Combined severe plastic deformation processing of commercial purity titanium enables superior fatigue resistance for next generation implants.

Commercial purity titanium (cp-Ti) is considered for replacing Ti64 as an implant material in various applications, due to the potential toxicity associated with the release of Al and V ions. However, the mechanical properties of cp-Ti, particularly fatigue resistance, are inadequate for this purpose. In this study, cp-Ti grade 4 rods were processed using a combination of equal channel angular pressing and rotary swaging (ECAP/RS). Tensile and fatigue tests were conducted, along with detailed microscopy and evaluation of corrosion resistance and biocompatibility. An average yield strength of 1383 MPa was obtained while maintaining moderate ductility of 10 %. This represents the highest strength ever recorded for cp-Ti, even exceeding that of Ti64. Additionally, fatigue endurance limit increased by 43 % up to 600 MPa, almost obtaining that of Ti64. Strengthening mechanisms were attributed to the ultrafine-grained (UFG) microstructure generated by ECAP/RS, along with strong crystallographic texture and formation of sub-grain structure. Furthermore, the corrosion resistance and biocompatibility of cp-Ti were largely unaffected, potentially easing regulatory transition in future medical devices. Thus, these results demonstrate high potential of combined ECAP/RS processing to manufacture UFG cp-Ti grade 4 materials that prospectively allow for the substitution of questionable alloys and downsizing of medical implants.

Investigation of TaC and TiC for Particle Strengthening of Co-Re-Based Alloys.

Cobalt-Rhenium (Co-Re)-based alloys are currently investigated as potential high-temperature materials with melting temperatures beyond those of nickel-based superalloys. Their attraction stems from the binary Co-Re phase diagram, exhibiting complete miscibility between Co and Re, whereby the melting temperature steadily increases with the Re-content. Thus, depending on the Re-content, one can tune the melting temperature between that of pure Co (1495 °C) and that of pure Re (3186 °C). Current investigations focus on Re-contents of about 15 at.%, which makes melting with standard equipment still feasible. In addition to solid solution strengthening due to the mixture of Co- and Re-atoms, particle strengthening by tantalum carbide (TaC) and titanium carbide (TiC) precipitates turned out to be promising in recent studies. Yet, it is currently unclear which of the two particle types is the best choice for high temperature applications nor has the strengthening mechanism associated with the monocarbide (MC)-precipitates been elucidated. To address these issues, we perform compression tests at ambient and elevated temperatures on the particle-free base material containing 15 at.% of rhenium (Re), 5 at.% of chromium (Cr) and cobalt (Co) as balance (Co-15Re-5Cr), as well as on TaC- and TiC-containing variants. Additionally, transmission electron microscopy is used to analyze the shape of the precipitates and their orientation relationship to the matrix. Based on these investigations, we show that TiC and TaC are equally suited for precipitation strengthening of Co-Re-based alloys and identify climb over the elongated particles as a rate controlling particle strengthening mechanism at elevated temperatures. Furthermore, we show that the Re-atoms are remarkably strong obstacles to dislocation motion, which are overcome by thermal activation at elevated temperatures.

Cold Gas Spraying of Nickel-Titanium Coatings for Protection Against Cavitation.

Cavitation erosion is a sever wear mechanism that takes place in hydrodynamic systems. Examples are turbine vanes of hydropower plants or components of valves and pumps in hydraulic systems. Nickel-titanium shape memory alloys (NiTi) are attractive materials for cavitation-resistant coatings because of their pronounced intrinsic damping mitigating cavitation-induced erosion. In this work, NiTi coatings were produced by cold gas spraying. The phase transformation behaviors of the powder feedstock and the as-sprayed coatings were investigated. Regarding the obtained transformation temperatures, the measured substrate temperatures during spraying rule out that either the shape memory effect or the pseudoelasticity of NiTi could affect the deposition efficiency under the applied conditions of cold gas spraying. Another potential effect is stress-induced amorphization which could occur at the particle-substrate interfaces and impair particle bonding by stress relaxation. Moreover, also oxide formation can be significant. Thus, the presence of amorphous phases and oxides in the near-surface zone of particles bounced off after impact was investigated. Oxidation could be confirmed, but no indication of amorphous phase was found. Besides, also the evolution of local microstrains implies that the substrate temperatures affect the deposition efficiency. These temperatures were significantly influenced by the spray gun travel speed.

