An electrochemical quartz crystal microbalance (EQCM) based on microelectrode arrays allows to distinguish between adsorption and electrodeposition.

Using a precise electrochemical quartz crystal microbalance (EQCM), it was shown that electrogravimetry can be carried out with microelectrode arrays (MEAs). MEAs were prepared on the resonator surface by coating it with a thin polymer layer containing holes, where the holes constitute the microelectrodes. The preparation procedures, their benefits, and their limitations are discussed. Microelectrode-based electrogravimetry is challenging because the reduced active area reduces the QCM signal. It is still feasible. This work is limited to linear voltage ramps (as opposed to steps). The processes chosen for demonstration were the electrodeposition/stripping of copper and the redox cycling of methyl viologen dichloride (MVC). The current trace often showed microelectrodic behavior, depending on the sweep rate. For the case of copper deposition, the mass transfer rate was proportional to the electric current. For the case of MVC, the electric current showed a plateau at the ends of the current-voltage diagram, but the mass transfer rate did not change. The difference can be explained by adsorption and desorption going into saturation at the two ends of the voltage range. Based on whether or not a microelectrodic gravimetric signal is seen, it can be stated whether the mass transfer is closely linked to the current. Further advantages of the microelectrode-based EQCM are an improved access to fast processes, reduced effects of double layer recharging, and the possibility to work at a low electrolyte support.

Effect of Noise on Determining Ultrathin-Film Parameters from QCM-D Data with the Viscoelastic Model.

Quartz crystal microbalance with dissipation monitoring (QCM-D) is a well-established technique for studying soft films. It can provide gravimetric as well as nongravimetric information about a film, such as its thickness and mechanical properties. The interpretation of sets of overtone-normalized frequency shifts, ∆f/n, and overtone-normalized shifts in half-bandwidth, ΔΓ/n, provided by QCM-D relies on a model that, in general, contains five independent parameters that are needed to describe film thickness and frequency-dependent viscoelastic properties. Here, we examine how noise inherent in experimental data affects the determination of these parameters. There are certain conditions where noise prevents the reliable determination of film thickness and the loss tangent. On the other hand, we show that there are conditions where it is possible to determine all five parameters. We relate these conditions to the mathematical properties of the model in terms of simple conceptual diagrams that can help users understand the model's behavior. Finally, we present new open source software for QCM-D data analysis written in Python, PyQTM.

Square-Wave Electrogravimetry Combined with Voltammetry Reveals Reversible Submonolayer Adsorption of Redox-Active Ions.

Square-wave voltammetry on electrolytes containing reversible redox pairs in solution was complemented by acoustic microgravimetry, where multifrequency lock-in amplification provides for a time resolution of 2.5 ms and a frequency resolution after accumulation of 12 mHz. The instrument operates similar to a quartz crystal microbalance with dissipation monitoring (QCM-D). The use of square-waves rather than linear ramps makes the analysis more transparent because it reduces the contribution of non-Faraday currents. Also, square-wave electrogravimetry determines the rates of mass transfer with much better sensitivity than its counterpart based on linear voltage ramps. The shifts of frequency and bandwidth are in agreement with the Sauerbrey prediction, meaning that the overtone-normalized frequency shifts, Δf/n, are similar on the different overtones and that the shifts in half bandwidth, ΔΓ, are smaller than the shifts in frequency. Small deviations from the Sauerbrey prediction presumably result from the softness of the adsorbed layer. Because the response time of the QCM signals is much longer than the RC time of double layer recharging as determined with electrochemical impedance spectroscopy (EIS), interpretation in terms of adsorption and desorption is more plausible than interpretation in terms of changed viscosity in the diffuse double layer. Ions of methyl viologen (MV) were found to adsorb to the electrode surface more strongly in the state with a single charge than in the fully oxidized state carrying two charges. The difference in apparent thickness between the oxidized and the reduced state was up to 2 nm, depending on concentration. The gravimetric results obtained on flavin adenine dinucleotide (FAD) depended on pH. At neutral pH, adsorption was largest close to the redox potential. Presumably, the adsorbed molecules are semiquinones, that is, are the intermediates of the underlying two-electron process.

Fast and slow EQCM response of zwitterionic weak electrolytes to changes in the electrode potential: a pH-mediated mechanism.

