Jolanta Romanowska

Bismuth activity measurements and thermodynamic re-optimization of the Ni–Bi System

Abstract Bismuth thermodynamic activities in Ni – Bi liquid solutions have been measured by the modified isothermal isopiestic method at 1723, 1753 and 1773 K. These results are coupled with thermochemical and topological data from literature, in order to achieve reliable re-optimization of the Ni – Bi system by the CALPHAD method. The model of disordered substitutional solutions has been applied to the liquid phase and to the face-centered cubic solid solutions (Ni). The compound NiBi3 is stoichiometric and is modeled by a two-sublattice model corresponding to its formula. The nickel solubility in the solid bismuth is negligible, which is why the phase (Bi) is considered as consisting of bismuth only. The description Bi: Ni, Va has been used for the thermodynamic modeling of the nonstoichiometric NiBi phase.

Microstructure and oxidation behaviour investigation of rhodium modified aluminide coating deposited on CMSX 4 superalloy

The CMSX 4 superalloy was coated with rhodium 0.5‐μm thick layer and next aluminized by the CVD method. The coating consisted of two layers: the additive and the interdiffusion one. The outward diffusion of nickel from the substrate turned out to be a coating growth dominating factor. The additive layer consists of the β‐NiAl phase, whereas the interdiffusion layer consists of the β‐NiAl phase with precipitates of σ and μ phases. Rhodium has dissolved in the coating up to the same level in the matrix and in the precipitates. The oxidation test proved that the rhodium modified aluminide coating showed about twice better oxidation resistance than the nonmodified one.

The Effect of Zirconium Addition on the Oxidation Resistance of Aluminide Coatings

Nickel, Mar M247, and Mar M200 superalloys were coated with zirconium-doped aluminide deposited by the chemical vapor deposition method. All coatings consisted of two layers: an additive one, comprising of the β-NiAl phase and the interdiffusion one. The interdiffusion layer on pure nickel consisted of the γ′-Ni3Al phase and β-NiAl phase on superalloys. Precipitations of zirconium-rich particles were found near the coating’s surface and at the interface between the additive and the interdiffusion layer. Zirconium doping of aluminide coating improved the oxidation resistance of aluminide coatings deposited both on the nickel substrate and on the Mar M200 superalloy. Precipitations of ZrO2 embedded by the Al2O3 oxide were formed during oxidation. It seems that the ZrO2 oxide increases adhesion of the Al2O3 oxide to the coating and decreases the propensity of the Al2O3 oxide rumpling and spalling.

Sn-Ni-Bi liquid phase thermodynamic properties

AbstractExperimental data of bismuth activity coefficients at 1773 K were obtained by isopiestic method and compared to calculated values. Thermodynamic properties of the Sn-Ni-Bi liquid phase were estimated by means of the general solution model and by the methods of Kohler. Description of the ternary liquid phase (Gibbs excess energy dependence on the temperature and the composition) was achieved by using available thermodynamic data of the constitutive binary systems (Ni-Bi, Sn-Bi, Sn-Ni). A comparison between calculated quantities and experimental data wasconducted. The present assessment with thermodynamically optimized values of the system Sn-Ni-Bi (obtained by the CALPHAD approach) was in good agreement. The suggested appearance of a liquid phase miscibility gap at high temperatures is in agreement with the experimental bismuth activity data and with the assessed thermochemical functions.

The Ni-Al-Zr Multiphase Diffusion Simulations

Abstract The generalized Darken method allows a quantitative description of diffusion mass transport in multi-phase materials. The method characterizes the diffusion zone by phase volume fractions. The results of the calculations are compared with experimental concentration’s profiles of nickel, zirconium and aluminum in zirconium doped aluminide coatings deposited on pure nickel by the PVD and CVD methods.

SEM/TEM Investigation of Aluminide Coating Co-Doped with Pt and Hf Deposited on Inconel 625

The effect of simultaneous introduction of Hf and Pt into aluminide coating deposited on Inconel 625 alloy was investigated using scanning and transmission electron microscopy (SEM/TEM) methods. The coating consisted of two layers: the additive and the interdiffusion. The additive layer and part of the interdiffusion layer consist of the β-NiAl type phase. The middle part of the interdiffusion layer comprised an interpenetrating finger-like structure formed by the β-NiAl and TCP—σ type phases with numerous fine Cr precipitates in the former and occasional larger precipitates of NbC carbides interspersed in between them. The σ type phase inclusions are situated at the border between the substrate and the interdiffusion layer. The experiment showed that platinum fully dissolves in the β-NiAl-type matrix, while most of the introduced hafnium accumulates in HfO2 dioxide precipitates located close to the additive/interdifusion interface.

