Visualization of the Sol-Gel Transition in Porous Networks Using Fluorescent Viscosity-Sensitive Probes.

The sol-gel transition involves the transformation of a colloidal suspension into a system-spanning, interconnected gel. This process is widely used to reinforce mechanically weakened porous artifacts, such as sculptures but the impact of the restricted geometry (porous network) on the gelation dynamics of the solution remains unclear. Here, using fluorescent viscosity-sensitive molecular rotors, confocal microscopy, and model pores, we visualize the local viscosity changes at the microscale that accompany the sol-gel transition of a methyltriethoxysilane solution into a gel network. We show that, with evaporation of the solvent, a viscosity gradient develops near the free surface, triggering the sol-gel transition inside small pores near the surface. In homogeneous porous media, this leads to skin formation, which reduces the evaporation rate. In heterogeneous porous media, a gradient in gel density develops toward the heart of the porous material, where the gel formation mainly occurs as capillary bridges within smaller pores.

Adsorption of a water-soluble molecular rotor fluorescent probe on hydrophobic surfaces.

Environmentally sensitive molecular rotors are widely used to probe the local molecular environment in e.g. polymer solutions, polymer glasses, and biological systems. These applications make it important to understand its fluorescence properties in the vicinity of a solid surface, since fluorescence microscopy generically employs cover slides, and measurements are often done in its immediate vicinity. Here, we use a confocal microscope to investigate the fluorescence of (4-DASPI) in glycerol/water solutions close to the interface using hydrophilic or hydrophobic cover slips. Despite the dye's high solubility in water, the observed lengthening of the fluorescence lifetime close to the hydrophobic surface, implies a surprising affinity of the dye with the surface. Because the homogeneous solution and the refractive index mismatch reduces the optical sectioning power of the microscope, we quantify the affinity with the help of a simple model of the signal vs. depth of focus, exhibiting surface and bulk contributions. The model reduces artefacts due to refractive index mismatch, as supported by Monte Carlo ray tracing simulations.

Molecular rotors to probe the local viscosity of a polymer glass.

We investigate the local viscosity of a polymer glass around its glass transition temperature by using environment-sensitive fluorescent molecular rotors embedded in the polymer matrix. The fluorescence of the rotors depends on the local viscosity, and measuring the fluorescence intensity and lifetime of the probe therefore allows us to measure the local free volume in the polymer glass when going through the glass transition. This also allows us to study the local viscosity and free volume when the polymer film is put under an external stress. We find that the film does not flow homogeneously but undergoes shear banding that is visible as a spatially varying free volume and viscosity.

Transition from viscoelastic to fracture-like peeling of pressure-sensitive adhesives.

We investigate the process of the slow unrolling of a roll of typical pressure-sensitive adhesive, Scotch tape, under its own weight. Probing the peeling velocities down to nm s-1 resolution, which is three orders of magnitudes lower than earlier measurements, we find that the speed is still non-zero. Moreover, the velocity is correlated to the relative humidity. A humidity increase leads to water uptake, making the adhesive weaker and easier to peel. At very low humidity, the adhesive becomes so stiff that it mainly responds elastically, leading to a peeling process akin to interfacial fracture. We provide a quantitative understanding of the peeling velocity in the two regimes.

Fluorescent Liquid Tetrazines.

Tetrazines with branched alkoxy substituents are liquids at ambient temperature that despite the high chromophore density retain the bright orange fluorescence that is characteristic of this exceptional fluorophore. Here, we study the photophysical properties of a series of alkoxy-tetrazines in solution and as neat liquids. We also correlate the size of the alkoxy substituents with the viscosity of the liquids. We show using time-resolved spectroscopy that intersystem crossing is an important decay pathway competing with fluorescence, and that its rate is higher for 3,6-dialkoxy derivatives than for 3-chloro-6-alkoxytetrazines, explaining the higher fluorescence quantum yields for the latter. Quantum chemical calculations suggest that the difference in rate is due to the activation energy required to distort the tetrazine core such that the nπ*S1 and the higher-lying ππ*T2 states cross, at which point the spin-orbit coupling exceeding 10 cm-1 allows for efficient intersystem crossing to occur. Femtosecond time-resolved anisotropy studies in solution allow us to measure a positive relationship between the alkoxy chain lengths and their rotational correlation times, and studies in the neat liquids show a fast decay of the anisotropy consistent with fast exciton migration in the neat liquid films.

