Spontaneous Formation of Stable Capillary Bridges for Firming Compact Colloidal Microstructures in Phase Separating Liquids: A Computational Study

Computer modeling and simulations are performed to investigate capillary bridges spontaneously formed between closely packed colloidal particles in phase separating liquids. The simulations reveal a self-stabilization mechanism that operates through diffusive equilibrium of two-phase liquid morphologies. Such mechanism renders desired microstructural stability and uniformity to the capillary bridges that are spontaneously formed during liquid solution phase separation. This self-stabilization behavior is in contrast to conventional coarsening processes during phase separation. The volume fraction limit of the separated liquid phases as well as the adhesion strength and thermodynamic stability of the capillary bridges are discussed. Capillary bridge formations in various compact colloid assemblies are considered. The study sheds light on a promising route to in-situ (in-liquid) firming of fragile colloidal crystals and other compact colloidal microstructures via capillary bridges

Pickering emulsions stabilized by hydrophilic nanoparticles: in situ surface modification by oil

We propose a novel route for the stabilization of oil-in-water Pickering emulsions using inherently hydrophilic nanoparticles. In the case of dialkyl adipate oils, in situ hydrophobisation of the particles by dissolved oil molecules in the aqueous phase enables stable emulsions to be formed. Emulsion stability is enhanced upon decreasing the chain length of the oil due to its increased solubility in the precursor aqueous phase. The oil thus acts like a surfactant in this respect in which hydrogen bonds form between the carbonyl group of the ester oil and the hydroxyl group on particle surfaces. The particles chosen include both fumed and precipitated anionic silica and cationic zirconia. Complementary experiments including relevant oil–water–solid contact angles and infra-red analysis of dried particles after contact with oil support the proposed mechanism

Solidification/stabilisation of soil contaminated with metal: a review

Solidification/stabilisation (S/S) is generically defined as a chemical and physical alteration technique of reducing the mobility as well as solubility of contaminants in wastes in order to convert them into chemically inert form. The technique is specifically developed to confine the movement of contaminants in wastes so that their concentrations in the surrounding environment (e.g. subsurface soil matrices and groundwater) will not exceed stipulated environmental regulatory levels. This technique necessitates application of cementitious materials such as cement which also provides a favorable solidification effect on the stabilised wastes so that the end product can be easily transported to disposal sites or reused as construction materials. This paper reviews the S/S technology as applied to contaminated soil treatment with emphasis on its chemical binder systems, mechanisms, interferences and post-treatment leaching tests. S/S is an important soil contamination remediation technology as evident by its simplicity, technical and cost-effectiveness

The effects of MgO, Na2O and SO3 on industrial clinkering process: phase composition, polymorphism, microstructure and hydration, using a multidisciplinary approach

Preprint publicado en: Materials Characterization Volume 155, September 2019, 109809The present investigation deals with how minor elements (their oxides: MgO, Na2O and SO3) in industrial kiln feeds affect (i) chemical reactions upon clinkering, (ii) resulting phase composition and microstructure of clinker, (iii) hydration process during cement production. Our results show that all these points are remarkably sensitive to the combination and interference effects between the minor chemical species mentioned above. Upon clinkering, all the industrial raw meals here used exhibit the same formation temperature and amount of liquid phase. Minor elements are preferentially hosted by secondary phases, such as periclase. Conversely, the growth rate of the main clinker phases (alite and belite) is significantly affected by the nature and combination of minor oxides. MgO and Na2O give a very fast C3S formation rate at T > 1450 K, whereas Na2O and SO3 boost C2S After heating, if SO3 occurs in combination with MgO and/or Na2O, it does not inihibit the C3S crystallisation as expected. Rather, it promotes the stabilisation of M1-C3S, thus indirectly influencing the aluminate content, too. MgO increseases the C3S amount and promotes the stabilisation of M3-C3S, when it is in combination with Na2O. Na2O seems to be mainly hosted by calcium aluminate structure, but it does not induce the stabilisation of the orhtorhombic polymorph, as supposed to occur. Such features play a key role in predicting the physicalmechanical performance of a final cement (i.e. rate of hydration and hardening) when used as a bulding material.The present study has been partly funded by the project PRIN 2017 (2017L83S77), of the Italian Ministry for Education, University and Research (MIUR)

Double walled carbon nanotube/polymer composites via in-situ nitroxide mediated polymerisation of amphiphilic block copolymers

Because of their unique physical, chemical, and structural properties, carbon nanotubes (CNT) are playing an increasingly important role in the development of new engineering materials [1]. Across many different applications, CNT/polymer composites have been extensively studied [2] S.B. Sinnot and R. Andrews, Carbon nanotubes: synthesis, properties, and applications, Crit Rev Solid State Mater Sci 26 (2001), pp. 145–249.[2]. The key problem for CNT/polymer composite elaboration is the dispersion, compatibilization, and stabilization of the CNT in the polymer matrix. To solve this problem, a structure with di-block copolymers, one with a good affinity to CNT (monomer M1), the other being the matrix (monomer M2), is proposed in this study, as shown on the two steps mechanism of Fig. 1

The Geometry of the Catalytic Active Site in [FeFe]-hydrogenases is Determined by Hydrogen Bonding and Proton Transfer

[FeFe]-hydrogenases are efficient metalloenzymes that catalyze the oxidation and evolution of molecular hydrogen, H2. They serve as a blueprint for the design of synthetic H2-forming catalysts. [FeFe]-hydrogenases harbor a six-iron cofactor that comprises a [4Fe-4S] cluster and a unique diiron site with cyanide, carbonyl, and hydride ligands. To address the ligand dynamics in catalytic turnover and upon carbon monoxide (CO) inhibition, we replaced the native aminodithiolate group of the diiron site by synthetic dithiolates, inserted into wild-type and amino acid variants of the [FeFe]-hydrogenase HYDA1 from Chlamydomonas reinhardtii. The reactivity with H2 and CO was characterized using in situ and transient infrared spectroscopy, protein crystallography, quantum chemical calculations, and kinetic simulations. All cofactor variants adopted characteristic populations of reduced species in the presence of H2 and showed significant changes in CO inhibition and reactivation kinetics. Differences were attributed to varying interactions between polar ligands and the dithiolate head group and/or the environment of the cofactor (i.e., amino acid residues and water molecules). The presented results show how catalytically relevant intermediates are stabilized by inner-sphere hydrogen bonding suggesting that the role of the aminodithiolate group must not be restricted to proton transfer. These concepts may inspire the design of improved enzymes and biomimetic H2-forming catalysts