Al–Ga system, the quasi chemical model for regular alloy and a model for phase segregating alloy systems were applied, while for the Al–Ge system the quasi chemical model for regular and compound forming binary alloys were applied. In the case of Al–Ga, the models for the regular alloys and that for the phase segregating alloys produced the same value of order energy and same values of thermodynamic and surface properties, while for the Al–Ge system, the model for the regular alloy reproduced better the thermodynamic properties of the alloy. The model for the compound forming systems showed a qualitative trend with the measured values of the thermodynamic properties of the Al–Ge alloy and suggests the presence of a weak complex of the form Al₂Ge₃. The surface concentrations for the alloys show that Ga manifests some level of surface segregation in Al–Ga liquid alloy while the surface concentration of Ge in Al–Ge liquid alloy showed a near Roultian behavior below 0.8 atomic fraction of Ge.     

Creation of excitons and defects in a CsI crystal during pulsed electron irradiation

Data presented on the influence of the temperature in the range 80–650 K on the spectral kinetics of the luminescence and transient absorption of unactivated CsI crystals under irradiation by pulsed electron beams (〈E〉=0.25 MeV, t _1/2=15 ns, j=20 A/cm²). The structure of the short-wavelength part of the transient absorption spectra at T=80–350 K exhibits features, suggesting that the nuclear subsystem of self-trapped excitons (STE’s) transforms repeatedly during their lifetime until their radiative annihilation at T⩾80 K, alternately occupying di-and trihalide ionic configurations. It is established that a temperature-induced increase in the yield of radiation defects, as well as F and H color centers, and quenching of the UV luminescence in CsI occur in the same temperature region (above 350 K) and are characterized by identical thermal activation energies (∼0.22 eV). It is postulated that the STE’s in a CsI crystal can have a trihalide ionic core with either an on-center or off-center configuration; the high-temperature luminescence of CsI crystals is associated with the radiative annihilation of an off-center STE with the structure (I⁻(I⁰I⁻ e ⁻))*. Fiz. Tverd. Tela (St. Petersburg) 40, 640–644 (April 1998)     

Synthesis and dielectric characteristics of La0.5Bi0.5MnO3 ceramics

La_0.5Bi_0.5MnO₃ ceramics with a single phase were prepared by a solid-state reaction method, and their dielectric properties were characterized. Two dielectric relaxations with a giant dielectric constant were identified in the temperature range from 125 to 350 K. The electron hopping between Mn³⁺ and Mn⁴⁺ was found to be the origin of the dielectric relaxation at low temperatures (125–200 K) with an activation energy of 0.18 eV. The high temperature (200–350 K) dielectric relaxation can be attributed to the conduction.     

Peculiarities and thermal stability of microstructure and strength properties of Ti–Al–Si–O–C–N films

Peculiar relationship between the composition and fine structure and the variations in strength properties of nanostructured and nanocomposite, high-carbon, high-oxygen Ti–Al–Si–N films are investigated using Auger spectroscopy, electron microscopy, X-ray structural analysis and hardness measurements. It is shown that a TiN-based phase can form in these films, which exhibits nanocrystalline or two-level grain structure distributed in the x-ray amorphous phase whose volume fraction is 20–50%. The grain-structure character can be deliberately changed by incorporating aluminum or silicon into the films. It is found out that irrespective of their structural state and composition the films demonstrate high thermal stability of superhardness and microstructure up to the temperatures Т ≈ 1173 K. Hardness is seen to decrease at Т ≥ 1273 K as a result of dislocation recovery, stress relaxation and early recrystallization. It is suggested that the high strength properties demonstrated by these films are due to the presence of dislocation substructure and high shear resistance of the x-ray amorphous phases along nanocrystallite boundaries. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 57–65, November, 2008.     

