Dynamic performance of duolayers at the air/water interface. 2. Mechanistic insights from all-atom simulations

The novel duolayer system, comprising a monolayer of ethylene glycol monooctadecyl ether (C18E1) and the water-soluble polymer poly(vinylpyrrolidone) (PVP), has been shown to resist forces such as wind stress to a greater degree than the C18E1 monolayer alone. This paper reports all-atom molecular dynamics simulations comparing the monolayer (C18E1 alone) and duolayer systems under an applied force parallel to the air/water interface. The simulations show that, due to the presence of PVP at the interface, the duolayer film exhibits an increase in chain tilt, ordering, and density, as well as a lower lateral velocity compared to the monolayer. These results provide a molecular rationale for the improved performance of the duolayer system under wind conditions, as well as an atomic-level explanation for the observed efficacy of the duolayer system as an evaporation suppressant, which may serve as a useful guide for future development for thin films where resistance to external perturbation is desirable.

Manufacturing influence on the delamination fracture behavior of the T800H/3900-2 carbon fiber reinforced polymer composites

'Torayca' T800H/3900-2 is the first material qualified on Boeing Material Specification (BMS 8-276) which utilizes the thermoplastic-particulate interlayer toughening technology. Two manufacturing processes, the autoclave process and the fast heating rated Quickstep™ process, were employed to cure this material. The Quickstep process is a unique composite production technology which utilizes the fast heat transfer rate of fluid to heat and cure polymer composite components. The manufacturing influence on the mode I delamination fracture toughness of laminates was investigated by performing double cantilever beam tests. The composite specimens fabricated by two processes exhibited dissimilar delamination resistance curves (R-curves) under mode I loading. The initial value of fracture toughness GIC-INIT was 564 J/m2 for the autoclave specimens and 527 J/m2 for the Quickstep specimens. However, the average propagation fracture toughness GIC-PROP was 783 J/m2 for the Quickstep specimens, which was 2.6 times of that for the autoclave specimens. The mechanism of fracture occurred during delamination was studied under scanning electron microscope (SEM). Three types of fracture were observed: the interlayer fracture, the interface fracture, and the intralaminar fracture. These three types of fracture played different roles in affecting the delamination resistance curves during the crack growth. More fiber bridging was found in the process of delamination for the Quickstep specimens. Better fiber/matrix adhesion was found in the Quickstep specimens by conducting indentation-debond tests.

Characterisation of nickel(II) extraction by 2-hydroxy-5-nonylacetophenone oxime (LIX 84) in a micellar phase

The properties of the nickel(II)/2-hydroxy-5-nonylacetophenone oxime (HNAPO), an active ingredient in LIX 84, extraction system were characterised in a micellar system. The extinction coefficient, λ_max of HNAPO (316 nm) and the Ni²⁺ complex (387 nm) in a neutral micellar system, poly dispersed octa-ethyleneglycol mono-n-dodecyl ether (G₁₂A₈) were determined as 3100 and 3500 M⁻¹ cm⁻¹, respectively. HNAPO was found to have a neutral micellar phase and bulk aqueous phase pK_a of 11.5 and 12.5, respectively. The extraction equilibrium constant, K_ex, was determined to be 10^−8.0, and the deviation from theory observed at high pH can be accounted for by consideration of the competition for nickel(II) ions by hydroxide ions and HNAPO. A micellar phase of octa-ethyleneglycol mono-n-dodecyl ether (C₁₂E₈) was determined to be an appropriate model of the free oil/water interface from the solubilised location of HNAPO. Utilising the interfacial probe, 4-heptadecyl-7-hydroxy coumarin (HHC) allowed the determination of the electrostatic surface potential of mixed micelles of G₁₂A₈ and sodium dodecyl sulphate (SDS) or dodecyl trimethyl ammonium chloride (DTAC). The electrostatic surface potential was a linear function of the number of additional surfactant monomers within the G₁₂A₈ micelle, for the concentration range studied. For G₁₂A₈/DTAC mixed micelles, the surface potential was given by +1.1 mV per DTAC molecule per micelle, and for G₁₂A₈/SDS mixed micelles the relationship was −1.4 mV per SDS molecule per micelle.

