Scanning Probe Microscopy of Complex Polymer Systems: Beyond Imaging their Morphology

Leclère, Philippe; Viville, Pascal; Jeusette, M.; Aimé, Jean‐Pierre; Lazzaroni, Roberto

doi:10.1002/3527608516.ch7

Cited by 4 publications

(6 citation statements)

References 42 publications

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“…Only in recent years a quantitative understanding and analysis of AFM data is emerging, enabling a reconstruction of the interaction forces. 5,[9][10][11][12][13][14][15][16] In some cases numerical simulations of the motion of the cantilever for given interaction model forces are performed. 17,18 This approach allows detailed studies of cantilever dynamics but in general does not give easily and generally applicable relations between forces and measured parameters.…”

Section: Introductionmentioning

confidence: 99%

Quantitative Analysis of Scanning Force Microscopy Data Using Harmonic Models

et al. 2009

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Starting from established concepts that describe the dynamics of the cantilever in a scanning force microscope operated in intermittent contact mode as that of a driven harmonic oscillator, we introduce effective interaction parameters based on Fourier coefficients to describe the interaction forces. These interaction parameters are linear in the forces and separate conservative from dissipative contributions. They allow a qualitative description of the interaction process and enable a thorough discussion of the influence of experimental parameters on the measured data. Exemplary force spectroscopy data obtained from hard and soft polymeric model surfaces show that consistent data for the interaction parameters can be obtained which can be related to the material properties of the investigated surfaces. Images obtained in intermittent contact mode from a semicrystalline polymer as an exemplary nanostructured surface with hard-soft contrast illustrate that with the approach a clear identification of harder and softer domains is possible.

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Section: Introductionmentioning

confidence: 99%

Quantitative Analysis of Scanning Force Microscopy Data Using Harmonic Models

et al. 2009

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“…20 When approach−retract curves were analyzed, not only was the contrast in elastic modulus proven between the surface-exposed thermoplastic and elastomeric phases but more importantly the mixed mechanical response because of a region of embedded thermoplastic phase could be quantified. 6 Finally, Touhami et al demonstrated the detection of chitin accumulation in the walls of yeast cells, demonstrating the potential impact of further development of TM-AFM techniques toward sub-surface nanomechanical characterization. 19 It should be noted that the use of standard nanoindentation for comparison to the TM-AFM nanoindentation in this study was justifiable for the PS that was analyzed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In the direct-current (DC) force–volume measurements of a co-polymer film of PS- b -polybutadiene (PB), which contained regions of sub-micrometer-sized inclusions of glassy PS droplets embedded in the rubbery PB, an enhancement of the average elastic modulus was reported . When approach–retract curves were analyzed, not only was the contrast in elastic modulus proven between the surface-exposed thermoplastic and elastomeric phases but more importantly the mixed mechanical response because of a region of embedded thermoplastic phase could be quantified . Finally, Touhami et al demonstrated the detection of chitin accumulation in the walls of yeast cells, demonstrating the potential impact of further development of TM-AFM techniques toward sub-surface nanomechanical characterization …”

Section: Resultsmentioning

confidence: 99%

“…Tapping-mode atomic force microscopy (TM-AFM) enables the simultaneous imaging and nanoindentation measurements of systems with sub-micrometer compositional heterogeneities. − The objective of this work is to demonstrate that the variation in elastic behavior as a result of embedded phases can be manifested by a shift in phase angle of the cantilevered tip response to the excitation frequency . The complexity of the tip–sample interaction in TM-AFM has been broadly exploited to form images from spatial variations in phase contrast, initially in phase-separated block co-polymer systems and more recently in cells and supramolecular structures. ,− To interpret the relationship between the phase contrast and the structure being analyzed, techniques have also been developed for quantifying energy-dissipative processes that induce shifts in phase. ,− The ability to obtain sub-surface information is a compelling development on the instrumentation side, as well as on the interpretation of phase contrast, as demonstrated for chitin accumulation in yeast cell walls, for sub-micrometer inclusions of glassy polystyrene (PS) in rubbery polybutadiene, and for other complex material systems containing an embedded second phase. ,− …”

Section: Introductionmentioning

confidence: 99%

“…With oscillation of a cantilevered tip at a specific frequency, TM-AFM can be used to form an image of the sample from topographical variations, as well as from changes in phase angle, with minimal lateral deformation. ,,, The variations in phase angle from the excitation frequency were shown to produce contrast in images of a monolayer of diblock co-polymer reverse micelles loaded with zinc acetate dihydrate (ZnAc) in the micelle core. Although contrast in the phase image was associated with the relative compliancy, the details were as yet not well-understood for relating the local mechanical properties to the underlying compositional variations …”

Section: Introductionmentioning

confidence: 99%

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Nanoscale Elastic Modulus Variation in Loaded Polymeric Micelle Reactors

et al. 2012

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Tapping mode atomic force microscopy (TM-AFM) enables mapping of chemical composition at the nanoscale by taking advantage of the variation in phase angle shift arising from an embedded second phase. We demonstrate that phase contrast can be attributed to the variation in elastic modulus during the imaging of zinc acetate (ZnAc)-loaded reverse polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock co-polymer micelles less than 100 nm in diameter. Three sample configurations were characterized: (i) a 31.6 μm thick polystyrene (PS) support film for eliminating the substrate contribution, (ii) an unfilled PS-b-P2VP micelle supported by the same PS film, and (iii) a ZnAc-loaded PS-b-P2VP micelle supported by the same PS film. Force-indentation (F-I) curves were measured over unloaded micelles on the PS film and over loaded micelles on the PS film, using standard tapping mode probes of three different spring constants, the same cantilevers used for imaging of the samples before and after loading. For calibration of the tip geometry, nanoindentation was performed on the bare PS film. The resulting elastic modulus values extracted by applying the Hertz model were 8.26 ± 3.43 GPa over the loaded micelles and 4.17 ± 1.65 GPa over the unloaded micelles, confirming that phase contrast images of a monolayer of loaded micelles represent maps of the nanoscale chemical and mechanical variation. By calibrating the tip geometry indirectly using a known soft material, we are able to use the same standard tapping mode cantilevers for both imaging and indentation.

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Functional polymers: scanning force microscopy insights

Samorı́

Surin

Palermo

et al. 2006

Phys. Chem. Chem. Phys.

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Scanning force microscopy (SFM) and related techniques make it possible to visualize polymer systems with a molecular resolution. Beyond imaging, they also enable the unveiling of a variety of (dynamic) physico-chemical properties of both isolated polymer chains and their supramolecular architectures, including structural, mechanical and electronic properties. This article reviews recent progress in the use of SFM on polymers, with a particular emphasis on the mechanical properties of copolymers and single polymer chains, as well as on the bottom-up fabrication of supramolecular polymeric (helical) nanostructures in particular based upon pi-conjugated macromolecules as building blocks for nanoelectronics. Through a detailed understanding of the polymer behavior, we propose solutions for the generation of organic functional (nano)systems.

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Scanning Probe Microscopy of Complex Polymer Systems: Beyond Imaging their Morphology

Cited by 4 publications

References 42 publications

Quantitative Analysis of Scanning Force Microscopy Data Using Harmonic Models

Quantitative Analysis of Scanning Force Microscopy Data Using Harmonic Models

Nanoscale Elastic Modulus Variation in Loaded Polymeric Micelle Reactors

Functional polymers: scanning force microscopy insights

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