Thermal strain analysis of advanced manned spacecraft heat shields first quarterly status report, 1 sep. - 30 nov. 1963

Advanced manned spacecraft heat shield thermal strain analysis - equilibrium and stress equations, singular point, and computer progra

Reactive Magnetron Sputtering of ZrO2/Al2O3 Coatings: Alumina Content and Structure Stability

Ternary zirconia-alumina coatings with different compositional ratios, ranging from pure zirconia to 50% alumina content, were deposited by reactive sputtering from two targets, Zr and Al, in argon-oxygen mixtures. The coating composition was controlled by the Zr/Al target power ratio provided by two pulsed-DC power supplies. The coatings were ~1 µm thick and they were deposited on floating potential substrates at a temperature of 650±3K. XRD indicated that the pure zirconia coatings possessed a monoclinic structure with a grain size of 35-40 nm. Adding alumina to the zirconia coating stabilized the cubic zirconia phase and decreased the grain size to 10-15 nm. The alumina phase in the coatings remained amorphous. The hardness of the nanocomposite structure increased from 11.6±0.5 GPa to 16.1±0.5 GPa for an alumina content of 17%. At higher alumina concentrations, the zirconia phase became amorphous and the hardness decreased to 10-11 GPa. Structure stability of the zirconia-alumina coatings was studied by measuring the coating structure and hardness after annealing at temperatures up to 1173 K. Pure zirconia (m-ZrO2) coatings had low structure stability; the hardness reached a maximum value of 18±1 GPa after annealing at a temperature of 773-873K; however, at higher annealing temperatures the hardness decreased, reaching a minimum value of 12.3±0.6 GPa after annealing at 1173K. The hardness of the nanocomposite ZrO2/Al2O3 coating with various compositions increased with annealing temperature. The hardness of a coating with an alumina content of 17% reached a high value of 19.2±0.5 GPa after annealing at 1073-1173 K. Measurements of post annealing XRD analyses indicated that the stabilization of the coating structure with c-ZrO2/a-Al2O3 phases is the reason for the higher structure stability. From the analyses of phase stability and hardness before and after annealing, we conclude that adding alumina to the zirconia phase promotes the formation of nanocomposite c-ZrO2/a-Al2O3 coatings with a markedly higher stability than single-phase m-ZrO2. Highlights: 1. ZrO2/Al2O3 nanocomposite coatings were deposited by co-sputtering from Zr and Al targets. 2. Adding alumina to the zirconia coating stabilized the cubic zirconia phase. 3. ZrO2-17% Al2O3 coatings had a grain size of 10-15 nm and a hardness of 16.1±0.5 GPa. 4. ZrO2/Al2O3 coatings maintained a high hardness after annealing at 1173K with a high value of 19 GPa for alumina content of 17%. 5. The ZrO2/Al2O3 nanocomposite coatings were crack-free after annealing at 1173K

Bis[(4-methyl­phen­yl)ethyn­yl] telluride

The tellurium atom in the title bis-ethynyl telluride, Te(C9H7)2 or C18H14Te, is located on a crystallographic twofold axis, the C—Te—C angle being 92.23 (15)°. The dihedral angle between the rings is 87.27 (7)°. In the crystal structure, mol­ecules are connected in chains parallel to the b axis and mediated by C—H⋯π inter­actions

1-(4-Bromo­phen­yl)-2-ethyl­sulfinyl-2-(phenyl­selan­yl)ethanone monohydrate

In the title hydrate, C16H15BrO2SSe·H2O, the sulfinyl O atom lies on the opposite side of the mol­ecule to the Se and carbonyl O atoms. The benzene rings form a dihedral angle of 51.66 (17)° and are splayed with respect to each other. The observed conformation allows the water mol­ecules to bridge sulfinyl O atoms via O—H⋯O hydrogen bonds, generating a linear supra­molecular chain along the b axis; the chain is further stabilized by C—H⋯O contacts. The chains are held in place in the crystal structure by C⋯H⋯π and C—Br⋯π inter­actions

