Tailoring Waterborne Coating Rheology with Hydrophobically Modified Ethoxylated Urethanes (HEURs): Molecular Architecture Insights Supported by CG-MD Simulations.

A novel investigation of the effects of the hydrophilic and hydrophobic segments of hydrophobically modified ethoxylated urethanes (HEURs) on the rheological properties of their aqueous solutions, latex-based emulsions, and waterborne paints is demonstrated. Different HEUR thickeners were produced by varying the poly(ethylene glycol) (PEG) molecular weight and terminal hydrophobic size. Results reveal that the strength of hydrophobic associations and, consequently, the rheological properties of HEUR formulations can be effectively controlled by modifying the structure of the hydrophobic segment, specifically, the combination of diisocyanate and monoalcohol. This allows for the on-demand attainment of diverse rheological behaviors ranging from predominantly Newtonian profiles exhibiting lower viscosities to markedly pseudoplastic behaviors with significantly higher viscosities. The length of the hydrophilic group appears to affect viscosity only marginally up to a molecular weight of 23,000 g/mol, with more notable effects at 33,000 g/mol. Additionally, it was indicated that the rheological responses observed in water solutions provide a reliable forecast of their behavior in latex-based emulsions and waterborne paints. Coarse-grained molecular dynamics (CG-MD) simulations were also applied to gain insight into HEUR micelle dynamics in aqueous solutions. Guided by the DBSCAN algorithm, the simulations successfully captured the concentration-dependent behavior and the impact of hydrophilic chain length, aligning with the experimental viscosity trends. Various metrics were employed to provide a comprehensive analysis of the micellization process, including the hydrophobic cluster volume, the total micellar volume, the aggregation number, and the number of chains interconnecting with other micelles.

Valorizing the Steel Industry Off-Gases: Proof of Concept and Plantwide Design of an Electrified and Catalyst-Free Reverse Water-Gas-Shift-Based Route to Methanol.

Conversion of steel industry off-gases to value-added chemicals enabled by renewable electricity can significantly reduce the environmental burden of the steelmaking process. Herein, we demonstrate that CO2 reduction by H2, both contained in steel mill off-gases, to form syngas via the reverse water-gas-shift reaction is effectively performed by nanosecond pulsed discharges at atmospheric pressure. The experimental results suggest the following: (i) An optimum interelectrode distance exists, maximizing CO2 conversion. (ii) CO2 conversion at constant SEI follows a nonmonotonic trend with H2 excess. CO2 conversion increases with H2 excess up to H2:CO2 = 3:1 upon shifting the chemical equilibrium. At larger H2:CO2, both gas cooling, promoted by the high H2 content, and hindered CO2 collisions in a highly diluted stream hamper CO2 conversion. (iii) SEI enhances CO2 conversion, but the effect decreases with increasing SEI due to equilibrium limitations. A stoichiometric H2:CO2 feed ratio in the plasma reactor is recommended for higher energy efficiency. Intensifying MeOH productivity via SEI elevation is not advised as a 2-fold SEI increase results only in 17% higher MeOH throughput.

Understanding the ultrasound field of high viscosity mixtures: Experimental and numerical investigation of a lab scale batch reactor.

In this work, mixtures of increasing viscosity (from 0.9 to ≈720 mPas) are sonicated directly using an ultrasonic horn at 30 kHz to investigate the effect of viscosity on the ultrasound field both from an experimental and numerical point of view. The viscosity of the mixtures is modified by preparing water-polyethylene glycol solutions. The impact of the higher viscosity on the acoustic pressure distribution is studied qualitatively and semi-quantitatively using sonochemiluminescence. The velocity of light scattering particles added in the mixtures is also explored to quantify acoustic streaming effects using Particle Image Velocimetry (PIV). A numerical model is developed that is able to predict cavitationally active zones accounting for both thermoviscous and cavitation based attenuation. The results show that two cavitation zones exist: one directly under the horn tip and one around the part of the horn body that is immersed in the liquid. The erosion patterns on aluminum foil confirm the existence of both zones. The intensity of the cavitationally active zones decreases considerably with increasing viscosity of the solutions. A similar reduction trend is observed for the velocity of the particles contained in the jet directly under the tip of the horn. Less erratic flow patterns relate to the high viscosity mixtures tested. Finally, two numerical models were made combining different boundary conditions related to the ultrasonic horn. Only the model that includes the radial horn movements is able to qualitatively predict well the location of the cavitation zones and the decrease of the zones intensity, for the highest viscosities studied. The current findings should be taken into consideration in the design and modelling phase of horn based sonochemical reactors.

Insight Into Solventless Production of Hydrophobically Modified Ethoxylated Urethanes (HEURs): The Role of Moisture Concentration, Reaction Temperature, and Mixing Efficiency.