Hafnium and palladium modified aluminide coatings

D of biodegradable materials is highly in demand as large and rapid usage of plastic materials results million tons of plastic wastes in the landfill sites each year globally. It takes a long time for conventional plastics to degrade, leading to severe ecological problems too. The production capacities of biodegradable plastics, such as polylactic acid (PLA), polyhydroxyalkanoates, and starch blends, are also growing steadily, nearly doubling from 0.7 million metric tons in 2014 to well over 1.2 million metric tons by 2019. PLA, for its good compatibility and biodegradability, is preferred by people from all sectors. Also, PLA is a low energy consumption product, about 30-50% lower in energy consumption than the petroleum-based polymers. PLA as the most widely used, the lowest price of bioplastic in industrialization, in the aspect of practicality, is the biodegradable material that has the largest scope to replace the position of the petroleum based plastics on the current scenario of oil scarcity. The production cost of PLA is also approaching the cost of traditional plastic, and with the strong expansion of market applications, will get soon recognized globally. PLA based nanocomposites are widely used today in various applications. The review article aims to target on the topical progresses in the synthesis and characterization of PLA blends, PLA composites and PLA nanocomposites with different materials. Moreover, this article is a unique collection of vital information about PLA based blends and composites for drug delivery, packaging and barrier applications in a single platform.D intensive research and applications of different techniques to improve surface properties of vascular stents, currently available metal stents and their coatings (DES drug eluting stents) still lack of desired surface biocompatibility, mostly due to mechanical injuries, inflammation, as well as proliferation and migration of smooth muscle cells, often with progression to restenosis. Besides, the durability and stability of DES is still problematic and has been connected with high risk of thrombosis Biomimetic nanosized materials, with their crystal structure, surface morphology and chemical properties are one of critical features for their potential use in vascular stent applications, which should support adhesion, proliferation and differentiation of endothelial cells and prevent abnormal growth of smooth muscle cells. For example, it was shown that titanium dioxide (TiO2) nanotubes (NTs) topography is essential parameter in optimizing endothelial cell and smooth muscle cell responses to vascular implants. The purpose of this study is to investigate surface properties and crystal structure of TiO2 NTs. Since the oxygen, plasma treatment plays significant role in surface treatment of biomedical devices due to surface cleaning and sterilization, its effect on the mechanical stability and surface chemical properties was evaluated. Vertically aligned arrays of TiO2 NTs were synthesized on Ti metallic substrates with electrochemical anodization. The crystal structure was investigated with X-ray Diffraction Spectroscopy, while morphology and surface properties were analyzed with Scanning Electron Microscopy coupled with Energy Dispersive X-ray Analysis, X-ray Photoelectron Spectroscopy and Water Contact Angle analysis. Our results indicate that oxygen plasma treatment of TiO2 NTs surfaces induces the formation of oxide layer on the surface of TiO2 NT, which could result in enhanced biocompatibility. Moreover, plasma treatment removes undesired electrolyte residues on TiO2 NTs surface and highly improves its wettability. We showed that plasma treated TiO2 NTs possess long-term hydrophilicity and influence on crystallization of amorphous TiO2 NTs to anatase and/or rutile crystal phase, which could be the reason for improved wettability. The optimized conditions (power, frequency and time) of oxygen plasma treatment on the mechanical stability of TiO2 NTs are also presented. Oxygen plasma treatment can greatly improve the surface characteristics of biomimetic materials and enhance their biocompatibility. Restenosis and thrombosis still remain a serious concern and should be given a great deal of attention in order to produce improved tissue-material response.Resumen del trabajo presentado a la 11th International Conference on Advanced Materials & Processing, celebrada en Edimburgo (Escocia) del 7 al 8 de septiembre de 2017.P of thin lead zirconate titanate (PZT) films on metallic substrates has several advantages such as high frequency operation, low electrical series resistance, low dielectric loss and potential for embedded capacitor systems. As a suitable metal support for PZT films, titanium (Ti) seems to be the most natural choice as it possess high melting point, the thermal expansion coefficient of Ti matches closely to that of PZT and permits good adhesion with low reactivity. However, ferroelectric and piezoelectric responses of PZT films on Ti substrates are found to be not that encouraging. Presence of a non-ferroelectric pyrochlore/ fluorite (Py/Fl) phase on the surface of the PZT