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1.
Surf Coat Technol ; 4052021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37719657

RESUMO

The coating/substrate interface and oxide layers of the Inconel 625 film may have significant impacts on its material properties, especially the corrosion behavior of the film. However, since the interface and oxide layer can be very thin and experimental toolbox to characterize them is limited, the detailed vertical structure of Inconel 625 coatings remains poorly understood. In this study, a multi-layer structure in Inconel 625 film prepared by magnetron sputtering is revealed using X-ray reflectometry (XRR) and neutron reflectometry (NR) techniques. Thickness and major composition of each layer are obtained. The results indicate that there exists a ~2 nm-thick Cr-rich Inconel sublayer underneath the main Inconel 625 film. An oxide layer mainly consisting of NiO with thickness of ~2 nm is found on the surface of the main Inconel 625 film. In addition, we identified a ~2 Å contamination layer between sapphire substrate and Inconel film even after argon ion sputtering cleaning. We also found that the thickness of the main Inconel 625 film grows linearly with the deposition time, with thicknesses of other layers remaining constant. Our findings provide insight into the multi-layered structures of Inconel 625 coatings with atomic-scale spatial resolution and give directions for future study to improve the corrosion resistance of Inconel 625 coatings.

2.
Langmuir ; 36(50): 15240-15246, 2020 12 22.
Artigo em Inglês | MEDLINE | ID: mdl-33295178

RESUMO

The surface adsorption of bovine serum albumin in pure water and salted aqueous solutions was studied by neutron reflection. With the contrast match technique, the surface excess in null reflecting water as a function of the protein concentration was revealed. It is found that, in a concentration range from 1 ppm (parts per million, mg/L) to 1000 ppm, without salts, the surface excess shows a profound peak at around 20 ppm; with salts, the surface excess increases steadily with the protein concentration. When the surface excess at a specific protein concentration is viewed, the introduction of sodium chloride causes either a salting down effect (surface adsorption decline) or a salting up effect (surface adsorption increase), depending upon the protein concentration. The salting up effect is observed at the low (∼1 ppm) and high (∼1000 ppm) concentrations, and the salting down effect dominates the intermediate concentration range. The change in solution pH relative to the isoelectric point (PI) can act as a simple indicator for the salting up or salting down behavior. When the solution pH is shifted toward the PI by adding salts, surface adsorption enhances; when the solution pH is shifted away from the PI by adding salts, surface adsorption declines.


Assuntos
Cloreto de Sódio , Água , Adsorção , Sais , Soroalbumina Bovina
3.
Langmuir ; 36(13): 3393-3403, 2020 04 07.
Artigo em Inglês | MEDLINE | ID: mdl-32216370

RESUMO

Maintaining the integrity of cell membranes is indispensable for cellular viability. Poloxamer 188 (P188), a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer with a number-average molecular weight of 8700 g/mol and containing 80% by mass PEO, protects cell membranes from various external injuries and has the potential to be used as a therapeutic agent in diverse applications. The membrane protection mechanism associated with P188 is intimately connected with how this block copolymer interacts with the lipid bilayer, the main component of a cell membrane. Here, we report the distribution of P188 in a model lipid bilayer comprising 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) using neutron reflectivity (NR) and atomic force microscopy (AFM). We also investigated the association of a PEO homopolymer (PEO8.4K; Mn = 8400 g/mol) that does not protect living cell membranes. These experiments were conducted following incubation of a 4.5 mmol/L polymer solution in a buffer that mimics physiological conditions with supported POPC bilayer membranes followed by washing with the aqueous medium. In contrast to previous reports, which dealt with P188 and PEO in salt-free solutions, both P188 and PEO8.4K penetrate into the inner portion of the lipid bilayer as revealed by NR, with approximately 30% by volume occupancy across the membrane without loss of bilayer structural integrity. These results indicate that PEO is the chemical moiety that principally drives P188 binding to bilayer membranes. No defects or phase-separated domains were observed in either P188- or PEO8.4K-incubated lipid bilayers when examined by AFM, indicating that polymer chains mingle homogeneously with lipid molecules in the bilayer. Remarkably, the breakthrough force required for penetration of the AFM tip through the bilayer membrane is unaffected by the presence of the large amount of P188 and PEO8.4K.


