Microwave spectrometry for the Evaluation of the structural integrity of metallic stents

Purpose: To assess the feasibility of a method based on microwave spectrometry to detect structural distortions of metallic stents in open air conditions and envisage the prospects of this approach toward possible medical applicability for the evaluation of implanted stents. Methods: Microwave absorbance spectra between 2.0 and 18.0 GHz were acquired in open air for the characterization of a set of commercial stents using a specifically design setup. Rotating each sample over 360º, 2D absorbance diagrams were generated as a function of frequency and rotation angle. To check our approach for detecting changes in stent length (fracture) and diameter (recoil), two specific tests were performed in open air. Finally, with a few adjustments, this same system provides 2D absorbance diagrams of stents immersed in a water-based phantom, this time over a bandwidth ranging from 0.2 to 1.8 GHz. Results: The authors show that metallic stents exhibit characteristic resonant frequencies in their microwave absorbance spectra in open air which depend on their length and, as a result, may reflect the occurrence of structural distortions. These resonances can be understood considering that such devices behave like dipole antennas in terms of microwave scattering. From fracture tests, the authors infer that microwave spectrometry provides signs of presence of Type I to Type IV stent fractures and allows in particular a quantitative evaluation of Type III and Type IV fractures. Recoil tests show that microwave spectrometry seems able to provide some quantitative assessment of diametrical shrinkage, but only if it involves longitudinal shortening. Finally, the authors observe that the resonant frequencies of stents placed inside the phantom shift down with respect to the corresponding open air frequencies, as it should be expected considering the increase of dielectric permittivity from air to water. Conclusions: The evaluation of stent resonant frequencies provided by microwave spectrometry allows detection and some quantitative assessment of stent fracture and recoil in open air conditions. Resonances of stents immersed in water can be also detected and their characteristic frequencies are in good agreement with theoretical estimates. Although these are promising results, further verifica tion in a more relevant phantom is required in order to foresee the real potential of this approach.

Estudos da eletrodeposição de metais em regime de subtensão

This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.

The contributions of Henri Victor Regnault in the context of organic chemistry of the first half of the nineteenth century

A very little known aspect of the scientific career of Regnault is his contribution to the emerging organic chemistry in the first half of the nineteenth century. The purpose of this article is not only to describe two of his most important researches in this field, as were the discovery of two series of halogenated derivates of certain organic compounds and the precise identification of some of the then recently discovered alkaloids, but also the main features that identified his research method. With the involvement in these subjects, Regnault unintentionally positioned himself in the midst of some of the polemics about the classification of organic compounds that characterized this age of science.

First principles modeling of metallic alloys and alloy surfaces

By alloying metals with other materials, one can modify the metal’s characteristics or compose an alloy which has certain desired characteristics that no pure metal has. The field is vast and complex, and phenomena that govern the behaviour of alloys are numerous. Theories cannot penetrate such complexity, and the scope of experiments is also limited. This is why the relatively new field of ab initio computational methods has much to give to this field. With these methods, one can extend the understanding given by theories, predict how some systems might behave, and be able to obtain information that is not there to see in physical experiments. This thesis pursues to contribute to the collective knowledge of this field in the light of two cases. The first part examines the oxidation of Ag/Cu, namely, the adsorption dynamics and oxygen induced segregation of the surface. Our results demonstrate that the presence of Ag on the Cu(100) surface layer strongly inhibits dissociative adsorption. Our results also confirmed that surface reconstruction does happen, as experiments predicted. Our studies indicate that 0.25 ML of oxygen is enough for Ag to diffuse towards the bulk, under the copper oxide layer. The other part elucidates the complex interplay of various energy and entropy contributions to the phase stability of paramagnetic duplex steel alloys. We were able to produce a phase stability map from first principles, and it agrees with experiments rather well. Our results also show that entropy contributions play a very important role on defining the phase stability. This is, to the author’s knowledge, the first ab initio study upon this subject.

Some defects in two-dimensional spin-1/2 Heisenberg antiferromagnets: a numerical study of magnetic effects