film is believed to be the primary cause for poor electrical performance. In this work, effect of re-crystallization of PZT films with a thin Pb-overcoat has been investigated though structural, morphological, compositional and electrical studies. Sputter deposited PZT thin films on Ti-substrates are found to contain a Pb-deficient and Zr-enriched Py/Fl phase of type Pb2 (Zr,Ti)2O6 on the surface of the PZT film. Re-crystallization of these PZT films with a thin lead (Pb) overcoat improves the degree of crystallization, morphology and dielectric/ Ferroelectric properties of the films by converting the top Pb-lean and Zr-rich Py/Fl phase into perovskite phase. Structural changes that occur in PZT films upon re-crystallization with a Pb-overcoat have been correlated with ferroelectric characteristics of the PZT films.P nanoparticles have a broad spectrum of applications including dispersion (emulsion) paints or thin films. However, the understanding of their behavior and properties, especially at high concentrations is still limited. We model the dispersions of polymeric nanoparticles using the dynamic model based on Discrete Element Method (DEM). The interaction model represents particles that are elastic, adhesive and electrostatically stabilized. The flow-field computation that is included in the model enables us to evaluate the rheological properties of the dispersion, which are crucial for its behavior. Further characterization of both dispersions and gels is done using oscillatory simulations, from which the viscoelastic properties are obtained. The model was successfully used to describe the dynamic behavior of a flowing dispersion including the processes of coagulation, fouling and breakage. These processes and their relative importance in a specific system determine the transition from a dispersed state to a gel. Due to their specific position on the boundary between solids and liquids, gels have unique properties that make them suitable to be used e.g., as a porous structures (or) matrices for drug delivery in the pharmaceutical industry.O surgery has grown from the hand of new materials that made possible to perform procedures as total hip replacement with feasibility. These procedures are common in most orthopaedic departments, and more than 70 000 hip or knee replacements are performed in Spain every year. The survival of these implants is critical to prevent loosening and the need for revision arthroplasty. The ideal surface to interact with bone has not been created. We created laser induced periodic surface structures (LIPSS) in the surface of titanium and tantalium to study the behaviour of stem cells compared to polished surfaces. We created 12 discs of each material and polished them. Later we created LIPSS in 6 discs of each material. We cultured them in human stem cells in a concentration of 25000 cell per cm2 for 20 days. We determined MTT, TNF-Alfa, alkaline phosphatase, IL-6, osteopontin and osteocalcin every 5 days until the day 20. We confirmed outcomes behave as a normal distribution after applying the Kolmogorov Smirnov test. We compared materials and surfaces with the T-student test. We accepted a difference of 0.05 as significant. LIPSS created increase statistically cell metabolism (best values in MTT assay) and decrease inflammatory response to the material (IL-6 and TNF-alfa values). Collagen is produced in more quantity and cells differentiate to osteoblast easily. These differences are seen from the beginning until the endpoint (day 20). When LIPSS improved osteogenic properties of titanium and tantalium compared to smooth surfaces.I the last 5 years, methylammonium lead halide or MALH perovskites (e.g., CH3NH3PbA3-xBx, where A and B are I, Cl or Br) have shown tremendous potential for low-cost optoelectronic device integration, including light-emitting diodes, solar cells and photodetectors. For example, the power-conversion efficiencies from organometallic halide perovskite solar cells have increased from 3.8% in 2009 to 22.1% in 2016. This spectacular progress is largely attributed to improved processing and longer chargecarrier lifetimes, directly related to increased material quality. While significant progress was made, many key parameters including compatibility, interface engineering, surface treatment and processability remain essential to achieving the best device performances. These fundamental challenges prevent integration into commercial-grade devices. For one, relatively low carrier mobilities still prevent large-area devices with performances competing with state-of-the-art technologies. Several groups began exploring hybrid perovskite films in the last 3 years. In the last year, we have made major progress towards viable MALH devices (1) by dramatically enhancing structure and properties through solvent engineering, (2) enhancing conductivities by several orders of magnitude using MALH hybrids, (3) extending their operation to the near-infrared and (4) significantly improving their stability and lifetime by doping with SCN. Preliminary results shown in Fig.1 are greatly encouraging and suggest that the carefully-controlled processing capability allowed by the Ceradrop