On the electrochemical response and interfacial properties of steel–Ca(OH)2 and the steel–concrete system measured using galvanostatic pulses

The interfacial properties of the steel–concrete system are examined via a new approach for evaluation of galvanostatic pulse data. This methodology allows for rapid determination of the corrosion activity of steel, and readily yields values for parameters related to corrosion such as the polarisation resistance and interfacial capacitance. The method of analysis is based on the iterative fitting of a non-exponential model based on a modified Kohlrausch–Williams–Watt (KWW) formalism. The transient behaviour of steel in concrete is non-exponential in its form and, when analysed this way, an exponent β can be determined characterising the exponential non-ideality of the transient. This non-ideality parameter is found to differ significantly for actively corroding and passive specimens, thereby serving as a useful index to the level of corrosion being experienced. Furthermore, the investigation of the interfacial characteristics of the system, previously unobtainable in a reproducible manner via other electrochemical methods, reveal information regarding the kinetic factors governing corrosion of steel in concrete.

Ceramic-polymer interface in composite electrolytes of lithium aluminium titanium phosphate and polyetherurethane polymer electrolyte

Composite electrolytes of the lithium-ion-conducting ceramic Li_1.3Al_0.3Ti_1.7(PO₄)₃ and polyetherurethane/lithium triflate polymer electrolyte have been prepared. Microscopy has shown that adhesion between the ceramic and polymer phases is poor, with gaps up to 1 μm at the interface. When dry, the composites are no more conductive than the pure polymer electrolyte. Exposing the samples to the vapour of solvents such as DMF, acetonitrile or water produces a significant increase in conductivity, over and beyond simple plasticization of the polymer. Pretreating the ceramic with a compatibilizing agent improves adhesion at the interface with the polymer, but decreases overall conductivity in the case investigated.

Double layer structure of ionic liquids at the Au(111) electrode interface : an atomic force microscopy investigation

The double layer structure of two ionic liquids (ILs), 1-butyl-1- methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py ₁,₄]FAP) and 1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([EMIm]FAP) at the polarized Au(111) electrode interface is probed using Atomic Force Microscopy force measurements. The force-separation profiles suggest a multilayered morphology is present at the electrified Au(111)-IL interface, with more near surface layers detected at higher potentials. At the (slightly negative) open circuit potential, multiple ion layers are present, and the innermost layer, in contact with the Au(111) surface, is enriched in the cation due to electrostatic adsorption. Upon applying negative electrode potentials (-1.0 V, -2.0 V), stronger IL near surface structure is detected: both the number of ion layers and the force required to rupture these layers increases. Positive electrode potentials (+1.0 V, +2.0 V) also enhance IL near surface structure, but not as much as negative potentials, because surface-adsorbed anions are less effective at templating structure in subsequent layers than cations. This interfacial structure is not consistent with a double layer in the Stern-Gouy-Chapman sense, as there is no diffuse layer. The structure is consistent with a capicitative double-layer model, with a very small separation distance between the planes of charge.

Optical phase change at the interface between mica and thin silver film

We describe a simple experiment which allows unequivocal determination of optical phase change upon reflection of light at the mica-silver interface. While the physical origin of such a phase change at the dielectric-metal interface is well understood to lie in absorption of electromagnetic energy by the metal, inconsistency and ambiguity has persisted as to what its sign and magnitude should be in the field of thin film optics. Most commonly, it has been assigned to be negative for mathematical convenience or just arbitrarily. Our finding shows that with the convention exp(-iωt) for time dependence of the electromagnetic wave, the phase change at the interface between mica and the thin silver film is necessarily positive and its magnitude falls between π and 3π/2 for silver thicknesses down to nanometres. This gives a physically reasonable correspondence to an increased equivalent thickness of the dielectric material, and it clarifies the assignment of interference orders in the harmonic series in a spectrum.

Effects of tool positioning on joint interface microstructure and fracture strength of friction stir lap Al-to-steel welds

Friction stir lap welding (FSLW) experiments have been conducted to study the effects of tool positioning on microstructures formed in the Al-to-steel interface region and on joint strength, defined as maximum applied force over the width (F m/w s) of the test sample, of the welds. Various pin positioning and speed conditions were used in the FSLW experiments followed by microstructure examination on the interface regions and tensile-shear testing on the welds, including an examination on crack propagation in mixed stir zone. It was found that when the pin was close to the bottom steel piece, Al-to-steel reaction occurred resulting in intermetallic outbursts formed along the interface. This represents the case of incomplete metallurgical joint. When the pin was lowered to just reach the steel, a thin and continued interface intermetallic layer formed. Evidences and consideration on growth kinetics have suggested that the layer could only remain thin (≤2.5 μm) during FSLW. This layer could bear a high load during tensile-shear testing and the adjacent aluminium deformed and fractured instead. The resulting F m/w s was high. When the pin penetrated to steel, F m/w s reduced due to brittle fracture being dominant inside mixed stir zone. Evidences have shown that the amount of penetration and speed condition during FSLW do not have large effects on F m/w s.