Oxygen Surface Exchange and Tracer Diffusion in Differently Oriented Thin Films of Gd-Doped CeO2.

The exchange of 18O between gaseous molecular oxygen and thin-film samples of Ce0.99Gd0.01O1.995 with two different, nominal surface orientations [(111) and (110)] was studied. Oxygen isotope exchange experiments were conducted in the temperature range of 573 ≤ T/K ≤ 673 at an oxygen activity of aO2 = 0.2. Subsequently, secondary ion mass spectrometry (SIMS) measurements were performed on the thin-film samples to obtain 18O isotope depth profiles. All 18O diffusion profiles showed two features, suggesting spatially nonuniform oxygen tracer diffusion coefficients in the samples. A numerical solution to the diffusion equation was used to describe the experimental profiles and yielded oxygen tracer diffusion coefficients D* and oxygen surface exchange coefficients k*. Values of D* obtained were found, surprisingly, to be different for the two orientations and also orders of magnitude lower than values for ceramic samples in this temperature range. As possible explanations, we examine quantitatively the effect of halide anion impurities and the effect of ultrasmall columnar grains on oxygen tracer diffusion. Surface exchange coefficients for the (111) oriented surface were found to be roughly 1 order of magnitude higher than those for (110). We discuss two possible explanations for the observed behavior: the enrichment of anion impurities at the surface and the interaction between the surface and vapor water in the gas phase.

The blocking effect of surface dislocations on oxygen tracer diffusion in SrTiO3.

The existence of a polishing-induced damaged zone at the surface of standard, nominally undoped, single-crystal SrTiO3 is exploited in diffusion studies in order to investigate the interaction between oxygen vacancies and dislocations. Tracer diffusion profiles for such crystals are proposed to exhibit three features: a short feature arising from a surface space-charge layer; an intermediate, longer feature arising from the high density of dislocations in the damaged zone; and finally, a much longer feature corresponding to diffusion in the homogeneous bulk crystal. Quantitative information is provided by finite-element-method calculations. First, the distribution of oxygen vacancies in a sample in which space-charge zones depleted of oxygen vacancies form at dislocations and at the sample surface is calculated; subsequently, oxygen tracer diffusion profiles for such vacancy distributions are simulated. The proposed model is experimentally validated by performing conventional oxygen isotope exchange and depth-profiling experiments on commercial single-crystal SrTiO3. In this way, we confirm directly that arrays of dislocations in acceptor-doped SrTiO3, by virtue of the attendant space-charge tubes, hinder the diffusion of oxygen. Finally, in order to aid the prediction of oxygen tracer diffusion profiles in polished perovskite single-crystal substrates, we suggest a one-dimensional continuum approach that takes account of the complex, three-dimensional diffusion problem posed by dislocation arrays with depletion space-charge tubes.

Periodic cation segregation in Cs0.44[Nb2.54W2.46O14] quantified by high-resolution scanning transmission electron microscopy.

The atomic structure of Cs0.44[Nb2.54W2.46O14] closely resembles the structure of the most active catalyst for the synthesis of acrylic acid, the M1 phase of Mo10V2(4+)Nb2TeO42-x. Consistently with observations made for the latter compound, the high-angle electron scattering signal recorded by scanning transmission electron microscopy shows a significant intensity variation, which repeats periodically with the projected crystallographic unit cell. The occupation factors for the individual mixed Nb/W atomic columns are extracted from the observed intensity variations. For this purpose, experimental images and simulated images are compared on an identical intensity scale, which enables a quantification of the cation distribution. According to our analysis specific sites possess low tungsten concentrations of 25%, whereas other sites have tungsten concentrations above 70%. These findings allow us to refine the existing structure model of the target compound, which has until now described a uniform distribution of the niobium and tungsten atoms in the unit cell, showing that the similarity between Cs0.44[Nb2.54W2.46O14] and the related catalytic compounds also extends to the level of the cation segregation.

