Porous polymeric microparticles foamed with supercritical CO2as scattering white pigments.

Nowadays, titanium dioxide (TiO2) is the most commercially relevant white pigment. Nonetheless, it is widely criticized due to its energy-intensive extraction and costly disposal of harmful by-products. Furthermore, recent studies discuss its potential harm for the environment and the human health. Environment-friendly strategies for the replacement of TiO2as a white pigment can be inspired from nature. Here whiteness often originates from broadband light scattering air cavities embedded in materials with refractive indices much lower than that of TiO2. Such natural prototypes can be mimicked by introducing air-filled nano-scale cavities into commonly used polymers. Here, we demonstrate the foaming of initially transparent poly(methyl methacrylate) (PMMA) microspheres with non-toxic, inert, supercritical CO2. The properties of the foamed, white polymeric pigments with light scattering nano-pores are evaluated as possible replacement for TiO2pigments. For that, the inner foam structure of the particles was imaged by phase-contrast x-ray nano-computed tomography (nano-CT), the optical properties were evaluated via spectroscopic measurements, and the mechanical stability was examined by micro compression experiments. Adding a diffusion barrier surrounding the PMMA particles during foaming allows to extend the foaming process towards smaller particles. Finally, we present a basic white paint prototype as exemplary application.

Experimental data showing the influence of different boron nitride particles on the silica network, the butyl stearate and the porogens in shape-stabilized phase change materials.

Shape-stabilized phase change materials (ss-PCMs) based on silica and butyl stearate were thermally enhanced via the addition of different hexagonal boron nitride particles (BN) to the in situ sol-gel synthesis. The dataset is used in conjunction with the experimental data of the influence of the particle size and surface area of BN on the thermal and mechanical properties of ss-PCMs discussed in Marske et al. (2021). To study the effect of the different BN particles on the hydrolysis degree of the silica network and on the chemical nature of the porogens sodium dodecyl sulfate and poly(vinyl alcohol) used for the ss-PCM synthesis, the ss-PCM samples are measured via High Power Decoupling (HPDEC) Magic Angle Spinning (MAS) 29Si NMR and attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy, respectively. Additionally, data of the influence of BN on the thermal properties is presented as thermogravimetric analysis (TG). The 29Si MAS NMR spectra are referenced to tetramethylsilane and show the different silica species in ppm. The different value of wavenumber and intensity of each reference and ss-PCM sample is listed in the IR spectra. The decomposition points of the ss-PCMs are calculated from the TG data via OriginLab. The spectra and data can be used as a reference for other researchers and engineers to use in synthesizing ss-PCMs based on silica and other polymeric materials or as reference for pure BN, SDS, stabilized silica sol and PVA.

Multiscale Tomographic Analysis for Micron-Sized Particulate Samples.

The three-dimensional characterization of distributed particle properties in the micro- and nanometer range is essential to describe and understand highly specific separation processes in terms of selectivity and yield. Both performance measures play a decisive role in the development and improvement of modern functional materials. In this study, we mixed spherical glass particles (0.4­5.8 µm diameter) with glass fibers (diameter 10 µm, length 18­660 µm) to investigate a borderline case of maximum difference in the aspect ratio and a significant difference in the characteristic length to characterize the system over several size scales. We immobilized the particles within a wax matrix and created sample volumes suitable for computed tomographic (CT) measurements at two different magnification scales (X-ray micro- and nano-CT). Fiber diameter and length could be described well on the basis of the low-resolution micro-CT measurements on the entire sample volume. In contrast, the spherical particle system could only be described with sufficient accuracy by combining micro-CT with high-resolution nano-CT measurements on subvolumes of reduced sample size. We modeled the joint (bivariate) distribution of fiber length and diameter with a parametric copula as a basic example, which is equally suitable for more complex distributions of irregularly shaped particles. This enables us to capture the multidimensional correlation structure of particle systems with statistically representative quantities.

Publisher Correction: Plate-nanolattices at the theoretical limit of stiffness and strength.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Plate-nanolattices at the theoretical limit of stiffness and strength.

Though beam-based lattices have dominated mechanical metamaterials for the past two decades, low structural efficiency limits their performance to fractions of the Hashin-Shtrikman and Suquet upper bounds, i.e. the theoretical stiffness and strength limits of any isotropic cellular topology, respectively. While plate-based designs are predicted to reach the upper bounds, experimental verification has remained elusive due to significant manufacturing challenges. Here, we present a new class of nanolattices, constructed from closed-cell plate-architectures. Carbon plate-nanolattices are fabricated via two-photon lithography and pyrolysis and shown to reach the Hashin-Shtrikman and Suquet upper bounds, via in situ mechanical compression, nano-computed tomography and micro-Raman spectroscopy. Demonstrating specific strengths surpassing those of bulk diamond and average performance improvements up to 639% over the best beam-nanolattices, this study provides detailed experimental evidence of plate architectures as a superior mechanical metamaterial topology.

Synthesis of monolithic shape-stabilized phase change materials with high mechanical stability via a porogen-assisted in situ sol-gel process.

