Impact of Solvent Quality on the Density Profiles of Looped Triblock Copolymer Brushes by Neutron Reflectivity Measurements

Preferential adsorption of poly(2-vinylpyridine)-deuterated polystyrene-poly(2-vinylpyridine) (PVP-dPS-PVP) triblock copolymers from toluene onto silicon leads to the formation of dPS loops tethered by the PVP end blocks. Using neutron reflectometry, we have determined the segment density profiles of these looped polymer brushes in toluene, a good solvent for the dPS block, and in cyclohexane at 20 °C (poor solvent), 32 °C, (near-Θ solvent), and 50 °C (marginal solvent). While the swelling behavior qualitatively agrees with that observed for singly grafted brushes, there are interesting differences in the local structural details: In a good solvent, the segment density profiles are composed of an inner parabolic region and a long, extended tail. In cyclohexane, the profiles are described by exponential decays. We ascribe these features to a novel polydispersity effect that arises due to tethering the PS loops by both ends. The results also show that the less dense layers undergo more significant changes in swollen height as solvent quality is changed and that the looped brushes of different molecular weight, asymmetry, and tethering density adhere to scaling relationships derived for lightly cross-linked polymer gels.

Stability of Order in Solvent-Annealed Block Copolymer Thin Films

ABSTRACT: One way to produce high order in a block copolymer thin film is by solution casting a thin film and slowly evaporating the solvent in a sealed vessel. Such a solvent-annealing process is a versatile method to produce a highly ordered thin film of a block copolymer. However, the ordered structure of the film degrades over time when stored under ambient conditions. Remarkably, this aging process occurs in mesoscale thin films of polystyrene-polyisoprene triblock copolymer where the monolayer of vitrified 15 nm diameter polystyrene cylinders sink in a 20 nm thick film at 22 °C. The transformation is studied by atomic force microscopy (AFM). We describe the phenomena, characterize the aging process, and propose a semiquantitative model to explain the observations. The residual solvent effects are important but not the primary driving force for the aging process. The study may lead to effective avenue to improve order and make the morphology robust and possibly the solvent-annealing process more effective.

Association and Structure of Thermosensitive Comblike Block Copolymers in Aqueous Solutions

The structures and association properties of thermosensitive block copolymers of poly(methoxyoligo( ethylene glycol) norbornenyl esters) in D2O were investigated by small angle neutron scattering (SANS). Each block is a comblike polymer with a polynorbornene (PNB) backbone and oligo ethylene glycol (OEG) side chains (one side chain per NB repeat unit). The chemical formula of the block copolymer is (OEG3NB) 79- (OEG6.6NB) 67, where subscripts represent the degree of polymerization (DP) of OEG and NB in each block. The polymer concentration was fixed at 2.0 wt % and the structural changes were investigated over a temperature range between 25 and 68°C. It was found that at room temperature polymers associate to form micelles with a spherical core formed by the block (OEG3NB) 79 and corona formed by the block (OEG6.6NB) 67 and that the shape of the polymer in the corona could be described by the form factor of rigid cylinders. At elevated temperatures, the aggregation number increased and the micelles became more compact. At temperatures around the cloud point temperature (CPT) T ) 60 °C a correlation peak started to appear and became pronounced at 68 °C due to the formation of a partially ordered structure with a correlation length ∼349 Å.

High-Pressure Micellar Solutions of Polystyrene-block-polybutadiene and Polystyrene-block-polyisoprene in Propane Exhibit Cloud-Pressure Reduction and Distinct Micellization End Points

Micellar solutions of polystyrene-block-polybutadiene and polystyrene-block-polyisoprene in propane are found to exhibit significantly lower cloud pressures than the corresponding hypothetical nonmicellar solutions. Such a cloud-pressure reduction indicates the extent to which micelle formation enhances the apparent diblock solubility in near-critical and hence compressible propane. Concentration-dependent pressure-temperature points beyond which no micelles can be formed, referred to as the micellization end points, are found to depend on the block type, size, and ratio. The cloud-pressure reduction and the micellization end point measured for styrene-diene diblocks in propane should be characteristic of all amphiphilic diblock copolymer solutions that form micelles in compressible solvents.

