Cutting to measure the elasticity and fracture of soft gels.

The fracture properties of very soft and/or brittle materials are challenging to measure directly due to the limitations of existing fracture testing methods. To address this issue, we introduce a razorblade-initiated fracture test (RIFT) to measure the mechanical properties related to fracture for soft polymeric gels. We use RIFT to quantify the elasticity, crack initiation energy, and the fracture energy of gellan hydrogels as a function of gellan concentration. Additionally, we use RIFT to study the role of friction in quantifying the fracture properties for poly(styrene-b-ethylene butadiene-b-styrene) gels as a function of test velocity. This new method provides a simple and efficient means to quantify the fracture properties of soft materials.

Colloidal Properties of Aqueous Poly(vinyl acetate)-Borate Dispersions with Short-Chain Glycol Ethers.

We report the influence of adding five short-chain glycol ethers (SCGEs) on the structure, stability, and viscoelastic properties of aqueous dispersions of partially hydrolyzed poly(vinyl acetate) and borax. The properties of these gel-like materials have been investigated as a function of the structure of the added SCGE both below and above the critical aggregation (or micellar) concentrations using (11) B and (13) C NMR, rheology, and small-angle neutron scattering. The results indicate that the SCGE aggregation behavior is not affected by incorporation into the gel-like network. However, changes in the viscoelasticity and structural properties of the dispersions were detected that can be correlated to the nature of the solvent system. Also, the ability of these materials to clean an unvarnished acrylic paint surface coated with synthetic soil has been evaluated using colorimetery, and the surface of the dispersion after cleaning was visualized with scanning electron microscopy.

Non-Aqueous Poly(dimethylsiloxane) Organogel Sponges for Controlled Solvent Release: Synthesis, Characterization, and Application in the Cleaning of Artworks.

Polydimethylsiloxane (PDMS) organogel sponges were prepared and studied in order to understand the role of pore size in an elastomeric network on the ability to uptake and release organic solvents. PDMS organogel sponges have been produced according to sugar leaching techniques by adding two sugar templates of different forms and grain sizes (a sugar cube template and a powdered sugar template), in order to obtain materials differing in porosity, pore size distribution, and solvent absorption and liquid retention capability. These materials were compared to PDMS organogel slabs that do not contain pores. The sponges were characterized by Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) and compared with PDMS slabs that do not contain pores. Scanning electron microscopy (SEM) provided information about their morphology. X-ray micro-tomography (XMT) allowed us to ascertain how the form of the sugar templating agent influences the porosity of the systems: when templated with sugar cubes, the porosity was 77% and the mean size of the pores was ca. 300 µm; when templated with powdered sugar, the porosity decreased to ca. 10% and the mean pore size was reduced to ca. 75 µm. These materials, porous organic polymers (POPs), can absorb many solvents in different proportions as a function of their polarity. Absorption capacity, as measured by swelling with eight solvents covering a wide range of polarities, was investigated. Rheology data established that solvent absorption did not have an appreciable impact on the gel-like properties of the sponges, suggesting their potential for applications in cultural heritage conservation. Application tests were conducted on the surfaces of two different lab mock-ups that simulate real painted works of art. They demonstrated further that PDMS sponges are a potential innovative support for controlled and selective cleaning of works of art surfaces.

Maximizing Contact of Supersoft Bottlebrush Networks with Rough Surfaces To Promote Particulate Removal.

Efficient removal of particulates from a rough surface with a soft material through a "press and peel" method (i.e., an adhesion and release approach) depends on good conformal contact at the interface; a material should be sufficiently soft to maximize contact with a particle while also conforming to rough surface features to clean the entire substrate surface. Here, we investigate the use of bottlebrush networks-extremely soft elastomers composed of macromolecules with polymeric side chains-as materials for cleaning model substrates of varying roughness. Formed through free-radical polymerization of mono- and dimethacrylate functionalized polysiloxanes, these solvent-free supersoft elastomers exhibit moduli comparable to those of solvated gels, allowing for a lower moduli regime of elastomers to be used in contact experiments than previously possible. By varying the macromonomer to cross-linker ratio, we study the effect of modulus on conformal contact and cleaning for materials that are as soft as gels while minimizing/negating physical and/or chemical concerns that using a traditional material may involve (e.g., changes in component concentrations, solvent evaporation, and syneresis). We study cleaning efficacy by quantifying the conformal contact between soft materials and rough substrates via a contact adhesion-based measurement. These results give insight into the correlation between shear modulus and conformal contact with surfaces of varying feature height. Not only does a decrease in shear modulus leads to improved conformal contact with rough surfaces, but also it facilitates adhesion to particulates situated on the rough surface, thus aiding removal. We highlight this property control with a case study illustrating the removal of an artificial soil mixture from a rough, acrylic surface via peeling rather than rubbing, which can cause damage to delicate surfaces.

Soft, Peelable Organogels from Partially Hydrolyzed Poly(vinyl acetate) and Benzene-1,4-diboronic Acid: Applications to Clean Works of Art.

We have developed soft, peelable organogels from 40% hydrolyzed poly(vinyl acetate) (40PVAc) and benzene-1,4-diboronic acid (BDBA). The organic liquids gelated include dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, 2-ethoxyethanol, and methanol. The rheology of these soft materials can be tuned by altering the concentration of the polymer and/or crosslinker. Insights into the mechanisms leading to gelation were obtained from 1H NMR experiments, fluorescence measurements, and studies comparing properties of materials made from BDBA and phenylboronic acid, a molecule incapable of forming covalent crosslinks between the polymer chains. These organogels can be easily peeled off a surface, leaving no residue detectable by UV-vis spectroscopy. They are demonstrated to be effective at softening and removing deteriorated coatings from water-sensitive works of art and delicate surfaces. They have the needed characteristics to clean topographically complex surfaces: good contact with the surface, easy removal, and little to no residue after removal. A 2-ethoxyethanol organogel was used to remove oxidized varnish from a 16th century reliquary decorated with painted gold leaf, and an ethanol gel was used to remove solvent-resistant coatings from 16th and 18th century oil paintings.