Electron Microscopy in Polymer Science

In many fields of research in science, engineering, and medicine, electron microscopy as a method for directly imaging submicroscopic structures has become increasingly important in recent decades. Electron microscopy (EM) includes several different techniques: conventional transmission electron microscopy (TEM), high-resolution electron microscopy (HREM), highvoltage electron microscopy (HVEM), scanning electron microscopy (SEM), analytical electron microscopy (AEM), emission electron microscopy (EEM), and others. In the past the central aim of using electron microscopy was structure determination, but recently it has been of growing importance for also investigating different processes, i.e., changes in materials by interaction with several influential factors (e.g., heat, electric or mechanic fields, mechanical loading). Of particular interest is the study of the micromechanical processes of deformation and fracture. Therefore, electron microscopy is a very powerful tool for materials science. The present review reports on some capabilities and limitation of the application of electron microscopy to solid polymers. In Section II the techniques of electron microscopy are briefly reviewed, followed by a section that describes the main methods of specimen preparation of solid polymeric materials. In Section IV the results of several applications of electron microscopy are discussed to reveal the morphology as well as the micromechanical deformation processes of several polymeric materials.     

Challenges and strategies of surface modification of electrogalvanized coatings for electron microscopy analysis

Despite wide usage of electrogalvanized coatings in various applications, characterization studies on their micro/crystal structure, and the understanding of how they correspondingly affect the properties, such as corrosion, are rather limited. This is mainly attributed to some difficulties in preparing and examining the zinc coating layers, owing to their intrinsically low corrosion resistance and refined nano-scaled crystallite size. This study aims to examine such challenges systematically and propose some mitigation strategies. Particularly, sample preparation processes, including surface finishing for metallography and sample thinning processes are explored. Furthermore, a range of electron microscopy techniques, including scanning electron microscopy (SEM), electron back scattered diffractometry (EBSD), and transmission electron microscopy (TEM) are investigated in relation to the achievable clarity of microstructural details of electrogalvanized coatings.     

Preliminary study on different technological tools and polymeric materials towards superhydrophobic surfaces for automotive applications

Nature-inspired fabrication of micro-structured superhydrophobic plastic film was aimed in this work in order to achieve smart materials with self-cleaning properties. Replicas of silicon masters were fabricated from different mixtures of base elements and by different processes. Corresponding microstructures were investigated by contact angle measurements, scanning electron microscopy and spectrophotometric analysis. Independently of the technology employed, the obtained films exhibited high contact angle value (larger than 150°), but while the acrylic polymers presented strong demoulding drawbacks, the polydimethylsiloxane (PDMS) films had good properties in terms of both contact angle and optical transparency. The results showed that most of the patterns realized by replica moulding and hot-embossing (on PDMS and polypropylene (PP), respectively) produced superhydrophobic self-cleaning surfaces.     

Nanoparticle Distribution in Three‐Layer Polymer–Nanoparticle Composite Films: Comparison of Experiment and Theory

The distribution of hydrophobic nanoparticles deposited on a hydrophilic polymer film is investigated by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy before and after spin‐coating a polymer solution on the particle film and drying it at room temperature. Various polymers and solvents are used. To reach equilibrium, all investigated systems are annealed additionally above the glass transition temperature (T_g) of the polymers. The compatibility of the interacting components is estimated by calculating their surface energy, solubility, and mutual interaction parameters. The experimental results show a redistribution of the particles on both interfaces of the polymer film. This corresponds to the calculated immiscibility of particles and polymers. The distribution of the nanoparticles at the interfaces is related mainly to the vapor pressure of the solvent, that is, kinetic effects during spin‐coating. Only minor contributions result from surface energy, solubility, and interaction parameters.     

Scanning transmitted and reflected light microscopy: a novel microscopy for visualizing biomaterials at interfaces

Two new types of light microscopy, scanning transmitted light and scanning reflected light microscopy (STLM and SRLM, respectively) were developed. STLM and SRLM are based on optical density recognition (ODR) of the scanned transmitted or reflected light, respectively, from the object to be visualized. The obtained image is a result of enhanced interference between the scanning and transmitted/reflected beams from the object. The new microscopy, in its initial phase, is ideally suited for monitoring macroscopic and sub-millimeter size self-assembly and for elucidating the connection between the macroscopic and nanoscopic worlds if combined with atomic force microscopy (AFM) or electron microscopy (EM). The method is demonstrated by monitoring the growth of 3D crystals from their original liquid phase. Some preliminary measurements carried out using the prototype of the new microscopy are presented and its current and future possible applications are described.     

