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.
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.
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 fast electrochemical quartz crystal microbalance with dissipation monitoring (EQCM−D) was applied to copper electrodeposition and subsequent stripping. Accumulation brings the frequency noise down to the mHz range, corresponding to 0.1 % of a monolayer. With this precision, the apparent mass transfer rate as determined from the time‐derivative of the frequency shift can be directly compared to the current. Small but systematic deviations between the two can be attributed to nanoscale roughness. In the voltage range of underpotential deposition (UPD), the apparent mass transfer rate shows peaks and shoulders. The plating additive benzotriazole (BTA) leaves the magnitude of electrogravimetric signals unchanged, but shifts the UPD onset potential. The additive thiourea (TU) promotes UPD and strongly increases the bandwidth.
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.