Disentangling Nano- and Macroscopic Viscosities of Aqueous Polymer Solutions Using a Fluorescent Molecular Rotor.

The macroscopic viscosity of polymer solutions in general differs strongly from the viscosity at the nanometer scale, and the relation between the two can be complicated. To investigate this relation, we use a fluorescent molecular rotor that probes the local viscosity of its molecular environment. For a range of chain lengths and concentrations, the dependence of the fluorescence on the macroscopic viscosity is well described by the classical Förster-Hoffmann (FH) equation, but the value of the FH exponent depends on the polymer chain length. We show that all data can be collapsed onto a master curve by plotting the fluorescence versus polymer concentration, which we explain in terms of the characteristic mesh size of the polymer solution. Using known scaling laws for polymers then allows us to quantitatively explain the relation between the FH exponent and the polymer chain length, allowing us to link the nano- to the macroviscosity.

Viscoelasticity-Induced Onset of Slip at the Wall for Polymer Fluids.

The progressive onset of slip at the wall, which corresponds to a slip length increasing with the solicitation time before reaching a plateau, has been investigated for model viscoelastic polymer solutions, allowing one to vary the longest relaxation time while keeping constant solid-fluid interactions. A hydrodynamic model based on a Maxwell fluid and the classical Navier's hypothesis of a linear response for the friction stress at the interface fully accounts for the data. In the limit of the linear viscoelasticity of the fluid, we could postulate a Newtonian response for the interfacial friction coefficient, reflecting the local character of solid-liquid friction mechanisms. Deviations between the experiments and our model are observed when the fluid is far from its linear viscoelastic behavior.

Temperature-Controlled Slip of Polymer Melts on Ideal Substrates.

The temperature dependence of the hydrodynamic boundary condition between a polydimethylsiloxane melt and two different nonattractive surfaces made of either an octadecyltrichlorosilane self-assembled monolayer or a grafted layer of short polydimethylsiloxane chains has been characterized. We observe a slip length proportional to the fluid viscosity. The temperature dependence is deeply influenced by the surfaces. The viscous stress exerted by the polymer liquid on the surface is observed to follow exactly the same temperature dependences as the friction stress of a cross-linked elastomer sliding on the same surfaces. Far above the glass transition temperature, these observations are rationalized in the framework of a molecular model based on activation energies: increase or decrease of the slip length with increasing temperatures can be observed depending on how the activation energy of the bulk viscosity compares to that of the interfacial Navier's friction coefficient.

Capillary fracture of ultrasoft gels: variability and delayed nucleation.

A droplet of surfactant spreading on an ultrasoft (E ≲ 100 Pa) gel substrate will produce capillary fractures at the gel surface; these fractures originate at the contact-line and propagate outwards in a starburst pattern. There is an inherent variability in both the number of fractures formed and the time delay before fractures form. In the regime where single fractures form, we observe a Weibull-like distribution of delay times, consistent with a thermally-activated process. The shape parameter is close to 1 for softer gels (a Poisson process), and larger for stiffer gels (indicative of aging). For single fractures, the characteristic delay time is primarily set by the elastocapillary length of the system, calculated from the differential in surface tension between the droplet and the substrate, rather than the elastic modulus as for stiffer systems. For multiple fractures, all fractures appear simultaneously and long delay times are suppressed. The experimental protocol provides a new technique for probing the energy landscape and fracture toughness of ultrasoft materials through measurement of the delay time distribution.