Effect of physical wear and triboelectric interaction on surface charge as measured by Kelvin probe microscopy

Surface charge of human hair has a significant effect on manageability, feel, and appearance. For this reason, controlling charge buildup to improve these factors is an important issue in the commercial hair care industry. Physical wear has been shown to cause surface potential change in conductors and semiconductors, and it is of interest whether or not physical wear alone can cause a surface potential change on hair and other insulating materials. It is known that interaction of hair with dissimilar materials, such as plastic combs, hands, and latex balloons, creates a charge on hair, and determining the mechanisms of this phenomenon is the purpose of this study. In this study the surface potential of human hair is measured using the Kelvin probe method with an atomic force microscope (AFM). A variety of samples are worn with a diamond tip to study the effect of physical wear on surface potential. Hair samples are rubbed with latex to study the effect of triboelectric charging on the microscale. The potential on the sample surface is then measured with a conductive tip. Caucasian virgin (undamaged), chemically damaged, and mechanically damaged hair samples are studied to determine the effect of damaging treatments on surface charge properties. Samples treated with PDMS silicone conditioner as well as those treated with an amino silicone conditioner are also studied to determine the effect of conditioner treatment. Mechanisms for the given results are discussed and recommendations given.     

Nanotribological and nanomechanical properties of skin with and without cream treatment using atomic force microscopy and nanoindentation

Various beauty care products involve surface interaction between the product and the skin surface they are applied to. Friction, adhesion and wear during sliding between the treated surface and the rubbing surfaces need to be optimized. Skin cream is used to improve skin health and create a smooth, soft, and flexible surface with moist perception by altering the surface roughness, friction, adhesion, elastic modulus, and surface charge of the skin surface. Rheology of skin cream as a function of cream thickness and strain rate and the binding interaction between skin cream and skin surface and operating environment are some of the important factors affecting the smooth feel and repair of the skin surface. Atomic force microscopy (AFM) and nanoindentation have recently become important tools for studying the micro/nanoscale properties of human hair, hair conditioner, skin, and skin cream. In this paper, we present an overview of the nanotribological and nanomechanical properties of skin with and without cream treatment as a function of operating environment. Relevant mechanisms are discussed. Next, the result of a triboelectrification study of skin with and without cream treatment is presented. Finally, an overview of attempts to develop a synthetic skin for research purposes is presented.     

Mechanism of nematic molecular alignment based on friction charges and surface topology by rubbing

A new and simple electric charge interaction mechanism has been proposed to explain the behaviour of the tilt angle of liquid crystals by rubbing. The mechanism of the molecular alignment is elucidated based on the effect of a static electric charge on a substrate surface treated by rubbing. An electric field which is dependent on the topology of a substrate surface allows a planar orientation of molecules with positive dielectric anisotropy. With increasing rubbing strength, the tilt angle varies slowly. The director of molecules with negative dielectric anisotropy is uniform and has a tilt angle determined by the molecular permanent dipole direction. The air-liquid crystal interface case is also considered. This model enables us to give a unified picture of the molecular alignment mechanism.     

Highly conductive nanostructured C-TiO2 electrodes with enhanced electrochemical stability and double layer charge storage capacitance

The present work reports the structural and electrochemical properties of carbon-modified nanostructured TiO(2) electrodes (C-TiO(2)) prepared by anodizing titanium in a fluoride-based electrolyte followed by thermal annealing in an atmosphere of methane and hydrogen in the presence of Fe precursors. The C-TiO(2) nanostructured electrodes are highly conductive and contain more than 1 × 10(10) /cm(2) of nanowires or nanotubes to enhance their double layer charge capacitance and electrochemical stability. Electrogenerated chemiluminescence (ECL) study shows that a C-TiO(2) electrode can replace noble metal electrodes for ultrasensitive ECL detection. Dynamic potential control experiments of redox reactions show that the C-TiO(2) electrode has a broad potential window for a redox reaction. Double layer charging capacitance of the C-TiO(2) electrode is found to be 3 orders of magnitude higher than an ideal planar electrode because of its high surface area and efficient charge collection capability from the nanowire structured surface. The effect of anodization voltage, surface treatment with Fe precursors for carbon modification, the barrier layer between the Ti substrate, and anodized layer on the double layer charging capacitance is studied. Ferrocene carboxylic acid binds covalently to the anodized Ti surface forming a self-assembled monolayer, serving as an ideal precursor layer to yield C-TiO(2) electrodes with better double layer charging performance than the other precursors.     