inkjet printer can yield high-quality MALH films. This is a major step towards the integration of MALH perovskites within commercial printable photovoltaic devices, LEDs and sensors.C normally causes damage in hydraulic machineries such as pumps and screw propellers, as severe impacts are produced at cavitation collapses. However, cavitation impacts can be utilized for surface mechanics design for improvement of fatigue strength in the same way of shot peening. The peening method using cavitation impacts is named as “cavitation peening”. The advantage of cavitation peening is that the increase of surface roughness is small comparing with conventional shot peening, as shots are not required in cavitation peening. In order to mitigate stress corrosion cracking, introduction of compressive residual using cavitation impact was proposed, and it has been applied for nuclear power plants. By enhancing cavitation impacts, improvement of fatigue strength was demonstrated.The aspect of cavitation peening of gear by using a submerged water jet with cavitation, i.e., a cavitating jet. In order to investigate mechanism of improvement of fatigue strength, a special fatigue tester was developed to investigate crack propagation in surface modified layer. Cavitation peening also suppress hydrogen embrittlement. At laser peening, it is believed that impact caused by laser abrasion produces plastic deformation for surface treatment. However, a bubble is generated after laser abrasion, and it produces impact at bubble collapse like cavitation, then it can be called as laser cavitation. As shown in Fig. 2, when the impact passing through the material was measured, the impact induced by laser abrasion is larger than that of laser abrasion. Namely, at submerged laser peening, peening effect would be improved by considering the laser cavitation. In the presentation, the principal of cavitation peening is introduced with applications of cavitation peening such as improvement of fatigue strength and suppression of hydrogen embrittlement. The work was partly supported by Osawa Scientific Studies Grants Foundation.E of materials subjected to electric current and Joule heating has been studied by many researchers and fruitful results have been reported. In my presentation, crack problems in a conductive material are first discussed. The path-independent integral for an electric crack problem in a plate subjected to current is explained with its relations to Joule heating near the crack tip and the increase in electric resistance of the plate due to a unit crack extension. Regarding nondestructive evaluation of cracks, highly sensitive direct current potential drop technique, that is closely coupled probes potential drop (CCPPD) technique, is explained with its principle and superior characteristics for evaluation of closed cracks. Also evaluation of multiple cracks is mentioned. In the second, a topic in the field of micro and nano materials evaluation is explained, which is a subject of electrical failure of a metallic nanowire mesh due to Joule heating. Characteristic nature of sequential melting of nanowires in the mesh is explained for respective conditions of current control and voltage control. Next, electromigration (EM) phenomenon, which is atomic diffusion due to electron flow in high density, in metallic thin-film materials related to reliability of integrated circuits is discussed, where the effect of passivation on damage suppression is focused. Finally, fabrication of micro materials of wire and sphere is explained as utilization of EM, where the effect of temperature caused by Joule heating on the shape of formed micro material is mentioned. In addition, the other phenomena of atomic migration such as stress migration and ionic migration are discussed in comparison with EM from a few points of view. Electric field and Joule heating are connected with materials science and evaluation on many equipments, machines and structures. As written above, four topics related to these physical quantities are reviewed in this presentation.D the rapid evolution of material science, it remains difficult to deploy new polymers that are inadequate to meet the stringent demands of industrial membrane separations. Polymer membranes must be ultrapermeable, selective, and resistant to both physical aging, and plasticization. Polymers with intrinsic microporosity (PIMs) are ultrapermeable, yet vulnerable to physical aging and plasticization. Here we show that aging and plasticization in PIMs can be switched on and off through compatibility with a microporous polymer, porous aromatic frameworks (PAFs). By replacing bulky methyl groups with smaller hydro groups, we remove the ability of a PIM polymer matrix to interact with PAFs; accelerating both physical aging and plasticization. Meanwhile PAFs tailors physical aging and annihilates plasticization in the original methylated PIM via physical interactions at specific locations on the PIM polymer chains. This benefits hydrogen recovery at realistic operating conditions; enabling the implementation of polymer membranes as a stand-alone separation technology, a paradigm shift from existing hybrid methods.