Photoluminescence of single crystals of cadmium diarsenide

An investigation is made of the low-temperature (4.2–78 K) photoluminescence of single crystals of cadmium diarsenide grown from the gas phase and by the Bridgman method. Radiation near the fundamental absorption edge is detected, which is attributed to annihilation of free excitons with simultaneous emission of phonons (the lines 1.0029 and 0.9840 eV at 4.2 K). The optical width of the forbidden band is estimated at 4.2 K. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 149–152, January–February, 1998.     

Correlation between optical,structural, and sensor properties of nanostructures of nickel oxide on aluminum oxide substrates

We have established a correlation between diffuse reflection of nickel oxide-based composites in the red region of the spectrum and the nanostructural properties of the roughness profile of the composite. We present calculations of the absorption spectra for samples of nanostructured nickel oxide of thickness 0.25–0.35 μm on aluminum oxide substrates from diffuse reflection and transmission of the layers by multiple scattering methods, taking into account the luminescence of the samples in the weak absorption region. Using a special optical system, we have determined the selective sensitivity to carbon monoxide exposure of a nanostructured nickel oxide composite at room temperature. The result is of fundamental importance for development of optical selective gas sensor technology in the visible region of the spectrum.     

Synthesis and characterization of electron beam evaporated LiCoO<Subscript>2</Subscript> thin films

LiCoO₂ thin films were prepared by electron beam evaporation technique using LiCoO₂ target with Li/Co ratio 1.1 in an oxygen partial pressure of 5 × 10⁻⁴ mbar. The films prepared at substrate temperature T _s < 573 K were amorphous in nature, and the films prepared at T _s > 573 K exhibited well defined (104), (101), and (003) peaks among which the (104) orientation predominates. The X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) data revealed that the films prepared in the substrate temperature range 673–773 K are nearly stoichiometric. The grain size increases with an increase of substrate temperature. The Co–e_g absorption bands, are empty and their peak position lies at around 1.7 eV above the top to the Co–t_2g bands. The fundamental absorption edge was observed at 2.32 eV. The films annealed at 1,023 K in a controlled oxygen environment exhibit (104) out plane texture with large grains. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Structural changes during annealing of submicro- and nanocrystalline aluminum alloys

The annealing-induced evolution of the structure and microhardness of submicro-and nanocrystalline Al—3% Mg and Al 1570 alloys produced by torsional severe plastic deformation are studied. Annealing of the Al-3% Mg alloy at 373–423 K and annealing of the Al 1570 alloy at 373–473 K are shown to result in the relaxation of internal stresses and subsequent normal grain growth. As the annealing temperature increases, the microhardness decreases. At higher temperatures (473 K for the Al—3% Mg alloy and 573 K for the Al 1570 alloy), anomalous grain growth takes place. This growth is accompanied by the appearance of numerous grains with a high dislocation density, a high concentration of impurity atoms in grain boundaries, and an increase in the microhardness. These effects are explained.     

Laser ablation of phenylazide in an argon matrix: direct observation and chemical reactivity of ablated fragments

Ablation of pentafluorophenylazide (FPA) in an Ar matrix at 8–10 K was carried out upon irradiation with ns-pulsed UV lasers in a vacuum. The plume of ablated products was monitored by a time-resolved imaging/spectroscopic technique using a gated and intensified CCD camera system. A large amount of pentafluorophenylnitrene (FPN) having a high kinetic energy (≈6 eV) was ejected as fragments from the matrix film during ablation. A quantitative formation of triplet FPN from the photolysis of the FPA was observed by spectroscopic measurements in the IR and UV-visible regions, and was confirmed by a theoretical IR spectrum calculated according to density functional theory. A FPN beam is useful for chemical surface modification of organic materials, such as aromatic polyester and alkylthiol. A surface analysis of these materials by X-ray photoelectron spectroscopy and Fourier transform infrared reflection absorption spectroscopy showed that the FPN was immobilized onto the surface through chemical bonds. This technique for the chemical surface modification of materials is made possible by a pulsed beam of reactive fragments with a high density in the laser ablation process. Received: 14 June 1999 / Accepted: 18 June 1999 / Published online: 21 October 1999