Assuntos
Bicamadas Lipídicas , Propilenoglicóis , Polietilenoglicóis , Polímeros
4.
Soft Matter ; 16(5): 1287-1297, 2020 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-31915772

RESUMO

Spin casting has become an attractive method to fabricate polymer thin films found in organic electronic devices such as field-effect transistors, and light emitting diodes. Many studies have shown that altering spin casting parameters can improve device performance, which has been directly correlated to the degree of polymer alignment, crystallinity, and morphology of the thin film. To provide a thorough understanding of the balance of thermodynamic and kinetic factors that influence the stratification of polymer blend thin films, we monitor stratified polymer blend thin films developed from poly(3-hexylthiophene-2,5-diyl) and poly(methyl methacrylate) blends at controlled loading ratios, relative molecular weights, and casting speed. The structures of these thin films were characterized via neutron reflectivity, and the results show that at the fastest casting speed, polymer-polymer interactions and surface energy of the polymers in the blend dictate the final film structure, and at the slowest casting speed, there is less control over the film layering due to the polymer-polymer interactions, surface energy, and entropy simultaneously driving stratification. As well, the relative solubility limits of the polymers in the pre-deposition solution play a role in the stratification process at the slowest casting speed. These results broaden the current understanding of the relationship between spin casting conditions and vertical phase separation in polymer blend thin films and provide a foundation for improved rational design of polymer thin film fabrication processes to attain targeted stratification, and thus performance.

5.
Langmuir ; 35(16): 5549-5556, 2019 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-30929428

RESUMO

We investigated the effect of the morphological structure of a graphene oxide (GO) monolayer on the dewetting dynamics of the upper polymer thin films. The Langmuir-Schaefer (LS) technique was used to prepare a wrinkled GO ( wrGO) structure with a root mean square (rms) roughness of 22.7 Å. The dewetting behavior of poly(methyl methacrylate) (PMMA) thin films on the wrGO monolayers was perfectly prevented, whereas the PMMA thin films on a flat GO monolayer were dewetted at 203 °C. This wrinkle effect of the GO can be also obtained when the GOs monolayers are intercalated to the PMMA/polystyrene (PS) interface. In this multilayer, the flat GO monolayer at the interface between the PS and PMMA layers was spontaneously roughened with rms roughness of 46.9 Å after annealing and also prohibited the dewetting behavior. From the results, we found that to improve the compatibility of polymer blends by adding the two-dimensional nanosheets, it is important to control the morphological structure of the sheets at the interface, along with manipulation of the GO-polymer interactions.

6.
Langmuir ; 34(23): 6757-6765, 2018 06 12.
Artigo em Inglês | MEDLINE | ID: mdl-29781623

RESUMO

Structure and dynamics inside permanently charged polyelectrolyte brushes, sodium polystyrene sulfonate brushes, during their response to the introduction of external ions (NaCl) are investigated by neutron reflectivity and dielectric spectroscopy. Neutron reflectivity measurements show that the segmental density of the inner part of the brushes decreases and that of the outer part increases when the salt level is tuned from the salt-free condition to a moderate level (<10-2 M)-the brushes swell further compared with the salt-free condition. This is attributed to the breakup of the multiplets formed by dipole-dipole pairs, and by this process, the previously constrained chain segments by the multiplets are released. Dielectric spectroscopy discovers a giant dipole by the charge separation of the adsorbed counterions and the PSS- chains, induced by electric field. The dynamics of the induced giant dipole is accelerated with the increase of external salt, as a result of the charge regularization by elevated salt level. At high-enough salt level, the screening effect reduces the electrostatic repulsion between the neighboring chains and makes the brushes shrink.

