Biomedical subjects

Peter F Green

Publications and source records attributed to Peter F Green.

9 recordsLinked to original sources

PubMed2007

Ordering in asymmetric block copolymer films by a compressible fluid.

We examine the morphological structures of asymmetric poly(ethylene oxide)-b-poly(1,1'-dihydroperflurooctyl methacrylate) (PEO-b-PFOMA) thin films upon annealing in a compressible fluid, supercritical CO2 (Sc-CO2). The strong affinity between PFOMA and CO2 is found to induce phase segregation when annealing PEO-b-PFOMA films at the same temperature as compared with vacuum. In vacuum, PEO-b-PFOMA films remain disordered from 80 to 180 degrees C, whereas, in Sc-CO2 at 13.9 MPa, an upper order-disorder transition (UODT) between 116 and 145 degrees C is found. In Sc-CO2, the observed ordered structure is layers of PEO spheres embedded in the matrix of PFOMA, followed by a brush layer, in which PEO wets the substrate. The swelling isotherms of PFOMA and PEO in CO2 are correlated with the Sanchez-Lacombe equation of state (SLEOS) to estimate the interaction parameters, XPFOMA-CO2 and XPEO-CO2. The phase segregation (order) induced by CO2 relative to vacuum at a given temperature is explained in terms of two factors: (1) copolymer volume fraction upon dilution with CO2, phi, and (2) the relative interaction parameter, DeltaX= XPEO-CO2 - XPFOMA-CO2. The latter factor favors order and is dominant at low temperatures over the phi factor, which always favors disorder. At high temperatures (above the T(ODT)), the preferential swelling of PFOMA by CO2 is less pronounced ( DeltaX decreases), and the copolymer is disordered.

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PubMed2006

Glass transition of miscible binary polymer-polymer thin films.

The average glass transition temperatures, Tg, of thin homopolymer films exhibit a thickness dependence, Tg(h), associated with a confinement effect and with polymer-segment-interface interactions. The Tg's of completely miscible thin film blends of tetramethyl bisphenol-A polycarbonate (TMPC) and deuterated polystyrene (dPS), supported by SiO(x)/Si, decrease with decreasing h for PS weight fractions phi >0.1. This dependence is similar to that of PS and opposite to that of TMPC thin films. Based on an assessment of Tg(h, phi), we suggest that the Tg(h, phi) of miscible blends should be rationalized, additionally, in terms of the notion of a self-concentration and associated heterogeneous component dynamics.

Elasticity↗

PubMed2005

Ordering transition of block copolymer films.

It is well-known that a bulk, symmetric, A-b-B diblock copolymer forms a lamellar morphology, with period L, below an order-disorder transition (T(ODT)) temperature, for chiN < 10.5; chi is the Flory-Huggins interaction parameter and N is the degree of polymerization of the copolymer. The ordering temperatures of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) thin film diblock copolymers of thickness h </= 2L, supported by SiO(x)/Si substrates, in vacuum environments, are shown to increase beyond the bulk, and estimates of the temperature shifts indicate that small changes of chiN are associated with unusually large shifts of the transition temperature. Further, we find that in compressed CO(2) environments, these films are ordered at temperatures where the films are disordered in vacuum (or air) environments. This latter observation is of particular significance because small molecule diluents, including compressed CO(2), are known to decrease the ODT of the bulk (enhanced miscibility).

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PubMed2004

Moving fronts in entangled polymeric films.

Thin liquid films can become structurally unstable and dewet, forming holes which subsequently grow on the substrate. Considerable research has been conducted on the structural evolution and growth of holes, which invariably are shown to be circular. We show that morphologies characterized by circular holes comprise one of three possible morphological regimes. In polystyrene films, supported by silicon oxide substrates, two other regimes are observed with decreasing film thickness. In the second regime, the moving boundary of the growing hole may become unstable and form fingers. The spacing between the fingers is characterized by a well-defined wavelength lambda proportional to h(7/6) M(-1/2) , where h is the film thickness and M is the molecular weight. A dense branchlike morphology characterizes the peripheral regions of the holes in the third regime and is found only in the thinnest films.

