A cross-sectional preparation method for TEM and AFM investigations on layered poylmer interfaces

Summary The epitaxial crystallization of polyethylene (PE) on uniaxially oriented isotactic polypropylene (iPP) has been investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The cross-sectional morphology of the epitaxial interfaces of multi-layered samples prepared by a new preparation method has been observed with view direction parallel to the epitaxial interfaces. It is found that fairly oriented PE lamellae grow perpendicular to the iPP layers with nucleation initiation on the iPP surfaces.     

Effect of lamellar thickness on the epitaxial crystallization of PE on oriented iPP films

The effects of lamellar thickness on the epitaxial crystallization of polyethylene on the oriented isotatic polypropylene have been studied by means of transmission electron microscopy. The results obtained from the bright field electron microscopy and electron diffraction show that the epitaxial orientation of the PE crystals on the iPP substrate depends not only on the thickness of the oriented iPP lamellae, but also on the lamellar thickness of PE crystals. No epitaxial orientation relationship between PE crystal and iPP substrate can be found, when the PE crystals are thicker than the lamellar thickness of iPP along the matching direction. This suggests, that the epitaxial nucleation of PE in the PE/iPP epitaxial system is controlled not only by the chain-row matching, but also by a secondary nucleation process. Received: 11 July 1996/Revised version: 30 September 1996/Accepted: 30 September 1996     

Epitaxial crystallization of olefin block copolymers (OBCs) on uniaxially oriented isotactic polypropylene and high-density polyethylene films

The epitaxial crystallization behavior of olefin block copolymers (OBCs) on uniaxially oriented isotactic polypropylene (iPP) and high-density polyethylene (HDPE) films has been investigated by transmission electron microscopy (TEM). The crystallizable blocks of the OBCs under investigation were epitaxially nucleated by both iPP and HDPE substrates and epitaxial growth of OBC lamellae was observed. Epitaxial crystallization of the OBCs has been found for slow and fast cooling conditions from the melt which pointed to the strong interaction between the polyolefin substrates and the OBCs. However, the epitaxial morphology of the OBCs strongly depends on their octene concentration difference (Δ_C8) between crystallizable and non-crystallizable blocks, which probably is related to the OBC segregation strength in the melt. With high Δ_C8 the development of epitaxial crystallization of the OBC was restricted within isolated crystalline domains surrounded by the amorphous phase. In contrast, with low Δ_C8 the oriented lamellae of the OBC were distributed homogeneously on iPP but formed separated crystalline domains on HDPE, which has a stronger nucleation capability than iPP on the crystalline OBC blocks because of its similar molecular architecture. Our study points to epitaxy as another reason for the strong interaction between OBC and polyolefins which causes the advanced compatibilization behavior of OBCs when compared with conventional random copolymers.     

Critical crystallization temperature for the occurrence of epitaxy between high-density polyethylene and isotactic polypropylene

The crystallization behavior of high-density polyethylene (HDPE) on highly oriented isotactic polypropylene (iPP) at elevated temperatures (e.g., from 125 to 128°C), was studied using transmission electron microscopy and electron diffraction. The results show that epitaxial crystallization of HDPE on the highly oriented iPP substrates occurs only in a thin layer which is in direct contact with the iPP substrate, when the HDPE is crystallized from the melt on the oriented iPP substrates at 125°C. The critical layer thickness of the epitaxially crystallized HDPE is not more than 30 nm when the HDPE is isothermally crystallized on the oriented iPP substrates at 125°C. When the crystallization temperature is above 125°C, the HDPE crystallizes in the form of crystalline aggregates and a few individual crystalline lamellae. But both the crystalline aggregates and the individual crystalline lamellae have no epitaxial orientation relationship with the iPP substrate. This means that there exists a critical crystallization temperature for the occurrence of epitaxial crystallization of HDPE on the melt-drawn oriented iPP substrates (i.e., 125°C). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2029–2034, 1997     

Relating the molecular structure and crystallization behavior of polypropylene

The crystallization behavior of two polypropylene (PP) resins as used for biaxially oriented polypropylene (BOPP) and general injection mold applications, respectively, has been intensively investigated and compared by means of polarized light optical micrography (POM), differential scanning calorimetry (DSC), conventional transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM). It is found that both molecular weight distribution and isotacticity of polypropylene strongly affect its crystallization characteristics, e.g., the number of crystal nuclei at the initial stage, crystallization dynamics, the morphology, size and perfection of crystals in the final product, and so on. The results indicate an appropriate molecular structure is vital in producing high‐quality BOPP film. Polym. Eng. Sci. 44:1749–1754, 2004. © 2004 Society of Plastics Engineers.     