En del av de intressantaste fenomenen inom dagens materialfysik uppstår ur ett intrikat samspel mellan myriader av elektroner. Högtemperatursupraledare är det mest berömda exemplet. Varken klassiska teorier eller modeller där elektronerna är oberoende av varandra kan förklara de häpnadsväckande effekterna i de starkt korrelerade elektronsystemen. I vissa kopparoxider, till exempel La2CuO4, är det känt att valenselektronerna till följd av en stark ömsesidig växelverkan lokaliseras en och en till kopparatomerna i föreningens CuO2 plan. Laddningarnas inneboende magnetiska moment—spinnet—får då en avgörande roll för materialets elektriska och magnetiska egenskaper, vilka i exemplets fall kan beskrivas med Heisenbergmodellen som är den grundläggande teoretiska modellen för mikroskopisk magnetism. Men exakt varför föreningarna kan bli supraledande då de dopas med överskottsladdningar är än så länge en obesvarad fråga. Min avhandling undersöker orenheters inverkan på Heisenbergmodellens magnetiska egenskaper—ett problem av både experimentell och teoretisk relevans. En etablerad numerisk metod har använts—en kvantmekanisk Monte Carlo teknik—för att utföra omfattande datorsimuleringar av den matematiska modellen på två dedikerade Linux datorkluster. Arbetet hör till området beräkningsfysik. De teoretiska modellerna för starkt korrelerade elektronsystem, däribland Heisenbergmodellen, är ytterst invecklade matematiskt sett och de kan inte lösas exakt. Analytiska utredningar bygger för det mesta på antaganden och förenklingar vars inverkningar på slutresultatet är ofta oklara. I det avseende kan numeriska studier vara exakta, det vill säga de kan behandla modellerna som de är. Oftast behövs bägge tillvägagångssätten. Den röda tråden i arbetet har varit att numeriskt testa vissa högaktuella analytiska förutsägelser rörande effekterna av orenheter i Heisenbergmodellen. En del av dem har vi på basen av mycket noggranna data kunnat bekräfta. Men våra resultat har också påvisat felaktigheter i de analytiska prognoserna som sedermera delvis reviderats. En del av avhandlingens numeriska upptäckter har i sin tur stimulerat till helt nya teoretiska studier.

Erikoispuristimen kehitys liikkuvalle raaka-ainerainalle

Tutkimuksen tavoitteena oli kehittää Lappeenrannan teknilliselle yliopistolle nopeasti ja ketterästi liikkuva, lävistyksiä ja muovauksia tekevä puristin. Laitteisto on tarkoitus liittää osaksi tuotantolinjaa, jossa suulakepuristin eli ekstruuderi tuottaa pehmeä, ei-metallista materiaalia katkeamattomasti. Teoriaosuudessa esitellään vaihtoehdot puristimen, ohjauksen, työkalun ja liikutuslaitteiston osalta. Empiriaosuudessa suoritetaan laitteiston eri komponenttien valinta hinnan, nopeuden, kestävyyden, käytettävyyden ja koon perusteella. Tutkimuksen lopussa arvioidaan laitteistokokonaisuuden nopeutta suulakepuristimen tuotaman materiaalin maksiminopeuteen. Laitteiston nopeuden rajoittavana tekijänä toimii puristimen iskunopeus, jonka perusteella suulakepuristimen tuottaman materiaalin etenemisnopeus joudutaan pudottamaan hieman alle puoleen tavoitteena olleesta nopeudesta. Laitteiston kestävyyden heikon kohta on työstöä tekevien komponenttien liikuttamiseen tarkoitettu laitteisto. Puristuslaitteistoa on tarkoitus käyttää kahdeksan tuntia päivässä, viitenä päivänä viikossa, 52 viikkoa vuodessa. Näiden käyttötietojen perusteella koko laitteiston käyttöikä on useita vuosia.

Modern Metallic Materials for Arctic Environment

This thesis is part of the Arctic Materials Technologies Development –project, which aims to research and develop manufacturing techniques, especially welding, for Arctic areas. The main target of this paper is to clarify what kind of European metallic materials are used, or can be used, in Arctic. These materials include mainly carbon steels but also stainless steels and aluminium and its alloys. Standardized materials, their properties and also some recent developments are being introduced. Based on this thesis it can be said that carbon steels (shipbuilding and pipeline steels) have been developed based on needs of industry and steels exist, which can be used in Arctic areas. Still, these steels cannot be fully benefited, because rules and standards are under development. Also understanding of fracture behavior of new ultra high strength steels is not yet good enough, which means that research methods (destructive and non-destructive methods) need to be developed too. The most of new nickel-free austenitic and austenitic-ferritic stainless steels can be used in cold environment. Ferritic and martensitic stainless steels are being developed for better weldability and these steels are mainly developed in nuclear industry. Aluminium alloys are well suitable for subzero environment and these days high strength aluminium alloys are available also as thick sheets. Nanotechnology makes it possible to manufacture steels, stainless steels and aluminium alloys with even higher strength. Joining techniques needs to be developed and examined properly to achieve economical and safe way to join these modern alloys.

Using the best linear predictor (BLP) in the selection between and among half-sib progenies of the CMS-39 maize population

Data of corn ear production (kg/ha) of 196 half-sib progenies (HSP) of the maize population CMS-39 obtained from experiments carried out in four environments were used to adapt and assess the BLP method (best linear predictor) in comparison with to the selection among and within half-sib progenies (SAWHSP). The 196 HSP of the CMS-39 population developed by the National Center for Maize and Sorghum Research (CNPMS-EMBRAPA) were related through their pedigree with the recombined progenies of the previous selection cycle. The two methodologies used for the selection of the twenty best half-sib progenies, BLP and SAWHSP, led to similar expected genetic gains. There was a tendency in the BLP methodology to select a greater number of related progenies because of the previous generation (pedigree) than the other method. This implies that greater care with the effective size of the population must be taken with this method. The SAWHSP methodology was efficient in isolating the additive genetic variance component from the phenotypic component. The pedigree system, although unnecessary for the routine use of the SAWHSP methodology, allowed the prediction of an increase in the inbreeding of the population in the long term SAWHSP selection when recombination is simultaneous to creation of new progenies.

