Phosphorus-Implanted Glass for Radiotherapy: Effect of Implantation Energy

A chemically durable glass that contains a large amount of phosphorus is useful for in situ irradiation of cancers. It can be activated to be a β-emitter with a half-life of 14·3 d by using neutron bombardment. Microspheres of the activated glass that are injected to tumors can irradiate the tumors directly with β-rays without irradiating neighboring normal tissues. In the present study, P⁺ ions in various doses have been implanted into a pure silica glass in a plate form at 200 keV. Almost all the implanted phosphorus is present in the inner region of the glass rather than in the surface region, taking the form of phosphorus colloids for all the doses in the range of 5 × 10¹⁶-1 × 10¹⁸ cm^-2. A large number of amorphous phosphorus colloid particles with diameters of 10-150 nm are formed in the silica glass that has been implanted with a dose of 1 × 10¹⁸ cm^-2; these colloid particles are distributed widely in a layer that is centered at a depth of 200-250 nm. All the investigated glasses hardly release any phosphorus and silicon into water at a temperature of 95°C, even after 7 d. A silica glass that has been implanted with P⁺ ions at 200 keV with a dose of 1 × 10¹⁸ cm^-2 is believed to be useful as a radiotherapy glass with sufficient phosphorus content and high chemical durability.     

Annealing of Irradiation-Induced Thermal Conductivity Changes in ThO2-1.3 wt% UO2

The thermal conductivities of sintered pellets of ThO₂-1.3 wt% U0₂ were measured at 60°C before and after irradiation. The irradiation temperature was below 156°C, and the exposures varied from 3.1 × 10¹⁴ to 4.7 × lo^L7 fissions/cm³. Each fission fragment damaged a region of 2.2 × 10^-16 cm³ with the reduction in conductivity saturating by about 10¹⁷ fissions/cm³. Samples having exposures from 10¹⁵ to 10¹⁶ fissions/cm³ were annealed isothermally at 651 °C or isochronally from 300° to 1200° C to study the annealing of damage. Most of the annealing occurred between 500° and 900°C. The width of this interval plus the slow isothermal annealing suggest that the damage is annealed by a number of single order processes with a spectrum of activation energies from 1.8 to 3.9 eV or, less probably, by a high order process with an activation energy of 3.55 ± 0.4 eV.     

Linear and Nonlinear Optical Properties of TeO2 Glass

A thin plate of TeO₂ glass of 5.0 × 4.0 × 0.25 mm³ size, which was large enough for various optical measurements, was obtained by a rapid quenching method. The linear refractive index was measured as a function of wavelength from 486.1 to 1000 nm. The refractive index at 486.1 nm was as high as 2.239. The optical energy band gap was estimated as 3.37 eV from the optical absorption spectrum. The third-order nonlinear optical susceptibility, χ⁽³⁾, was determined by the third-harmonic generation (THG) method. The χ⁽³⁾ value was as high as 1.4 × 10⁻¹² esu, about 50 times as large as that of SiO₂ glass. The results are discussed based on Lines' model in which an influence of cationic empty d -orbitals on the nonlinear properties was taken into account.     

Electrical Conduction in Single-Crystal Thallic Oxide: I, Crystals "As-Grown" from the Vapor in Air

Thallic oxide, "T1₂O₃," has been shown to be a degenerate n -type semiconductor with resistivity varying from 60 to 150 μΩ-cm over the range 4° to 900°K. The carrier concentration was 7 × 10²⁰ cm⁻³ and is temperature independent. Room-temperature Hall mobility was 105 cm² V⁻¹ s⁻¹, increasing to 130 cm² V⁻¹ s⁻¹ below 70°K. Donor states were shown to be native defects, probably oxygen vacancies.     

Point Defect Hardening in MgO·3Al2O3

Vickers hardness in spinel increases by 23% after neutron irradiation to a fluence of 8.3 × 10²² n/m² at 100°C. Annealing at high temperatures above 100°C gradually decreases the hardness. Above 500°C, the hardness is reduced to almost the same value as that of unirradiated material. The hardness of spinel, irradiated at 470°C to a fluence of 2.4 × 10²⁴ n/m², is unchanged both after irradiation and after annealing up to 1000°C. The length change during annealing was also measured and is similar to the hardness change. Frank dislocation loops with a density of 3 × 10¹⁴/cm³ are induced by neutron irradiation at 470°C but they apparently do not affect the hardening in spinel. Thus, point defects are concluded to act as obstacles against dislocation movement. The yield stress measured at 1400°C is also unchanged after irradiation. It is believed that not only the point defects but also the loops are annihilated by annealing at 1400°C.     

