This review addresses the advances made with specular neutron reflectometry in studies of aqueous mixtures of polymers and surfactants at fluid interfaces during the last decade (or so). The increase ...in neutron flux due to improvements in instrumentation has led to routine measurements at the air/water interface that are faster and involve samples with lower isotopic contrast than in previous experiments. One can now resolve the surface excess of a single deuterated component on the second time scale and the composition of a mixture on the minute time scale, and information about adsorption processes and dynamic rheology can also be accessed. Research areas addressed include the types of formed equilibrium surface structures, the link to foam film stability and the range of non-equilibrium effects that dominate the behavior of oppositely charged polyelectrolyte/surfactant mixtures, macroscopic film formation in like-charged polymer/surfactant mixtures, and the properties of mixtures of bio-polymers with surfactants and lipids.
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•Advances of specular NR to study polymer/surfactant mixtures•Exploitation of isotopic contrast variation•Surface excess and local distribution of polymer and surfactant•Correlation with macroscopic properties
Surfactants are promising additives for water-based lubricant surfaces due to their ability to adsorb on metal surfaces and reduce friction under boundary lubrication. In this study, the aggregation ...behavior of surfactants in aqueous solutions and their effects on friction and anti-wear properties were investigated using sodium 2-hexyldecanoate (2HDNa) as an example. The results revealed that 2HDNa forms vesicles at low concentrations and transits to micelles at higher concentrations. The presence of vesicles led to a significant reduction in friction coefficient and improved anti-wear properties by forming an absorbed film, which was confirmed by neutron reflectometry (NR). The findings of this study emphasize the lubrication and anti-wear performance of vesicles and the importance of surfactant concentration control in water-based lubrication.
We present a high-rate 6Li-based pixelated neutron detector developed for neutron reflectometry instruments at the Spallation Neutron Source (SNS). The neutron detector has a pixelated design: each ...6Li scintillator element has its own photosensor and independent channel readout. This paper focuses on the general overview of the detector design and construction, the characterization of the pixelated detector, and the results of the first neutron reflectivity experiments conducted using the pixelated neutron detector at the SNS Liquid Reflectometer (BL-4B). The pixelated neutron detector demonstrated a global time-average count rate of ≥1.8×106cps, at least 3 orders of magnitude higher than that of the existing neutron detector (3He-based Multi-Wire Proportional Counter), and a local instantaneous count rate of ≥1.73×106cps/cm2. The maximum counting rate of the detector has not yet been determined as the detector is capable of handling the maximum flux available at the beamline. The outcome of the neutron reflectivity experiments showed that the pixelated neutron detector is a promising candidate for next-generation neutron reflectometry instruments at the SNS.
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Grafted poly(ethylene glycol) methyl ether methacrylate (POEGMA) copolymer brushes change conformation in response to temperature ('thermoresponse'). In the presence of different ions ...the thermoresponse of these coatings is dramatically altered. These effects are complex and poorly understood with no all-inclusive predictive theory of specific ion effects. As natural environments are composed of mixed electrolytes, it is imperative we understand the interplay of different ions for future applications. We hypothesise anion mixtures from the same end of the Hofmeister series (same-type anions) will exhibit non-additive and competitive behaviour.
The behaviour of POEGMA brushes, synthesised via surface-initiated ARGET-ATRP, in both single and mixed aqueous electrolyte solutions was characterised with ellipsometry and neutron reflectometry as a function of temperature.
In mixed fluoride and chloride aqueous electrolytes (salting-out ions), or mixed thiocyanate and iodide aqueous electrolytes (salting-in ions), a non-monotonic concentration-dependent influence of the two anions on the thermoresponse of the brush was observed. A new term, δ, has been defined to quantitively describe synergistic or antagonistic behaviour. This study determined the specific ion effects imparted by salting-out ions are dependent on available solvent molecules, whereas the influence of salting-in ions is dependent on the interactions of the anions and polymer chains.
refnx is a model‐based neutron and X‐ray reflectometry data analysis package written in Python. It is cross platform and has been tested on Linux, macOS and Windows. Its graphical user interface is ...browser based, through a Jupyter notebook. Model construction is modular, being composed from a series of components that each describe a subset of the interface, parameterized in terms of physically relevant parameters (volume fraction of a polymer, lipid area per molecule etc.). The model and data are used to create an objective, which is used to calculate the residuals, log‐likelihood and log‐prior probabilities of the system. Objectives are combined to perform co‐refinement of multiple data sets and mixed‐area models. Prior knowledge of parameter values is encoded as probability distribution functions or bounds on all parameters in the system. Additional prior probability terms can be defined for sets of components, over and above those available from the parameters alone. Algebraic parameter constraints are available. The software offers a choice of fitting approaches, including least‐squares (global and gradient‐based optimizers) and a Bayesian approach using a Markov‐chain Monte Carlo algorithm to investigate the posterior distribution of the model parameters. The Bayesian approach is useful for examining parameter covariances, model selection and variability in the resulting scattering length density profiles. The package is designed to facilitate reproducible research; its use in Jupyter notebooks, and subsequent distribution of those notebooks as supporting information, permits straightforward reproduction of analyses.
The refnx Python modules for neutron and X‐ray reflectometry data analysis are introduced. A sample analysis illustrates a Bayesian approach using a Markov‐chain Monte Carlo algorithm to understand the confidence in the fit parameters.
