On-Chip Photonic Detection Techniques for Non-Invasive In Situ Characterizations at the Microfluidic Scale.

Microfluidics has emerged as a robust technology for diverse applications, ranging from bio-medical diagnostics to chemical analysis. Among the different characterization techniques that can be used to analyze samples at the microfluidic scale, the coupling of photonic detection techniques and on-chip configurations is particularly advantageous due to its non-invasive nature, which permits sensitive, real-time, high throughput, and rapid analyses, taking advantage of the microfluidic special environments and reduced sample volumes. Putting a special emphasis on integrated detection schemes, this review article explores the most relevant advances in the on-chip implementation of UV-vis, near-infrared, terahertz, and X-ray-based techniques for different characterizations, ranging from punctual spectroscopic or scattering-based measurements to different types of mapping/imaging. The principles of the techniques and their interest are discussed through their application to different systems.

A multi-analytical methodology for the characterization of industrial samples of spent Ni-MH battery powders.

A multi-analytical methodology is implemented to characterize several sieving fractions of industrial samples of Black Mass (BM) powders originating from the thermo-mechanical treatment of cylindrical and prismatic-type spent nickel metal-hydride (Ni-MH) batteries. Elemental analyses of 17 elements (including C and O) indicate that the elemental composition of the powders (greater than93 %wt) does not depend on the battery type nor on the sieving fraction. XRD analyses evidence several phases (including Ni, NiO, CeO2 and C) but their quantification is not possible. Beyond these standard characterisations, magnetic susceptibility measurements demonstrate that the amount of metallic nickel versus nickel oxide increases with the sieving fraction, and that powders from prismatic-type batteries contain twice as much metallic nickel than cylindrical ones. Thanks to statistical analysis (based on clustering algorithms) of an electron probe µ-analysis (EPMA) compositional map, the complete methodology allows us to propose a full phase distribution for the BM particles. Three types of particles are identified and quantified. They originate from the partial oxidation of the battery components (anode active mass, anode current collector, cathode active mass and cathode current collector). The whole picture highlights the joint importance of battery ageing mechanisms, thermal deactivation and BM sieving steps on powder composition.

Performance of green antiscalants and their mixtures in controlled calcium carbonate precipitation conditions reproducing industrial cooling circuits.

Cooling circuits in many industrial sectors are faced with daily issues of scaling. One preventive treatment consists in injecting a polymer additive in the circuit to inhibit precipitation of calcium carbonate. Among the used additives, very few are "green" and the efficiency of new candidates are difficult to test directly in industrial conditions. The present study compared performance between two "green" polymer additives, polyaspartic acid (PASP) and polyepoxysuccinic acid (PESA), versus a traditional gold-standard, homopolymer of acrylic acid (HA) in a laboratory scale set-up designed to be representative of an industrial circuit. Results showed that HA and PASP are both inhibitors of calcium carbonate crystal growth. This inhibition resulted from adsorption of polymer additive molecules on the crystal surface, as confirmed by adsorption measurement. Under the same conditions, PESA additive, showed a high rate of calcium ion complexation and a very low inhibition rate. But, PESA was shown to be a nucleation delayer. Mixing PESA and PASP can gave nucleation retardation of about 19 h, which approximates the 24 h water residence time in industrial cooling circuits, as well as almost 90% calcium carbonate crystal growth inhibition. This synergy offers promising prospects for preventive scaling treatment.

Leaching Mechanisms of Industrial Powders of Spent Nickel Metal Hydride Batteries in a Pilot-Scale Reactor.

In view of a sustainable recycling process, the leaching mechanisms of nickel and rare-earth elements (REEs) contained within industrial samples of spent nickel metal hydride battery powders were investigated in HCl and H2 SO4 , under mild temperature (25-60 °C) and pH (3-5.5). First, in-depth characterization of the heterogeneous battery powder was carried out with powder XRD, SEM, electron probe microanalyzer wavelength-dispersive spectroscopy (EPMA-WDS) quantitative analyses of individual particles, and inductively coupled plasma optical emission spectrometry (ICP-OES) elemental analysis. An unusual result is the identification of particles that exhibit a core-shell structure, which is related to anode active mass aging mechanisms. Then, a leaching study in a 10 L pilot-scale reactor demonstrated the selective dissolution of REEs, with respect to nickel, at pH 3, which is attributed to 1) the kinetic inhibition of nickel metal dissolution, and 2) the specific core-shell structure of aged mischmetal particles. Furthermore, the use of H2 SO4 led to coprecipitation of lanthanide-alkali double sulfates and nickel salts.