Using a fast electrochemical quartz crystal microbalance (EQCM), zwitterionic electrolytes were studied with regard to changes of resonance frequency and resonance bandwidth after the electrode potential was switched. In addition to a fast change of frequency (within milliseconds), a further, slower process with opposite direction is observed. Both the fast and the slow process change sign when the pH is varied across the isoelectric point (pI). The fast process can be attributed to double layer recharging. Its characteristic time is slightly larger than the charge response time (the RC-time) as inferred from electrochemical impedance spectroscopy (EIS). With regard to the slow process, amino acids with moderate concentration behave markedly different from concentrated solutions of proteins. For amino acids, the slow process is larger in amplitude than the fast process and the QCM response is Sauerbrey-like. The shift in half bandwidth is smaller than the shift in frequency and the overtone-normalized frequency shifts agree between overtones (-Δf/n ≈ const. with n the overtone order). This can be explained with a viscosity change in the diffuse double layer. Independent measurements show that the viscosities of these electrolytes are higher than the average in a pH range around the pI. Presumably, the slow process reflects a rearrangement of molecules after the net charge on the molecule has increased or decreased, changing the degree of dipolar coupling and, in consequence, the viscosity. For concentrated solutions of bovine serum albumin (BSA), the QCM response does not follow Sauerbrey behaviour, which can be explained with viscoelasticity and viscoelastic dispersion. The slow process lets the frequency and the bandwidth relax towards a baseline, which is the same for jumps to more positive and to more negative potentials. Presumably, the slow process in this case is caused by a reorientation of molecules inside the Helmholtz layer, such that they screen the electric field more efficiently than immediately after the voltage jump.

Soft Viscoelastic Particles in Contact with a Quartz Crystal Microbalance (QCM): A Frequency-Domain Lattice Boltzmann Simulation.

Shifts of frequency and bandwidth of a quartz crystal microbalance (QCM) in contact with a structured, viscoelastic sample have been computed with a linearized version of the lattice Boltzmann method (LBM). The algorithm operates in the frequency domain and covers viscoelasticity. The different domains are characterized by different values of the complex viscosity, η, equivalent to different values of the shear modulus, G. Stiff particles are given large |ηSph|, where |ηSph| must be less than ∼100 ηbulk with ηbulk the viscosity of the ambient liquid. Critical to the computational efficiency is a match of the LBM populations at the upper boundary of the simulation box to an analytical solution of the Stokes equation in the bulk above the box. The application example is a test of the ΔΓ/(-Δf)-extrapolation scheme, where Δf and ΔΓ are the shifts in resonance frequency and half bandwidth, respectively. For adsorbed particles, plots of ΔΓ/(-Δf) versus - Δf/n (with n the overtone order) show almost straight lines. The extrapolation of these lines to zero yields a frequency shift, which, after conversion to a thickness with the Sauerbrey equation, closely agrees with the height of the particles. Plots of Δf/n and ΔΓ/n versus n look similar to the corresponding plots obtained for viscoelastic films, where the parameters, which would usually be extracted from those plots (apparent mass and apparent compliance), depend on the geometry and the sample's viscoelasticity in a nontrivial way.

Studying Soft Interfaces with Shear Waves: Principles and Applications of the Quartz Crystal Microbalance (QCM).

The response of the quartz crystal microbalance (QCM, also: QCM-D for "QCM with Dissipation monitoring") to loading with a diverse set of samples is reviewed in a consistent frame. After a brief introduction to the advanced QCMs, the governing equation (the small-load approximation) is derived. Planar films and adsorbates are modeled based on the acoustic multilayer formalism. In liquid environments, viscoelastic spectroscopy and high-frequency rheology are possible, even on layers with a thickness in the monolayer range. For particulate samples, the contact stiffness can be derived. Because the stress at the contact is large, the force is not always proportional to the displacement. Nonlinear effects are observed, leading to a dependence of the resonance frequency and the resonance bandwidth on the amplitude of oscillation. Partial slip, in particular, can be studied in detail. Advanced topics include structured samples and the extension of the small-load approximation to its tensorial version.

Kinetics of viscoelasticity in the electric double layer following steps in the electrode potential studied by a fast electrochemical quartz crystal microbalance (EQCM).