7.
Langmuir ; 34(4): 1681-1690, 2018 01 30.
Artigo em Inglês | MEDLINE | ID: mdl-29293348

RESUMO

We have studied an orientation structure of self-assembled block copolymers (dPS-b-PMMA) of deuterated polystyrene (dPS) and poly(methyl methacrylate) (PMMA) confined between graphene oxide (GO) surfaces. The results of combination techniques, such as neutron reflectivity, time-of-flight secondary-ion mass spectrometry, grazing-incidence small-angle X-ray scattering, and scanning electron microscopy, show that self-assembled domains of the block copolymers in thin films near the GO sheets are oriented perpendicular to the surface of the GO monolayers, in contrast to the horizontal lamellar structure of the copolymer thin film in the absence of the GO monolayers. This is due to the amphiphilic nature of the GO, which leads to a nonpreferential interaction of both dPS and PMMA blocks. Double-sided confinement with the GO monolayers further extends the ordering behavior of the dPS-b-PMMA thin films. Continuous vertical orientation of the block copolymer thin films is also obtained in the presence of alternating GO layers within thick copolymer films.

8.
Soft Matter ; 14(7): 1108-1119, 2018 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-29340434

RESUMO

Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

9.
Soft Matter ; 12(37): 7863-7872, 2016 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-27714350

RESUMO

In this study, the attraction between large hard polystyrene (PS) spheres is studied by using three types of small microgels as bridging agents. One is a purely soft poly(N-isopropylacrylamide) (PNIPAM) microgel, the other two have a non-deformable PS hard core surrounded by a soft PNIPAM shell but are different in the core-shell ratio. The affinity for bridging the large PS spheres is provided and thus affected by the PNIPAM constituent in the microgels. The bridging effects caused by the microgels can be indirectly incorporated into their influence on the effective attraction interaction between the large hard spheres, since the size of the microgels is very small in comparison to the size of the PS hard spheres. At a given volume fraction of large PS spheres, they behave essentially as hard spheres in the absence of small microgels. By gradually adding the microgels, the large spheres are connected to each other through the bridging of small particles until the attraction strength reaches a maximum value, after which adding more small particles slowly decreases the effective attraction strength and eventually the large particles disperse individually when saturated adsorption is achieved. The aggregation and gelation behaviors triggered by these three types of small microgels are compared and discussed. A way to tune the strength and range of the short-range attractive potential via changing the softness of bridging microgels (which can be achieved either by using core-shell microgels or by changing the temperature) is proposed.

10.
J Chem Phys ; 145(1): 014904, 2016 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-27394122

RESUMO

Two types of colloidal particles, which are nearly the same in chemical composition but carry opposite surface charges, are mixed in water. Depending on the relative proportion of the oppositely charged particles, the process of aggregation leads to the formation of discrete clusters of various sizes in dilute dispersions, and to the development of particle gel networks in more concentrated systems. Due to the significant difference in the absolute values of surface charges (negative particle: -48 mV, positive particle: +24 mV), the phase separation and the gelation behaviors are asymmetric with respect to the mixing ratio. Mixtures with excess negative particles are more stable, while mixtures with excess positive particles are easily affected by phase separation. The hetero-aggregation triggered by the addition of microscopically large macro-ions is similar to what is often observed in a mono-component charged colloidal system, i.e., phase separation occurs through addition of small electrolyte ions. Within the concentration region investigated here, it is clear that the gel line is buried inside the phase separation region. Gelation occurs only when the number and size of the clusters are large and big enough to connect up into a space-spanning network. Our results indicate that, in this binary mixture of oppositely charged colloids, although the interaction between unlike species is attractive and that between like species is repulsive, the onset of gelation is in fact governed by the equilibrium phase separation, as in the case of purely attractive systems with short-range isotropic interaction.

11.
Soft Matter ; 11(12): 2494-503, 2015 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-25679297

RESUMO

In this study, mixed suspensions of large hard polystyrene microspheres and small soft poly(N-isopropylacrylamide) microgels are used as model systems to investigate the static and viscoelastic properties of suspensions which go through liquid to gel transitions. The microgels cause short-range attraction between microspheres through the bridging and depletion mechanism whose strength can be tuned by the microgel concentration. Rheological measurements are performed on suspensions with the volume fraction (Φ) of microspheres ranging from 0.02 to 0.15, and the transitions from liquid-like to solid-like behaviors triggered by the concentration of microgels are carefully identified. Two gel lines due to bridging attraction under unsaturated conditions are obtained. Ultra-small angle neutron scattering is used to probe the thermodynamic properties of suspensions approaching the liquid-solid transition boundaries. Baxter's sticky hard-sphere model is used to extract the effective inter-microsphere interaction introduced by the small soft microgels. It is found that the strength of attraction (characterized by a single stickiness parameter τ) on two gel lines formed by bridging is very close to the theoretical value for the spinodal line in the τ-Φ phase diagram predicted by Baxter's model. This indicates that the nature of the gel state may have the same thermodynamic origins, independent of the detailed mechanism of the short-range attraction. The relationship between the rheological criterion for the liquid-solid transition and the thermodynamic criterion for the equilibrium-nonequilibrium transition is also discussed.

