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The thermal accommodation coefficient is a measure for the quality of thermal energy exchange between gas molecules and a solid surface. It is an important parameter to describe heat flow in rarefied gases, for example, in aerospace or vacuum technology. As special application, it plays a decisive role for the thermal transport theory in silica filled vacuum insulation panels. So far, no values have been available for the material pairings of silica and various gases. For that reason, this paper presents thermal conductivity measurements under different gas-pressure conditions for precipitated and fumed silica in combination with the following gases: helium, air, argon, carbon dioxide (CO2), sulfur dioxide (SO2), krypton, and sulfur hexafluoride (SF6). Additionally, a calculation method for determining thermal accommodation coefficients from the thermal conductivity curves in combination with the pore size distribution of silica determined by mercury intrusion porosimetry is introduced. The results are compared with existing models.

Quality control in a production plant shows its maximum potential in the form of inline measurements. Defects and imperfections can be detected early and directly, and waste and costs can be reduced. Nuclear Magnetic Resonance offers a wide range of applications but requires dedicated adaptation to the respective process and material conditions. A V-shaped low-field NMR sensor was developed for non-invasive inline measurements on anode slurries in a battery production plant. In battery production, inline monitoring of the quality of anode slurries is demanded, offering the possibility of predictive control of the following process steps. Methods of low-field NMR to determine flow properties were adapted to the desired application. Further, magnetic resonance imaging measurements were made to determine the flow properties of model substances and anode slurries, thus providing verification. The sensor measurements show the ability to measure the flow behavior of, amongst other fluids, anode slurries in a form suitable for inline quality control in a battery production plant.

The carbon-free chemical storage and release of renewable energy is an important task to drastically reduce CO 2 emissions. The high specific energy density of iron and its recyclability makes it a promising storage material. Energy release by oxidation with air can be realized by the combustion of micron-sized iron powders in retro-fitted coal fired power plants and in fixed-bed reactors under milder conditions. An experimental parameter study of iron powder oxidation with air was conducted based on thermogravimetric analysis in combination with wide-angle X-ray scattering and Mössbauer spectroscopy. In agreement with literature the oxidation was found to consist of a very fast initial oxidation of the outer particle layer followed by much slower oxidation due to diffusion of iron ions through the Fe 2 O 3 /Fe 3 O 4 layer being the rate-limiting step. Scanning electron microscopy analysis of the iron particle before and after oxidation reveal a strong particle morphology transformation. This impact on the reaction was studied by cyclization experiments. Up to 10 oxidation-reduction cycles show that both, oxidation and reduction rates, increase strongly with cycling due to increased porosity., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

To reduce unwanted fat bloom in the manufacturing and storage of chocolates, detailed knowledge of the chemical composition and molecular mobility of the oils and fats contained is required. Although the formation of fat bloom on chocolate products has been studied for many decades with regard to its prevention and reduction, questions on the molecular level still remain to be answered. Chocolate products with nut-based fillings are especially prone to undesirable fat bloom. The chemical composition of fat bloom is thought to be dominated by the triacylglycerides of the chocolate matrix, which migrate to the chocolate's surface and recrystallize there. Migration of oils from the fillings into the chocolate as driving force for fat bloom formation is an additional factor in the discussion. In this work, the migration was studied and confirmed by MRI, while the chemical composition of the fat bloom was measured by NMR spectroscopy and HPLC-MS, revealing the most important triacylglycerides in the fat bloom. The combination of HPLC-MS with NMR spectroscopy at 800 MHz allows for detailed chemical structure determination. A rapid routine was developed combining the two modalities, which was then applied to investigate the aging, the impact of chocolate composition, and the influence of hazelnut fillings processing parameters, such as the degree of roasting and grinding of the nuts or the mixing time, on fat bloom formation.

