Studies of surface and interface segregation in polymer blends by secondary ion mass spectrometry

Schwarz, S. A.; Wilkens, B. J.; Pudensi, M. A. A.; Rafailovich, Miriam; Sokolov, J.; Zhao, Xiaolin; Zhao, Wei; Zheng, Xuemei; Russell, Thomas P.; Jones, Richard

doi:10.1080/00268979200101771

Cited by 88 publications

(87 citation statements)

References 19 publications

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“…24 This is an optimal situation for analysis of a heterogeneous interface, and it should be noted that these analysis conditions (i.e., detection of positive secondary ions) could not be implemented with the commonly used quadrupole SIMS instrument, with its inferior mass resolution (typical m/∆m ∼ 300) and, hence, inability to mass resolve D + from H 2 + . 4,25 Therefore, the phenomena observed at the hPS:dPS/hPMMA interface in Figure 1b,c are not artifacts of the SIMS analysis. This is also evidenced in Figure 1a with the absence of any discernible features near the hPS:dPS/ hPMMA interface for t ) 0. a For systems A-G the bottom layer (hPMMA or hP2VP) was ≈200 nm, while the hPMMA layer thickness was 100 nm for system H. Concentrations (% v/v) are based on volume fraction at t ) 0.…”

Section: Resultsmentioning

confidence: 99%

“…4,5 Although labeling is often necessary for experimental characterization, it is well-known that deuterium labeling (deuteration) can alter the thermodynamic properties of the polymer constituents. [6][7][8] In fact, many simple mixtures involving a polymer species and its deuterated analogue are known to have a small, but finite, mean-field interaction parameter and are characterized by upper-critical solutiontype phase behavior (UCST).…”

Section: Introductionmentioning

confidence: 99%

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Investigation of the Effects of Isotopic Labeling at a PS/PMMA Interface Using SIMS and Mean-Field Theory

2006

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Isotopic labeling (deuteration) is known to affect the phase behavior of polystyrene (PS) and poly-(methyl methacrylate) (PMMA) blends, but little is known regarding the changes in the interfacial properties at the PS/PMMA interface due to deuteration of PS and/or PMMA. To investigate these potential changes, secondary ion mass spectrometry (SIMS) was used to measure real-space depth profiles of dPS in hPS:dPS/hPMMA bilayers, with the hPS:dPS blend being well within the single-phase region of the phase diagram. Profound changes in the thermodynamic behavior of this system at the polymer/polymer interface are observed in the form of significant segregation of dPS to the hPS:dPS/hPMMA interface. The observation of a depletion hole during the formation of an equilibrium excess of dPS implies that the energetic gain at the interface per dPS chain has to be >kT. These results cannot be described, even qualitatively, using previously reported changes in for PS/PMMA due to isotopic labeling. The previously reported values of for dPS/hPMMA and hPS/hPMMA actually predict a depletion of dPS at the hPS:dPS/hPMMA interface rather than the observed segregation. The observed interfacial excess is quantified by generating theoretical profiles, using self-consistent mean-field theory (SCMF), and fitting an effective interaction energy parameter ∆ p as a function of temperature. This parameter represents the asymmetry in dPS/hPMMA and hPS/PMMA interactions. The temperature dependency of ∆ p was found to be a factor of 3-4 greater than any of those reported for of PS/PMMA. It was also found that SCMF theory accurately describes the concentration dependency of dPS segregation at a constant dPS molecular weight using a concentration-independent ∆ p ; however, ∆ p was found to be dependent on dPS molecular weight.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Investigation of the Effects of Isotopic Labeling at a PS/PMMA Interface Using SIMS and Mean-Field Theory

2006

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“…In profiling mode of dynamic SIMS (Fig. 3b) [45][46][47] The 3D and lateral phase domain structure was revealed by the mapping mode of dynamic SIMS (Fig. 3b) [13] and by AFM combined with selective dissolution (Fig.…”

Section: C Experimental Techniques Revealing Blend Film Morphologymentioning

confidence: 99%

“…3): Nuclear Reaction Analysis (NRA) [43,44], profiling [45][46][47] and mapping [13] mode of dynamic Secondary Ion Mass Spectroscopy (SIMS), and with Atomic Force Microscopy (AFM) combined with selective dissolution [15]. The free surface undulations were determined with AFM [48].…”

Section: C Experimental Techniques Revealing Blend Film Morphologymentioning

confidence: 99%

Surface-directed phase separation in nanometer polymer films: self-stratification and pattern replication

et al. 2002

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Phase separation occurs in thin films of polymer blends when molecular mobility is promoted by a temperature above the glass transition but inside the twophase region (temperature quench), or a common solvent added to the polymers (solvent quench). This phenomenon can be altered by a homogeneous surface or pre-patterned substrate, resulting, e.g., in self-stratification or pattern replication, respectively. Such self-organisation processes ordering polymer phases were observed for model polymer blends (deuterated/hydrogenated polystyrene, dPS/hPS, and deuterated/partially brominated PS, dPS/PBrS, both with hPSpolyisoprene diblocks added; dPS/poly(vinylpyridine) and PBrS/PVP) with highresolution ion beam techniques (Nuclear Reaction Analysis, profiling and mapping mode of dynamic Secondary Ion Mass Spectrometry) and Atomic Force Microscopy. The self-stratification process is strongly affected by both the range as well as the strength of the surface/polymer interactions. This is illustrated for the temperature-quenched blends with surface-active copolymer additives tuning the interactions exerted by both external surfaces. The pattern transfer from the substrate to the films is demonstrated for the solvent-quenched blends. Patterndirected composition variations (SIMS maps) coincide with free surface undulations (AFM images). The most effective pattern replication is achieved for the length scale of phase domain morphology comparable with the pattern periodicity and for carefully adjusted polymer/substrate interactions.

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“…One such application has been onedimensional depth profiling of polymer films and multilayers, which has provided a significant driving force for growth in experimental and theoretical polymer physics over the past 20 years [6]. Deuterium substitution is by far the most common type of tracer labeling used for analysis of polymer films and multilayers [7], with the commercial availability of various labeled reagents and monomers. Unfortunately, it can introduce changes in the properties being measured.…”

mentioning

confidence: 99%

Carbon-13 labeling for improved tracer depth profiling of organic materials using secondary ion mass spectrometry

Harton

Stevie

Ade

2006

J. Am. Soc. Mass Spectrom.

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Studies of surface and interface segregation in polymer blends by secondary ion mass spectrometry

Cited by 88 publications

References 19 publications

Investigation of the Effects of Isotopic Labeling at a PS/PMMA Interface Using SIMS and Mean-Field Theory

Investigation of the Effects of Isotopic Labeling at a PS/PMMA Interface Using SIMS and Mean-Field Theory

Surface-directed phase separation in nanometer polymer films: self-stratification and pattern replication

Carbon-13 labeling for improved tracer depth profiling of organic materials using secondary ion mass spectrometry

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