Effect of epitaxial crystallization on adhesive strength in impact-toughened isotactic polypropylene

The influence of the epitaxial crystallization of the polyethylene (PE) content on the adhesive interface strength of impact-toughened isotactic polypropylene (iPP) has been investigated. The morphologies and crystal arrangements of four different matrix/rubber combinations were observed by transmission electron microscopy (TEM) and were correlated with the interface strengths measured by a peel test. It was found that the adhesion is best at interfaces, where an epitaxial morphology of the PE was observed.     

Eutectic solidification and oriented growth in mixtures of polyethylene and 1,3,5-tribromobenzene

The melting and crystallization behaviour of mixtures of linear polyethylene and 1,3,5-tribromobenzene has been investigated by differential scanning calorimetry, optical and electron microscopy. The phase diagram reveals the existence of a pseudo-binary eutectic (polymer volume fraction of about 58%; T_m=116°C). The experimental observations are compared with the predictions of the Flory-Huggins theory of melting point depression. The polyethylene component of the eutectic assumes a habit in which lamellae are highly oriented with the chains in the [110] contact plane parallel to the tribromobenzene needle axes. This well defined orientation is most probably based on an epitaxial relation between polymer and substrate.     

Effect of multi-walled carbon nanotubes on the lamellae morphology of polyamide-6

We show that crystal organization on both micro and nanoscales can be profoundly modified by dispersing carbon nanotubes (CNTs) in polyamide-6 by melt compounding. X-ray diffraction and transmission and scanning electron microscopies all indicate that when CNTs are well dispersed, crystalline spherulites are not present and remarkably crystalline lamellae grow aligning perpendicularly to the surface of the nanotubes. Such an epitaxial growth induced by CNTs during melt processing is particular to polyamide-6 because of crystallographic matching of CNTs and polyamide-6 crystal lattices. Macroscopically this epitaxial nucleation and growth can be detected and quantified by examining the splitting of the exothermic peak in calorimetric (DSC) experiments. Using optical microscopy and image analysis we show that the amount of trans-crystalline epitaxial crystallites increases when CNTs' dispersion quality is improved.     

多金属氧簇纳米粒子对聚乳酸薄膜材料等温结晶行为的影响

制备了聚乳酸／多金属氧簇（EPOM）纳米复合薄膜材料，并利用差示扫描量热仪（DSC）、偏光显微镜（POM）、透射电子显微镜（TEM）研究了多金属氧簇（EPOM）对该薄膜材料等温结晶行为及形态的影响。研究发现：加入EPOM后PLLA样品的结晶度有一定程度的提高，且PLLA的球晶尺寸也变大。EPOM在复合物薄膜表面和内部能够较均匀分散，形成直径为几百nm的非晶微区。     

聚合物在取向聚合物薄膜上的附生结晶研究进展

总结了近年来以取向聚合物为基底的聚合物附生结晶的部分研究成果,重点综述了聚合物附生结晶的机理及晶格匹配、链段规整度、结晶动力学、二次成核等因素对聚合物附生结晶的影响,并对其今后的发展进行了展望。     

Deepening our understanding of bioactive glass crystallization using TEM and 3D nano-CT