In this work, we report for the first time on the influence of the quality of reactants and reaction conditions on the production of hydrophobically modified ethoxylated urethanes (HEURs) and selected prepolymers without the use of solvents. We show that the polyol water concentration is detrimental to the progress of the main urethane forming reaction, confirming the necessity of carefully drying the reactants below 1000 ppm to suppress the consumption of diisocyanate toward urea during HEUR synthesis. Increasing the mixing speed (≈30 to 750 rpm), reaction temperature (80-110 °C), and catalyst concentration (0.035-2.1 wt % bismuth carboxylate) can significantly increase the rate of molecular weight buildup, but their effect decreases with time as the bulk viscosity increases and mixing limitations eventually take over, leading to the Weissenberg effect and chain growth termination. Consequently, for the selected formulation, the maximum product molecular weight attained lies in the range of ≈20 000-22 000 g/mol, irrespective of the specific process conditions applied.

Applications of Artificial Intelligence and Machine Learning Algorithms to Crystallization.

Artificial intelligence and specifically machine learning applications are nowadays used in a variety of scientific applications and cutting-edge technologies, where they have a transformative impact. Such an assembly of statistical and linear algebra methods making use of large data sets is becoming more and more integrated into chemistry and crystallization research workflows. This review aims to present, for the first time, a holistic overview of machine learning and cheminformatics applications as a novel, powerful means to accelerate the discovery of new crystal structures, predict key properties of organic crystalline materials, simulate, understand, and control the dynamics of complex crystallization process systems, as well as contribute to high throughput automation of chemical process development involving crystalline materials. We critically review the advances in these new, rapidly emerging research areas, raising awareness in issues such as the bridging of machine learning models with first-principles mechanistic models, data set size, structure, and quality, as well as the selection of appropriate descriptors. At the same time, we propose future research at the interface of applied mathematics, chemistry, and crystallography. Overall, this review aims to increase the adoption of such methods and tools by chemists and scientists across industry and academia.

Glycerol: An Optimal Hydrogen Source for Microwave-Promoted Cu-Catalyzed Transfer Hydrogenation of Nitrobenzene to Aniline.

The search for sustainable alternatives for use in chemical synthesis and catalysis has found an ally in non-conventional energy sources and widely available green solvents. The use of glycerol, an abundant natural solvent, as an excellent "sacrificial" hydrogen source for the copper-catalyzed microwave (MW)-promoted transfer hydrogenation of nitrobenzene to aniline has been investigated in this work. Copper nanoparticles (CuNPs) were prepared in glycerol and the efficacy of the glycerol layer in mediating the interaction between the metal active sites has been examined using HRTEM analyses. Its high polarity, low vapor pressure, long relaxation time, and high acoustic impedance mean that excellent results were also obtained when the reaction media was subjected to ultrasound (US) and MW irradiation. US has been shown to play an important role in the process via its ability to enhance CuNPs dispersion, favor mechanical depassivation and increase catalytic active surface area, while MW irradiation shortened the reaction time from some hours to a few minutes. These synergistic combinations promoted the exhaustive reduction of nitrobenzene to aniline and facilitated the scale-up of the protocol for its optimized use in industrial MW reactors.

On the Effect of Secondary Nucleation on Deracemization through Temperature Cycles.

Herein, the pivotal role of secondary nucleation in a crystallization-enhanced deracemization process is reported. During this process, complete and rapid deracemization of chiral conglomerate crystals of an isoindolinone is attained through fast microwave-assisted temperature cycling. A parametric study of the main factors that affect the occurrence of secondary nucleation in this process, namely agitation rate, suspension density, and solute supersaturation, confirms that an enhanced stereoselective secondary nucleation rate maximizes the deracemization rate. Analysis of the system during a single temperature cycle showed that, although stereoselective particle production during the crystallization stage leads to enantiomeric enrichment, undesired kinetic dissolution of smaller particles of the preferred enantiomer occurs during the dissolution step. Therefore, secondary nucleation is crucial for the enhancement of deracemization through temperature cycles and as such should be considered in further design and optimization of this process, as well as in other temperature cycling processes commonly applied in particle engineering.

Applications of ultrasound to chiral crystallization, resolution and deracemization.

Industrial synthesis of enantiopure compounds is nowadays heavily based on the separation of racemates through crystallization processes. Although the application of ultrasound in solution crystallization processes (sonocrystallization) has become a promising emerging technology, offering several benefits (e.g. reduction of the induction time and narrowing of the metastable zone width, control over the product size, shape and polymorphic modification), little attention has been paid so far to the effects of ultrasound on chiral crystallization processes. Several recent studies have reported on the application of acoustic energy to crystallization processes that separate enantiomers, ranging from classical (diastereomeric) resolution and preferential crystallization to new and emerging processes such as attrition-enhanced deracemization (Viedma ripening). A variety of interesting effects have been observed, which include among others, enhanced crystallization yield with higher enantiomeric purity crystals, spontaneous mirror symmetry breaking crystallization, formation of metastable conglomerate crystals and enhanced deracemization rates. The objective of this review is to provide an overview of the effects of ultrasound on chiral crystallization and outline several aspects of interest in this emerging field.

Complexity and Challenges in Noncontact High Temperature Measurements in Microwave-Assisted Catalytic Reactors.