Inline analytics in industrial processes reduce operating costs and production rejection. Dedicated sensors enable inline process monitoring and control tailored to the application of interest. Nuclear Magnetic Resonance is a well-known analytical technique but needs adapting for low-cost, reliable and robust process monitoring. A V-shaped low-field NMR sensor was developed for inline process monitoring and allows non-destructive and non-invasive measurements of materials, for example in a pipe. In this paper, the industrial application is specifically devoted to the quality control of anode slurries in battery production. The characterization of anode slurries was performed with the sensor to determine chemical composition and detect gas inclusions. Additionally, flow properties play an important role in continuous production processes. Therefore, the in- and outflow effects were investigated with the V-shaped NMR sensor as a basis for the future determination of slurry flow fields.

NMR methods were applied for lubricant analysis. Different factors influence the real aging of lubricants on diverse length scales and are captured by NMR. Chemical conversion of additives is addressed by NMR spectroscopy. High-field NMR experiments allow the identification and quantification of chemical components and are transferred to benchtop devices. Molecular dynamics and contaminations like fuel or abrasion are addressed via NMR relaxation and diffusion. Quality parameters were extracted via suitable data analysis of NMR raw data, which allow the detection of aging and indicate changes in the oil composition. At the same time, the methodology is optimized to the conditions in quality control. The feasibility is shown the example of a series of lubricants from applications in regenerative energy production, namely, wind turbine oils and biogas motor oils., (© 2023 John Wiley & Sons Ltd.)

Phospholipids (PLs) are widely used in the pharma industry and a better understanding of their behavior under different conditions is helpful for applications such as their use as medical transporters. The transition temperature T m affects the lipid conformation and the interfacial tension between p er f luoroperhydro p henanthrene (PFP) and an aqueous suspension of 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC), 1,2-distearoyl-sn-glycero-3-phosphatidylcholine (DSPC), as well as a mixture of these PLs with cholesterol. Interfacial tensions were measured with the Du Noüy ring at quasi-equilibrium; the area per molecule was calculated according to the Gibbsian approach and a time-dependent tension gradient. Results show that the time t ε to reach quasi-equilibrium was shorter when the temperature was above T m , indicating a faster adsorption process ( t ε ,DPPC = 48 h, 36 °C = 24 h) for PL in the liquid crystalline state than in the gel state (T < T t ε ,DPPC,48 °C = 24 h) for PL in the liquid crystalline state than in the gel state (T < T m ). In addition, concentration-dependent results of the interfacial tension revealed that above the respective T m and at all concentrations c > 0.1 mM, the average minimum interfacial tension for DPPC and DSPC (14.1 mN/m and 15.3 mN/m) does not differ significantly between those two lipids. Equilibrium between monolayers and bilayers shows that for T < T m , surface pressures ∏ ≈ 31 mN/m are reached while for T > T m , ∏ ≈ 41 mN/m. Mixtures with cholesterol only reach ∏ ≤ 31 mN/m T m , with no significant difference between the two PLs. The higher interfacial tension of the mixture indicates stabilization of the liposomal conformation in the aqueous phase by the addition of cholesterol. The high diffusion coefficients show that adsorption is mainly based on liposomes.