Morphology,miscibility and mechanical properties of PMMA/PC blends

This study deals with some results on morphology, miscibility and mechanical properties for polymethyl methacrylate/polycarbonate (PMMA/PC) polymer blends prepared by solution casting method at different concentration between 0 and 100 wt%. Dynamic storage modulus and tan δ were measured in a temperature range from 30 to 180°C using dynamical mechanical analyzer (DMA). The value of the storage modulus was found to increase with the addition of the PC in the matrix. Transition temperature of pure PMMA and pure PC is found to be 83.8 and 150°C, respectively. The result shows that the two polymers are miscible for whole concentration of PC in PMMA. The distribution of the phases in the blends was studied through scanning electron microscopy (SEM). Also the mechanical properties like elongation at break and fracture energy of the PMMA/PC blends increase with the increase in concentration of PC in PMMA.     

A correlative optical microscopy and scanning electron microscopy approach to locating nanoparticles in brain tumors

The growing use of nanoparticles in biomedical applications, including cancer diagnosis and treatment, demands the capability to exactly locate them within complex biological systems. In this work a correlative optical and scanning electron microscopy technique was developed to locate and observe multi-modal gold core nanoparticle accumulation in brain tumor models. Entire brain sections from mice containing orthotopic brain tumors injected intravenously with nanoparticles were imaged using both optical microscopy to identify the brain tumor, and scanning electron microscopy to identify the individual nanoparticles. Gold-based nanoparticles were readily identified in the scanning electron microscope using backscattered electron imaging as bright spots against a darker background. This information was then correlated to determine the exact location of the nanoparticles within the brain tissue. The nanoparticles were located only in areas that contained tumor cells, and not in the surrounding healthy brain tissue. This correlative technique provides a powerful method to relate the macro- and micro-scale features visible in light microscopy with the nanoscale features resolvable in scanning electron microscopy.     

Computer-assisted quantification of the multi-scale structure of films made of nanofibrillated cellulose

Films made of nanofibrillated cellulose (NFC) are most interesting for use in packaging applications. However, in order to understand the film-forming capabilities of NFC and their properties, new advanced methods for characterizing the different scales of the structures are necessary. In this study, we perform a comprehensive characterisation of NFC-films, based on desktop scanner analysis, scanning electron microscopy in backscatter electron imaging mode (SEM-BEI), laser profilometry (LP) and field-emission scanning electron microscopy in secondary electron imaging mode (FE-SEM-SEI). Objective quantification is performed for assessing the (i) film thicknesses, (ii) fibril diameters and (iii) fibril orientations, based on computer-assisted electron microscopy. The most frequent fibril diameter is 20–30 nm in diameter. A method for acquiring FE-SEM images of NFC surfaces without a conductive metallic layer is introduced. Having appropriate characterisation tools, the structural and mechanical properties of the films upon moisture were quantified.     

Modification in etching characteristics and surface topography of some electron irradiated polymers

Track formation in polymers is a complex phenomenon in which not only primary but also secondary processes, such as formation of radicals and chemical processes, are involved. In the present work, the influence of 2 MeV electrons on the etching properties and the surface topography of polyethylene terephthalate (PET) and polyimide (PI) are studied. The increase in the bulk etch-rate and a decrease in the activation energy of etching were observed for both the polymers. The surface roughness of both polymers was reduced due to electron irradiation.     

A method of correlative light and electron microscopy for yeast cells

Correlative light and electron microscopy (CLEM) is a method of imaging in which the same specimen is observed by both light microscopy and electron microscopy. Specifically, CLEM compares images obtained by light and electron microscopy and makes a correlation between them. After the advent of fluorescent proteins, CLEM was extended by combining electron microscopy with fluorescence microscopy to enable molecular-specific imaging of subcellular structures with a resolution at the nanometer level. This method is a powerful tool that is used to determine the localization of specific molecules of interest in the context of subcellular structures. Knowledge of the localization of target proteins coupled with the functions of the structures to which they are localized yields valuable information about the molecular functions of these proteins. However, this method has been mostly applied to adherent cells due to technical difficulties in immobilizing non-adherent target cells, such as yeasts, during sample preparation. We have developed a method of CLEM applicable to yeast cells. In this report, we detail this method and present its extension to Live CLEM. The Live CLEM method enabled us to link the dynamic properties of molecules of interest to cellular ultrastructures in the yeast cell. Since yeasts are premier organisms in molecular genetics, combining CLEM with yeast genetics promises to provide important new findings for understanding the molecular basis of the function of cellular structures.     