12.
Langmuir ; 30(37): 11011-8, 2014 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-25180890

RESUMO

The liquid-gel-liquid transition tuned by increasing concentration of linear and hyperbranched polyethyleneimine in suspension of silica colloids, and the accompanying shear-thickening phenomena, were investigated by rheological measurements. The influence from linear and hyperbranched polymer conformation and from different size-ratio between particle and polymer on the rheological properties of suspensions flocculated by absorbing polyelectrolyte were considered. Charge neutralization and bridging mechanism are the main reasons for the flocculation of silica colloid in this study. Because of charge reversal, the irreversible bridges are turned into flexible reversible bridges with increasing adsorption amount of oppositely charged polymer, which leads to an abrupt transition from gel to liquid. Over a narrow composition range, around the gel to liquid transition region, shear-thickening flow is observed. It is found that, for given particle volume fraction, the composition region exhibiting shear-thickening for mixed suspension with linear polyethyleneimine is broader than that for mixed suspension with hyperbranched polyethyleneimine, and the onset of shear-thickening depends only on size-ratio, regardless of the actual size of particle and polymer in the range of this study. The relationship between the gel to liquid transition and shear-thickening was discussed.

13.
Soft Matter ; 10(44): 8905-12, 2014 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-25280208

RESUMO

Gelation and glass transition in a mixed suspension of polystyrene (PS) microsphere and poly(N-isopropylacrylamide) (PNIPAM) microgel were studied as a function of the total colloid volume fraction and mixing ratio of these two components. The PNIPAM microgel, which is adsorbable on the PS microsphere surface, can induce bridging or stabilizing effect between microspheres depending on whether the volume fraction of microgel (ΦMG) is smaller or larger than the saturated adsorption concentration (Φ*MG) for a given volume fraction of the microsphere (ΦMS). Φ*MG is in a linear relationship with ΦMS, and the value of ΦMG/Φ*MG can be taken as an approximate measure of surface coverage. A state diagram of gelation and glass transition is constructed with the short-ranged attractive interaction, resulting from the well-defined bridging bonding. Keeping ΦMG/Φ*MG = 0.20 and increasing ΦMS from 0.25 to 0.55, the mixed suspension transforms from a bridging gel into an attractive glass; moreover, while keeping ΦMS = 0.45 and increasing ΦMG/Φ*MG from 0.20 to 1.2, the mixed suspension changes from a bridging gel into an attractive glass, and then to a repulsive glass. The bridging effect and the cage effect can be distinguished by the yielding behaviors in rheological measurements. In the nonlinear dynamic rheological experiments, one-step yielding, corresponding to the disconnecting of bridge network, is observed in the bridging gel, and one-step yielding, corresponding to the breaking of cage, is observed in the repulsive glass. However, a two-step yielding behavior is found in the bridging-induced attractive glass, which is attributed to the bridging effect of microgels and the caging effect of the dense environment.

14.
Langmuir ; 29(39): 12110-7, 2013 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-24001334

RESUMO

The rheological property of mixed suspensions of silica colloid and hyperbranched polyethyleneimine (hPEI) was studied as functions of particle volume fraction, ratio of polymer to particle, and pH value. A mechanism of liquid-gel-liquid transition for this mixed system was proposed based on the amount and the conformation of polyelectrolyte bridges which were able to self-arrange with solution environments. The hPEI, which is adsorptive to the surface of silica colloid, can induce bridging or stabilizing effect between particles depending on whether the concentration of hPEI (Cp) is smaller or larger than the equilibrium adsorbed amount (Cp*) for a given volume fraction of particles. In dilute colloid suspensions, the Cp* can be determined by dynamic light scattering as the correlation function returns back to a narrow distributing single relaxation with increasing Cp. In concentrated colloid suspensions, the Cp* can be determined by rheological measurement as gel-liquid transition occurs with increasing Cp. The Cp* is an important concentration ratio of polymer to particle denoting the transition of irreversible and reversible bridging. For mixed suspensions at equilibrium adsorbed state (Cp ≈ Cp*), the adsorption-desorption of polymer bridges on the particles can reversibly take place, and shear thickening is observed under a steady shear flow as a result of rapid extension of bridges when the relaxation time scale of extension is shorter than that of desorption.

