Mesoscale Science and Technology Classical Sciences Atomistic & Molecular Sciences Applications: - Lubrication - Photonics - Fuel Cells - Data Storage The realm of the Mesoscale fosters new perceptions and approaches. Illustration of a 2D Phenomenon A highly organized plastic deformation: often referred to as Schallamach Waves AFM Scan: Probe Width: ~ 10 nm Line Separation: > 100 nm (a) (b) a slow moving (~ µm/s ) sliding contact (~10-5 µm 2 ) affects a scan area on the order of 10 3 µm 2 in an apparently coherent fashion. (c) (d) 2
Flatland An entertaining satire by Edwin A. Abbott A Sphere, an inhabitant from Spaceland, a Square, an inhabitant from Flatland introduces to a higher Dimensionality E.A. Abbott, Flatland, A Romance of Many Dimensions. Dover Publ. Inc., New York (1992) first published 1884 under the title A. Square Flatland An entertaining satire by Edwin A. Abbott Perception Dimensionality nurtures perceptions and limits possibilities. Objects are perceived in Flatland as lines or points. To distinguish objects in Flatland the observer has to travel around the objects. A Circle is perceived as an angularly length- invariant object. A Sphere is reduced to its crosssectional area with Flatland, and thus, perceived as a Circle. 3
Flatland Shrinking, Disappearing and Reappearing Act Boundaries in lower dimensionalities are lifted from the perspective of a higher dimensionality Door Door?? Flatland: Physical Laws Abbott spent a significant part for a his satire on developing the two-dimensional world of Flatland by introducing imaginary laws of nature that apply in one and 2-dimensions. Although these laws that for instance explain how rain is experienced in 2-dimensions are unrealistic, they impressively illustrate the mystery of lower dimensionalities. Direction of Rain North South 4
Illustration of Dimensionality: Acoustic Wave (3D vs. 2D) Huygens Body Waves (3D solution) A spatially localized initial disturbance gives rise to a limited and fast decaying disturbance only, at any accessible location away from the source of the disturbance. Rayleigh Surface Waves Waves, propagating over the surface of a body with a small penetration distance into the interior of the body, acquire at a great distance from the source a continually increasing preponderance. --> important in the study of seismic phenomena NanoScience Tool Atomic Force Microscopy (AFM) Photodiode LASER Topography Friction PIEZO CANTILEVER 100 µm 50 µm A B 32.33 µm SAMPLE Glass Transition 16.17 µm 0 µm 0 µm 50 µm 100 µm Material Distinction 0 µm 0 µm 16.17 µm 32.33 µm Elasticity T g = 374K AFM 5
SFM Setup In environmental chamber with sample heating /cooling stage C SFM/AFM Explorer (Topometrix) Heating/Cooling Stage: (MMR Techn.) Confined Boundary Layer of Spincast Films Lateral Force and Dewetting Studies suggest that the PEP phase is rheological Mean field modified theories within consider a 100 the nm effect boundary of pinning region at that interfaces exceeds only by two orders within of a magnitude pinning regime the theoretically (0.6 1 nm predicted «R g ) pinning regime of annealed elastomers at interfaces with negative spreading coefficient. Classical Actual Mean field theories consider the effect of pinning at interfaces only within a pinning regime (0.6 1 nm «R g ) ~1 nm BULK S ICZ S ICZ SRZ BULK ~ 100 nm Diffusion into Disentangled Sublayer 6
Glass Transition Properties of Confined Films Glass transition studies on polystyrene indicate confinement effects similar to those found in PEP shear studies. Near-Surface T g Measurements of Thick Films (t > 100 nm) are bulk-like. Shear Response x L Cantilever Tip Shear Displacement x mod Sample 105 100 S IC Z SRZ BULK 12.0 kda PS FOX-FLORY (BULK) Heating/Cooling Stage R.M. Overney et al., J. Thermal Analysis and Calorimetry, 59, 205-225 (2000). S.Ge, et al. Phys. Rev. Lett., 85, 2340-2343 (2000) T g ( o C ) 95 90 85 0 50 100 150 200 250 300 FILM THICKNESS, δ ( nm ) NORMALIZED VALUE (A.U.) Liquid Structuring: Entropic Cooling Interfacial confinement leads to an entropically cooled boundary layer in simple fluids like hexadecane. 1.0 0.8 0.6 0.4 0.2 0.0-0.2 DISPLACEMENT (nm) -6-5 -4-3 -2-1 0 1 2 3 4 MODULUS CONTACT FORCE Lubrication?Shear Modulated SFM approach curves indicate a hexadecane boundary layer thickness of ~2.5 nm on SiO 2. He, et al., Phys. Rev. Lett. 88, 15 (2002)?Molecular Dynamics simulations predict a boundary layer thickness of 1.5-1.8 nm. Xia, et al., Phys. Rev. Lett. 69, 1967 (1992) I II III I: BULK LIQUID II: BOUNDARY LAYER III: SOLID SUBSTRATE 7