Characterisation of colloidal drug delivery systems from the naked eye to Cryo-FESEM

Poly(ethylcyanoacrylate) nanoparticles prepared by interfacial polymerisation on the basis of microemulsions were prepared in this study and both colloidal systems, nanoparticles and microemulsions, were analysed by visual observation and several microscopic techniques. Phase boundaries for the microemulsions of the two pseudoternary systems ethyloleate, polyoxyethylene 20 sorbitan mono-oleate/sorbitan monolaurate and water with and without butanol as a cosurfactant were determined by visual observation of the samples. Microemulsions containing liquid crystals were determined by polarisation light microscopy. Using freeze-fracture transmission electron microscopy and Cryo-field emission scanning electron microscopy the type of microemulsion (w/o droplet, bicontinuous, solution) was characterised. Nanoparticles prepared from the different types of microemulsion were additionally observed by conventional scanning electron microscopy. The size of the nanoparticles obtained from electron microscopy was in good agreement with particle sizing techniques (photon correlation spectroscopy) from earlier studies and no morphological differences could be observed in particles prepared from the different types of microemulsions. Cryo-field emission scanning electron microscopy proved to be a most valuable technique in the visualisation of the colloidal systems as samples could be observed close to their natural state.     

Physical-morphological and chemical changes leading to an increase in adhesion between plasma treated polyester fibres and a rubber matrix

The effects of plasma treatment, used to increase adhesion strength between poly(ethylene terephtalate) (PET) fibres and a rubber matrix, were investigated and compared. Morphological changes as a result of atmospheric plasma treatment were observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Wettability analysis using a surface energy evaluation system (SEE system) suggested that the plasma treated fibre was more wetting towards a polar liquid. When treated, these fibres showed a new lamellar crystallization, as shown by a new melting peak using differential scanning calorimetry (DSC). X-ray photoelectron spectroscopy (XPS) has been used to study the chemical effect of inert (argon), active and reactive (nitrogen and oxygen) microwave-plasma treatments of a PET surface. Reactive oxygen plasma treatment by a de-convolution method shows new chemical species that drastically alter the chemical reactivity of the PET surface. These studies have also shown that the surface population of chemical species formed after microwave-plasma treatment is dependent on the plasma gas. All these changes cause better adhesion strength of the PET fibres to the rubber matrix.     

A comparative study on the effects of Co-60 gamma radiation on polypropylene and polyimide

Polypropylene (PP) and polyimide (PI), which belong to entirely different classes of polymers, are irradiated by Co-60 gamma radiation under similar doses and similar conditions in the dose range varying from 57.6 to 230.4 kGy. The radiation responses of these two polymers are analyzed by various characterizations such as Fourier transform infrared, UV–visible, energy-dispersive spectroscopy, X-ray diffraction, scanning electron microscopy and contact angle. PP shows substantial modifications in its structure and properties while in the same dose range, PI shows remarkable stability. These two different responses are interpreted in terms of physicochemical structure and properties of these polymers.     

Nitriding molybdenum: Effects of duration and fill gas pressure when using 100-Hz pulse DC discharge technique

Molybdenum is nitrided by a 100-Hz pulsed DC glow discharge technique for various time durations and fill gas pressures to study the effects on the surface properties of molybdenum. X-ray diffractometry(XRD), scanning electron microscopy(SEM), and atomic force microscopy(AFM) are used for the structural and morphological analysis of the nitrided layers. Vickers’ microhardness tester is utilized to investigate surface microhardness. Phase analysis shows the formation of more molybdenum nitride molecules for longer nitriding durations at fill gas pressures of 2 mbar and 3 mbar(1 bar = 105Pa). A considerable increase in surface microhardness(approximately by a factor of 2) is observed for longer duration(10 h) and 2-mbar pressure. Longer duration(10 h) and 2-mbar fill gas pressure favors the formation of homogeneous, smooth, hard layers by the incorporation of more nitrogen.     

Polymerization of Langmuir–Blodgett films of diacetylenes

Monolayer and multilayer assemblies of Langmuir–Blodgett films of 10–12 pentacosadyinoic acid (12–8 diacetylene) were deposited on flat gold substrates. Micrometre-size features were patterned by polymerization of the films by using standard electron beam lithography. Polymerized areas on a monolayer and bilayer, as well as multilayer films, were examined by scanning electron microscopy, atomic force microscopy and resonant Raman spectroscopy. It was established that polymerized areas on a monolayer and bilayer LB film adhere onto the gold substrate after development. The exposure curve, sensitivity, contrast and resolution of the polymer have been determined by using atomic force microscopy and correlated with the deposition conditions and molecular parameters. Stresses induced in the organic film during polymerization lead to an in-plane buckling of the micrometre-size polymer structure. A simple self-consistent theory was developed to predict critical strain and critical length of buckling. The observed effect of buckling of polymers might open an avenue for a wide range of important practical applications in the area of nanomechanical engineering.     