Light-mediated heterogeneous cross dehydrogenative coupling reactions: metal oxides as efficient, recyclable, photoredox catalysts in C-C bond-forming reactions.

Let there be light: A heterogeneous photocatalytic system based on easily recyclable TiO(2) or ZnO allows cross dehydrogenative coupling reactions of tertiary amines. The newly developed protocols have successfully been applied to various C-C and C-P bond-forming reactions to provide nitro amines as well as amino ketones, nitriles and phosphonates.

Relaxation behavior study of ultrasmall superparamagnetic iron oxide nanoparticles at ultralow and ultrahigh magnetic fields.

Ultrasmall superparamagnetic iron oxide nanoparticles (USPIOs) have attracted attention because of their current and potential usefulness as contrast agents for magnetic resonance imaging (MRI) and nuclear magnetic resonance (NMR). USPIOs are usually used for their significant capacity to produce predominant proton relaxation effects, which result in signal reduction. However, most previous studies that utilized USPIOs have been focused on the relaxation behavior at commonly used magnetic fields of clinical MRI systems (typically 1-3 T). In this paper, magnetic relaxation processes of protons in water surrounding the USPIOs are studied at ultralow (≤10 mT) and ultrahigh magnetic fields (14.1 T). USPIOs used in our experiments were synthesized with a core size of 6 nm, and transferred from organic to water by ligand exchange. The proton spin-lattice relaxation time (T(1)) and spin-spin relaxation time (T(2)) were investigated at ultralow (212 µT for T(2) and 10 mT for T(1)) and at 14.1 T with different iron concentrations. At all of the fields, there is a linear relationship between the inverse of relaxation times and the iron concentration. The spin-spin relaxivity (r(2)) at 14.1 T is much larger than that value of the ultralow field. At ultralow field, however, the spin-lattice relaxivity (r(1)) is larger than the r(1) at ultrahigh field. The results provide a perspective on potential in vivo and in vitro applications of USPIOs in ultralow and ultrahigh field NMR and MRI.

A kinetic study of the decomposition of the cubic perovskite-type oxide Ba(x)Sr(1-x)Co(0.8)Fe(0.2)O(3-delta) (BSCF) (x = 0.1 and 0.5).

The decomposition of the cubic perovskite-type oxide Ba(x)Sr(1-x)Co(0.8)Fe(0.2)O(3-delta) (BSCF) into hexagonal and cubic perovskite-type phases has been examined by means of Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Selected Area Electron Diffraction (SAED) and X-Ray Diffraction (XRD). SEM and TEM measurements reveal that the new hexagonal phase grows predominantly at the grain boundaries of BSCF ceramics and that the cation composition of the newly formed hexagonal phase differs from that of the starting material. An orientational relationship between the hexagonal and the parent cubic phase was also observed. By means of ex situ XRD the phase fraction of the hexagonal phase was determined as a function of annealing time. A kinetic analysis of the data, based on Avrami-type kinetics, indicates that the decomposition is independent of the initial A-site composition, and the obtained reaction order supports the conclusion that the hexagonal phase grows at the grain boundaries in dense ceramic samples.

Ultrastructural analysis of vascular calcifications in uremia.

Accelerated intimal and medial calcification and sclerosis accompany the increased cardiovascular mortality of dialysis patients, but the pathomechanisms initiating microcalcifications of the media are largely unknown. In this study, we systematically investigated the ultrastructural properties of medial calcifications from patients with uremia. We collected iliac artery segments from 30 dialysis patients before kidney transplantation and studied them by radiography, microcomputed tomography, light microscopy, and transmission electron microscopy including electron energy loss spectrometry, energy dispersive spectroscopy, and electron diffraction. In addition, we performed synchrotron x-ray analyses and immunogold labeling to detect inhibitors of calcification. Von Kossa staining revealed calcification of 53% of the arteries. The diameter of these microcalcifications ranged from 20 to 500 nm, with a core-shell structure consisting of up to three layers (subshells). Many of the calcifications consisted of 2- to 10-nm nanocrystals and showed a hydroxyapatite and whitlockite crystalline structure and mineral phase. Immunogold labeling of calcification foci revealed the calcification inhibitors fetuin-A, osteopontin, and matrix gla protein. These observations suggest that uremic microcalcifications originate from nanocrystals, are chemically diverse, and intimately associate with proteinaceous inhibitors of calcification. Furthermore, considering the core-shell structure of the calcifications, apoptotic bodies or matrix vesicles may serve as a calcification nidus.