Changes in the viscoelasticity of the electric double layer following steps in electrode potential were studied with an electrochemical quartz crystal microbalance (EQCM). The overtone scaling was the same as in gravimetry (-Δf/n≈ const with Δf the frequency shift and n the overtone order). Changes in half-bandwidth were smaller than changes in frequency. This Sauerbrey-type behaviour can be explained with either adsorption/desorption or with changes of the (Newtonian) viscosity of the diffuse double layer. While the QCM data alone cannot distinguish between these two processes, independent information supports the explanation in terms of double layer viscosity. Firstly, the magnitudes of the frequency response correlated with the expected changes of the viscosity-density product in the diffuse double layer. With regard to viscosity, these expectations are based on the viscosity B-coefficients as employed in the Jones-Dole equation. Expected changes in density were estimated from the densities of the respective salts. Secondly, the explanation in terms of liquid-like response matches the kinetic data. The response times of frequency and bandwidth were similar to the response times of the charge as determined with electrochemical impedance spectroscopy (EIS). Rearrangements in the Helmholtz layer should have been slower, given this layer's rigidity. Kinetic information obtained with a QCM can aid the understanding of processes at the electrode-electrolyte interface.

A Quartz Crystal Microbalance, Which Tracks Four Overtones in Parallel with a Time Resolution of 10 Milliseconds: Application to Inkjet Printing.

A quartz crystal microbalance (QCM) is described, which simultaneously determines resonance frequency and bandwidth on four different overtones. The time resolution is 10 milliseconds. This fast, multi-overtone QCM is based on multi-frequency lockin amplification. Synchronous interrogation of overtones is needed, when the sample changes quickly and when information on the sample is to be extracted from the comparison between overtones. The application example is thermal inkjet-printing. At impact, the resonance frequencies change over a time shorter than 10 milliseconds. There is a further increase in the contact area, evidenced by an increasing common prefactor to the shifts in frequency, Δf, and half-bandwidth, ΔΓ. The ratio ΔΓ/(-Δf), which quantifies the energy dissipated per time and unit area, decreases with time. Often, there is a fast initial decrease, lasting for about 100 milliseconds, followed by a slower decrease, persisting over the entire drying time (a few seconds). Fitting the overtone dependence of Δf(n) and ΔΓ(n) with power laws, one finds power-law exponents of about 1/2, characteristic of semi-infinite Newtonian liquids. The power-law exponents corresponding to Δf(n) slightly increase with time. The decrease of ΔΓ/(-Δf) and the increase of the exponents are explained by evaporation and formation of a solid film at the resonator surface.

Fast pH-mediated changes of the viscosity of protein solutions studied with a voltage-modulated quartz crystal microbalance.

An electrochemical quartz crystal microbalance is described, which achieves a time resolution down to 100 µs. Accumulation and averaging over a few hours bring the noise down to about 30 mHz. The application examples are pH-driven viscosity changes in albumin solutions. The pH was switched with the electrode potential. The characteristic response time is in the millisecond range. The focus is on experimental aspects as well as advantages and limitations of the technique.

An ultrafast quartz crystal microbalance based on a frequency comb approach delivers sub-millisecond time resolution.

Quartz crystal microbalance with dissipation monitoring (QCMD) is a simple and versatile sensing technique with applications in a wide variety of academic and industrial fields, most notably electrochemistry, biophysics, quality control, and environmental monitoring. QCMD is limited by a relatively poor time resolution, which is of the order of seconds with conventional instrument designs at the noise level usually required. In this work, we present a design of an ultrafast QCMD with submillisecond time resolution. It is based on a frequency comb approach applied to a high-fundamental-frequency (HFF) resonator through a multifrequency lock-in amplifier. The combination allows us to reach data acquisition rates >10 kHz. We illustrate the method using a toy model of a glass sphere dropped on the resonator surfaces, bare or coated with liposomes, in liquid. We discuss some interesting features of the results obtained with the dropped spheres, such as bending of the HFF resonators due to the impact, sphere bouncing (or the absence of it), and contact aging.

Gaseous "nanoprobes" for detecting gas-trapping environments in macroscopic films of vapor-deposited amorphous ice.

Vapor-deposited amorphous ice, traditionally called amorphous solid water (ASW), is one of the most abundant materials in the universe and a prototypical material for studying physical vapor-deposition processes. Its complex nature arises from a strong tendency to form porous structures combined with complicated glass transition, relaxation, and desorption behavior. To gain further insights into the various gas-trapping environments that exist in ASW and hence its morphology, films in the 25-100 µm thickness range were codeposited with small amounts of gaseous "nanoprobes" including argon, methane, helium, and carbon dioxide. Upon heating in the 95-185 K temperature range, three distinct desorption processes are observed which we attribute to the gas desorption out of open cracks above 100 K, from internal voids that collapse due to the glass transition at ∼125 K and finally from fully matrix-isolated gas induced by the irreversible crystallization to stacking disordered ice (ice Isd) at ∼155 K. Nanoscale films of ASW have only displayed the latter desorption process which means that the first two desorption processes arise from the macroscopic dimensions of our ASW films. Baffling the flow of water vapor toward the deposition plate greatly reduces the first desorption feature, and hence the formation of cracks, but it significantly increases the amount of matrix-isolated gas. The complex nature in which ASW can trap gaseous species is thought to be relevant for a range of cosmological processes.

