Zeolite-based chiral ion-exchangers for chromatographic enantioseparations and potential applications in membrane separation processes.

Chiral resolution of racemic compounds represents an important task in research and development and, most importantly, in the large-scale production of pharmaceuticals. Zeolites, which are already frequently utilized for their unique properties, represent materials that can be used for the development of new chiral stationary phases for liquid chromatography, simulated moving bed or enantioselective membranes. The aim of this study was to modify a series of MWW zeolites by a chiral anion-exchange type selector thereby creating a chiral stationary phase for enantiomeric resolution of acidic compounds. To evaluate the applicability of the prepared chiral stationary phase in liquid chromatography, we used N-protected amino acids as model analytes. First, we tested the new sorbents preferential sorption using N-(3,5-dinitrobenzoyl)leucine. We observed outstanding sorption properties of a zeolite-based sorbent (MCM-36), which were comparable to spherical chromatographic silica. This particular material was subsequently packed into a chromatographic column, which was tested under polar organic mode HPLC conditions facilitating baseline resolution of 5 out of 8 N-protected amino acids. Although the chromatographic performance shows several drawbacks (high backpressure, low column efficiency), it clearly documents the potential of the novel materials in chiral separation. To the best of our knowledge, this is the first example of the preparation of the chiral stationary phase based on MWW zeolites ever.

Fatigue Crack Growth Rate Description of RF-Plasma-Sprayed Refractory Metals and Alloys.

A fitting method capable of describing the fatigue crack growth rate (FCGR) data in all stages of crack propagation by a simple Forman-style analytical formula was developed. To demonstrate its robustness, this method was used to quantify the fracture behavior of RF-plasma-sprayed W, Mo, W-Mo composite, and four selected Ni-based tungsten heavy alloys (WHA). The fitted FCGR parameters categorized the studied materials into two distinct sets. W, Mo, and W-Mo composite deposits made from inherently brittle refractory metals that contained a range of defects inherent to plasma spray process represented the first class. This class was characterized by low fracture toughness and a relatively wide range of fatigue crack growth thresholds. The second class of materials was represented by WHA. Here, the deposit defects were suppressed by liquid state diffusion that formed a typical WHA structure consisting of a Ni-rich matrix and large spherical W reinforcement particles. The WHA generally showed higher fatigue crack growth thresholds, but differed in fracture toughness values based on the W particle concentrations. The obtained fracture mechanical data represent a reference dataset of plasma-sprayed refractory materials, and their classification into groups clearly demonstrates the capabilities of the developed method to capture a wide range of different types of FCGR behavior.

Optically active polyimides with different thermal histories of their preparation.

Optically active linear polyimides and hyperbranched poly (amic acid-imide) were prepared by using procedures varying in particular in the maximum temperature employed in their synthesis. The two types of linear polyimides were based on 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 1,2-diaminocylohexane enantiomers or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 2,2'-diamino-1,1'-binaphthalene enantiomers. The amine-terminated hyperbranched poly (amic acid-imide) was prepared from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 4,4',4″-triaminotriphenylmethane, and its end groups were modified with the chiral selectors N-acetyl-D-phenylalanine or N-acetyl-L-phenylalanine. The final structure of the products was analyzed by IR spectroscopy, and their optical activity was evaluated and confirmed by polarimetry or circular dichroism.

Beneficial osseointegration effect of hydroxyapatite coating on cranial implant - FEM investigation.

A firm connection of the bone-implant-fixation system is of utmost importance for patients with cranial defects. In order to improve the connection reliability, the current research focuses on finding the optimal fixation method, as well as selection of the implant manufacturing methods and the used materials. For the latter, implementation of bioactive materials such as hydroxyapatite or other calcium phosphates has also been considered in the literature. The aim of this study was to investigate the effect of gradual osseointegration on the biomechanical performance of cranial Ti6Al4V implants with a deposited HA coating as the osseointegration agent. This effect was assessed by two different computational approaches using finite element method (FEM) modeling. The values of key input parameters necessary for FEM were obtained from experimental plasma spray deposition of HA layers onto Ti6Al4V samples. Immediately upon implantation, the HA layer at the bone-implant contact area brought only a slight decrease in the values of von Mises stress in the implant and the micro-screws when compared to a non-coated counterpart; importantly, this was without any negative trade-off in other important characteristics. The major benefit of the HA coatings was manifested upon the modeled osseointegration: the results of both approaches confirmed a significant reduction of investigated parameters such as the total implant displacements (reduced from 0.050 mm to 0.012 mm and 0.002 mm while using Approach I and II, respectively) and stresses (reduced from 52 MPa to 10 MPa and 1 MPa) in the implanted components in comparison to non-coated variant. This is a very promising result for potential use of thermally sprayed HA coatings for cranial implants.