Block & Bridle Annual 1956-1957

Charles Adams (Faculty Advisor), Delbert Kuhlman, John Klingenberg, Ardyce Haring, Harvey Jorgensen, Roy Volzke, Billie Reed, Paul Yeutter Prof. Loeffel, Carolyn Hall, Byron Kort, Larry Paul, Elwin Mosier, Charles Corkle, Kay Robohm, Daniel Stilwell Duane Stokebrand, Gary Briggs, Walt Patterson, Wendell Mousel, Keith Smith, Darrel Zessin, Richard Bonne, Donald Kasbohm, Bruce Skinner Bob Discoe, Doyle Hulme, Jim Smith, Carl Lorenzen, Jay Cook, Gary Berke, Bob Volk, Roger Hild Donald Kuhl, Russell Person, Ray Cada, Ray DeBower, Bob Dannert, Phil Starck, Kay Knudsen, Jerry Brownfield, Allan McClure, Wally Bierman Morris Ochsner, Warren Mitchell, Ed McReynolds, Gerald Dart, Arza Snyder, Mervy Schliefert, Arley Waldo, Tom Hoffman, John Wink, Virgil Gellermann, Duane Neuman

Block & Bridle Annual 1957-1958

Gary Briggs, Paul Yeutter, Ray Cada, Darrel Zessin, Byron Kort. Louis Welch, Kay Robohm, Darrel Eberspacher, Elwin Mosier, Ardyce Haring, Carolyn Hall. Larry Lutz, Maurice Bonne, Max Waldo, Duane Stokebrand, Ted Klug, Prof. Richard B. Warren (Faculty Advisor). Eli Thomssen, Phil Starck, Ray DeBower, Gary Berke, Jay Cook, Roger Hild. Russell Person, Morris Ochsner, Del Kuhlman, John Wink, Jerry Dart, Tom Kraeger.

Block & Bridle Annual 1959-1960

President Roger Wehrbein Vice President Ted Klug Secretary George B. O'Neal Treasurer Ralph Hazen Marshal Bud Reece Historian Tom Kraeger Co-Historian John Zauha Ag. Executive Representative Larry Williams Faculty Advisor Dr. E. B. Peo, Jr. George Ahlschwede Richard Hahn Henry Beel Ralph Hazen Gary Briggs Gary Heineman Leslie Cook Max Hauser Richard Eberspacher Buce Jameson Russ Edeal Leon Janovy William Ehresman Alan Jorgensen Rolland Eubanks John Joyner Mickey Evertson Marshall Jurgens Jesse Felker Ron Kahle Mylon Filkins Donald Kavan Richard Frahm Max Keasling Roger French Ronald Kennedy Angus Garey Ted Klug Ed Gates Herb Kraeger Gerald Gogan Tom Kraeger Gerald Goold Fernando Lagos Jay Graf Gerald Lamberson Lloyd Langemeier Ralph Langemeier Gerald Loseke Donald Meiergerd Lowell Minert John Oeltjen George B. O'Neal Don Ormesher Larry Ott Bud Reece Ron Sabatka Keith Smith Ronald Smith Donn Simonson Daryl Starr Galen Stevens Eugene Turdy Ernest Thayer Charles Thompson Jerry Thompson Eli Thomssen William Watkins Allen Trumble Robert Weber Lawrence Turner Dan Wehrbein Reginald Turner Roger Wehrbein Vance Uden Dick White Max Waldo Billy Williams Blair Williams Larry Williams D. Patrick Wright John Zauha

Role of Branching on the Structure of Polymer Brushes Formed from Comb Copolymers

The distinguishing feature of a polymer brush at equilibrium is the stretched configuration of the chains that results from tethering the polymer chains by one end at the solid-fluid interface. The stretched configuration of the chains and the crowded nature of the interfacial layer is the origin of many of the useful properties of polymer brushes: these layers resist compression and aggregation, effectively dissipate shear stresses, and respond reversibly to changes in their solution environment.

Comparison of crystalline thin poly(vinylidene (70%)–trifluoroethylene (30%)) copolymer films with short chain poly(vinylidene fluoride) films

We compare the photoemission and electron energy loss spectra of crystalline poly(vinylidene-fluoride with trifluoroethylene: 70%: 30%), P(VDF–TrFE), films, fabricated by the Langmuir–Blodgett technique and annealed in vacuum, with in situ thermally evaporated films of poly(vinylidene-fluoride) (PVDF) in vacuum. The electronic structure and vibrational modes of the short chain PVDF films compare well with the crystalline P(VDF–TrFE) films indicating that vacuum annealed films prepared ex situ are free of significant surface contamination once vacuum annealed. The electronic structure for the short chain PVDF films exhibits, however, different temperature dependence than the crystalline P(VDF–TrFE) films. PACS: 68.47.Mn; 71.20.Rv; 63.22.+m; 73.22.-f