Michael Rodahl

Viscoelastic Acoustic Response of Layered Polymer Films at Fluid-Solid Interfaces: Continuum Mechanics Approach

We have derived the general solution of a wave equation describing the dynamics of two-layer viscoelastic polymer materials of arbitrary thickness deposited on solid (quartz) surfaces in a fluid environment. Within the Voight model of viscoelastic element, we calculate the acoustic response of the system to an applied shear stress, i.e. we find the shift of the quartz generator resonance frequency and of the dissipation factor, and show that it strongly depends on the viscous loading of the adsorbed layers and on the shear storage and loss moduli of the overlayers. These results can readily be applied to quartz crystal acoustical measurements of the viscoelasticity of polymers which conserve their shape under the shear deformations and do not flow, and layered structures such as protein films adsorbed from solution onto the surface of self-assembled monolayers.

Quartz crystal microbalance setup for frequency and Q‐factor measurements in gaseous and liquid environments

An experimental setup has been constructed for simultaneous measurements of the frequency, the absolute Q factor, and the amplitude of oscillation of a quartz crystal microbalance (QCM). The technical solution allows operation in vacuum, air, or liquid. The crystal is driven at its resonant frequency by an oscillator that can be intermittently disconnected causing the crystal oscillation amplitude to decay exponentially. From the recorded decay curve the absolute Q factor (calculated from the decay time constant), the frequency of the freely oscillating crystal, and the amplitude of oscillation are obtained. All measurements are fully automated. One electrode of the QCM in our setup was connected to true ground which makes possible simultaneous electrochemistry. The performance is illustrated by experiments in fluids of varying viscosity (gas and liquid) and by proteinadsorptionin situ. We found, in addition to the above results, that the amplitude of oscillation is not always directly proportional to the Q factor, as the commonly used theory states. This puts limitations on the customary use of the amplitude of oscillation as a measure of the Q factor.

A comparative study of protein adsorption on titanium oxide surfaces using in situ ellipsometry, optical waveguide lightmode spectroscopy, and quartz crystal microbalance/dissipation

Abstract The adsorption kinetics of three model proteins—human serum albumin, fibrinogen and hemoglobin—has been measured and compared using three different experimental techniques: optical waveguide lightmode spectroscopy (OWLS), ellipsometry (ELM) and quartz crystal microbalance (QCM-D). The studies were complemented by also monitoring the corresponding antibody interactions with the pre-adsorbed protein layer. All measurements were performed with identically prepared titanium oxide coated substrates. All three techniques are suitable to follow in-situ kinetics of protein–surface and protein–antibody interactions, and provide quantitative values of the adsorbed adlayer mass. The results have, however, different physical contents. The optical techniques OWLS and ELM provide in most cases consistent and comparable results, which can be straightforwardly converted to adsorbed protein molar (‘dry’) mass. QCM-D, on the other hand, produces measured values that are generally higher in terms of mass. This, in turn, provides valuable, complementary information in two respects: (i) the mass calculated from the resonance frequency shift includes both protein mass and water that binds or hydrodynamically couples to the protein adlayer; and (ii) analysis of the energy dissipation in the adlayer and its magnitude in relation to the frequency shift (c.f. adsorbed mass) provides insight about the mechanical/structural properties such as viscoelasticity.

Simultaneous frequency and dissipation factor QCM measurements of biomolecular adsorption and cell adhesion

We have measured the energy dissipation of the quartz crystal microbalance (QCM), operating in the liquid phase, when mono- or multi-layers of biomolecules and biofilms form on the QCM electrode (with a time resolution of ca. 1 s). Examples are taken from protein adsorption, lipid vesicle adsorption and cell adhesion studies. Our results show that even very thin (a few nm) biofilms dissipate a significant amount of energy owing to the QCM oscillation. Various mechanisms for this energy dissipation are discussed. Three main contributions to the measured increase in energy dissipation are considered. (i) A viscoelastic porous structure (the biofilm) that is strained during oscillation, (ii) trapped liquid that moves between or in and out of the pores due to the deformation of the film and (iii) the load from the bulk liquid which increases the strain of the film. These mechanisms are, in reality, not entirely separable, rather, they constitute an effective viscoelastic load. The biofilms can therefore not be considered rigidly coupled to the QCM oscillation. It is further shown theoretically that viscoelastic layers with thicknesses comparable to the biofilms studied in this work can induce energy dissipation of the same magnitude as the measured ones.

Bone response to surface-modified titanium implants: studies on the early tissue response to machined and electropolished implants with different oxide thicknesses

The bone formation around titanium implants with varied surface properties is investigated. Machined and electropolished samples with and without thick, anodically formed surface oxides were prepared, surface characterized and inserted in the cortical bone of rabbits (1, 3 and 6 weeks). Scanning electron microscopy, scanning Auger electron spectroscopy and atomic force microscopy revealed marked differences in oxide thickness, surface topography and roughness, but no significant differences in surface chemical composition, between the different groups of implants. Light microscopic morphology and morphometry showed that all implants were in contact with bone and had a large proportion of bone within the threads at 6 weeks. The smooth, electropolished implants, irrespective of anodic oxidation, were surrounded by less bone than the machined implants after 1 week. After 6 weeks the bone volume as well as the bone-implant contact were lower for the merely electropolished implants than for the other three groups. Our study shows that a high degree of bone contact and bone formation are achieved with titanium implants which are modified with respect to oxide thickness and surface topography. However, the result with the smooth (electropolished) implants indicates that a reduction of surface roughness, in the initial phase, decreases the rate of bone formation in rabbit cortical bone.