Lipid phase behavior studied with a quartz crystal microbalance: A technique for biophysical studies with applications in screening.

Quartz crystal microbalance (QCM) is emerging as a versatile tool for studying lipid phase behavior. The technique is attractive for fundamental biophysical studies as well applications because of its simplicity, flexibility, and ability to work with very small amounts of material crucial for biomedical studies. Further progress hinges on the understanding of the mechanism, by which a surface-acoustic technique such as QCM, senses lipid phase changes. Here, we use a custom-built instrument with improved sensitivity to investigate phase behavior in solid-supported lipid systems of different geometries (adsorbed liposomes and bilayers). We show that we can detect a model anesthetic (ethanol) through its effect on the lipid phase behavior. Further, through the analysis of the overtone dependence of the phase transition parameters, we show that hydrodynamic effects are important in the case of adsorbed liposomes, and viscoelasticity is significant in supported bilayers, while layer thickness changes make up the strongest contribution in both systems.

Probing the electrical impedance of thin films on a quartz crystal microbalance (QCM), making use of frequency shifts and piezoelectric stiffening.

Using a temperature-responsive polymer film as an example, it was shown that a conventional quartz crystal microbalance (QCM) can probe a sample's electrical properties in addition to its thickness and softness. The film's electrical impedance was accessed by alternating between the driving voltage being applied to the front electrode and the back electrode. The opposing electrode was grounded in both cases. In the first configuration, the electrical properties of the sample do have an influence on the resonance frequency because of piezoelectric stiffening. In the second, they do not. Using this scheme, it was monitored how the electrical impedance of a film composed of a mixture of poly-N-isopropylacrylamide and polyvinylalcohol changes when the film swells and deswells.

Coupled resonances allow studying the aging of adhesive contacts between a QCM surface and single, micrometer-sized particles.

Interparticle contacts and contacts between particles and surfaces are known to change over time. The contact area, the contact stiffness, and the contact strength usually increase as the contact ages. Contact aging is mostly driven by capillary forces, but also by plastic deformation. Making use of acoustic resonators, we have studied the stiffness of contacts between the surface of a quartz crystal microbalance (QCM) and individual, micrometer-sized particles adsorbed to the resonator surface. Studying single particles avoids ensemble-averaging. Central to the analysis is the coupled resonance, occurring when a surface-attached particle together with the link forms a resonator of its own. If the frequency of this second resonator comes close to one of the crystal's overtones, plots of shifts in resonance bandwidth versus overtone order display a resonance curve. This secondary resonance is caused by the coupling between the particle's resonance and the main resonance. One can read the frequency of the coupled resonance from this plot. Similarly, resonance curves are observed in plots of frequency and bandwidth versus time, if the contact stiffness varies smoothly with time. Because the coupled resonance is a characteristic feature, it is easily identified even in cases where frequency shifts of some other origin are superimposed onto the data. For the cases studied here, the links stiffened while they dried. Interestingly, the efficiency of coupling between the particle resonance and the main resonance decreased at the same time. This can be explained with an increase in the link's bending stiffness. The analysis highlights that a QCM experiment amounts to vibrational spectroscopy on surface-attached particles. Among the application examples is the adsorption and drying of a lycopodium spore. Clearly, the technique is also applicable to problems of bioadhesion.

Steady flows above a quartz crystal resonator driven at elevated amplitude.

A steady flow of liquid was observed above the surface of a quartz crystal microbalance under conditions where the oscillation amplitude exceeded 10 nm. The streaming flow occurs parallel to the displacement vector and is directed towards the center of the plate. It is expected to have applications in acoustic sensing, in microfluidics, and in micromechanics in a wider sense. The flow is caused by the nonlinear term in the Navier-Stokes equation, which can produce a nonzero time-averaged force from a periodic velocity field. Central to the explanation are the flexural admixtures to the resonator's mode of vibration. Unlike pressure-driven flows, the acoustically driven steady flow attains its maximum velocity at a distance of a few hundred nanometers from the surface. It is therefore efficient in breaking bonds between adsorbed particles and the resonator surface. As a side aspect, the flow pattern amounts to a diagnostic tool, which gives access to the pattern of vibration. In particular, it leads to an estimate of the magnitude of the flexural admixtures to the thickness-shear vibration.