Charge regulation and ionic screening of patchy surfaces

The properties of surfaces with charge-regulated patches are studied using nonlinear Poisson-Boltzmann theory. Using a mode expansion to solve the nonlinear problem efficiently, we reveal the charging behavior of Debye-length sized patches. We find that the patches charge up to higher charge densities if their size is relatively small and if they are well separated. The numerical results are used to construct a basic analytical model which predicts the average surface charge density on surfaces with patchy chargeable groups.     

Single molecule charging by atomic force microscopy

AFM/KPM charging and charge mapping of polyamine charge carriers in a PMMA matrix is reported. Selective charging of the designed charge carrier is demonstrated at concentrations down to a single molecule. This works constitutes electrochemical charging and detection of single redox-active organic molecules in low dielectric matrices by probe microscopy.     

Rubbing-induced charge domains observed by electrostatic force microscopy: effect on liquid crystal alignment

The rubbing of polymer-coated substrates is one of the most frequently used techniques for liquid crystal alignment. However, the aligning mechanisms are not completely understood. The influence of friction charges induced by the rubbing process has been taken into account in theoretical publications. In this work we investigate the rubbing-induced charge domains of three polymers (PMMA, PI and PVA) with the electrostatic force microscopy technique, which allows the simultaneous determination of the surface topography and electrostatic potential. We observed a large intensity of the potential for the PMMA substrate, whereas no charge domains were observed for PVA. In addition, we followed the time evolution of the surface charge domains, and surprisingly after five days the charges were still present with a small reduction of intesity. Using polarizing optical microscopy we studied the influence of the charge domains on the LC aligning properties.     

Understanding suspension rheology of anisotropically-charged platy minerals from direct interaction force measurement using AFM

Based on the classical DLVO (Derjaguin–Landau–Verwey–Overbeek) theory, the maximum coagulation of fine particle suspensions would be predicated to occur at the point of zero charge (pzc) of the particles. Although this prediction has been fairly accurate for isotropic particles, the mismatch has been frequently reported for suspensions of anisotropically-charged or charge-mosaic particles, such as talc. Followed by successful preparation of sufficiently smooth talc edge surfaces using the ultramicrotome method for the colloidal force measurements using atomic force microscope (AFM), the anisotropic surface charge properties, i.e., surface charge characteristics of basal planes and edge surfaces of talc at different pH values were determined by fitting the measured force profiles between the AFM tip and both basal plane and edge surfaces to the DLVO theory. The talc basal planes were found to carry a permanent negative charge, while the charge on its edge surfaces was highly pH-dependent. The AFM-derived surface (Stern) potential values of talc basal planes and edge surfaces enable us to calculate the interaction energy for various associations between different charge-mosaic surfaces. The attractive interaction between talc basal planes and edge surfaces was found to dominate the rheological behavior. This study clearly demonstrates the necessity of determining anisotropic surface charge characteristics to improve the understanding of rheological properties and hence to better control their process performance.     

Solid‐to‐Liquid Charge Transfer for Generating Droplets with Tunable Charge

Charged liquid droplets are typically generated by a high‐voltage power supply. Herein, a previously unreported method is used for charging liquid droplets: by transferring charge from an insulating solid surface charged by contact electrification to the droplets. Charging the solid surface by contact electrification involves bringing it into contact with another solid surface for generating static charge. Subsequently, water droplets that flow across the surface are found to be charged—thus, the charge is readily transferred from solid to liquid. The charge of the droplets can be tuned continuously from positive to negative by varying the way the solid surface is charged. The amount of charge generated is sufficient for manipulating, coalescing, and sorting the water droplets by solid surfaces charged by contact electrification. This method of generating charged droplets is general, simple, inexpensive, and does not need any additional equipment or power supply.     