Analysis of calcifications in patients with coral reef aorta.

BACKGROUND: Coral reef aorta is a rare vascular disease with intraluminal calcifications of the dorsal part of the visceral aorta. The pathogenesis of this disease with its topographic and morphologic characteristics is unknown. The aim of our study was to investigate calcification inhibitors and the ultrastructure of calcifications in patients with coral reef aorta. METHODS: Ten patients with coral reef aorta were examined. Calcified specimens were investigated by immunohistochemical techniques for the expression of the calcification inhibitors matrix gla protein (MGP) and fetuin-A. Vessel walls were also assessed by electron microscopic techniques including electron energy-lost spectroscopy, electron dispersive spectroscopy, and electron diffraction. Sera of patients were analyzed for fetuin-A, uncarboxylated MGP (ucMGP), and osteoprotegerin. RESULTS: As assessed by immunohistochemistry, most MGP was detected in the vicinity of calcified regions. Serum levels of the calcification inhibitors ucMGP, fetuin-A, and osteoprotegerin were 370+/-107 nmol/L, 0.57+/-0.03 g/L, and 5.64+/-0.79 pmol/L, respectively. Ultrastructural analysis of calcified specimens showed a core-shell structure with multiple calcification nuclei. Calcifications displayed a fine-crystalline character, and elemental analysis revealed hydroxyl apatite as the chemical compound. CONCLUSION: The coral reef aorta represents an extreme exophytic growth of vascular calcification with multiple nuclei which resemble typical media calcification. Positive vascular immunostaining and low serum levels of both fetuin-A and ucMGP suggest a pathophysiologic role of these calcification inhibitors in the development of coral reef aorta.

Chemical vapor synthesis of nanocrystalline perovskites using laser flash evaporation of low volatility solid precursors.

One key requirement for the production of multinary oxide films by chemical vapor deposition (CVD) or nanocrystalline multinary oxides particles by chemical vapor synthesis (CVS) is the availability of precursors with high vapor pressure. This is especially the case for CVS where much higher production rates are required compared to thin films prepared by CVD. However, elements, which form low valent cations such as alkaline earth metals, are typically only available as solid precursors of low volatility, e.g., in form of beta-diketonates. This study describes laser flash evaporation as precursor delivery method for CVS of nanocrystalline perovskites. Laser flash evaporation exploits the nonequilibrium evaporation of solid metal organic precursors of low vapor pressure by absorption of the infrared radiation of a CO(2) laser. It is shown that stoichiometric, nanocrystalline particles consisting of SrZrO(3) and SrTiO(3) can be formed from corresponding mixtures of beta-diketonates which are evaporated nonselectively and with high rates by laser flash evaporation.

Ab initio determination of the framework structure of the heavy-metal oxide Cs(x)Nb2.54W2.46O14 from 100 kV precession electron diffraction data.

