Spatial Differentiation of Sub-Micrometer Domains in a Poly(hydroxyalkanoate) Copolymer Using Instrumentation that Combines Atomic Force Microscopy (AFM) and Infrared (IR) Spectroscopy (original) (raw)
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Recent Applications of Advanced Atomic Force Microscopy in Polymer Science: A Review
Polymers, 2020
Atomic force microscopy (AFM) has been extensively used for the nanoscale characterization of polymeric materials. The coupling of AFM with infrared spectroscope (AFM-IR) provides another advantage to the chemical analyses and thus helps to shed light upon the study of polymers. This paper reviews some recent progress in the application of AFM and AFM-IR in polymer science. We describe the principle of AFM-IR and the recent improvements to enhance its resolution. We also discuss the latest progress in the use of AFM-IR as a super-resolution correlated scanned-probe infrared spectroscopy for the chemical characterization of polymer materials dealing with polymer composites, polymer blends, multilayers, and biopolymers. To highlight the advantages of AFM-IR, we report several results in studying the crystallization of both miscible and immiscible blends as well as polymer aging. Finally, we demonstrate how this novel technique can be used to determine phase separation, spherulitic str...
Recent Progressive Use of Advanced Atomic Force Microscopy in Polymer Science: A Review
2020
Atomic force microscopy (AFM) has been extensively used for the nanoscale characterization of polymeric materials. The coupling of AFM with infrared spectroscope (AFM-IR) provides another advantage to the chemical analyses and thus helps to shed light upon the study of polymers. In this perspective paper, we review recent progress in the use of AFM-IR in polymer science. We describe first the principle of AFM-IR and the recent improvements to enhance its resolution. We discuss then the last progress in the use of AFM-IR as a super-resolution correlated scanned-probe IR spectroscopy for chemical characterization of polymer materials dealing with polymer composites, polymer blends, multilayers and biopolymers. To highlight the advantages of AFM-IR, we report here several results in studying crystallization of both miscible and immiscible blends as well as polymer aging. Then, we demonstrate how this novel technique can be used to determine phase separation, spherulitic structure and c...
In this paper, the use of a hybrid atomic force microscopy/infrared spectroscopy/mass spectrometry imaging platform was demonstrated for the acquisition and correlation of nanoscale sample surface topography and chemical images based on infrared spectroscopy and mass spectrometry. The infrared chemical imaging component of the system utilized photothermal expansion of the sample at the tip of the atomic force microscopy probe recorded at infrared wave numbers specific to the different surface constituents. The mass spectrometry-based chemical imaging component of the system utilized nanothermal analysis probes for thermolytic surface sampling followed by atmospheric pressure chemical ionization of the gas phase species produced with subsequent mass analysis. The basic instrumental setup, operation, and image correlation procedures are discussed, and the multimodal imaging capability and utility are demonstrated using a phase separated poly(2-vinylpyridine)/poly(methyl methacrylate) polymer thin film. The topography and both the infrared and mass spectral chemical images showed that the valley regions of the thin film surface were comprised primarily of poly(2-vinylpyridine) and hill or plateau regions were primarily poly(methyl methacrylate). The spatial resolution of the mass spectral chemical images was estimated to be 1.6 μm based on the ability to distinguish surface features in those images that were also observed in the topography and infrared images of the same surface. A nalytical tools that can provide spatially resolved sample surface morphology, or other physical information, as well as chemical information at the very low micrometer to nanometer scale, are inherently useful. For example, such correlated, or " multimodal " , information is beneficial for characterizing and understanding the composition and function of chemical interfaces in diverse fields like chemical science, material science, biology, and geology. 1−4 One important tool used in this correlated, multimodal imaging pursuit has been atomic force microscopy (AFM). 5,6 Topography and a wide range of physical properties of a surface, such as electric, magnetic, and thermal properties, can be obtained and correlated with a single AFM instrument and sample. However, chemical characterization is not possible with AFM alone. 7 To overcome this limitation and extend the capability of the AFM technique, a variety of optical spectroscopy techniques, including infrared (IR) 8 and Raman 9 spectroscopies, have been used with AFM to create hybrid tools that can obtain spatially resolved chemical signatures from a sample surface. 7,10 An alternative chemical imaging approach that has been combined with AFM is mass spectrometry imaging (MSI). 11 MSI provides spatially resolved selective detection and identification within complex matrices, either through (accurate) mass measurements or through the use of tandem mass spectrometry (MS/MS). 12,13 When performing MSI, the particular combination of surface sampling process, ionization method, and mass analyzer used will determine the surface types and chemical species that can be analyzed and the specific limits of detection and degree of chemical detection specificity. MSI, albeit destructive, typically provides greater chemically specific information about a sample than the spectroscopic methods but, at a minimum, can be a complementary approach to spectroscopy and AFM techniques. When combining MS and AFM, the AFM cantilever probe, in addition to performing the typical AFM physical measurements of a surface, can be exploited to sample from a surface by various mechanisms (e.g., field evaporation, thermal desorption or thermolysis, and near-field laser ablation) and in some cases ionize the sampled material for mass spectral detection. 11 Because the sampling phenomena takes place at a spatial scale the size of the cantilever probe tip, low micrometer to nanoscale sampling is possible. By utilizing the AFM cantilever probe in this manner, correlated topography, physical, and chemical images of a surface can be produced in a relatively straightforward manner for the sample surface of interest.