Effects of surface site distribution and dielectric discontinuity on the charging behavior of nanoparticles: a grand canonical Monte Carlo study

The surface site distribution and the dielectric discontinuity effects on the charging process of a spherical nanoparticle (NP) have been investigated. It is well known that electrostatic repulsion between charges on neighbouring sites tends to decrease the effective charge of a NP. The situation is more complicated close to a dielectric breakdown, since here a charged site is not only interacting with its neighbours but also with its own image charge and the image charges of all its neighbours. Coexistence of opposite charges, titration sites positions, and pH dependence are systematically studied using a grand canonical Monte Carlo method. A Tanford and Kirkwood approach has been applied to describe the interaction potentials between explicit discrete ampholytic charging sites. Homogeneous, heterogeneous and patch site distributions were considered to reproduce the titration site distribution at the solid/solution interface of natural NPs. Results show that the charging process is controlled by the balance between Coulomb interactions and the reaction field through the solid-liquid interface. They also show that the site distribution plays a crucial role in the charging process. In patch distributions, charges accumulate at the perimeter of each patch due to finite size effects. When homogeneous and heterogeneous distributions are compared, three different charging regimes are obtained. In homogeneous and heterogeneous (with quite low polydispersity indexes) distributions, the effects of the NP dielectric constant on Coulomb interactions are counterbalanced by the reaction field and in this case, the dielectric breakdown has no significant effect on the charging process. This is not the case in patch distributions, where the dielectric breakdown plays a crucial role in the charging process.     

Wetting and electrical properties of the human hair surface: delipidation observed at the nanoscale

The electrostatic properties and the wetting behaviour of the human hair surface at the nanometric scale have been investigated by using atomic force microscopy (AFM). Surface potential imaging was used to determine the electrostatic properties while non-contact mode AFM was used to investigate the wetting properties of a test liquid, squalane. We have studied natural hair and hair in which different covalently (18-methyleicosanoic acid) and non-covalently bound fatty acids present at the cuticle surface were selectively extracted. This study shows how the removal of these acids causes various profound changes in hair wettability at the cuticle scale.     

Dynamic response of AFM cantilevers to dissimilar functionalized silica surfaces in aqueous electrolyte solutions

The dynamic response of an oscillating microcantilever with a gold-coated tip interacting with dissimilar functionalized silica surfaces was studied in electrolyte solutions with pH ranging from 4 to 9. Silica surfaces were chemically modified, yielding dissimilar surfaces with -Br, -NH(2), and -CH(3) functional group terminations. The relative hydrophobicity of the surfaces was characterized by contact angle measurements. The surface charge of the functionalized surfaces was first probed with commonly used static AFM measurements and serves as a reference to the dynamic response data. The amplitude and phase of the cantilever oscillation were monitored and used to calculate the effective interaction stiffness and damping coefficient, which relate to the electrical double layer interactions and also to distance-dependent hydrodynamic damping at the solid/water interface. The data for the dynamic response of the AFM over silica surfaces as a function of chemical functionalization and electrolyte pH show that the effective stiffness has a distinctive dependence on the surface charge of functionalized silica surfaces. The hydrodynamic damping also correlates strongly with the relative hydrophobicity of the surface. The data reported here indicate that interfacial properties can be strongly affected by changing the chemical composition of surfaces.     