Bone response to surface modified titanium implants: studies on electropolished implants with different oxide thicknesses and morphology

In a series of experimental studies, bone formation was analysed around systematically modified titanium implants. In the present study, machined, electropolished and anodically oxidized implants were prepared, surface characterized and inserted in the cortical bone of rabbits (7 wks and 12 wks). SEM, scanning Auger electron spectroscopy and atomic force microscopy revealed no differences in surface composition but marked differences in oxide thickness, surface topography and roughness. Light microscopic morphology and morphometry showed that all implants were in contact with bone, and had a large proportion of bone within the threads. The smooth, electropolished implants were surrounded by less bone than the machined implants with similar oxide thickness, (4-5 nm) and the anodically oxidized implants with thicker oxides (21 nm and 180 nm, respectively) after 7 wks. These studies show that a high degree of bone contact and bone formation can be achieved with titanium implants which are modified with respect to oxide thickness and surface topography. However, it appears that a reduction of surface roughness may influence the rate of bone formation in rabbit cortical bone.

A simple setup to simultaneously measure the resonant frequency and the absolute dissipation factor of a quartz crystal microbalance

An experimental setup is described that can simultaneously measure the absolute dissipation factor and the resonant frequency of a short‐circuited quartz crystal microbalance. The crystal is driven at approximately its resonant frequency by a signal generator which is intermittently disconnected by a relay, causing the crystal oscillation amplitude to decay exponentially. The decay is measured using a ferrite toroid transformer. One of the crystal leads is fed through the center of the ferrite toroid and thereby acts as the primary winding of the transformer. The secondary winding of the transformer is connected to a digitizing oscilloscope which records the decay of the crystal oscillation. From the recorded decay curve, the absolute dissipation factor (calculated from the decay time constant) and the series resonant frequency of the freely oscillating crystal are obtained. Alternatively, the dissipation factor and resonant frequency can be measured for the crystal oscillating under open‐circuit conditio...

On the measurement of thin liquid overlayers with the quartz-crystal microbalance

We present a simple model that predicts the changes in resonance frequency and dissipation factor for a quartz-crystal microbalance (QCM) when it is coated with a viscous film that may or may not slip on the crystal. In this context, the validity of the Sauerbrey equation (change in resonance frequency α change in applied mass) is discussed. The Sauerbrey equation gives an accurate estimate of the film thickness, tf, only if (i) the film is thin compared to the shear-wave penetration depth, δ, into the liquid, i.e., tf ⪡ δ, and (ii) the film does not slide on the QCM electrode (s). We have shown that by measuring both the QCM resonance frequency and the dissipation factor simultaneously, the thickness range over which tf can be measured accurately can be extended to about 2δ for non-slipping films. If the film slips, which we have only observed for molecularly thin films, changes in dissipation factor can be used to calculate the coefficient of friction between the film and the substrate. We also show the usefulness of measuring the dissipation factor of the QCM when studying solid to liquid phase transitions.

Titanium with different oxides: in vitro studies of protein adsorption and contact activation

Adsorption of albumin (HSA) and fibrinogen (Fib) from human blood plasma onto titanium surfaces with varying oxide properties was studied with an enzyme-linked immunosorbent assay. The intrinsic activation of blood coagulation (contact activation) was studied in vitro using a kallikrein-sensitive substrate. The sample surfaces were characterized with Fourier transform Raman spectroscopy. Auger electron spectroscopy and atomic force microscopy. Low Fib and high HSA adsorption was observed for all titanium samples except for the radio frequency plasma-treated and water-incubated samples, which adsorbed significantly lower amounts of both. Oxide thickness and carbon contamination showed no influence on protein adsorption or contact activation. Smooth samples with a surface roughness (Rrms) < 1 nm showed some correlation between surface wettability and adsorption of Fib and HSA, whereas rough surfaces (Rrms > 5 nm) did not. To varying degrees, all titanium surfaces indicated activation of the intrinsic pathway of coagulation as determined by their kallikrein formation in plasma.

Frequency and dissipation-factor responses to localized liquid deposits on a QCM electrode

Abstract We have investigated how a quartz-crystal microbalance (QCM) responds in resonance frequency, f, and dissipation factor, D , to local liquid deposits (droplets) at different positions on the QCM electrodes. The changes in resonance frequency and dissipation factor versus position of the deposited droplet are well described by Gaussian curves that peal at the centre of the electrode. The widths of the f and D Gaussian curves are not significantly different. The shape of the frequency-shift versus position curve is nearly identical to the corresponding classical sensitivity curve reported by Sauerbrey for solid deposits. An increase in surface roughness of the electrode film, onto which the droplets are deposited, affects f more than D , in agreement with results reported by Martin et al. We demonstrate for a water-glycerol mixture how this effect can be utilized to measure independently the density and viscosity of the contacting liquid or, alternatively, to obtain a measure of the surface roughness of a film deposited on the QCM. Varying the conductivity of the liquid (by adding salt) does not affect the resonance frequency when the liquid is deposited as droplets. This is in contrast to when one entire side of the crystal is completely covered by a liquid. In the latter case, f and D are sensitive to the conductivity of the liquid.