Realizing Vat-Photocycloaddition 3D Printing with Recyclable Synthetic Photorheological Silicone Fluids.

Synthetic silicone rubbers are finding a broad spectrum of applications, yet there is a demand for developing greener silicone rubbers with processability, recyclability, and reversible tunability in their mechanical properties. Here, a recyclable photorheological silicone fluid (RPSF) is developed, which realizes completely reversible wavelength-selective liquid-rubber conversion upon photoirradiation, relying on the reversible photocycloaddition of coumarin upon alternating irradiation of light with wavelengths of 365 (UV365 ) and 254 nm (UV254 ). Rheological studies demonstrate that the storage modulus of the developed RPSF increases by a factor of more than 100 000 upon UV365 irradiation to reach 20-50 kPa, while it decreases to ≈0.01 kPa upon UV254 irradiation. The reversibility of the photocycloaddition of coumarin enables the application of RPSF as a photodismantlable adhesive. Furthermore, unprecedented vat-photocycloaddition 3D printing of silicone rubber is realized by taking advantage of the excellent photocurability, that is, the dramatic increase in viscoelasticity upon UV365 irradiation.

Thermal and optical properties of the femtosecond-laser-structured and stress-induced birefringent regions in sapphire.

Temperature diffusivity of laser micro-structured regions in sapphire is determined by a temperature wave method with a lateral resolution reduced to ~10 microm using a directly sputtered micro-sensor and heater. A record high reduction of the temperature diffusivity of sapphire by 12% from its (1.26+/-0.02) x 10(-5)m(2)/s in-bulk value inside the femtosecond laser-structured volumes is determined; in a BK7 glass (~4.8x10(-7) m(2)/s), a 2% decrease of the thermal diffusivity has been observed. Origin of the reduction is consistent with disorder and scattering of phonons around the laser photo-modified micro-volumes. The stress-induced birefringence is directly measured by polariscopy together with its radial distribution, and azimuthal orientation of the polarization ellipsis near the laser structured regions in sapphire. The maximum birefringence of Deltan approximately 1x10(-3) is achieved without crack formation and corresponds to a local stress of ~1.3 GPa. The stress (and birefringence) decay radially with a single-exponential constant of tau(R) = 24 microm while the azimuthal orientation of the polarization ellipsis is spiraling around the laser structured volume. Such structures are promising in waveguiding and lasing applications of optical vortices where spatial control of birefringence and optical activity are required.