One key issue influencing a broader application of Bioglass 45S5 in tissue engineering is its inherent crystallization tendency, severely limiting the mechanical strength of 3D porous scaffolds. Despite numerous studies, Bioglass 45S5 crystallization is not yet fully understood with regard to the mechanisms involved or morphology of the crystal phases forming. Here we show how two cutting-edge imaging techniques, state-of-the-art transmission electron microscopy (TEM) with image correction including energy dispersive X-ray spectroscopy and X-ray nano-computed tomography (nano-CT), allowed us to visualize changes in microstructure from near-nucleation to almost full crystallization in bulk Bioglass 45S5. At early times of heat treatment at 660 °C the formation of phase-separated nano-droplets within the glassy matrix was observed. Later, besides surface crystallization, bulk crystallization of combeite spheres was predominant. The formation of the first combeite spheres, their coarsening with time and finally their merging at near full crystallization were recorded by in situ high-temperature optical microscopy videos. The 3D nature of these spheres was confirmed by nano-CT, while TEM showed that their internal structure was composed of sub-micron grains. X-ray diffraction analysis at early time points showed a much higher crystalline fraction in bulk samples compared to powder samples, highlighting the influence of processing and sample morphology. These results show the importance of using complementary techniques for gaining insight into the crystallization process in the volume. In addition, we show that TEM and nano-CT are suitable characterization techniques to visualize the crystallization even in fast crystallizing systems, such as bioactive glasses.     

Thin Films in Electron Microscopy

Thin films play an important role in electron microscopy as they can be used to improve the contrast and stability of specimens, as well as to make specimens electrically conductive. In order to avoid overlapping of specimen and coating structures, it is necessary to understand how thin films are formed in the various coating technologies and how to create them reproducibly as part of the different preparation techniques for electron microscopy. In contrast, electron microscopy can be applied to learn more about the structural details of thin films used, for instance, in the optical coating industry. Heat shock fracturing and Pt-C surface replication of the cross sections resulted in reliable transmission electron micrographs (TEM) of the coating microstructure. These studies demonstrate that, under optimal conditions, it is possible to find a correlation between the measured optical properties and the microstructure of the coatings. TEM replica investigations reveal single events, so they can be useful if discrepancies in the (statistical) physical data have to be investigated.     

Crystalline order of silver–gold nanocatalysts with hollow-core and alloyed-shell

This paper reports the internal structure of Ag–Au bimetallic nanoparticles with hollow interiors and alloyed shells, synthesized by chemical reduction of metallic precursor and subsequent galvanic replacement reaction. By taking advantage of advanced electron microscopy methods such as high-resolution transmission electron microscopy (HRTEM), scanning TEM (STEM), weak beam dark-field (WBDF) microscopy, X-ray energy dispersive spectroscopy (EDS) and nano-beam electron diffraction (NBD), sufficient and necessary evidences confirm the sacrificial role of silver nanoparticles as templates for the epitaxial deposition of gold-rich atomic layers.     

Structure of blown films of polyethylene/polybutene‐1 blends

The structure of blown films of blends of low‐density polyethylene (PE‐LD) and isotactic polybutene‐1 (iPB‐1) with different content of iPB‐1 was investigated using wide‐ and small‐angle X‐ray scattering (WAXS and SAXS), transmission electron microscopy (TEM), and polarizing optical microscopy (POM). TEM proves formation of a matrix–particle phase structure due to immiscibility of the blend components. Within the iPB‐1 particles, needle‐like crystals with c‐axis orientation were observed. The PE‐LD matrix showed two populations of crystals. WAXS data indicate that the majority of crystals were oriented with the c‐axis perpendicular to machine direction (MD), while SAXS data prove additional presence of stacks of lamellae, oriented parallel to MD. Quantitative birefringence measurements showed that the majority of molecule segments were oriented in the direction of the circumference of the film, confirming the WAXS data. The crystal orientation has direct impact on mechanical properties, which was demonstrated by measurement of the anisotropy of the modulus of elasticity. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Crystallization behavior and morphology of poly(ethylene 2,6-naphthalate)