Third-Harmonic Generation from Some Chalcogenide Glasses

Third-order optical nonlinear susceptibilities (χ⁽³⁾) of some high-refractive-index chalcogenide glasses were evaluated from third-harmonic generation. Compared with oxide glasses whose χ⁽³⁾ has been known, χ⁽³⁾ of the present glasses was higher by an order of magnitude. The addition of selenium drastically increased χ⁽³⁾. The highest χ⁽³⁾ was 1.4 × 10^–11 esu, being comparable with those of high-χ⁽³⁾-organic compounds. Further, χ⁽³⁾ generally increased with increasing density in the present glasses.     

Protons and Deuterons in Magnesium-Doped Sapphire Crystals

The OH^- and OD^- stretching frequencies in magnesium-doped aluminum oxide crystals were determined by infrared absorption measurements. Two very broad bands centered at }3005 and 2228 cm^-1 were observed for OH^- and OD^-, respectively. Polarization experiment results were compatible with OH^- (OD^-) ions lying in the basal plane, as is the case in undoped crystals. The threshold temperature for the in-diffusion of deuterons was obtained by annealing the samples in flowing D₂O vapor; the resulting value was }1050 K. At 1223 K, the diffusion coefficient was }3× 10^-7 cm²/s, and the activation energy was 1.6 eV.     

Transition from Ionic to Electronic Conduction in Pure ThO2 Under Reducing Conditions

Open-circuit emf and ac conductivity studies were conducted on two batches of dense polycrystalline ThO₂. The open-circuit emf data were used to delineate the low- p o₂ ionic domain boundary for "pure" ThO₂, which is presented as a log P_θ line on a log Po₂-1/ T diagram. In addition the ionic conductivity, σ_ion, and the high-Po₂ log P_θ boundary were also determined, mainly from ac conductivity measurements, which also confirmed the Po₂^I/4 dependence of σ_p, the p-type electronic conductivity, shown by other investigators. The main results are, for the first batch, log Pθ= 12.7−220.2 × 10³/4.575T, log σ_ion= 1.9−44.3×10³/4.575T, and log P_θ=−1.0−31.4 × 10³/4.575T; for the second batch, log Pθ=11.2−219.7 × 10³/4.575T, log σ_ion= 1.7−41.6 × 10³/4.575T, and log Pθ=0.6−40.4 × 10³/4.575T. The oxygen permeability of ThO₂ tubes and the oxidation rate constant of Th were predicted from the conductivity and emf data and compared with direct measurements previously reported. The calculated and previously measured permeabilities agreed very well; however, the correlation between the predicted and previously measured oxidation kinetics was somewhat less satisfactory.     

Chemical States of Implanted Aluminum Ions in Silica and Silicon Ions in Alumina

Aluminum and silicon ions have been implanted in silica glass and α-alumina single crystal, respectively, to doses ranging from 1 × 10¹⁵ to 1 × 10¹⁷ ions·cm^-2. The chemical states of these implanted ions have been studied by X-ray fluorescence spectroscopy. It is found that the implanted aluminum atoms are coordinated only by oxygen atoms, irrespective of implantation dose. On the other hand, the implanted silicon atoms are coordinated only by oxygen atoms at low doses and by both oxygen and silicon atoms at high doses. Although the chemical state of the aluminum atoms is unchanged by heat treatment, that of the silicon atoms is changed toward a less positively charged state. It is inferred that the chemical states of the implanted atoms are controlled by the transport process, although these tend to obey the thermodynamic stability.     

Deviation from Stoichiometry in Cr2O3 at High Oxygen Partial Pressures

The deviation from stoichiometry, δ, in Cr₂−δO₃ was measured by a tensivolumetric method in the high pO₂ range of ≊10⁴ to 10⁴ Pa at 1100°C. The value of δ, or chromium vacancy concentration, was≊9×10⁻⁵ mol/mol Cr₂O₃ in air for Cr₂O₃ with 99.999% purity. The chemical diffusion coefficient, DT, determined from equilibration data was ≊4.6× cm²·s⁻¹ at 1100°C for pO₂= 2.2 ×10¹ Pa. The self-diffusion coefficient of Cr ions was calculated from and δ and found to be≊1.6×10-17 cm²-s⁻¹, in good agreement with recently measured values.     