15.
J Chem Phys ; 138(18): 184902, 2013 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-23676069

RESUMO

The linear and nonlinear rheological measurements were utilized to study the mechanical response of concentrated mixtures of colloidal particles with opposite charges. The particle volume fraction (Φ) spans the region from low volume fraction (Φ = 0.18) gel to high volume fraction (Φ = 0.53) glass. In the linear viscoelastic region, the storage moduli G' exhibits deferent Φ dependence at low and high Φ's. It follows a power law relationship as G' ~ Φ(6.2±0.2) for Φ < 0.46, and follows an exponential relationship as G' ~ exp[(13.8 ± 0.6)Φ] for Φ ≥ 0.46. The difference can be taken as a distinction between a colloidal gel and an attractive glass (or dense gel) for the present system. The loss moduli G" is almost frequency independent within the whole experimental frequency range (10(-1)-10(2) rad∕s) for colloidal gel, and G" exhibits a weak minimum for attractive glass. In the nonlinear large amplitude rheological measurement, samples with Φ < 0.46 show one-step yielding, and samples with Φ ≥ 0.46 exhibit two-step yielding which is in agreement with numerous experiments in attractive glassy systems. The first yielding is due to the breaking of short range interactions which bond the interconnected clusters or local clusters, while the second yielding is attributed to the breaking of long range interaction, normally the caging forming or glass forming interactions. The qualitative distinction between attractive glass and gel in terms of their yielding behavior is consistent with the linear rheological results. The particle-particle interactions were modulated by salt concentration. It was found that, when the attraction interaction is enhanced, both yielding points in attractive glass shift to higher strain amplitude and the gap between the two yielding points become more separated.

16.
J Control Release ; 331: 472-479, 2021 03 10.
Artigo em Inglês | MEDLINE | ID: mdl-33549717

RESUMO

The drug loading and releasing properties of poly(lactic-co-glycolic acid) (PLGA) were approached with the application of neutron techniques. The neutron reflection (NR) study on the response of PLGA material to vapor and to bulk water revealed that the hydration of PLGA origins from the molecular compatibility between water and PLGA. Hydration is reversible with regard to the change in humidity and temperature. Capecitabine as drug was embedded in the electrospun PLGA fibers. Small angle neutron scattering (SANS) was able to disclose the domain of entrapped drug inside the fibers and trace its evolution over time when the electrospun membrane was incubated in D2O buffer solution. The evolution of drug domains is discussed in terms of the concentration dependence, the temperature dependence, and the relevance between the drug diffusion inside the polymer matrix and the drug release out to the medium. It was observed that, at 20 °C the drug-related domains are relatively small (~ 100 Å) and relax extremely slow while at 37 °C the drug-related domains are relatively larger (~ 200 Å) and relax faster. These behaviors can be related to the glassy property of structural material. The transportation of drug through the polymer matrix relies on the global relaxation of PLGA chains. The variation of fiber diameter vs. incubation time was followed by ultra-small angle neutron scattering (USANS). The bi-phasic or tri-phasic release kinetics from a series of fibers with different drug loading (2%, 5%, 10%, 20%, 30%, 40%, 50%) were discussed based on the SANS and USANS discovery.


