Grafted Rods: A Tilting Phase Transition

A tilting phase transition is predicted for systems comprising rod like molecules which are irreversibly grafted to a flat surface, so that the non interacting rods are perpendicularly oriented. The transition is controlled by the grafting density $\rho$. It occurs as $\rho$ increases as a result of the interplay between two energies. Tilt is favoured by the van-der-Waals attraction between the rods. It is opposed by the bending elasticity of the grafting functionality. The role of temperature is discussed, and the tilting mechanism is compared to other tilting transitions reported in the literature.Comment: 21 pages, 2 figures, to appear in Journal de Physique I

τ\tau-tilting theory: a self-contained introduction

A self-contained introduction to the basics of Tau-tilting theory. We assume that the reader is familiar with Auslander-Reiten theory, but circumvent the need for the Brenner-Butler tilting theorem completely.Comment: 50 pages, originally submitted as a master thesis at Bielefeld University under William Crawley-Boevey, revamped and revise

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

The response of the quartz crystal microbalance (QCM) 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 with the acoustic multilayer formalism. In liquid environments, viscoelastic spectros-copy and high-frequency rheology are possible, even on layers with a thickness in the monolayer range. For particulate samples, rheology is replaced by contact mechanics. The contact stiffness can be derived. Because the stress at the contact is large, nonlinear effects are seen. 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

Studying soft interfaces with shear waves: principles and applications of the quartz crystal microbalance (QCM)

The response of the quartz crystal microbalance (QCM) 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 with the acoustic multilayer formalism. In liquid environments, viscoelastic spectros-copy and high-frequency rheology are possible, even on layers with a thickness in the monolayer range. For particulate samples, rheology is replaced by contact mechanics. The contact stiffness can be derived. Because the stress at the contact is large, nonlinear effects are seen. 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

A modulation QCM applied to copper electrodeposition and stripping

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 simple equation predicting the amplitude of motion of quartz crystal resonators

The amplitude of motion of quartz crystal resonators, u 0 , has been calculated on the basis of the transmission line model by Mason ͓Piezoelectric Crystals and Their Applications to Ultrasonics ͑Van Nostrand, Princeton, 1948͔͒. It is predicted to be u 0 =4/͑n͒ 2 Qd 26 U el,0 , where n is the overtone order, Q is the quality factor, d 26 is the piezoelectric strain coefficient, and U el,0 is the amplitude of the driving voltage. This simple result is in good agreement with previous numerical calculations, with an experimental value from the literature, and with our own experimental checks. As a side result, an equation is provided which allows to estimate the active area of the crystal from the product of the motional resistance R 1 and the Q factor

Fouling pathways in emulsion polymerization differentiated with a quartz crystal microbalance (QCM) integrated into the reactor wall

Emulsion polymerization fouling at hot interfaces is studied in situ, making use of a quartz crystal microbalance with dissipation monitoring (QCM-D). The resonator crystal is heated with a ring-shaped thermal pad from the back, turning it into a plate with elevated temperature. Configured to be one of the walls of a small reactor for emulsion polymerization, this resonator is prone to heat-transfer fouling, similar to regular heated parts of process equipment. The fouling kinetics is readily quantified with this QCM. During polymerization at constant temperature (80 °C), some deposition is always observed. However, a film with a thickness of less than 1 μm (determined gravimetrically with the QCM) is sometimes found, which stabilizes the surface against the deposition of much thicker layers. When reaction fouling proceeds directly to thick deposits, a small increase in resonance bandwidth often occurs a few minutes prior to the main transition, presumably caused by coagulum formed in the bulk making first contact with the surface. Furthermore, particle fouling is studied with temperature ramps on nonreactive dispersions. Fouling, if present, is readily observed

The influence of ionic strength on the adhesive bond stiffness of oral streptococci possessing different surface appendages as probed using AFM and QCM-D

Bacterial adhesion to surfaces poses threats to human-health, not always associated with adhering organisms, but often with their detachment causing contamination elsewhere. Bacterial adhesion mechanisms may not be valid for their detachment, known to proceed according to a visco-elastic mechanism. Here we aimed to investigate influences of ionic strength on the adhesive bond stiffness of two spherically shaped Streptococcus salivarius strains with different lengths of fibrillar surface appendages. The response of a Quartz-Crystal-Microbalance-with-Dissipation (QCM-D) upon streptococcal adhesion and changes in the ionic strength of the surrounding fluid indicated that the bond stiffness of S. salivarius HB7, possessing a dense layer of 91 nm long fibrils, was unaffected by ionic strength. Atomic-force-microscopic (AFM) imaging in PeakForce-QNM mode showed a small decrease in bond stiffness from 1200 to 880 kPa upon decreasing ionic strength from 57 to 5.7 mM, while Total-Internal-Reflection-Microscopy suggested a complete collapse of fibrils. S. salivarius HBV51, possessing a less dense layer of shorter (63 nm) fibrils, demonstrated a strong decrease in bond stiffness both from QCM-D and AFM upon decreasing the ionic strength, and a partial collapse of fibrils. Probably, the more hydrophobic and less negatively charged long fibrils on S. salivarius HB7 collapse side-on to the cell surface, while the more hydrophilic and negatively charged fibrils of S. salivarius HBV51 remain partially stretched. In summary, we demonstrate how a combination of different methods can yield a description of the structural changes occurring in the interfacial region between adhering, fibrillated streptococci and a substratum surface upon changing the ionic strengt