Experimental Studies on Non-Metallic Composite Bone Implants With a Special Reference to Staphylococcal Biofilm Infection

Non-metallic implants made of bioresorbable or biostable synthetic polymers are attractive options in many surgical procedures, ranging from bioresorbable suture anchors of arthroscopic surgery to reconstructive skull implants made of biostable fiber-reinforced composites. Among other benefits, non-metallic implants produce less interference in imaging. Bioresorbable polymer implants may be true multifunctional, serving as osteoconductive scaffolds and as matrices for simultaneous delivery of bone enhancement agents. As a major advantage for loading conditions, mechanical properties of biostable fiber-reinforced composites can be matched with those of the bone. Unsolved problems of these biomaterials are related to the risk of staphylococcal biofilm infections and to the low osteoconductivity of contemporary bioresorbable composite implants. This thesis was focused on the research and development of a multifunctional implant model with enhanced osteoconductivity and low susceptibility to infection. In addition, the experimental models for assessment, diagnostics and prophylaxis of biomaterial-related infections were established. The first experiment (Study I) established an in vitro method for simultaneous evaluation of calcium phosphate and biofilm formation on bisphenol-Aglycidyldimethacrylate and triethylenglycoldimethacrylate (BisGMA-TEGDMA) thermosets with different content of bioactive glass 45S5. The second experiment (Study II) showed no significant difference in osteointegration of nanostructured and microsized polylactide-co-glycolide/β-tricalcium phosphate (PLGA /β-TCP) composites in a minipig model. The third experiment (Study III) demonstrated that positron emission tomography (PET) imaging with the novel 68Ga labelled 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) CD33 related sialic-acid immunoglobulin like lectins (Siglec-9) tracer was able to detect inflammatory response to S. epidermidis and S. aureus peri-implant infections in an intraosseous polytetrafluoroethylene catheter model. In the fourth experiment (Study IV), BisGMATEGDMA thermosets coated with lactose-modified chitosan (Chitlac) and silver nanoparticles exhibited antibacterial activity against S. aureus and P. aeruginosa strains in an in vitro biofilm model and showed in vivo biocompatibility in a minipig model. In the last experiment (Study V), a selective androgen modulator (SARM) released from a poly(lactide)-co-ε-caprolactone (PLCL) polymer matrix failed to produce a dose-dependent enhancement of peri-implant osteogenesis in a bone marrow ablation model.

Accuracy of dose planning for prostate radiotherapy in the presence of metallic implants evaluated by electron spin resonance dosimetry

Radiotherapy is one of the main approaches to cure prostate cancer, and its success depends on the accuracy of dose planning. A complicating factor is the presence of a metallic prosthesis in the femur and pelvis, which is becoming more common in elderly populations. The goal of this work was to perform dose measurements to check the accuracy of radiotherapy treatment planning under these complicated conditions. To accomplish this, a scale phantom of an adult pelvic region was used with alanine dosimeters inserted in the prostate region. This phantom was irradiated according to the planned treatment under the following three conditions: with two metallic prostheses in the region of the femur head, with only one prosthesis, and without any prostheses. The combined relative standard uncertainty of dose measurement by electron spin resonance (ESR)/alanine was 5.05%, whereas the combined relative standard uncertainty of the applied dose was 3.35%, resulting in a combined relative standard uncertainty of the whole process of 6.06%. The ESR dosimetry indicated that there was no difference (P>0.05, ANOVA) in dosage between the planned dose and treatments. The results are in the range of the planned dose, within the combined relative uncertainty, demonstrating that the treatment-planning system compensates for the effects caused by the presence of femur and hip metal prostheses.

On the Ewald method and the quartic Helmholtz free energy of an anharmonic metallic crystal

Thesis (M. Sc.) - Brock University, 1978.

Pressure dependence of spin fluctuations in metallic glasses Zrâ â Niâ â ,Zrâ â (Nix/Feâ â â -x)â â and /Zrx/feâ â â -x

The superconducting transition temperature Tc of metallic glasses ZrxFelOO-x (x=80, 75), Zr75(NixFelOO-x)25 (x=75, 50, 25), and CU2SZr75 were measured under quasi-hydrostatic pressure up to 8 OPa (80kbar). The volume (pressure) dependence of the electron-phonon coupling parameters Aep for CU25Zr75 was calculated using the McMillan equatio11. Using this volume dependence of Aep and the modified McMillan equation which incorporates spin-fluctuations, the volume dependence of the spin fluctuation parameter, Asf, was determined in Zr75Ni25, ZrxFelOO-x , a11d Zr75(NixFelOO-x)25. It was found that with increasing pressure, spinfluctuations are suppressed at a faster rate in ZrxFe lOO-x and Zr75(NixFelOO-x)25, as Fe concentration is increased. The rate of suppression of spin-fluctuations with pressure was also found to be higher in Fe-Zr glasses than in Ni-Zr glasses of similar composition.