Ion-Probe Measurement of Oxygen Self-Diffusion in Single-Crystal Al2O3

Anion self-diffusion coefficients normal to (1102) were obtained for single-crystal Al₂O₃ in a 1.3 × 10 ³ N/m² (10⁻⁵ torr) vacuum at 1585° to 1840°C. Tracer was supplied from an initial 650 to 1300 A Al₂¹⁸O₃ layer produced by the oxidation of vapor-deposited Al metal films in an ¹⁸O₂ atmosphere at 520°C. Concentration gradients extended over depths of 3000 to 5000 A and were measured by mass spectrometry of material sputtered from the samples with a beam of Ar⁺ ions. Crystals which had not been preannealed to remove surface damage displayed enhanced diffusion. Diffusion coefficients from preannealed crystals may be described by D₀ =6.4×10⁵cm²/s, with an activation energy of 188 ± 7 kcal/mol. The diffusion is interpreted as an extrinsic vacancy mechanism.     

Investigation of Some Glasses for High-Level Gamma-Radiation Dosimeters

Several glass systems were evaluated as dosimeters to measure integrated doses in the range from 10⁶ to 10⁹ rads by measuring optical density as a function of radiation dose. The two more promising glasses of those studied were Corning's Code 8392 and a special high-antimony glass. The maximum dosage that can be measured with these two glasses has not yet been determined. In exposures up to 3 × 10⁸ rads, there was continuous increase in optical density with dose, and no evidence of saturation at the highest doses used. Glasses also were prepared that darkened only slightly at dosages up to about 8.7 × 10⁷ rads. Such glasses may have utility for measuring dosages above 10⁹ rads.     

Synthesis of Vanadate and Arsenate Spodiosites and Interpretation of Optical Spectra of Manganese-Doped Sr2VO4C1

New vanadate and arsenate analogs of spodiosite (Sr₂-(VO₄)C1 and Sr₂(AsO₄)C1) were prepared. Isomorphism between chromium and vanadium spodiosites was established by formation of complete solid solutions. The vanadate analogs of calcium and barium, the arsenate analog of calcium, phosphate analogs of strontium and barium, and the fluorine analogs, Ca₃(VO₄)₂·CaF₂ and Sr₃(VO₄)₂·SrF₂, could not be synthesized. The optical absorption spectra of manganese-doped Sr₂(VO₄)Cl showed the presence of Mn⁵⁺ in the vanadium position, the site symmetry being approximately _Td. Three transitions, ³T₂( F ), ³T₁( F ), and ¹A_l( G ) at (12,000 and 13,000 cm^-1), (16,700 cm^-1), and (14,300 cm^-1), respectively, were observed from the ground state, ³A₂( F ). The lower symmetry components were strong enough to split the energy level, ³T₂( F ). The crystal field parameter Dq and the Racah parameters B and C were calculated to be 1200, 470, and 1927 cm^-1, respectively.     

Thermal Expansion of the Hexagonal (6H) Polytype of Silicon Carbide

The thermal expansion of the hexagonal (6H) polytype of α-SiC was measured from 20° to 1000°C by the X-ray diffraction technique. The principal axial coefficients of thermal expansion were determined and can be expressed for that temperature range by second-order polynomials: α¹¹= 3.27 × 10^–6+ 3.25 × 10^–9T – 1.36 × 10^–12 T ² (1/°C), and ş₃₃= 3.18 × 10^–6+ 2.48 × 10^–9 T – 8.51 × 10^–13 T ² (1/°C). The σ₁₁ is larger than α₃₃ over the entire temperature range while the thermal expansion anisotropy, the δş value, increases continuously with increasing temperature from about 0.1 × 10^–6/°C at room temperature to 0.4 × 10^–6/°C at 1000°C. The thermal expansion and thermal expansion anisotropy are compared with previously published results for the (6H) polytype and are discussed relative to the structure.     

Characterization of the Thermally Contracting Tungstates Ta22W4O67, Ta2WO8, and Ta16W18O94

An investigation of the properties of high-purity (>99 wt%) tantalum tungstates (Ta₂₂W₄O₆₇, Ta, WO₈, and Ta₁₆W₁₈O₉₄) included determination of density (bulk and theoretical), refined lattice constants, maximum use temperatures, micro-hardness, heat capacity, thermal expansion (contraction) and diffusivity, calculated thermal conductivity, and electrical resistivity. Usable to ∼ 1700 K in air or inert atmospheres, these tantalum tungstates have theoretical densities of 7.3 to 8.5 g/cm³, are relatively soft (120 to 655 kg/mm² hardnesses), and are electrical insulators (6× 10³ to 2× 10⁸Ω^.cm resistivities). The distinguishing properties of the materials are their thermal expansion (average CTE values from + 0.6×10⁻⁸/K to −5.1× 10⁻⁶/K at 293 to 1273 K), thermal expansion hysteresis with minimal observable microcracking, and thermal diffusivity     

