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1. Comparing the impact of different adsorbed layers on the local glass transition of polymer matrices

   https://doi.org/10.1063/5.0182541  

   Thees, Michael F; Merrill, James H; Huang, Xinru; Roth, Connie B (January 2024, The Journal of Chemical Physics)

   Chain adsorption to nanofiller interfaces creating bound layers has become central to understanding property changes in polymer nanocomposites. We determine the impact different kinds of adsorbed layers can have on the local glass transition temperature Tg of polymer matrices in a model film system using a localized fluorescence method. This work compares the adsorption and desorption of adsorbed layers grown in solution with the solution washing characteristics of adsorbed layers formed in the melt, leveraging knowledge about polymer adsorption in solution to infer the structure of adsorbed layers formed in the melt. In the limit of zero concentration after a long time in solution, we find that both kinds of adsorbed layers reach the same limiting adsorbed amount h∞(c → 0) ≈ 1 nm, appearing to evolve to the same thermodynamic equilibrium state of a near monolayer of surface coverage. We propose that melt annealing leads to a coarsening of polymer segment–surface contacts, increasing the length of trains and shrinking loops and tails, slowing the subsequent kinetics of these adsorbed chains in solution. Considering how the pyrene-labeled chains intermix with the adsorbed layer enables us to discriminate between the impact of tails, loops, and trains as threading of loops takes longer. We find that large fluffy loops, tails, and trains have little to no impact on the local Tg. A large 30 K increase in local Tg is observed for 30-min solvent washed well-annealed films at long intermixing times that we attribute to the threading of small tight loops. 

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2. Chemical heterogeneity in interfacial layers of polymer nanocomposites

   https://doi.org/10.1039/c8sm00663f  

   Yang, Siyang; Liu, Siqi; Narayanan, Suresh; Zhang, Chongfeng; Akcora, Pinar (January 2018, Soft Matter)

   It is well-known that particle–polymer interactions strongly control the adsorption and conformations of adsorbed chains. Interfacial layers around nanoparticles consisting of adsorbed and free matrix chains have been extensively studied to reveal their rheological contribution to the behavior of nanocomposites. This work focuses on how chemical heterogeneity of the interfacial layers around the particles governs the microscopic mechanical properties of polymer nanocomposites. Low glass-transition temperature composites consisting of poly(vinyl acetate) coated silica nanoparticles in poly(ethylene oxide) and poly(methyl acrylate) matrices, and of poly(methyl methacrylate) silica nanoparticles in a poly(methyl acrylate) matrix are examined using rheology and X-ray photon correlation spectroscopy. We demonstrate that miscibility between the adsorbed and matrix chains in the interfacial layers led to the observed unusual reinforcement. We suggest that packing of chains in the interfacial regions may also contribute to the reinforcement in the polymer nanocomposites. These features may be used in designing mechanically adaptive composites operating at varying temperature. 

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3. Thickness and temperature dependence of the atomic-scale structure of SrRuO3 thin films

   https://doi.org/10.1063/5.0087791  

   Zhang, Xuanyi; Penn, Aubrey_N; Wysocki, Lena; Zhang, Zhan; van_Loosdrecht, Paul_H_M; Kornblum, Lior; LeBeau, James_M; Lindfors-Vrejoiu, Ionela; Kumah, Divine_P (May 2022, APL Materials)

   The temperature-dependent layer-resolved structure of 3 to 44 unit cell thick SrRuO3 (SRO) films grown on Nb-doped SrTiO3 substrates is investigated using a combination of high-resolution synchrotron x-ray diffraction and high-resolution electron microscopy to understand the role that structural distortions play in suppressing ferromagnetism in ultra-thin SRO films. The oxygen octahedral tilts and rotations and Sr displacements characteristic of the bulk orthorhombic phase are found to be strongly dependent on temperature, the film thickness, and the distance away from the film–substrate interface. For thicknesses, t, above the critical thickness for ferromagnetism (t > 3 uc), the orthorhombic distortions decrease with increasing temperature above TC. Below TC, the structure of the films remains constant due to the magneto-structural coupling observed in bulk SRO. The orthorhombic distortions are found to be suppressed in the 2–3 interfacial layers due to structural coupling with the SrTiO3 substrate and correlate with the critical thickness for ferromagnetism in uncapped SRO films. 

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4. The Thickness and Structure of Dip-Coated Polymer Films in the Liquid and Solid States

   https://doi.org/10.3390/mi13070982  

   Zhang, Zhao; Peng, Fei; Kornev, Konstantin (July 2022, Micromachines)

   Films formed by dip coating brass wires with dilute and semi-dilute solutions of polyvinyl butyral in benzyl alcohol were studied in their liquid and solid states. While dilute and semi-dilute solutions behaved as Maxwell viscoelastic fluids, the thickness of the liquid films followed the Landau-Levich-Derjaguin prediction for Newtonian fluids. At a very slow rate of coating, the film thickness was difficult to evaluate. Therefore, the dynamic contact angle was studied in detail. We discovered that polymer additives preserve the advancing contact angle at its static value while the receding contact angle follows the Cox–Voinov theory. In contrast, the thickness of solid films does not correlate with the Landau-Levich-Derjaguin predictions. Only solutions of high-molecular-weight polymers form smooth solid films. Solutions of low-molecular-weight polymers may form either solid films with an inhomogeneous roughness or solid polymer domains separated by the dry substrate. In technological applications, very dilute polymer solutions of high-molecular-weight polymers can be used to avoid inhomogeneities in solid films. These solutions form smooth solid films, and the film thickness can be controlled by the experimental coating conditions. 

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5. Effect of processing conditions on the mechanical properties of bio-inspired mechanical gradient nanocmposites

   Zhang, Y.; Edelbrook, A.N.; Rowan, S. J. (March 2019, European Polymer Journal)

   Photo-induced thiol-ene crosslinking of allyl-functionalized cellulose nanocrystal (CNC)/polymer nanocomposites allows access to films that mimic the water-enhanced mechanical gradient characteristics of the squid beak. These films are prepared by mixing the functionalized CNCs and polymer in a solvent before solution casting and drying. The photocrosslinking agents are then imbibed into the film before UV exposure. Reported herein are studies aimed at better understanding the effect of the film preparation procedure, film thickness and the conditions under which the UV treatment is carried out. It was found that when the film is heated at a temperature higher than its glass transition temperature (Tg) during the UV irradiation step there is a greater enhancement in the mechanical properties of the films, presumably on account of more efficient crosslinking between the CNC fillers. Moreover, composite films that were compression molded (at 90°C) before the imbibing step displayed lower mechanical properties compared to the as-cast films, which is attributed to phase separation of the CNC fillers and polymer matrix during this additional processing step. Finally, the film thickness was also found to be a critical factor that affects the degree of crosslinking. For example, thinner films (50 µm) displayed a higher wet modulus ca. 130 MPa compared to ca. 80 MPa for the thicker films (150 µm). Understanding the processing conditions allows access to a larger range of mechanical properties which is important for the design of new bio-inspired mechanical gradient nanocomposites. 

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