The present work deals with the ab initio determination of the heavy metal framework in Cs(x)(Nb, W)(5)O(14) from precession electron diffraction intensities. The target structure was first discovered by Lundberg and Sundberg [Ultramicroscopy 52 (1993) 429-435], who succeeded in deriving a tentative structural model from high-resolution electron microsopy (HREM) images. The metal framework of the compound was solved in this investigation via direct methods from hk0 precession electron diffraction intensities recorded with a Philips EM400 at 100 kV. A subsequent (kinematical) least-squares refinement with electron intensities yielded slightly improved co-ordinates for the 11 heavy atoms in the structure. Chemical analysis of several crystallites by EDX is in agreement with the formula Cs(0.44)Nb(2.54)W(2.46)O(14). Moreover, the structure was independently determined by Rietveld refinement from X-ray powder data obtained from a multi-phasic sample. The compound crystallises in the orthorhombic space group Pbam with refined lattice parameters a=27.145(2), b=21.603(2), and c=3.9463(3)A. Comparison of the framework structure from electron diffraction with the result from Rietveld refinement shows an average agreement for the heavy atoms within 0.09 A.

First-principles calculations as a tool for structure validation in electron crystallography.

The crystal structures of Ti(11)Se(4) [Weirich, Ramlau, Simon, Hovmöller & Zou (1996). Nature (London), 382, 144-146] and Ti(45)Se(16) [Weirich (2001). Acta Cryst. A57, 183-191] determined previously from selected-area electron diffraction (SAED) data have been checked for their correctness by means of total energy calculations within the non-local density functional theory. The reliability of the used method was verified by test calculations carried out for the structurally related compound Ti(8)Se(3), which is well known from single-crystal X-ray diffraction [Weirich, Pöttgen & Simon (1996). Z. Kristallogr. 212, 929-930]. For Ti(8)Se(3), structural models from both experiment and calculation show a perfect match (average agreement 0.01 A). This proves that the geometrical optimized models from first-principles calculation can be used as a reliable alternative when good-quality X-ray results cannot be obtained. Calculations carried out for the two structures determined from electron crystallography yielded average improvement of the atomic coordinates of 0.04 and 0.09 A for Ti(11)Se(4) and Ti(45)Se(16), respectively. The optimized cell parameters of the monoclinic structures (both space group C2/m, No. 12) are a = 25.51, b = 3.43, c = 19.19 A, beta = 117.9 degrees for Ti(11)Se(4) and a = 36.31, b = 3.45, c = 16.59 A, beta = 92.1 degrees for Ti(45)Se(16). These results prove that crystals that are too small for single-crystal X-ray diffraction and are difficult to solve by powder diffraction may nevertheless be amenable to accurate structure determination by electron diffraction structure analysis using data from standard SAED and the assumption of quasi-kinematical scattering. Moreover, this study shows that geometry optimization by first-principles calculations is the perfect tool for validation and improvement of complex structural models, which are suspected to have errors owing to the poor quality of experimental data.

Characterization of Co25Ag75 and (Co90Al10)28Ag72 granular films by electron diffraction, high-resolution transmission electron microscopy and electron spectroscopic imaging.

Series of sputter-deposited Co25Ag75 and (Co90Al10)28Ag72 giant-magnetoresistance granular films were characterized by electron diffraction, high-resolution transmission electron microscopy and electron spectroscopic imaging. Crystalline particles of fcc silver and hcp cobalt were detected in both thin-film systems before annealing. Annealing of (Co90Al10)28Ag72 films at 773 and 823 K yielded mixtures of fcc and hcp cobalt clusters and notably enlarged silver particles. In addition, crystallites of bcc Ag3Al were detected in the sample annealed at 823 K. The mesoscopic structure of the as-deposited films was investigated by dark-field imaging showing columnar growth-domains for silver. The columns were preserved during thermal treatment up to 773 K, whereas annealing at 823 K destroyed these domains.

Structure and stability of alpha- and beta-Ti2Se. Electron diffraction versus density-functional theory calculations.

The alpha structure as well as the new beta modification of Ti(2)Se were recently characterized by electron diffraction structural analysis of nanosize crystallites. In this study, both structures are investigated by means of total energy calculations within the non-local density-functional theory in order to validate the experimental results. The calculated parameters for both modifications are in excellent agreement with data determined from electron microscopy. From the calculated equation of states, beta-Ti(2)Se is predicted to be a high-pressure modification. The present investigation proves by a well established non-crystallographic method that unknown structures, which are not accessible by other standard crystallographic techniques, can be solved and refined with high accuracy using electron diffraction data.