Combination of Reaction and Separation in Heterogeneous Catalytic Hydrogenation of Ethylformate

Continuous hydrogenation reaction of ethyl benzoylformate was studied over a (–)‐cinchonidine (CD)‐modified Pt/Al₂O₃ catalyst. The catalyst showed a good stability, and high enantioselectivity was achieved in the fixed‐bed reactor. Chromatographic separation of (R)‐ and (S)‐ethyl mandelate originating from a post‐continuous hydrogenation reaction of ethyl benzoylformate over the (–)‐CD‐modified Pt/Al₂O₃ catalyst was investigated in the same reaction mixture. A commercial column filled with a chiral selector resin was chosen as a perspective preparative‐scale adsorbent. Since adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post‐reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug‐flow model with linear driving force approximation.     

A simple model for the semicontinuous heterophase polymerization: Ethyl methacrylate as a case example

A simple but comprehensive model considering homogeneous and micellar nucleation, coagulation, entry of radicals to particles and to micelles and radicals' exit from particles, is presented. The model is validated, in a starved semicontinuous heterophase polymerization of ethyl methacrylate, at three monomer addition rates. The model accurately describes the overall and instantaneous conversion, the average particle density and diameter, and the number and weight average molar masses evolutions over time. It is found that even though the average number of radicals is much smaller than 0.5, the system is not 0-1. An empirical function was used to describe the gel effect. The homogeneous nucleation was the prevailing mechanism for particle formation and large exit rates of radicals were observed. POLYM. ENG. SCI., 60: 223–232, 2019. © 2019 Society of Plastics Engineers     

Energy-efficient operation of indirect adiabatic data center cooling systems via Newton-like phasor extremum seeking control

This paper considers the problem of optimizing the operation of Indirect Adiabatic Cooling (IAC) systems with application to data centers. Optimal operation is achieved when the required cooling demand is satisfied at the minimum energy cost. For this purpose, we design a supervisory control system, where the higher layer determines the optimal set-points for the local controllers by employing an Extremum Seeking Control (ESC) scheme. In particular, we consider a Newton-like phasor ESC, which augments the derivative estimator underlying the phasor approach to capture also the Hessian of the plant index and then it uses these estimates to steer the system along a Newton-like direction. The effectiveness of the considered approach is tested in simulation by exploiting a Matlab-based simulation environment including an IAC system and a computer room.     

A radiomics pipeline dedicated to Breast MRI: validation on a multi-scanner phantom study

Magnetic Resonance Materials in Physics, Biology and Medicine - Quantitative analysis in MRI is challenging due to variabilities in intensity distributions across patients, acquisitions and...     

Physical,mechanical, and biological properties of electrophoretically deposited lithium-doped calcium phosphates

In the present work, the preparation of sintered lithium-doped tricalcium phosphates was studied, along with their physical, mechanical, and biological properties. Calcium phosphates were shaped via the use of electrophoretic deposition (EPD), using colloidally milled dispersions of hydroxyapatite (HAp) particles. The dispersions were stabilised with monochloroacetic acid. Lithium was incorporated into the structure via an addition of lithium chloride, which also served to optimise the deposition process. The dispersions were milled colloidally for periods of 0–48 h. The colloidal milling resulted in two effects: i) disintegration of the commercial HAp powder (10 µm) agglomerates, ii) unimodal distribution of the HAp particles (~ 170 nm). The fine particles of the milled HAp dispersions accelerated the deposition rate, and increased the mass of the deposit. The reduced size of the initial particles, owed to the milling, led to the superior arrangement of the particles during deposition and to reduced porosity after sintering (1050–1250 °C). The HAp decomposed into tricalcium phosphate phases during sintering. At a sintering temperature of 1250 °C, grain growth occurred, which consequently resulted in a slight degradation of the mechanical properties (reduction in hardness and Young's modulus). In contrast, the hardness and Young's modulus increased as the dispersion milling time increased (smaller grain size after sintering); however, the fracture toughness did not change. The results of the biological testing confirmed the bioactivity of the material through the growth of the apatite layer in the simulated body fluid (SBF), and the biodegradation of the prepared materials in the Tris-HCl solution. With regard to the preparation of compact lithium-doped tricalcium phosphates, the best results were obtained in the case of the sample that utilised the dispersion that was milled for 48 h, and was sintered at 1050 °C.     

Robocast zirconia-toughened alumina scaffolds: Processing,structural characterisation and interaction with human primary osteoblasts

Zirconia-toughened alumina (ZTA) is the gold-standard ceramic in hip arthroplasty, but still lacks direct osseointegration and a metal shell, often coated with a bioactive layer, is currently required. The latter could potentially be replaced by a thinner, architectured ZTA layer, thereby allowing for larger acetabular components, with larger range of motion and lower dislocation risk. Robocasting may be an adequate technique to fabricate the architectured layer. Therefore, as a first step, this study aimed to produce ZTA scaffolds (3D-ZTA) by robocasting and assess their in vitro response. Shape retention was achieved by using a stable, well-dispersed, high solid loading ink injected in acid pH waterbath. 3D-ZTA exhibit regularly spaced microporous, rough struts and fully interconnected macroporosity. Human primary osteoblasts were homogenously distributed inside 3D-ZTA and showed increased osteogenic marker expression compared to 2D-ZTA control. Further work will focus on optimizing scaffold design to improve cell retention and extracellular matrix maturation.     