Influence of the sonication temperature on the debundling kinetics of carbon nanotubes in Propan-2-ol

The effect of sonication temperature on the debundling of carbon nanotube (CNT) macro-bundles is reported and demonstrated by analysis with different particle sizing methods. The change of bundle size over time and after several comparatively gentle sonication cycles of suspensions at various temperatures is reported. A novel technique is presented that produces a more homogeneous nanotube dispersion by lowering the temperature during sonication. We produce evidence that temperature influences the suspension stability, and that low temperatures are preferable to obtain better dispersion without increasing damage to the CNT walls.

Structure and properties of citrate overlayers adsorbed at the aqueous Au(111) interface.

One of the most common means of gold nanoparticle (AuNP) biofunctionalization involves the manipulation of precursor citrate-capped AuNPs via ligand displacement. However, the molecular-level structural characteristics of the citrate overlayer adsorbed at the aqueous Au interface at neutral pH remain largely unknown. Access to atomistic-scale details of these interfaces will contribute much needed insight into how AuNPs can be manipulated and exploited in aqueous solution. Here, the structures of such citrate overlayers adsorbed at the aqueous Au(111) interface at pH 7 are predicted and characterized using atomistic molecular dynamics simulations, for a range of citrate surface densities. We find that the overlayers are disordered in the surface density range considered, and that many of their key characteristics are invariant with surface density. In particular, we predict the overlayers to have 3-D, rather than 2-D, morphologies, with the anions closest to the gold surface being oriented with their carboxylate groups pointing away from the surface. We predict both striped and island morphologies for our overlayers, depending on the citrate surface density, and in all cases we find bare patches of the gold surface are present. Our simulations suggest that both citrate-gold adsorption and citrate-counterion pairing contribute to the stability of these citrate overlayer morphologies. We also calculate the free energy of adsorption at the aqueous Au(111) interface of a single citrate molecule, and compare this with the corresponding value for a single arginine molecule. These findings enable us to predict the conditions under which ligand displacement of surface-adsorbed citrate by arginine may take place. Our findings represent the first steps toward elucidating a more elaborate, detailed atomistic-scale model relating to the biofunctionalization of citrate-capped AuNPs.

EEG signal classification for BCI applications by wavelets and interval type-2 fuzzy logic systems

The nonlinear, noisy and outlier characteristics of electroencephalography (EEG) signals inspire the employment of fuzzy logic due to its power to handle uncertainty. This paper introduces an approach to classify motor imagery EEG signals using an interval type-2 fuzzy logic system (IT2FLS) in a combination with wavelet transformation. Wavelet coefficients are ranked based on the statistics of the receiver operating characteristic curve criterion. The most informative coefficients serve as inputs to the IT2FLS for the classification task. Two benchmark datasets, named Ia and Ib, downloaded from the brain-computer interface (BCI) competition II, are employed for the experiments. Classification performance is evaluated using accuracy, sensitivity, specificity and F-measure. Widely-used classifiers, including feedforward neural network, support vector machine, k-nearest neighbours, AdaBoost and adaptive neuro-fuzzy inference system, are also implemented for comparisons. The wavelet-IT2FLS method considerably dominates the comparable classifiers on both datasets, and outperforms the best performance on the Ia and Ib datasets reported in the BCI competition II by 1.40% and 2.27% respectively. The proposed approach yields great accuracy and requires low computational cost, which can be applied to a real-time BCI system for motor imagery data analysis.

Facilitating effects of transcranial direct current stimulation on motor imagery brain-computer interface with robotic feedback for stroke rehabilitation

OBJECTIVE: To investigate the efficacy and effects of transcranial direct current stimulation (tDCS) on motor imagery brain-computer interface (MI-BCI) with robotic feedback for stroke rehabilitation. DESIGN: A sham-controlled, randomized controlled trial. SETTING: Patients recruited through a hospital stroke rehabilitation program. PARTICIPANTS: Subjects (N=19) who incurred a stroke 0.8 to 4.3 years prior, with moderate to severe upper extremity functional impairment, and passed BCI screening. INTERVENTIONS: Ten sessions of 20 minutes of tDCS or sham before 1 hour of MI-BCI with robotic feedback upper limb stroke rehabilitation for 2 weeks. Each rehabilitation session comprised 8 minutes of evaluation and 1 hour of therapy. MAIN OUTCOME MEASURES: Upper extremity Fugl-Meyer Motor Assessment (FMMA) scores measured end-intervention at week 2 and follow-up at week 4, online BCI accuracies from the evaluation part, and laterality coefficients of the electroencephalogram (EEG) from the therapy part of the 10 rehabilitation sessions. RESULTS: FMMA score improved in both groups at week 4, but no intergroup differences were found at any time points. Online accuracies of the evaluation part from the tDCS group were significantly higher than those from the sham group. The EEG laterality coefficients from the therapy part of the tDCS group were significantly higher than those of the sham group. CONCLUSIONS: The results suggest a role for tDCS in facilitating motor imagery in stroke.