Charge heterogeneity of surfaces: mapping and effects on surface forces

The DLVO theory treats the total interaction force between two surfaces in a liquid medium as an arithmetic sum of two components: Lifshitz–van der Waals and electric double layer forces. Despite the success of the DLVO model developed for homogeneous surfaces, a vast majority of surfaces of particles and materials in technological systems are of a heterogeneous nature with a mosaic structure composed of microscopic and sub-microscopic domains of different surface characteristics. In such systems, the heterogeneity of the surface can be more important than the average surface character. Attractions can be stronger, by orders of magnitude, than would be expected from the classical mean-field DLVO model when area-averaged surface charge or potential is employed. Heterogeneity also introduces anisotropy of interactions into colloidal systems, vastly ignored in the past. To detect surface heterogeneities, analytical tools which provide accurate and spatially resolved information about material surface chemistry and potential — particularly at microscopic and sub-microscopic resolutions — are needed.Atomic force microscopy (AFM) offers the opportunity to locally probe not only changes in material surface characteristic but also charges of heterogeneous surfaces through measurements of force–distance curves in electrolyte solutions. Both diffuse-layer charge densities and potentials can be calculated by fitting the experimental data with a DLVO theoretical model. The surface charge characteristics of the heterogeneous substrate as recorded by AFM allow the charge variation to be mapped. Based on the obtained information, computer modeling and simulation can be performed to study the interactions among an ensemble of heterogeneous particles and their collective motions. In this paper, the diffuse-layer charge mapping by the AFM technique is briefly reviewed, and a new Diffuse Interface Field Approach to colloid modeling and simulation is briefly discussed.     

Free energy of charge transfer and intraprotein electric field: method of calculation depends on the charge state of protein at a given structure.

Free energy of charge transfer presents a basic characteristic of reactions such as protonation, oxido-reduction and similar. Evaluation of this quantity requires calculation of charging energy. Proteins are structured dielectrics, and a consistent incorporation of their structure into calculation of intraprotein electric field results in expression for charging energy of an active group in protein, which is essentially different from that for a simple dielectric. An algorithm for semi-continuum calculation of relevant free energies is described. First of the two components of charging energy in protein, energy of the medium response to charge redistribution in reactants, should be always calculated as the charging energy by the charge redistribution using the static dielectric constant of protein. The second term is interaction energy of the charge redistribution with the 'frozen' electric field of the system before reaction. Charges of protein groups, at which the protein structure has been determined, are often different from those before reaction of charge transfer, so is the corresponding intraprotein field. The field is expressed through either both the optical and static dielectric constants of protein or only optical one depending on whether the charges of protein groups before reaction and upon structural analysis are the same or not. Proper allowance for difference in charges of reacting groups before reaction and upon structural analysis of protein is thermodynamically necessary and quantitatively important. The expression for activation free energy for charge transfer in proteins is derived in the form presenting explicitly an invariant contribution of protein structure.     

Characterization of mineral oxide charging in apolar media

This paper presents an investigation of the charging behavior of mineral oxide particles dispersed in apolar media. There are a growing number of applications that seek to use electrostatic effects in apolar media to control particle movement and improve aggregation stability. Progress is limited, however, by incomplete knowledge of the mechanism(s) of particle charging in these systems. It has been shown in a number of cases that the acid-base properties of both the particles and the surfactants used to stabilize charge play key roles. A mechanism for acid-base charging has previously been established for mineral oxides in aqueous systems, where the surface hydroxyl groups act as proton donors or receivers depending on the pH of the surrounding solution. In water, the pH at which the surface charge density is zero, i.e., the point of zero charge (PZC), can be used to characterize the acid-base nature of the mineral oxide particles. The current work explores the possible extension of this charging behavior to apolar systems, with the key difference that the surface hydroxyl groups of the mineral oxides react with the surfactant molecules instead of free ions in solution. The apolar charging behavior is explored by measuring the electrophoretic mobility of a series of mineral oxides dispersed in a solution of Isopar-L and AOT, a neutral surfactant in water. The electrophoretic mobility of the particles is found to scale quantitatively, with respect to both sign and magnitude, with their aqueous PZC value. This provides support for the theory of acid-base charging in apolar media and represents a method for predicting and controlling particle charge of mineral oxides dispersed in apolar media.     

Kinetics of contact electrification between metals and polymers

Kinetics of charge transfer between metals and polymers was studied using an analytical rolling-sphere tool. The rates of charge transfer were related to the area of contact between contacting surfaces and the tunneling current between them. The derived rate equations accounted for the experimentally observed sigmoidal charging curves. Furthermore, for a model system of steel spheres rolling on modified polystyrene supports, it was shown that the magnitudes of separated charges can be varied by adjusting the polymer's surface properties and/or ambient conditions.     