Baghdadite coating formed by hybrid water-stabilized plasma spray for bioceramic applications: Mechanical and biological evaluations.

This work studies the mechanical and biological properties of Baghdadite (BAG, Ca3ZrSi2O9) coating manufactured on Ti6Al4V substrates by hybrid water-stabilized plasma spray (WSP-H). Hydroxyapatite (HAp, Ca10(PO4)6(OH)2) coating was produced by gas-stabilized atmospheric plasma spray and used as a reference material. Upon spraying, the BAG coating exhibited lower crystallinity than the HAp coating. Mechanical testing demonstrated superior properties of the BAG coating: its higher hardness, elastic modulus as well as a better resistance to scratch and wear. In the cell viability study, the BAG coating presented better human osteoblast attachment and proliferation on the coating surface after three days and seven days compared to the HAp counterpart. Furthermore, the gene expression study of human osteoblasts indicated that the BAG coating surface showed higher expression levels of osteogenic genes than those on the HAp coating. Overall, this study indicates that enhanced mechanical and bioactive properties can be achieved for the BAG coating compared to the benchmark HAp coating. It is therefore concluded here that the BAG coating is a potential candidate for coating orthopedic implants.

Desalination Performance Assessment of Scalable, Multi-Stack Ready Shock Electrodialysis Unit Utilizing Anion-Exchange Membranes.

Incumbent electromembrane separation processes, including electrodialysis (ED) and electrodeionization (EDI), provide competitive techniques for desalination, selective separation, and unique solutions for ultra-pure water production. However, most of these common electrochemical systems are limited by concentration polarization and the necessity for multistep raw water pre-treatment. Shock electrodialysis (SED) utilizes overlimiting current to produce fresh, deionized water in a single step process by extending ion depleted zones that propagate through a porous medium as a sharp concentration gradient or a shock wave. So far, SED has been demonstrated on small scale laboratory units using cation-exchange membranes. In this work, we present a scalable and multi-stack ready unit with a large, 5000 mm2 membrane active area designed and constructed at the Technical University of Liberec in cooperation with MemBrain s.r.o. and Mega a.s. companies (Czechia). We report more than 99% salt rejection using anion-exchange membranes, depending on a dimensionless parameter that scales the constant applied current by the limiting current. It is shown that these parameters are most probably associated with pore size and porous media chemistry. Further design changes need to be done to the separator, the porous medium, and other functional elements to improve the functionality and energy efficiency.

Characterization of bonding quality of a cold-sprayed deposit by laser resonant ultrasound spectroscopy.

Resonant ultrasound spectroscopy was utilized to determine the mechanical properties of a planar interface between a cold-sprayed iron deposit and an aluminum alloy substrate. The measurements were done at room temperature and with a thermal cycle from room temperature to 500 °C. The properties of the interface were assessed by analyzing the resonant frequencies of a sandwich-like sample by means of a numerical model. While the as-sprayed deposit at the room temperature exhibited a perfect adhesion to the substrate, the thermal cycle led to deterioration of the properties due to precipitation of FeAl3 along the interface and subsequent cracking. The modal analysis enabled localization of the damage zone along the interfaces and simulating its temperature evolution during the cooling run.

Improvement of Mechanical Properties of Plasma Sprayed Al2O3-ZrO2-SiO2 Amorphous Coatings by Surface Crystallization.