The influence of fine ferrite formation on the γ/α interface, fine bainite and retained austenite in a thermomechanically-processed transformation induced plasticity steel

An Fe-0.26C-1.96Si-2Mn with 0.31Mo (wt%) steel was subjected to a novel thermomechanical processing route to produce fine ferrite with different volume fractions, bainite, and retained austenite. Two types of fine ferrites were found to be: (i) formed along prior austenite grain boundaries, and (ii) formed intragranularly in the interior of austenite grains. An increase in the volume fraction of fine ferrite led to the preferential formation of blocky retained austenite with low stability, and to a decrease in the volume fraction of bainite with stable layers of retained austenite. The difference in the morphology of the bainitic ferrite and the retained austenite after different isothermal ferrite times was found to be responsible for the deterioration of the mechanical properties. The segregation of Mn, Mo, and C at distances of 2-2.5 nm from the ferrite and retained austenite/martensite interface on the retained austenite/martensite site was observed after 2700 s of isothermal hold. It was suggested that the segregation occurred during the austenite-to-ferrite transformation, and that this would decrease the interface mobility, which affects the austenite-to-ferrite transformation and ferrite grain size.

Supported silver nanoparticle and near-interface solution dynamics in a deep eutectic solvent

Type III deep eutectic solvents (DES) have attracted significant interest as both environmentally friendly and functional solvents that are, in some ways, advantageous to traditional aqueous systems. While these solvents continue to produce remarkable thin films and nanoparticle assemblies, their interactions with metallic surfaces are complex and difficult to manipulate. In this study, the near-surface region (2-600 nm) of a carbon surface is investigated immediately following silver nanoparticle nucleation and growth. This is accomplished, in situ, using a novel grazing transmission small-angle X-ray scattering approach with simultaneous voltammetry and electrochemical impedance spectroscopy. With this physical and electrochemical approach, the time evolution of three distinct surface interaction phenomena is observed: aggregation and coalescence of Ag nanoparticles, multilayer perturbations induced by nonaggregated Ag nanoparticles, and a stepwise transport of dissolved Ag species from the carbon surface. The multilayer perturbations contain charge-separated regions of positively charged choline-ethylene and negatively charged Ag and Cl species. Both aggregation-coalescence and the stepwise decrease in Ag precursor near the surface are observed to be very slow (∼2 h) processes, as both ion and particle transport are significantly impeded in a DES as compared to aqueous electrolytes. Altogether, this study shows how the unique chemistry of the DES changes near the surface and in the presence of nanoparticles that adsorb the constituent species.

Growth of bainitic ferrite and carbon partitioning during the early stages of bainite transformation in a 2 mass% silicon steel studied by in situ neutron diffraction, TEM and APT

In situ neutron diffraction, transmission electron microscopy (TEM) and atom probe tomography (APT) have been used to study the early stages of bainite transformation in a 2 mass% Si nano-bainitic steel. It was observed that carbon redistribution between the bainitic ferrite and retained austenite at the early stages of the bainite transformation at low isothermal holding occurred in the following sequence: (i) formation of bainitic ferrite nuclei within carbon-depleted regions immediately after the beginning of isothermal treatment; (ii) carbon partitioning immediately after the formation of bainitic ferrite nuclei but substantial carbon diffusion only after 33 min of bainite isothermal holding; (iii) formation of the carbon-enriched remaining austenite in the vicinity of bainitic laths at the beginning of the transformation; (iv) segregation of carbon to the dislocations near the austenite/ferrite interface; and (v) homogeneous redistribution of carbon within the remaining austenite with the progress of the transformation and with the formation of bainitic ferrite colonies. Bainitic ferrite nucleated at internal defects or bainite/austenite interfaces as well as at the prior austenite grain boundary. Bainitic ferrite has been observed in the form of an individual layer, a colony of layers and a layer with sideplates at the early stages of transformation.