Particle charging and charge screening in nonpolar dispersions with nonionic surfactants

The electrostatic stabilization of colloidal dispersions is usually considered the domain of polar media only because of the high energetic cost associated with introducing electric charge in nonpolar environments. Nevertheless, some surfactants referred to as "charge control agents" are known to raise the conductivity of liquids with low electric permittivity and to mediate charge stabilization of nonpolar dispersions. Here we study an example of the particularly counterintuitive charging and electrostatic interaction of colloidal particles in a nonpolar solvent caused by nonionic surfactants. PMMA particles in hexane solutions of nonionic sorbitan oleate (Span) surfactants are found to exhibit a field-dependent electrophoretic mobility. Extrapolation to zero field strength yields evidence for large electrostatic surface potentials that decay with increasing surfactant concentration in a fashion reminiscent of electrostatic screening caused by salt in aqueous solutions. The amount of surface charge and screening ions in the nonpolar bulk is further characterized via measurements of the particles' pair interaction energy. The latter is obtained by liquid structure analysis of quasi-2-dimensional equilibrium particle configurations studied with digital video microscopy. In contrast to the behavior reported for systems with ionic surfactants, we observe particle charging and a screened Coulomb type interaction both above and below the surfactant's critical micelle concentration.     

Super-stoichiometric charge neutralization in particle-polyelectrolyte systems

The adsorption of poly(vinylamine) (PVA) on poly(styrene sulfate) latex particles is studied, and its consequences on the charging behavior and suspension stability are investigated. The adsorption process is assessed by batch depletion experiments and time-resolved electrophoretic mobility measurements. The adsorption of PVA appears to be basically irreversible. The rate of adsorption decreases with decreasing polymer dose. At low polymer dose, the polymer coverage corresponds to the amount of the polyelectrolyte added, while at high polymer dose, the polymer coverage saturates the surface. Stability ratios are determined by dynamic light scattering, and strongly depend on the polymer dose and salt level. The aggregation is rapid near the isoelectric point (IEP), and it slows down when moving away from it. The charge neutralization is highly nonstoichiometric with charging ratios (CR) larger than unity, meaning that several charges on an adsorbed polyelectrolyte chain are necessary to neutralize a single charge on the particle surface. By comparing the IEP for particles and polyelectrolytes of different charge densities, we find a strong dependence of the CR on the mismatch between the average distances between individual charges on the surface and on the polyelectrolyte. A simple model is proposed to explain this trend.     

The interaction of cationic polymers with human hair

We present a combination of electrochemical methods, i.e. polyelectrolyte titration and streaming potential measurement, and AFM to characterise the adsorption and desorption behaviour and the morphology of a set of polyquaternium polymers on human hair. Specific charge density and molar mass are correlated to the amount of adsorbed polymer and the ease of desorption. Results are in line with a simple model of coulombic interaction between hair and polymer and are interpreted on this basis.     

Sliding-friction electrification of polymers and charge decay

Linear low-density polyethylene (LLDPE) and polypropylene (PP) were charged by sliding under a cylindrical aluminium contact. The surface charge accumulation on the polymer films was time dependent, and a function of the sliding velocity, metal contact force, and film type. The surface potential increased linearly with velocity in the range 0.33–0.75 m/s, and showed a square-root dependence on the contact force up to 6.5 N. Thermally stimulated charge decay (TSCD) studies showed longer charge lifetimes in samples friction-charged on one side than in corona-charged samples. Friction charging creates deeper near-surface traps than are normally present in the polymers. Charge stability is further imporved by simultaneously friction charging both surfaces of the films, increasing the half-value charge decay temperature (T_1/2) by 27°C and 37°C over that in corona-charged samples (i.e., to 98°C and 120°C for LLDPE and PP, respectively). These monopolarity electrets should prove useful in charge storage devices.