Coupling High Throughput Microfluidics and Small-Angle X-ray Scattering to Study Protein Crystallization from Solution.

In this work, we propose the combination of small-angle X-ray scattering (SAXS) and high throughput, droplet based microfluidics as a powerful tool to investigate macromolecular interactions, directly related to protein solubility. For this purpose, a robust and low cost microfluidic platform was fabricated for achieving the mixing of proteins, crystallization reagents, and buffer in nanoliter volumes and the subsequent generation of nanodroplets by means of a two phase flow. The protein samples are compartmentalized inside droplets, each one acting as an isolated microreactor. Hence their physicochemical conditions (concentration, pH, etc.) can be finely tuned without cross-contamination, allowing the screening of a huge number of saturation conditions with a small amount of biological material. The droplet flow is synchronized with synchrotron radiation SAXS measurements to probe protein interactions while minimizing radiation damage. To this end, the experimental setup was tested with rasburicase (known to be very sensitive to denaturation), proving the structural stability of the protein in the droplets and the absence of radiation damage. Subsequently weak interaction variations as a function of protein saturation was studied for the model protein lysozime. The second virial coefficients (A2) were determined from the X-ray structure factors extrapolated to the origin. A2 obtained values were found to be in good agreement with data previously reported in literature but using only a few milligrams of protein. The experimental results presented here highlight the interest and convenience of using this methodology as a promising and potential candidate for studying protein interactions for the construction of phase diagrams.

Structure of the calcium pyrophosphate monohydrate phase (Ca2P2O7·H2O): towards understanding the dehydration process in calcium pyrophosphate hydrates.

Calcium pyrophosphate hydrate (CPP, Ca(2)P(2)O(7) · nH2O) and calcium orthophosphate compounds (including apatite, octacalcium phosphate etc.) are among the most prevalent pathological calcifications in joints. Even though only two dihydrated forms of CPP (CPPD) have been detected in vivo (monoclinic and triclinic CPPD), investigations of other hydrated forms such as tetrahydrated or amorphous CPP are relevant to a further understanding of the physicochemistry of those phases of biological interest. The synthesis of single crystals of calcium pyrophosphate monohydrate (CPPM; Ca(2)P(2)O(7) · H2O) by diffusion in silica gel at ambient temperature and the structural analysis of this phase are reported in this paper. Complementarily, data from synchrotron X-ray diffraction on a CPPM powder sample have been fitted to the crystal parameters. Finally, the relationship between the resolved structure for the CPPM phase and the structure of the tetrahydrated calcium pyrophosphate ß phase (CPPT-ß) is discussed.

Optimization of struvite precipitation in synthetic biologically treated swine wastewater--determination of the optimal process parameters.

A sustainable way to recover phosphorus (P) in swine wastewater involves a preliminary step of P dissolution followed by the separation of particulate organic matter. The next two steps are firstly the precipitation of struvite crystals done by adding a crystallization reagent (magnesia) and secondly the filtration of the crystals. A design of experiments with five process parameters was set up to optimize the size of the struvite crystals in a synthetic swine wastewater. More than 90% of P was recovered as large crystals of struvite in optimal conditions which were: low Mg:Ca ratio (2.25:1), the leading parameter, high N:P ratio (3:1), moderate stirring rate (between 45 and 90 rpm) and low temperature (below 20 °C).These results were obtained despite the presence of a large amount of calcium and using a cheap reactant (MgO). The composition of the precipitates was identified by Raman analysis and solid dissolution. Results showed that amorphous calcium phosphate (ACP) co-precipitated with struvite and that carbonates were incorporated with solid fractions.