Natural materials are composed of a limited number of molecular building blocks and their exceptional properties are governed by their hierarchical structure. However, this level of precision is unattainable with current state-of-the-art materials for 3D printing. Herein, new self-assembled printable materials based on block copolymers (BCPs) enabling precise control of the nanostructure in 3D are presented. In particular, well-defined BCPs consisting of poly(styrene) (PS) and a polymethacrylate-based copolymer decorated with printable units are selected as suitable self-assembled materials and synthesized using controlled radical polymerization. The synthesized library of BCPs are utilized as printable formulations for the fabrication of complex 3D microstructures using two-photon laser printing. By fine-tuning the BCP composition and solvent in the formulations, the fabrication of precise 3D nano-ordered structures is demonstrated for the first time. A key point of this work is the achievement of controlled nano-order within the entire 3D structures. Thus, imaging of the cross-sections of the 3D printed samples is performed, enabling the visualization also from the inside. The presented versatile approach is expected to create new avenues for the precise design of functional polymer materials suitable for high-resolution 3D printing exhibiting tailor-made nanostructures., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The increasing demand for lithium-ion batteries requires constant improvements in the areas of production and recycling to reduce their environmental impact. In this context, this work presents a method for structuring carbon black aggregates by adding colloidal silica via a spray flame with the goal of opening up more choices for polymeric binders. The main focus of this research lies in the multiscale characterization of the aggregate properties via small-angle X-ray scattering, analytical disc centrifugation and electron microscopy. The results show successful formation of sinter-bridges between silica and carbon black leading to an increase in hydrodynamic aggregate diameter from 201 nm to up to 357 nm, with no significant changes in primary particle properties. However, segregation and coalescence of silica particles was identified for higher mass ratios of silica to carbon black, resulting in a reduction in the homogeneity of the hetero-aggregates. This effect was particularly evident for silica particles with larger diameters of 60 nm. Consequently, optimal conditions for hetero-aggregation were identified at mass ratios below 1 and particle sizes around 10 nm, at which homogenous distributions of silica within the carbon black structure were achieved. The results emphasise the general applicability of hetero-aggregation via spray flames with possible applications as battery materials.

The combustion of metal fuels as energy carriers in a closed-cycle carbon-free process is a promising approach for reducing CO 2 emissions in the energy sector. For a possible large-scale implementation, the influence of process conditions on particle properties and vice versa has to be well understood. In this study, the influence of different fuel-air equivalence ratios on particle morphology, size and degree of oxidation in an iron-air model burner is investigated by means of small- and wide-angle X-ray scattering, laser diffraction analysis and electron microscopy. The results show a decrease in median particle size and an increase in the degree of oxidation for leaner combustion conditions. The difference of 1.94 μm in median particle size between lean and rich conditions is twentyfold greater than the expected amount and can be connected to an increased intensity of microexplosions and nanoparticle formation for oxygen-rich atmospheres. Furthermore, the influence of the process conditions on the fuel usage efficiency is investigated, yielding efficiencies of up to 0.93. Furthermore, by choosing a suitable particle size range of 1 to 10 μm, the amount of residual iron content can be minimized. The results emphasize that particle size plays a key role in optimizing this process for the future.

Process monitoring and control require dedicated and reliable measures which reflect the status of the process under investigation. Although nuclear magnetic resonance is known to be a versatile analytical technique, it is only seldomly found in process monitoring. Single-sided nuclear magnetic resonance is one well known approach for being applied in process monitoring. The dedicated V-sensor is a recent approach that allows the inline investigation of materials in a pipe non-destructively and non-invasively. An open geometry of the radiofrequency unit is realized using a tailored coil, enabling the sensor to be applied for manifold mobile applications in in-line process monitoring. Stationary liquids were measured, and their properties were integrally quantified as the basis for successful process monitoring. The sensor, in its inline version, is presented along with its characteristics. An exemplary field of application is battery production in terms of anode slurries; thus, the first results on graphite slurries will demonstrate the added value of the sensor in process monitoring.

The crystallization of melt emulsions is of great interest to the food, cosmetic, and pharmaceutical industries. Surfactants are used in emulsions and suspensions to stabilize the dispersed phase; thus, questions arise about the liquid-liquid and solid-liquid interfaces of the droplets or particles and the distribution of the surfactant in the different phases (continuous and dispersed phase, interface). Nuclear magnetic resonance relaxation and diffusion measurements revealed that the internal and rotational mobility of surfactant molecules at the liquid-liquid interface decreases with increasing droplet sizes. Additionally, solid-liquid interfaces have fewer surfactants than liquid-liquid interfaces as a result of the desorption of the surfactant molecules during the crystallization of the droplets. Relaxation rates of surfactant molecules in aqueous solution as single molecules, micelles, and at the liquid-liquid and solid-liquid interface are analyzed for the first time., (© 2022 The Authors. Magnetic Resonance in Chemistry published by John Wiley & Sons Ltd.)