Attractive forces on hard and soft colloidal objects located close to the surface of an acoustic-thickness shear resonator.

Colloidal particles located close to the surface of an acoustic thickness shear resonator feel an attractive steady force, which is induced by the high-frequency tangential motion of the resonator surface. The range of the force is about half the penetration depth of the transverse viscous wave, that is, half of the thickness of the Stokes boundary layer. For an oscillation amplitude of 10 nm and a particle radius of 100 nm, the depth of attractive potential well corresponds to about 3 times the thermal energy, k(B)T. The force therefore suffices to overcome Brownian motion.

Controlled synthesis of cell-laden microgels by radical-free gelation in droplet microfluidics.

Micrometer-sized hydrogel particles that contain living cells can be fabricated with exquisite control through the use of droplet-based microfluidics and bioinert polymers such as polyethyleneglycol (PEG) and hyperbranched polyglycerol (hPG). However, in existing techniques, the microgel gelation is often achieved through harmful reactions with free radicals. This is detrimental for the viability of the encapsulated cells. To overcome this limitation, we present a technique that combines droplet microfluidic templating with bio-orthogonal thiol-ene click reactions to fabricate monodisperse, cell-laden microgel particles. The gelation of these microgels is achieved via the nucleophilic Michael addition of dithiolated PEG macro-cross-linkers to acrylated hPG building blocks and does not require any initiator. We systematically vary the microgel properties through the use of PEG linkers with different molecular weights along with different concentrations of macromonomers to investigate the influence of these parameters on the viability and proliferation of encapsulated yeast cells. We also demonstrate the encapsulation of mammalian cells including fibroblasts and lymphoblasts.

Self-stratification during film formation from latex blends driven by differences in collective diffusivity.

Coatings with vertical gradients in composition were produced by drying an aqueous polymer dispersion containing both charged and neutral particles. After drying, the neutral component was enriched at the film/air interface. The spontaneous vertical segregation between the two types of particles goes back to a difference in collective diffusivity. As the film dries, a layer enriched in polymer develops at the top. Due to their mutual repulsion, charged spheres escape from this layer more quickly than their neutral counterparts. Provided that the total time of drying is between the times of diffusion for the two types of particles (approximately H(0)(2)/D(c) with H(0) the initial film thickness and D(c) the collective diffusivity of the respective species), a concentration gradient persists after the film has turned dry. This effect can be used to create a functionally graded material (FGM) in a single coating step.

Kinetics of the photoferroelectric effect in chiral smectic-C liquid crystals studied by time-resolved measurements of spontaneous electric polarization and director tilt angle.

The origin of the photoferroelectric effect in liquid crystals, where the spontaneous polarization of a chiral ferroelectric smectic-C* (SmC*) host phase is changed by the E,Z-photoisomerization of azobenzene dopant molecules, was investigated by kinetic studies on the molecular isomerization and the subsequent changes in the SmC* order parameters, the director tilt angle, and the spontaneous electric polarization. The photoresponse of a liquid-crystal mixture consisting of 5 mol% 4,4'-bis-[(2-methyl)butyloxy]azobenzene dissolved in the SmC* host phase FLC 6430 was studied at low UV-light intensities (lambda = 366 nm, 15 microW cm-2) using an electrooptical technique that measured the desired parameters with a time resolution of about 1 s. The time-resolved measurements of optical absorption, tilt angle, and spontaneous polarization during the thermal reisomerization after ending the sample irradiation showed that the photoinduced changes in the spontaneous polarization simultaneously followed the molecular isomerization with the same rate constant and activation energy, while the director tilt angle remained basically unchanged. Minor changes in the tilt are explained by the local heating of the sample due to the optical absorption. Since the photoinduced change in polarization was observed at constant tilt, we conclude that in the limit of low UV intensity the photoferroelectric effect originates from a photo-induced change of the bilinear coupling coefficient between the polarization and the tilt. In the molecular theory of chiral SmC* liquid crystals, the coupling coefficient is related to the bias of molecular rotations. This bias may be considerably disturbed by the formation of the bent Z-isomers during the photoisomerization.