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Although protein adsorption at an interface is very common and important in biology and biotechnology, it is still not fully understood – mainly due to the intricate balance of forces ...that ultimately control it. In food processing (and medicine), controlling and manipulating protein adsorption, as well as avoiding protein adsorption (biofilm formation or membrane fouling) by the production of protein-resistant surfaces is of substantial interest. A major factor conferring resistance towards protein adsorption to a surface is the presence of tightly bound water molecules, as is the case in oligo ethylene glycol (OEG)-terminated self-assembled monolayers (SAMs). Due to strong attractive protein-protein and protein-surface interactions observed in systems containing trivalent salt ions, we hypothesize that these conditions may lead to a breakdown of protein resistance in OEG SAMs.
We studied the adsorption behavior of BLG in the presence of a lanthanum(III) chloride (LaCl3) at concentrations of 0, 0.1, 0.8 and 5.0 mM on normally protein resistant triethylene glycol-termianted (EG3) SAMs on a gold surface. We used quartz-crystal microbalance with dissipation (QCM-D) and neutron reflectivity (NR) to characterize the morphology of the interfacial region of the SAM.
We demonstrate that the protein resistance of the EG3 SAM breaks down beyond a threshold salt concentration c∗ and mirrors the bulk behaviour of this system, showing reduced adsorption beyond a second critical salt concentration c∗∗. These results demonstrate for the first time the controlled switching of the protein-resistant properties of this type of SAM by the addition of trivalent salt.
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Removal of organic species from solid surfaces is a crucial process. The use of oppositely charged surfactants provides a potential method for enhanced removal. Neutron reflectometry ...has been used to investigate the complex behaviour of a pre-adsorbed and tenacious layer of the cationic surfactant didodecyldimethylammonium bromide (DDAB) on a mica surface, during exposure to different organic species in solution. The anionic surfactant sodium dodecylsulfate (SDS) was shown to be able to remove the cationic layer, but only if anionic micelles were present in solution. To facilitate comparison with the behaviour of a non-ionic surfactant, the direct adsorption of pentaethylene glycol monododecyl ether (C12E5) to mica was also studied; low surface coverage adsorption was seen at the critical micelle concentration and above. C12E5 was then found not to remove the cationic layer, but did include into the layer to some degree. The presence of cationic surfactant on the mica was however shown to significantly modify the adsorption behaviour of the non-ionic surfactant.
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The adsorption of monoclonal antibodies (mAbs) on hydrophobic surfaces is known to cause protein aggregation and degradation. Therefore, surfactants, such as Poloxamer 188, are widely ...used in therapeutic formulations to stabilize mAbs and protect mAbs from interacting with liquid-solid interfaces. Here, the adsorption of Poloxamer 188, one mAb and their competitive adsorption on a model hydrophobic siliconized surface is investigated with neutron scattering coupled with contrast variation to determine the molecular structure of adsorbed layers for each case. Small angle neutron scattering measurements of the affinity of Poloxamer 188 to this mAb indicate that there is negligible binding at these solution conditions. Neutron reflectometry measurements of the mAb show irreversible adsorption on the siliconized surface, which cannot be washed off with neat buffer. Poloxamer 188 can be adsorbed on the surface already occupied by mAb, which enables partial removal of some adsorbed mAb by washing with buffer. The adsorption of the surfactant introduces significant conformational changes for mAb molecules that remain on the surface. In contrast, if the siliconized surface is first saturated with the surfactant, no adsorption of mAb is observed. Competitive adsorption of mAb and Poloxamer 188 from solution leads to a surface dominantly occupied with surfactant molecules, whereas only a minor amount of mAb absorbs. These findings clearly indicate that Poloxamer 188 can protect against mAb adsorption as well as modify the adsorbed conformation of previously adsorbed mAb.
Li‐Ion Batteries
In article number 2302402, Masaaki Hirayama and co‐workers clarify the mechanism of fast Li+‐intercalation in the Li‐ion battery using a Li2ZrO3‐modified LiCoO2 cathode with a model ...film electrode and in‐situ neutron reflectometry. The cathode electrolyte interphase on the modified LiCoO2 consists of inner and outer layers. The inner layer facilitates the desolvation of Li+, resulting in fast Li+‐intercalation.
Diffuse soft matter interfaces take many forms, from end-tethered polymer brushes or adsorbed surfactants to self-assembled layers of lipids. These interfaces play crucial roles across a multitude of ...fields, including materials science, biophysics, and nanotechnology. Understanding the nanostructure and properties of these interfaces is fundamental for optimising their performance and designing novel functional materials. In recent years, reflectometry techniques, in particular neutron reflectometry, have emerged as powerful tools for elucidating the intricate nanostructure of soft matter interfaces with remarkable precision and depth. This review provides an overview of selected recent developments in reflectometry and their applications for illuminating the nanostructure of diffuse interfaces. We explore various principles and methods of neutron and X-ray reflectometry, as well as ellipsometry, and discuss advances in their experimental setups and data analysis approaches. Improvements to experimental neutron reflectometry methods have enabled greater time resolution in kinetic measurements and elucidation of diffuse structure under shear or confinement, while innovation in analysis protocols has significantly reduced data processing times, facilitated co-refinement of reflectometry data from multiple instruments and provided greater-than-ever confidence in proposed structural models. Furthermore, we highlight some significant research findings enabled by these techniques, revealing the organisation, dynamics, and interfacial phenomena at the nanoscale. We also discuss future directions and potential advancements in reflectometry techniques. By shedding light on the nanostructure of diffuse interfaces, reflectometry techniques enable the rational design and tailoring of interfaces with enhanced properties and functionalities.
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