Defect Chemistry and Electrical Properties of Thallium Oxide Single Crystals

Ehdectrical resistivity and Hall voltage were measured between 4.2 and 300 K on T1₂O₃ crystals annealehd at 550°C for 24 h under oxygen pressures of 2×10⁴ to 10⁷ Pa. The carrier concentration varied from 7.97×10²⁰ to 5.08×10²⁰ cm⁻³, the low-temperature Hall mobility from 131 to 189 cm²/V.s, and the Fermi level from 7.1×10⁴ to 5.05×10⁴ J/mol above the bottom of the conduction band as P ₀₂ was increased from 2×10⁴ to 10⁷ Pa. The dependence of Fermi level on carrier concentration and P _0l was consistent with a parabolic density-of-states function describing the conduction band. Over the entire region of oxygen pressure investigated, Fermi-Dirac statistics were required to describe the dependence of carrier concentration on P ₀₂.     

Effect of Reoxidation on the Grain-Boundary Acceptor-State Density of Reduced BaTiO3 Ceramics

To investigate the effect of reoxidation on the grain-boundary acceptor-state density of reduced barium titanate, n -doped BaTiO₃ ceramics are sintered in a reducing atmosphere (2% H₂+ 98% N₂) and then annealed in oxygen. After annealing at 1150°C for different times, the experimental results show a relationship between temperature-averaged acceptor-state density and annealing time as N _s= N _so Bt ^1/n with n between 2 and 3. An inherent acceptorstate density N _so= 4.25 × 10¹² cm⁻² is obtained with an increase rate B = 4.8 × 10¹² cm⁻². min^−1/3, when n reaches 3. The inherent grain-boundary acceptor states in the reduced n -doped BaTiO₃ ceramics are believed not due to adsorbed oxygen ions.     

Solubilities of Magnesia, Titania, and Magnesium Titanate in Aluminum Oxide

On heat treatment in air the solubility of MgO or TiO₂, in Al₂₃ is too small to detect by lattice parameter shifts. The solubility of MgTiO₃ in Al₂O₃ in air increased to the measured values, expressed as atomic fractions Mg:A1or Ti:A1of0.82 × lo-², 1.43 × 10^-2, and 1.75 × 10^-2 at 1250°, 1650°, and 1850°C, respectively. In 1 atm hydrogen the TiO₂ solubility expressed as the atomic fraction Ti:A1 is 0.55 × lo^-2, 0.75 × 10W², 1.15 × 10^-2, and 1.50 × 10^p2 at 1400°, 1500°, 1600°, and 1700°C, respectively. The increased solubility in H₂ was attributed to reduction of the titanium ion. The solubility of MgO in A1₂O₃ in vacuum (0.3μ) expressed as the atomic fraction Mg:A1 was measured as 1.10 × loW⁴, 3.00 × 10"⁴, 6.80 × 10–⁴, and 1.40 × 10^-3 at 1530°, 1630°, 1730°, and 183O°C, respectively. These contents did not cause an observable change in lattice parameter, but a slight change was observed when MgO was dissolved in A1₂O₃ in a hydrogen atmosphere.     

Structure and Nonlinear Optical Properties of Lanthanide Borate Glasses

The third–order nonlinear optical susceptibility, χ⁽³⁾, of lanthanide (lanthanum, praseodymium, neodymium, and samarium) borate glasses has been measured by the third harmonic generation method. The structure of the present glass system has been studied by infrared and Raman spectroscopic methods. The network structures of the present Ln₂O₃–B₂O₃ glasses have been confirmed to be basically similar to each other. Praseodymium, neodymium, and samarium borate glasses exhibit χ⁽³⁾ values that are larger than lanthanum borate glasses, because of the optical resonance effect, in accordance with the f – f transition. Especially, the χ⁽³⁾ value for 30Pr₂O₃·70B₂O₃ glass is 1.8 × 10⁻¹² esu, which is a factor of ∼60 larger than that of SiO₂ glass. This striking enhancement of χ⁽³⁾ is mainly attributed to the large transition moment to the first excitation state.     

Effect of γ Radiation on High-Water-Content-Glasses

Na₂O−3SiO_z-glasses containing up to ∼11 wt% water were prepared under high-pressure, hydrothermal conditions. The samples were exposed to γ radiation of 5 × 10⁷ rad. Optical and ESR measurements were made before and after exposure to radiation and it was found that the induced absorption in the visible region decreased drastically with increasing H₂O concentration. The induced ESR signal-integrated intensity also decreased with increasing water content. After irradiation an increase was observed in the fundamental OH absorption bands in the ir region of the spectra of the water-containing specimens.