Thermal Stability of Filtered Vacuum Arc Deposited Er2O3 Coatings

Erbium oxide (Er2O3) coatings were deposited using filtered vacuum arc deposition (FVAD) and their structure and thermal stability were studied as a function of fabrication parameters. The coatings were deposited on silicon wafer and tantalum substrates with an arc current of 50 A and a deposition rate of 1.6 ± 0.4 nm/s. The arc was sustained on truncated cone Er cathodes. The influence of oxygen pressure (P= 0.40-0.93 Pa), bias voltage (Vb= -20, -40 or grounded) and substrate temperature (room temperature (RT) or 673K) on film properties was studied before and after post deposition annealing (1273K for 1 hour, at P~ 1.33 Pa). The coatings were characterized using X-ray diffraction (XRD), optical microscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Knoop Hardness. Optical microscope images indicated that the coatings had very low macroparticle concentration on their surface. The macroparticle diameters were less than 2.5 μm. The coatings were composed of only Er2O3 without any metallic phase under all deposition parameters tested. The coatings deposited on RT substrates were XRD amorphous and had a featureless cross-section microstructure. However, the coatings deposited on 673K heated substrates had a C-Er2O3 structure with (222) preferred orientation and weak columnar microstructure. The coating hardness varied with deposition pressure and substrate bias, and reached a maximum value of 10 GPa at P = 0.4 Pa and Vb = -40 V. The post-deposition annealing caused crystallization, and the coatings hardness dropped to 4 GPa with thermal treatment. However, after post-deposition annealing, no peeling or cracking appeared at the coating surface or the interface with the substrate

Synthesis of 1,3-diynes via detelluration of bis(ethynyl)tellurides

The synthesis of symmetric conjugated diyne systems with electron-withdrawing or electron-donating substituents via a palladium-catalyzed detelluration of bis(arylethynyl)tellurides and bis(alkylethynyl)tellurides is described. This procedure is effected under atmospheric conditions in DMF using Pd(OAc)2 as a catalyst and AgOAc as an additive in the presence of triethylamine. This route offers efficient access to conjugated diyne systems in short reaction time. X-ray crystallographic structure and solid-state conformation of bis(p-tolylethynyl)telluride show a supramolecular chain aligned along the b axis, sustained by C-H...π interactions.Neste artigo é descrita a síntese de sistemas diínicos conjugados contendo substituintes elétronatratores e elétron-doadores via a deteluração catalizada por paládio de bis-(ariletinil)teluretos e bis-(alquiletinil)teluretos. Este procedimento foi realizado sob condições atmosféricas em DMF usando Pd(Oac)2 como catalisador e AgOAc como um aditivo na presença de trietilamina. Esta rota oferece acesso eficiente a sistemas diínicos conjugados em um curto período de tempo. A estrutura cristalográfica por difração de raios X do telureto de bis(p-toluiletinila) e a conformação no estado sólido mostram uma cadeia supramolecular alinhada ao longo do eixo b, sustentada por interações CH...π.FAPESPCNP

Potassium trifluoro­[(Z)-3-(oxan-2-yl­oxy)prop-1-en-1-yl]borate monohydrate

The title compound, K+·C8H13BF3O2 −·H2O, which was obtained from the reaction of a modified form of Z-vinylic telluride via a transmetalation reaction with n-BuLi, crystallizes as K+ and C8H13BF3O2 − ions along with a water mol­ecule. The K+ cation is surrounded by four anions, making close contacts with six F atoms at 2.659 (3)–2.906 (3) Å and with two O atoms at 2.806 (3) and 2.921 (3) Å in a distorted bicapped trigonal-prismatic geometry

5-(4-Fluoro­phen­yl)-2,2,6-trimethyl-4H-1,3-dioxin-4-one

The 1,3-dioxine ring in the title compound, C13H13FO3, is in a half-boat conformation with the methyl-bonded C atom 0.612 (2) Å out of the plane defined by the remaining five atoms

Structural systematics of aryl-1,3-dithiane derivatives: crystal and energy-minimised structures, and Hirshfeld surface analysis

The crystal structure analysis of three aryl-1,3-dithiane derivatives, with aryl=4-methylphenyl (1), 4-chlorophenyl (2) and 2,4-dichlorophenyl (3), shows the three molecules to have very similar conformations, with the aryl ring lying on an approximate mirror plane that bisects the dithiane ring which adopts a chair conformation; the energy-minimised structures are consistent with the experimental structures. The greater barrier to rotation about the methine-C–C(ipso) bond in 3, cf. 1 and 2, is related to unfavourable intramolecular S···Cl interactions in the putative transition state. The molecular packing in 1–3, while globally similar, are distinct, being based on combinations of identifiable C–H···π(arene), C–H···S and C–Cl···π(arene) interactions. The lack of isostructural relationships points to the significance of the identified intermolecular interactions to direct molecular packing

Crystal structure of [(2R,3R,4S)-3,4-bis-(acetyloxy)-5-iodo-3,4-dihydro-2H-pyran-2-yl]methyl acetate

Acknowledgements We thank Professor Regina H. A. Santos from IQSC–USP for the X-ray data collection. The Brazilian agencies CNPq (305626/2013–2 to JZS; 306121/2013-2 to IC; 308320/2010-7 to HAS) and FAPESP are acknowledged for financial support.Peer reviewedPublisher PD