Mechanical behaviour of porous lanthanide oxide microspheres: Experimental investigation and numerical simulations

Actinide oxide microspheres are considered as promising substituents to powder precursors for the production of ceramic pellets of nuclear fuel or targets. Porous microspheres of sub-millimetric size are synthesised using the Weak Acid Resin process. Controlling their microstructure and their mechanical properties is essential to predict the microstructure of green compacts and sintered pellets. Here, cerium and gadolinium are used to mimic actinides as metal cation. Single microspheres are crushed experimentally using a micropress in a Scanning Electron Microscope (SEM) to investigate their mechanical properties and visualise their fracture behaviour. The results are compared to numerical simulations based on the Discrete Element Method (DEM). In DEM, a microsphere is modelled as an assembly of bonded spheres representing aggregates. Bonds may fracture in tension or shear. A limited number of material parameters (aggregate elastic modulus, bond strength) are sufficient for the accurate simulation of the fracture behaviour of a microsphere.     

Adsorption behavior and kinetics of H2S on a potassium-promoted hydrotalcite

Adsorption of H₂S and the influence of steam on its adsorption capacity and kinetics were studied on a commercial potassium-promoted hydrotalcite. The sorbent shows a very high cyclic working capacity for H₂S compared to CO₂ and H₂O, even at lower partial pressures and at different operating temperatures ranging between 300 and 500 °C. The operating temperature does not significantly influence the cyclic working capacity for half-cycle times of 30 min. The adsorption mechanism, however, changes at higher temperatures. At lower temperatures (300 °C) a fast adsorption with a fast approach to steady state was observed. At higher operating temperatures, H₂S reacts with the hydrotalcite structure, forming strongly bonded sulfuric species on the sorbent. When using dry regeneration conditions, the first cycles in cyclic operation at higher temperatures show a significantly higher adsorption of H₂S (especially the first cycle), which cannot be desorbed during regeneration with N₂. After the first fast initial adsorption rate a continuous slow adsorption of H₂S occurs, probably caused by a surface reaction between H₂S and the hydrotalcite structure. This reaction is, however, reversible if steam is used.The adsorption mechanism for H₂S and H₂O was determined using multiple cyclic experiments comparable to previous studies performed for CO₂ and H₂O adsorption. It is evident that the adsorption mechanism developed for CO₂ on the same sorbents is also valid for H₂S, indicating that the developed mechanism is consistent for sour gas adsorption on this type of sorbents. The cyclic working capacity can be significantly increased if steam is used during the regeneration step of the sorbent. The mechanistic model developed for the adsorption of CO₂ and H₂O was successfully validated with more than 160 different TGA experiments. An operating temperature of 400 °C seems to be optimal to achieve a high cyclic working capacity for H₂S, because at higher temperatures the regeneration of the formed sulfuric species seems to be hindered resulting in a significant decrease in the cyclic working capacity.     

Reliability of design approaches for axially loaded offshore piles and its consequences with respect to the North Sea

In the near future, several offshore wind farms are planned to be built in the North Sea. Therefore, jacket and tripod constructions with mainly axially loaded piles are suitable as support structures. The current design of axial bearing resistance of these piles leads to deviant results regarding the pile resistance when different design methods are adopted. Hence, a strong deviation regarding the required pile length must be addressed. The reliability of a design method can be evaluated based on a model error which describes the quality of the considered design method by comparing measured and predicted pile bearing resistances. However, only few pile load tests are reported with regard to the boundary conditions in the North Sea. This paper presents 6 large-scale axial pile load tests which were incorporated within a new model error approach for the current design methods used for the axial bearing resistance, namely API Main Text method and cone penetration test (CPT)-based design methods, such as simplified ICP-05, offshore UWA-05, Fugro-05 and NGI-05 methods. Based on these new model errors, a reliability-based study towards the safety was conducted by performing a Monte-Carlo simulation. In addition, consequences regarding the deterministic pile design in terms of quality factors were evaluated. It is shown that the current global safety factor (GSF) prescribed and the partial safety factors are only valid for the API Main Text and the offshore UWA-05 design methods; whereas for the simplified ICP-05, Fugro-05 and NGI-05 design methods, an increase in the required embedded pile length and thus in the GSF up to 2.69, 2.95 and 3.27, respectively, should be considered to satisfy the desired safety level according to DIN EN 1990 of β = 3.8. Further, quality factors for each design method on the basis of all reliability-based design results were derived. Hence, evaluation of each design method regarding the reliability of the pile capacity prediction is possible.