Ceramic Al2O3-ZrO2-SiO2 coatings with near eutectic composition were plasma sprayed using hybrid water stabilized plasma torch (WSP-H). The as-sprayed coatings possessed fully amorphous microstructure which can be transformed to nanocrystalline by further heat treatment. The amorphous/crystalline content ratio and the crystallite sizes can be controlled by a specific choice of heat treatment conditions, subsequently leading to significant changes in the microstructure and mechanical properties of the coatings, such as hardness or wear resistance. In this study, two advanced methods of surface heat treatment were realized by plasma jet or by high energy laser heating. As opposed to the traditional furnace treatments, inducing homogeneous changes throughout the material, both approaches lead to a formation of gradient microstructure within the coatings; from dominantly amorphous at the substrate-coating interface vicinity to fully nanocrystalline near its surface. The processes can also be applied for large-scale applications and do not induce detrimental changes to the underlying substrate materials. The respective mechanical response was evaluated by measuring coating hardness profile and wear resistance. For some of the heat treatment conditions, an increase in the coating microhardness by factor up to 1.8 was observed, as well as improvement of wear resistance behaviour up to 6.5 times. The phase composition changes were analysed by X-ray diffraction and the microstructure was investigated by scanning electron microscopy.

Nitrogen Interstitial Alloying of CoCrFeMnNi High Entropy Alloy through Reactive Powder Milling.

The present work is focused on the synthesis of CoCrFeMnNi high entropy alloy (HEA) interstitially alloyed with nitrogen via powder metallurgy routes. Using a simple method, nitrogen was introduced to the HEA from the protective N2 gas atmosphere during mechanical alloying (MA) processing. The lattice parameter and amount of nitrogen in HEA were observed to be linearly proportional to the milling duration. The limited solubility of nitrogen in the main face centered cubic (FCC) phase resulted in the in-situ formation of nitrides and, accordingly, significant increase in the hardness values. It has been shown that fabrication of such nitrogen-doped HEA bulk materials can be conveniently achieved by a simple combination of MA + spark plasma sintering processes, without the need for adding nitrogen from other sources.

Towards near-permanent CoCrMo prosthesis surface by combining micro-texturing and low temperature plasma carburising.

An advanced surface engineering process combining micro-texture with a plasma carburising process was produced on CoCrMo femoral head, and their tribological properties were evaluated by the cutting-edge pendulum hip joint simulator coupled with thin film colorimetric interferometry. FESEM and GDOES showed that precipitation-free C S-phase with a uniform case depth of 10µm was formed across the micro-textures after duplex treatment. Hip simulator tests showed that the friction coefficient was reduced by 20% for micro-metre sized texture, and the long-term tribological property of microtexture was enhanced by the C-supersaturated crystalline microstructure formed on the surface of duplex treated CoCrMo, thereby enhancing biotribological durability significantly. In-situ colorimetric interferometry confirmed that the maximum film thickness around texture area was 530nm, indicating that the additional lubricant during sliding motion might provide exceptional bearing life.

Fabrication and characterization of DLC coated microdimples on hip prosthesis heads.

Diamond like carbon (DLC) is applied as a thin film onto substrates to obtain desired surface properties such as increased hardness and corrosion resistance, and decreased friction and wear rate. Microdimple is an advanced surface modification technique enhancing the tribological performance. In this study, DLC coated microdimples were fabricated on hip prosthesis heads and their mechanical, material and surface properties were characterized. An Electro discharge machining (EDM) oriented microdrilling was utilized to fabricate a defined microdimple array (diameter of 300 µm, depth of 70 µm, and pitch of 900 µm) on stainless steel (SS) hip prosthesis heads. The dimpled surfaces were then coated by hydrogenated amorphous carbon (a-C:H) and tetrahedral amorphous carbon (Ta-C) layers by using a magnetron sputtering technology. A preliminary tribology test was conducted on these fabricated surfaces against a ceramic ball in simulated hip joint conditions. It was found that the fabricated dimples were perpendicular to the spherical surfaces and no cutting-tools wear debris was detected inside the individual dimples. The a-C:H and Ta-C coatings increased the hardness at both the dimple edges and the nondimpled region. The tribology test showed a significant reduction in friction coefficient for coated surfaces regardless of microdimple arrays: the lowest friction coefficient was found for the a-C:H samples (µ = 0.084), followed by Ta-C (µ = 0.119), as compared to the SS surface (µ = 0.248).