The confinement of phase change materials (PCMs) in construction materials has recently solved leakage, supercooling and low thermal conductivity problems in the industrial use of PCMs as monolithic thermal energy storage materials. To produce shape-stabilized PCMs (ss-PCMs) as crack-free monoliths, less than 15-30% v/v pure or encapsulated PCMs can be used in construction materials. Therefore, the heat storage capacity of these monolithic ss-PCM boards is comparatively low. In this study, we synthesized a novel class of monolithic ss-PCM boards with high compressive strength of 0.7 MPa at 30 °C (1.2 MPa at 10 °C), high PCM loadings of 86 wt%, and latent heats in the range of 100 J g-1 via a porogen-assisted in situ sol-gel process. We confined butyl stearate (BS) as PCM in a core-shell-like silica matrix via stabilized silica sol as silica source, sodium dodecyl sulfate as surfactant and poly(vinyl alcohol) as co-polymer. The ss-PCMs obtained are hydrophobic, thermally stable up to 320 °C and perform 6000 state transitions from solid to liquid and vice versa, without losing melting or freezing enthalpies. We analyzed the silica structure in the ss-PCMs to understand in detail the reasons for the high mechanical stability. The silica structure in ss-PCMs consists of spherical meso- and macropores up to 10 000 nm filled with PCM, formed mostly by BS droplets in water as templates during gelation. With an increasing BS amount in the synthesis of ss-PCMs, the total nanopore volume filled with PCM in ss-PCMs increases, resulting in higher compressive strengths up to 500% and thermal conductivities up to 60%.

Risperidone-Loaded PLGA-Lipid Particles with Improved Release Kinetics: Manufacturing and Detailed Characterization by Electron Microscopy and Nano-CT.

For parenteral controlled drug release, the desired zero order release profile with no lag time is often difficult to achieve. To overcome the undesired lag time of the current commercial risperidone controlled release formulation, we developed PLGA-lipid microcapsules (MCs) and PLGA-lipid microgels (MGs). The lipid phase was composed of middle chain triglycerides (MCT) or isopropylmyristate (IPM). Hydroxystearic acid was used as an oleogelator. The three-dimensional inner structure of Risperidone-loaded MCs and MGs was assessed by using the invasive method of electron microscopy with focused ion beam cutting (FIB-SEM) and the noninvasive method of high-resolution nanoscale X-ray computed tomography (nano-CT). FIB-SEM and nano-CT measurements revealed the presence of highly dispersed spherical structures around two micrometres in size. Drug release kinetics did strongly depend on the used lipid phase and the presence or absence of hydroxystearic acid. We achieved a nearly zero order release without a lag time over 60 days with the MC-MCT formulation. In conclusion, the developed lipid-PLGA microparticles are attractive alternatives to pure PLGA-based particles. The advantages include improved release profiles, which can be easily tuned by the lipid composition.

A step towards valid detection and quantification of lung cancer volume in experimental mice with contrast agent-based X-ray microtomography.

Tumor volume is a parameter used to evaluate the performance of new therapies in lung cancer research. Conventional methods that are used to estimate tumor size in mouse models fail to provide fast and reliable volumetric data for tumors grown non-subcutaneously. Here, we evaluated the use of iodine-staining combined with micro-computed tomography (micro-CT) to estimate the tumor volume of ex vivo tumor-burdened lungs. We obtained fast high spatial resolution three-dimensional information of the lungs, and we demonstrated that iodine-staining highlights tumors and unhealthy tissue. We processed iodine-stained lungs for histopathological analysis with routine hematoxylin and eosin (H&E) staining. We compared the traditional tumor burden estimation performed manually with H&E histological slices with a semi-automated method using micro-CT datasets. In mouse models that develop lung tumors with well precise boundaries, the method that we describe here enables to perform a quick estimation of tumorous tissue volume in micro-CT images. Our method overestimates the tumor burden in tumors surrounded by abnormal tissue, while traditional histopathological analysis underestimates tumor volume. We propose to embed micro-CT imaging to the traditional workflow of tumorous lung analyses in preclinical cancer research as a strategy to obtain a more accurate estimation of the total lung tumor burden.

Dual-energy micro-CT for quantifying the time-course and staining characteristics of ex-vivo animal organs treated with iodine- and gadolinium-based contrast agents.

Chemical staining of soft-tissues can be used as a strategy to increase their low inherent contrast in X-ray absorption micro-computed tomography (micro-CT), allowing to obtain fast three-dimensional structural information of animal organs. Though some staining agents are commonly used in this context, little is known about the staining agents' ability to stain specific types of tissues; the times necessary to provide a sufficient contrast; and the effect of staining solution in distorting the tissue. Here we contribute to studies of animal organs (mouse heart and lungs) using staining combined with dual-energy micro-CT (DECT). DECT was used in order to obtain an additional quantitative measure for the amount of staining agents within the sample in 3D maps. Our results show that the two staining solutions used in this work diffuse differently in the tissues studied, the staining times of some tens of minutes already produce high-quality micro-CT images and, at the concentrations applied in this work, the staining solutions tested do not cause relevant tissue distortions. While one staining solution provides images of the general morphology of the organs, the other reveals organs' features in the order of a hundred micrometers.

Novel insights on magadiite disaggregation: a multitechnique study on thermal stability.

Disaggregated magadiite was obtained through ion-exchange in acidic media from magadiite intercalated in the synthesis with cetyltrimethylamonium cations. The combination of Soxhlet extraction and ultrasound during the procedure resulted in different morphology and different properties when compared with the pristine material, as observed by SEM. Thermal and surface properties studies performed by VT-XRD, TG, VT-FTIR, HETCOR SS-NMR, and N2 physisorption show that disaggregated magadiite presents a basal space of 1.35 nm and that [SiO4] entities of adjacent magadiite silicate layers connect during ion-exchange under ultrasound. Despite these bonding events, the surface area increased from 20-26 m(2) g(-1) in CTA-magadiite to 55-72 m(2) g(-1) in disaggregated magadiite.