Numerical Prediction of the Thermodynamic Properties of Ternary Al-Ni-Pd Alloys

Abstract Thermodynamic properties of ternary Al-Ni-Pd system, such as exGAlNPd, µAl(AlNiPd), µNi(AlNiPd) and µPd(AlNiPd) at 1,373 K, were predicted on the basis of thermodynamic properties of binary systems included in the investigated ternary system. The idea of predicting exGAlNiPd values was regarded as calculation of values of the exG function inside a certain area (a Gibbs triangle) unless all boundary conditions, that is values of exG on all legs of the triangle are known (exGAlNi, exGAlPd, exGNiPd). This approach is contrary to finding a function value outside a certain area, if the function value inside this area is known. exG and LAl,Ni,Pd ternary interaction parameters in the Muggianu extension of the Redlich–Kister formalism were calculated numerically using the Excel program and Solver. The accepted values of the third component xx differed from 0.01 to 0.1 mole fraction. Values of LAlNiPd parameters in the Redlich–Kister formula are different for different xx values, but values of thermodynamic functions: exGAlNiPd, µAl(AlNiPd), µNi(AlNiPd) and µPd(AlNiPd) do not differ significantly for different xx values. The choice of xx value does not influence the accuracy of calculations.

Hafnium Modified Aluminide Coatings Obtained by the CVD and PVD Methods

Zirconium, hafnium or platinum modification of NiAl phase increases the oxidation resistance of diffusion aluminide coatings. Small hafnium addition to aluminide coatings decreases the oxidation rate of nickel superalloys at 1100 °C.The paper presents comparison of structures of hafnium modified aluminide coatings deposited in two different ways on pure nickel. In the first way double layers of hafnium 3 μm thick and aluminum 3 μm thick were deposited by the EB-PVD on the nickel substrate. The double layers were subjected to diffusion treatment at 1050 °C for 6 h and 20 h. In the second method, a hafnium layer was deposited by the EB-PVD method, whereas aluminum was deposited by the CVD method. The obtained coatings were examined by the use of an optical microscope (microstructure and coating thickness) and a scanning electron microscope (chemical composition on the cross-section of the modified aluminide coating). Microstructures and phase compositions of coatings obtained by different methods differ significantly. Diffusion treatment for 6 h leads into formation of the Ni5Hf phase. The elongation of the diffusion time from 6 to 20 h decrease the volume fraction of the Ni5Hf phase. An aluminide coating deposited by the CVD method at 1050 °C at the nickel substrate with prior hafnium layer (3 μm thick) has a triple zone structure. An outer zone consists of the NiAl phase, a middle zone consists of the Ni3Al phase, and the Ni(Al) phase forms an inner zone, close to the substrate. An NiHf intermetallic phase is between the outer and the middle zone, whereas Ni3Hf is between the inner zone and the substrate.

Zirconium Modified Aluminide Coatings Obtained by the CVD Method

The paper presents the comparison of the structures of the zirconium modified aluminide coatings deposited on pure nickel by the CVD and method for different conditions, that is the gas flow and the time of deposition. The time of the aluminizing processes varied from 1.5 to 10 hours and the gas (HCl) flow varied from 0.4 to 1.4 l/min. Aluminum was deposited from the AlCl3 and zirconium from the ZrCl3 gas phases at 1040 oC. The obtained coatings were examined using an optical microscope (microstructure and coating thickness) a scanning electron microscope (chemical composition on the cross-section of the modified aluminide coating) and an XRD phase analyzer. Microstructures and phase compositions of coatings obtained at different process parameters do not differ significantly. In all cases, it is a triple zone structure. Chemical compositions of zones correspond to β-NiAl, γ’-Ni3Al and γ-Ni (Al) phases. The elongation of the time of zirconium-aluminizing process from 1.5 to 10 hours leads to the increase of the coating thickness from 30 to about 60 μm. The EDS analysis and concentration profiles of the cross-section of the coating showed the nickel outward diffusion from the substrate and the aluminum inward diffusion from the surface to the nickel substrate. In coatings deposited at a slow gas flow porosity was observed on the border between β-NiAl and γ’-Ni3Al layers. In coatings deposited at fast gas flow, zirconium does not form any inclusions but dissolves in the matrix. The Kirkendall porosity was not observed.