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PubMed2004

Polystyrene thin films in CO(2).

In air, or vacuum environments, liquid polystyrene (PS) thin films (thickness, h<100 nm ) supported by SiOx /Si substrates are structurally metastable or unstable, depending on film thickness. They rupture and eventually form droplets on the SiOx /Si substrates (dewet) due to the influence of destabilizing long-ranged van der Waals dispersion forces. We used scanning force microscopy to examine the structural stability of liquid PS films in the thickness range 5 nm<h<100 nm in liquid and in supercritical carbon dioxide ( CO2 ) environments. All films in this thickness range were metastable; holes developed throughout the films and over time these holes grew, impinged, and eventually formed droplets. The rate of destabilization is controlled by three factors: film thickness, temperature, and CO2 pressure (which dictates CO2 volume fraction in the films). Calculations of the effective interface potentials suggest that the energy barrier for nucleation and growth of holes in CO2 is larger than that in air, and in the limit of vanishingly low PS volume fraction the films should be stable.

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PubMed2003

Pressure, temperature, and thickness dependence of CO2-induced devitrification of polymer films.

The glass transition temperature is known to increase with decreasing film thickness h for sufficiently thin poly(methyl methacrylate) films supported by silicon oxide substrates. We show that this system undergoes a CO2 pressure-induced devitrification transition, P(g), which is film thickness dependent, P(g)(h)=DeltaP(g)+P(bulk)(g). P(bulk)(g) is the bulk glass transition and DeltaP(g) can be positive or negative depending on T and P. The phenomenon of retrograde vitrification, wherein the polymer exhibits a rubbery-to-glassy-to-rubbery transition upon changing temperature isobarically, is also shown to occur in this system and it is film thickness dependent.

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PubMed2002

Late-stage coarsening of an unstable structured liquid film.

Thin films of poly(styrene-b-methyl methacrylate) diblock copolymers above the bulk order-disorder transition temperature, within a certain thickness range, are structurally unstable on SiO(x)/Si substrates. They dewet autophobically, forming droplets on a self-assembled brush. We investigated the late-stage evolution, coarsening, of the droplets on the brush. The average droplet cross-sectional area increased with time, proportional, variant t(gamma). This was accompanied by a decrease in the number of droplets per unit area with time, N(t) proportional, variant t(-gamma). We analyzed the droplet size distribution, F(S/ ) vs S/ , and found that the shape of the curve was virtually identical at different stages throughout the process. This suggests that a structural self-similarity is associated with the process. A comparison of F(S/ ) vs S/ data with distributions based on Ostwald ripening and coalescence cluster coarsening (dynamic and static) mechanisms strongly indicates that the dominant coarsening mechanism involved motion of droplets across the brush and subsequent coalescence, i.e., dynamic coalescence coarsening, not Ostwald ripening.

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PubMed2002

Hole formation in thin polymer films: a two-stage process.

Thin, supported liquid films are known to rupture, creating holes throughout the film, due to defects or to van der Waals interactions. We show that the hole formation process before rupturing occurs in two stages, each characterized by distinct dynamical and morphological features. The time scale for the formation process is orders of magnitude slower than the translational (reptation) relaxation time of the individual chains. This has implications regarding the transition from the formation regime to subsequent hole growth regime on the underlying substrate.

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PubMed2002

Viscosity of entangled polystyrene thin film melts: Film thickness dependence.

We determined the low-shear effective viscosity of entangled polystyrene thin film melts, in the thickness range of 27<h<100 nm, on SiO(x)/Si substrates. This was accomplished using a method based on the notion that thin liquid films can become unstable and rupture due to defects or to destabilizing, long-range van der Waals interactions (dewetting). The holes that are created in the film subsequently grow at a rate determined by a balance between the capillary driving forces and the viscous resistive forces. Based on the velocity of growth of holes on the substrate, we show that the viscosity decreases appreciably with decreasing thickness for 25<h<50 nm. These results are consistent with studies which suggest that the glass transition of entangled polystyrene thin film melts on SiO(x)/Si substrates exhibit an apparent decrease with decreasing film thickness over the same range of h.

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