Controllable synthesis of CuFe2O4 nanostructures through simple hydrothermal method in the presence of thioglycolic acid

In this paper a novel and simple route for the preparation of copper ferrite (CuFe₂O₄) is proposed. The present investigation reports, the novel synthesis of CuFe₂O₄ samples C1, C2, C3 and C4 using hydrothermal method and its physicochemical characterization. In order to elucidate the relationship between the constituent, structure, magnetic and PL properties product's particle size, morphological and structural properties were characterized by the X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), photoluminescence (PL) and magnetic properties. The crystallization, surface morphology, magnetic properties and luminescence properties of the samples have been investigated. The relatively high Ms of the samples suggests that this method is suitable for preparing high-quality nanocrystalline copper ferrites for practical applications. Different mechanisms to explain the obtained results and the correlation between magnetism and structure are discussed.     

二维原子晶体的低电压扫描透射电子显微学研究

二维原子晶体材料,如石墨烯和过渡金属硫族化合物等,具有不同于其块体的独特性能,有望在二维半导体器件中得到广泛应用.晶体中的结构缺陷对材料的物理化学性能有直接的影响,因此研究结构缺陷和局域物性之间的关联是当前二维原子晶体研究中的重要内容,需要高空间分辨率的结构研究手段.由于绝大部分二维原子晶体在高能量高剂量的电子束辐照下容易发生结构损伤,利用电子显微方法对二维原子晶体缺陷的研究面临诸多挑战.低电压球差校正扫描透射电子显微(STEM)技术的发展,一个主要目标就是希望在不损伤结构的前提下对二维原子晶体的本征结构缺陷进行研究.在STEM下,多种不同的信号能够被同步采集,包括原子序数衬度高分辨像和电子能量损失谱等,是表征二维原子晶体缺陷的有力工具,不但能对材料的本征结构进行单原子尺度的成像和能谱分析,还能记录材料结构的动态变化.通过调节电子束加速电压和电子辐照剂量,扫描透射电子显微镜也可以作为电子刻蚀二维原子晶体材料的平台,用于加工新型纳米结构以及探索新型二维原子晶体的原位制备.本综述主要以本课题组在石墨烯和二维过渡金属硫族化合物体系的研究为例,介绍低电压扫描透射电子显微学在二维原子晶体材料研究中的实际应用.     

High performance corrosion resistant polyaniline/alkyd ecofriendly coatings

The growing environmental concerns have led to the formulation of new coating strategies by employing inherently conductive polymers (ICPs) as a key component in order to eliminate the toxic heavy metals from protective coatings. Also, the renewable resources are given increasing priority within chemical industry and the energy community. Emphasis is therefore, processing of polymers from renewable resources which show advantages when compared with petrochemical raw materials and are regarded as an ideal raw material. The present work reports the investigations on the corrosion-resistance performance of soya oil alkyd, containing nano polyaniline (PANI) against mild steel (MS). The corrosion-protective performance was evaluated in terms of physico-mechanical properties, corrosion rate, open circuit potential measurements (OCP) and scanning electron microscopy (SEM) studies. The performance was compared to the reported PANI coatings.     

Infiltration of Glassy Bodies with Zirconia Nanoparticles

Zirconia nanoparticles (10–50 nm) were infiltrated into commercial glasses to modify their mechanical properties. The process developed allows a homogeneous distribution of the nanoparticles within the glassy matrix. Differential thermal analysis, thermo-gravimetric analysis, X-ray diffraction, scanning and transmission electron microscopy and energy dispersive spectroscopy mapping analysis where utilized to characterize the resulting composites.     

High-temperature pretreatment of Ni nanoparticles enhances the growth of high-density carbon fiber bundles during microwave plasma chemical vapor deposition

This paper presents an experimental study on the effect of the pretreatment procedure of Ni nanoparticles (NPs) on the growth of multiwalled carbon fiber (CNF) bundles by means of microwave plasma chemical vapor deposition (MPCVD). We used atomic force microscopy to investigate a series of pretreated Ni films. The structures and compositions of the CNFs on the via were investigated using scanning electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy.The geometric shape of the Ni NPs was identified in terms of their roughness, which decreased upon increasing the pretreatment temperature, resulting subsequently in the synthesis of high-density CNFs. The diameter and shape of the Ni NPs were the dominant factors affecting the size and density of the CNFs bundles. We obtained CNFs that fully filled the via effectively; they might serve as potential interconnects in future nanodevices.