The complexity and challenges in noncontact temperature measurements inside microwave-heated catalytic reactors are presented in this paper. A custom-designed microwave cavity has been used to focus the microwave field on the catalyst and enable monitoring of the temperature field in 2D. A methodology to study the temperature distribution in the catalytic bed by using a thermal camera in combination with a thermocouple for a heterogeneous catalytic reaction (methane dry reforming) under microwave heating has been demonstrated. The effects of various variables that affect the accuracy of temperature recordings are discussed in detail. The necessity of having at least one contact sensor, such as a thermocouple, or some other microwave transparent sensor, is recommended to keep track of the temperature changes occurring in the catalytic bed during the reaction under microwave heating.

Subtle Microwave-Induced Overheating Effects in an Industrial Demethylation Reaction and Their Direct Use in the Development of an Innovative Microwave Reactor.

A systematic study of the conventional and microwave (MW) kinetics of an industrially relevant demethylation reaction is presented. In using industrially relevant reaction conditions the dominant influence of the solvent on the MW energy dissipation is avoided. Below the boiling point, the effect of MWs on the activation energy Ea and k0 is found nonexistent. Interestingly, under reflux conditions, the microwave-heated (MWH) reaction displays very pronounced zero-order kinetics, displaying a much higher reaction rate than observed for the conventionally thermal-heated (CTH) reaction. This is related to a different gas product (methyl bromide, MeBr) removal mechanism, changing from classic nucleation into gaseous bubbles to a facilitated removal through escaping gases/vapors. Additionally, the use of MWs compensates better for the strong heat losses in this reaction, associated with the boiling of HBr/water and the loss of MeBr, than under CTH. Through modeling, MWH was shown to occur inhomogeneously around gas/liquid interfaces, resulting in localized overheating in the very near vicinity of the bubbles, overall increasing the average heating rate in the bubble vicinity vis-à-vis the bulk of the liquid. Based on these observations and findings, a novel continuous reactor concept is proposed in which the escaping MeBr and the generated HBr/water vapors are the main driving forces for circulation. This reactor concept is generic in that it offers a viable and low cost option for the use of very strong acids and the managed removal/quenching of gaseous byproducts.

Furfural Synthesis from d-Xylose in the Presence of Sodium Chloride: Microwave versus Conventional Heating.

We investigate the existence of specific/nonthermal microwave effects for the dehydration reaction of xylose to furfural in the presence of NaCl. Such effects are reported for sugars dehydration reactions in several literature reports. To this end, we adopted three approaches that compare microwave-assisted experiments with a) conventional heating experiments from the literature; b) simulated conventional heating experiments using microwave-irradiated silicon carbide (SiC) vials; and at c) different power levels but the same temperature by using forced cooling. No significant differences in the reaction kinetics are observed using any of these methods. However, microwave heating still proves advantageous as it requires 30 % less forward power compared to conventional heating (SiC vial) to achieve the same furfural yield at a laboratory scale.

On characterization of anisotropic plant protein structures.

In this paper, a set of complementary techniques was used to characterize surface and bulk structures of an anisotropic Soy Protein Isolate (SPI)-vital wheat gluten blend after it was subjected to heat and simple shear flow in a Couette Cell. The structured biopolymer blend can form a basis for a meat replacer. Light microscopy and scanning electron microscopy provided a detailed view of structure formation over the visible surfaces of the SPI-gluten blend. Protein orientation in the direction of the flow was evident and fibrous formation appeared to exist on the macro- and micro-scale. Furthermore, according to texture analysis, the structured biopolymer obtained from the Couette Cell after processing at 95 °C and 30 RPM for 15 min has high tensile stress and strain anisotropy indices (∼2 and ∼1.8, respectively), comparable to those of raw meat (beef). The novel element in this work is the use of the neutron refraction method, utilizing spin-echo small angle neutron scattering (SESANS), to provide a look inside the anisotropic biopolymer blend complementing the characterization provided by the standard techniques above. With SESANS, it is possible to quantify the number of fibre layers and the orientation distribution of fibres. For a specimen thickness of 5 mm, the obtained number of fibre layers was 36 ± 4 and the standard deviation of the orientation distribution was 0.66 ± 0.04 radians. The calculated thickness of one layer of fibres was 138 µm, in line with SEM inspection.

Analysis of niflumic acid prepared by rapid microwave-assisted evaporation.

Evaporative crystallization is widely applied in several industrial processes, including the pharmaceutical industry. Microwave irradiation can significantly speed up solvent evaporation in these crystallization processes, resulting in reduced particle size due to rapid crystallization. A single-mode microwave setup was used for evaporative crystallization of the model active pharmaceutical ingredient, niflumic acid, and the polymer, polyvinylpirrolidone (PVP). Production of crystals by microwave irradiation offers a modern way for drug formulation, and by reducing the particle size the dissolution rate and bioavailability of the active pharmaceutical ingredient can be enhanced. In this study, a 2.5-fold increase in the dissolution rate of the produced niflumic acid crystals was observed compared to the dissolution rate of the original drug in 120min. When niflumic acid was produced together with the PVP in the microwave system, an amorphous solid dispersion was created with particles in the nano-size range, which showed a 5-fold increase in dissolution rate in 120min compared to the dissolution of the crystalline niflumic acid samples created by the microwave irradiation in the absence of PVP.