Assuntos
Preparações Farmacêuticas , Ácido Poliglicólico , Liberação Controlada de Fármacos , Glicóis , Ácido Láctico , Copolímero de Ácido Poliláctico e Ácido Poliglicólico
17.
ACS Nano ; 15(7): 12042-12056, 2021 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-34255492

RESUMO

While the phase separation of binary mixtures of chemically different polymer-grafted nanoparticles (PGNPs) is observed to superficially resemble conventional polymer blends, the presence of a "soft" polymer-grafted layer on the inorganic core of these nanoparticles qualitatively alters the phase separation kinetics of these "nanoblends" from the typical pattern of behavior seen in polymer blends and other simple fluids. We investigate this system using a direct immersion annealing method (DIA) that allows for a facile tuning of the PGNPs phase boundary, phase separation kinetics, and the ultimate scale of phase separation after a sufficient "aging" time. In particular, by switching the DIA solvent composition from a selective one (which increases the interaction parameter according to Timmerman's rule) to an overall good solvent for both PGNP components, we can achieve rapid switchability between phase-separated and homogeneous states. Despite a relatively low and non-classical power-law coarsening exponent, the overall phase separation process is completed on a time scale on the order of a few minutes. Moreover, the roughness of the PGNP blend film saturates at a scale that is proportional to the in-plane phase separation pattern scale, as observed in previous blend and block copolymer film studies. The relatively low magnitude of the coarsening exponent n is attributed to a suppression of hydrodynamic interactions between the PGNPs. The DIA method provides a significant opportunity to control the phase separation morphology of PGNP blends by solution processing, and this method is expected to be quite useful in creating advanced materials.

18.
ACS Macro Lett ; 9(10): 1483-1488, 2020 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-35653667

RESUMO

The morphological structure and dynamics of confined polymers adjacent to the polymer-polymer interface have a profound effect on determining the overall physical properties of polymer blends. We measured the diffusion dynamics of poly(methyl methacrylate) (PMMA) melts confined between polystyrene (PS) layers using neutron reflectivity. Combinations of various thicknesses of PMMA and deuterated PMMA (dPMMA) allowed us to experimentally reveal the nonmonotonic behavior of polymer mobility near the PS-PMMA interface. From the neutron reflectivity results, we found that the polymers adjacent to the immiscible polymer-polymer interface showed enhanced diffusion dynamics because of the repulsive interaction between PS and PMMA, whereas the polymer at local regions farther from the interface exhibited reduced dynamics. This is probably due to the nonspherical conformation of PMMA and spatial confinement near the PS-PMMA interface.

19.
ACS Macro Lett ; 9(2): 210-215, 2020 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-35638684

RESUMO

For polymer-blend films, local dynamics in confined polymer domains tend to differ from the bulk because of significant contributions from the polymer-polymer interface. Herein, we investigated the diffusion dynamics of entangled polymer thin films confined between different polymers in a direction perpendicular to the surface using neutron reflectivity. We found that a bilayer of poly(methyl methacrylate) (PMMA) and deuterated PMMA (dPMMA) sandwiched between polystyrene (PS) layers exhibited significant increase in mobility near the polymer-polymer interface with decreasing PMMA thickness. This indicates that the contribution of repulsive interactions at the immiscible polymer-polymer interface becomes more significant as the film thickness decreases. We also found that the interfacial roughness between PMMA and PS (28 Å at equilibrium) and soft confinement of PS layers did not significantly affect the change in the diffusion dynamics of the adjacent PMMA. This was evidenced by comparison with the diffusion results of multilayers with a flat interface (8 Å at equilibrium) between PMMA and hard PS by UV cross-linking.

20.
ACS Appl Mater Interfaces ; 12(1): 1825-1831, 2020 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-31820621

RESUMO

Interactions between a catalyst and electrolyte have paramount importance for the performance of electrochemical devices. Here, we present the cation-hydroxide-water coadsorption on the Pt surface by a rotating disk electrode and neutron reflectometry. The rotating disk electrode experiments show that the current density of Pt rapidly dropped at hydrogen oxidation potentials due to tetramethylammonium hydroxide (TMAOH)-water coadsorption. Subsequent neutron reflectometry in 0.1 M TMAOD/D2O reveals that the thickness of the coadsorbed layer increased to 18 Å after 10.5 h exposure at 0.1 V vs reverse hydrogen electrode (RHE). The scattering length density analysis revealed that the TMAOD to water ratio in the coadsorbed layer was 4.5, which was significantly higher than the reportedly highest TMAOH concentration in aqueous solution. Finally, we discuss the potential impact of the coadsorbed layer on the performance and durability of alkaline membrane fuel cells, which sheds light on the material design of high-performance alkaline electrochemical devices.

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