We developed a system to effectively trap nanoparticles suspended in solution, in dedicated suspended nanochannels for in-situ liquid phase transmission electron microscopy (LPTEM) measurements.

Ettringite forms directly after Portland cement is mixed with water. Polycarboxylate ether-type superplasticizers can stabilize nano-ettringite particles in the pore solution and modify ettringite formation. It was previously impossible to isolate the nano-ettringite from the cement pore solution at commonly used water-to-cement (w/c) ratios of 0.5 and lower. Therefore, the exact morphology of ettringite in the pore solution has not been systematically studied. This paper presents a novel method for obtaining nano-ettringite from cement paste by centrifugation with a high-density liquid. Ettringite was isolated at three different water-to-cement ratios (0.3, 0.4, and 0.5) and four dosages of a polycarboxylate ether-type superplasticizer (0.05%, 0.1%, 0.25%, and 0.4%). The size and morphology of the obtained ettringite particles were analyzed using transmission electron microscopy (TEM). The chemical composition and structure of ettringite were confirmed using electron energy loss spectroscopy, high-resolution TEM imaging, and X-ray diffraction. The ettringite particle size decreases as the superplasticizer dosage increases. As a result, the specific surface area at higher superplasticizer dosages increases from 39 m2 g−1 to 58 m2 g−1. In-situ calorimetry was used to measure the initial heat release and estimate the amount of ettringite formed. Since the initial heat did not change significantly with varying superplasticizer dosages, it suggests that the studied superplasticizer has a minor influence on the amount of ettringite at the considered concentrations. In summary, cement paste centrifugation using a high-density fluid allows the isolation of superplasticizer-stabilized nano-ettringite from cement paste. The method could be valuable for other studies dealing with the impact of ettringite morphology.

Using Nano Channel Chips to Discover cutting-edge crystal growth research! By Prof. Ute Kaiser, PhD candidate David Mücke et al. from the University of Ulm, Germany, in this ACS article from Crystal Growth & Design

Liquid phase transmission electron microscopy (LPTEM) is rapidly developing as a powerful tool for probing processes in liquid environments with close to atomic resolution. Knowledge of the water thickness is needed for reliable interpretation and modelling of analytical studies in LPTEM, and is particularly essential when using thin liquid layers, required for achieving the highest spatial resolutions. The log-ratio method in electron energy-loss spectroscopy (EELS) is often applied in TEM to quantify the sample thickness, which is measured relative to the inelastic mean free path (λIMFP). However, λIMFP itself is dependent on sample material, the electron energy, and the convergence and divergence angles of the microscope electronoptics. Here, we present a detailed quantitative analysis of the λIMFP of water as functions of the EELS collection angle (β) at 120 keV and 300 keV in a novel nanochannel liquid cell. We observe good agreement with earlier studies conducted on ice, but find that the most widely used theoretical models significantly underestimate λIMFP of water. We determine an adjusted average energy-loss term Em, water, and characteristic scattering angle θE, water that improve the accuracy. The results provide a comprehensive knowledge of the λIMFP of water (or ice) for reliable interpretation and quantification of observations in LPTEM and cryo-TEM studies.

Improving our experimental and theoretical knowledge of electric potentials at liquid-solid boundaries is essential to achieve a deeper understanding of the driving forces behind interfacial processes. Electron holography has proved successful in probing solid-solid interfaces but requires knowledge of the materials’ mean inner potential, which is a fundamental bulk material property. Combining off-axis electron holography with liquid phase transmission electron microscopy (LPTEM), we provide the first quantitative MIP determination of liquid water. This value is larger than most theoretical predictions, and to explain the disagreement we assess the dominant factors needed in quantum simulations of liquid water. A precise MIP lays the foundations for nanoscale holographic potential measurements in liquids, and provides a benchmark to improve quantum mechanical descriptions of aqueous systems and their interfaces in, e.g., electrochemistry, solvation processes, and spectroscopy.

Black phosphorene quantum dots (BPQDs) are most commonly derived from high-cost black phosphorus, while previous syntheses from the low-cost red phosphorus (Pred) allotrope are highly oxidised. Herein, we present an intrinsically scalable method to produce high quality BPQDs, by first ball-milling Pred to create nanocrystalline Pblack and subsequent reductive etching using lithium electride solvated in liquid ammonia. The resultant ~25 nm BPQDs are crystalline with low oxygen content, and spontaneously soluble as individualized monolayers in tertiary amide solvents, as directly imaged by liquid-phase transmission electron microscopy. This new method presents a scalable route to producing quantities of high quality BPQDs for academic and industrial applications.