The bole of vibrational spectroscopy-microscopy techniques in polymer characterisation
Macromolecular Symposia, 1995
Detailed spectroscopic studies at the sub-millimetre level of the chemical composition and morphology of materials can provide insights into the constitution, performance and properties of polymeric products. Infrared and Raman microscopy/microprobe spectroscopic techniques are invaluable tools for the spatially-resolved identification, study and characterisation of polymers, their products and composites. The two vibrational spectroscopy techniques provide both complementary information and attributes to such investigations, which are discussed and exampled in this paper.
Probing Polymer Material Properties on the Nanometer Scale
Microscopy Today, 2010
Polymers play an essential role in modern materials science. Because of the wide variety of mechanical and chemical properties of polymers, they are used in nearly every industry. Knowledge about their physical and chemical properties on the nanometer scale is often required. However, some details about the phase-separation process in polymers are difficult to study with conventional characterization techniques because these methods cannot chemically differentiate phases with good spatial resolution without damage, staining, or preferential solvent washing.
Polarization modulated infrared spectroscopy: A pragmatic tool for polymer science and engineering
Polymer crystallization, 2020
In the area of polymer crystallization, the most widely used techniques to quantify structure, morphology and molecular orientation are fundamentally based on light or X-ray scattering and absorption. In particular, synchrotron X-rays are used for detailed studies on the semicrystalline structure in polymeric materials. The technical requirements for such techniques, especially when high spatial resolution is essential, make the application of X-ray diffraction not straightforward. Direct information on the chain orientation in different semicrystalline morphologies requires rather complex sampling and analysis procedures. Surprisingly, a simple yet versatile technique based on infrared spectroscopy is hardly applied in the field of polymer crystallization. By modulating the polarization of the incident light, local anisotropy can be studied in real time on a submolecular length scale. In this article, we provide the relevant details of the polarization modulated infrared microspectroscopy technique for the study of semicrystalline materials from an engineering perspective. We demonstrate the essence of the method using as model systems spherulitic and transcrystalline morphologies and present its applicability to polymer/fiber composite technology and the study of injection-molded parts. The results provided in the present work serve to illustrate the applicability of this informative technique in the field of semicrystalline polymer science.
2000
In this article, we demonstrate the versatility of use of cantilever-type resistive thermal probes. The probes used are of two kinds, Wollaston wire probes and batch-microfabricated probes. Both types of probe can be operated in two modes: a passive mode of operation whereby the probe acts as a temperature sensor, and an active mode whereby the probe acts also as a highly localized heat source. We present data that demonstrate the characterization of some composite polymeric samples. In particular, the combination of scanning thermal microscopy with localized thermomechanometry ͑or localized thermomechanical analysis, L-TMA͒ shows promise. Comparison with data from conventional bulk differential scanning calorimetry shows that inhomogeneities within materials that cannot be detected using conventional bulk thermal methods are revealed by L-TMA. We also describe a new mode of thermal imaging, scanning thermal expansion microscopy. Finally, we outline progress towards the development of localized Fourier transform infrared spectroscopy: here the probe, in this case operated in the temperature-sensing mode, detects the photothermal response of a specimen exposed to the beam and heated thereby.
Polymers
A chip-based fast scanning calorimeter (FSC) is used as a fast hot-stage in an atomic force microscope (AFM). This way, the morphology of materials with a resolution from micrometers to nanometers after fast thermal treatments becomes accessible. An FSC can treat the sample isothermally or at heating and cooling rates up to 1 MK/s. The short response time of the FSC in the order of milliseconds enables rapid changes from scanning to isothermal modes and vice versa. Additionally, FSC provides crystallization/melting curves of the sample just imaged by AFM. We describe a combined AFM-FSC device, where the AFM sample holder is replaced by the FSC chip-sensor. The sample can be repeatedly annealed at pre-defined temperatures and times and the AFM images can be taken from exactly the same spot of the sample. The AFM-FSC combination is used for the investigation of crystallization of polyamide 66 (PA 66), poly(ether ether ketone) (PEEK), poly(butylene terephthalate) (PBT) and poly(ε-capro...
How atomic force microscopy has contributed to our understanding of polymer crystallization
Polymer, 2009
Over the past two decades atomic force microscopy (AFM) has become one of the most frequently used tools for studying polymer crystallization. The combination of high resolution, minimal sample preparation and the ability to image non-destructively has allowed visualisation of crystallization, melting and reordering processes at a lamellar and sub-lamellar scale, revealing complexities that could only previously be guessed at. Here the insights that AFM has provided into some of the main over-arching questions relating to polymer crystallization are reviewed. The emphasis is on the use of AFM to image growth in real time, and on contributions that have been made to our understanding of polymer crystallization in general, rather than to specific systems.
Quantitative Nano-characterization of Polymers Using Atomic Force Microscopy
Chimia, 2017
The present article offers an overview on the use of atomic force microscopy (AFM) to characterize the nanomechanical properties of polymers. AFM imaging reveals the conformations of polymer molecules at solid- liquid interfaces. In particular, for polyelectrolytes, the effect of ionic strength on the conformations of molecules can be studied. Examination of force versus extension profiles obtained using AFM-based single molecule force spectroscopy gives information on the entropic and enthalpic elasticities in pN to nN force range. In addition, single molecule force spectroscopy can be used to trigger chemical reactions and transitions at the molecular level when force-sensitive chemical units are embedded in a polymer backbone.