Microplastic particles (MP) are efficiently retained in wastewater treatment plants and enriched in sewage sludge. For monitoring MP contents in wastewater systems, sewage sludge is thus well suited, but also requires an isolation of MP from the sludge matrix, as other sewage sludge components may interfere with the MP identification and quantification. Although organic matter in sludge samples can be removed through acid and enzymatic digestion procedures, cellulose - mainly from toilet paper - remains in the digests, due to its high chemical resistivity and similar density to MP. We apply the separation concept of magnetic seeded filtration to isolate MP through selective hetero-agglomeration with magnetic seed particles. MP and cellulose differ in their hydrophobic properties and we investigate to what extent these differences can be exploited to selectively form MP-magnetite hetero-agglomerates in the presence of cellulose. These hetero-agglomerates are subsequently separated using a magnet. Five MP types (Polyethylene terephthalate (PET), polypropylene (PP), low density polyethylene (LDPE), polyvinyl chloride (PVC) and polystyrene (PS)) and cellulose particles were mixed in different combinations with both hydrophilic and hydrophobic (silanized) magnetite particles. PET, PP, LDPE and PS only poorly agglomerated with pristine (hydrophilic) magnetite, but efficiently formed hetero-agglomerates with hydrophobic magnetite and were successfully removed from suspensions ( 80 - 100 % ). PVC agglomerated more efficiently with pristine than with hydrophobic magnetite and cellulose only agglomerated to a limited extent with either hydrophilic or hydrophobic magnetite, resulting in a high process selectivity. Results from experiments conducted at different ionic strengths and with hydrophilic and hydrophobic magnetite suggests that the agglomeration process was dominated by hydrophobic interactions. Enzymatic and oxidative treatment of the MP only marginally affected the separation efficiencies and (treated) MP spiked to sewage sludge extracts were successfully recovered using magnetic seeded filtration., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Author(s).)

A dynamic process model for the simulation of nanoparticle fractionation in tubular centrifuges is presented. Established state-of-the-art methods are further developed to incorporate multi-dimensional particle properties (traits). The separation outcome is quantified based on a discrete distribution of particle volume, elongation and flatness. The simulation algorithm solves a mass balance between interconnected compartments which represent the separation zone. Grade efficiencies are calculated by a short-cut model involving material functions and higher dimensional particle trait distributions. For the one dimensional classification of fumed silica nanoparticles, the numerical solution is validated experimentally. A creation and characterization of a virtual particle system provides an additional three dimensional input dataset. Following a three dimensional fractionation case study, the tubular centrifuge model underlines the fact that a precise fractionation according to particle form is extremely difficult. In light of this, the paper discusses particle elongation and flatness as impacting traits during fractionation in tubular centrifuges. Furthermore, communications on separation performance and outcome are possible and facilitated by the three dimensional visualization of grade efficiency data. Future research in nanoparticle characterization will further enhance the models use in real-time separation process simulation.

Nanoporous materials relying on supramolecular liquid crystals (LCs) are excellent candidates for size- and charge-selective membranes. However, whether they can be manufactured using printing technologies remained unexplored so far. In this work, we develop a new approach for the fabrication of ordered nanoporous microstructures based on supramolecular LCs using two-photon laser printing. In particular, we employ photo-cross-linkable hydrogen-bonded complexes, that self-assemble into columnar hexagonal (Col h ) mesophases, as the base of our printable photoresist. The presence of photopolymerizable groups in the periphery of the molecules enables the printability using a laser. We demonstrate the conservation of the Col h arrangement and of the adsorptive properties of the materials after laser microprinting, which highlights the potential of the approach for the fabrication of functional nanoporous structures with a defined geometry. This first example of printable Col h LC should open new opportunities for the fabrication of functional porous microdevices with potential application in catalysis, filtration, separation, or molecular recognition.