The crystallization behavior and morphology of poly(ethylene 2,6-naphthalte) (PEN) were investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and transmission electron microscopy (TEM). POM results revealed that PEN crystallized at 240 °C shows the coexistence of α and β-form spherulite morphology with different growth rates. In particular, when PEN crystallized at 250 °C, the morphology of spherulites showed a squeezed peanut shape. The Avrami exponents decreased from 3 to 2.8 above the crystallization temperature of 220 °C, indicating a decrease in growth dimension. Analysis from the secondary nucleation theory suggests that PEN crystallized at 240 °C has crystals with both regime I and regime II. In TEM observation, the ultra-thin PEN film crystallized at 200 °C showed the spherulitic texture with characteristic diffractions of α-form, while PEN crystallized at 240 °C generated an axialite structure with only β-form diffraction patterns. In addition, despite a long crystallization time of 24 h, amorphous regions were also observed in the same specimen. It was inferred that the initiation of PEN at 240 °C generates only β-form crystals from axialite structures.     

Interactions in the system isotactic polypropylene–calcite

Interaction in the system isotactic polypropylene–calcite was investigated using X-ray diffraction and transmission electron microscopy. Calcite acts as a weak nucleation agent for polypropylene crystallization and its activity could be increased or decreased by a suitable surface treatment. Investigation of the morphology on the polypropylene–calcite interface using calcite single crystals disclosed the tendency of polypropylene for epitaxial crystallization along preferred substrate crystallographic directions. This tendency was analogous to polymer crystallization on other ionic crystals.     

Effect of modified montmorillonite on biodegradable PHB nanocomposites

Polymer nanocomposites, based on a bacterial biodegradable thermoplastic polyester, poly(hydroxybutyrate) (PHB), and two commercial montmorillonites (MT), Na-M (MT) and 30B-M (organically modified MT), were prepared by melt-mixing technique at 165 °C. Both clays minerals were characterized by morphology, crystallochemical parameters, and thermal stability. Lower specific surface area (determined by adsorption methods) values were found for 30B-M. The apparent particle size from light scattering measurements, scanning electron microscopy observations, and crystallite size (determined from XRD patterns) of 30B-M indicated a higher degree of particles exfoliation than of Na-M.The nanocomposites PHBNa and PHB30B were characterized by differential scanning calorimetry (DSC), polarized optical microscopy (POM), X-ray diffraction (XRD), transmission electron microscopy (TEM), mechanical properties, and burning behaviour. Intercalation/exfoliation observed by TEM and XRD was more pronounced for PHB30B than PHBNa, indicating the better compatibility of 30B-M with the PHB matrix. An increase in crystallization temperature and a decrease in spherullites size were observed for PHB30B. The intercalation/exfoliation observed by TEM and structure XRD increased the moduli of the nanocomposites. The burning behaviour of PHB30B was influenced by the aggregation of the clay mineral particles.     

Effects of nanoparticle treatment on the crystallization behavior and mechanical properties of polypropylene/calcium carbonate nanocomposites

Effects of nanoparticle surface treatment on the crystallization behavior and mechanical properties of polypropylene (PP)/CaCO₃ nanocomposites were investigated by using differential scanning calorimetry (DSC), polarized optical microscope (POM), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The results demonstrated that the interfacial interaction formed between PP and nanoparticles significantly influenced the thermal and mechanical properties of nanocomposites. It was found that CaCO₃ nanoparticles modified by a single aluminate coupling agent (CA‐1) could improve the onset crystallization temperature more effectively than that modified by a compound surface‐treating agent (CA‐2) could. However, there is no significant difference in total rate of crystallization for the two PP/CaCO₃ nanocomposites (PPC‐1 and PPC‐2), which contained CA‐1 and CA‐2, respectively. In contrast, CA‐2 modified nanoparticles could cause smaller spherulites and induce much more β‐phase crystal in nanocomposites than that of CA‐1 modified nanoparticles. This may be explained by a synergistic effect of aluminate coupling agent and stearic acid in CA‐2, which also resulted in an improved toughness for PPC‐2. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 3480–3488, 2006     

Domain formation in diamond nucleation on iridium

Domain formation in epitaxial diamond nucleation on Ir(001) surfaces using the bias-enhanced nucleation (BEN) procedure has been studied. Bright areas of up to several microns lateral size with negligible topographic contrast are observed by scanning electron microscopy (SEM) after ion bombardment. When a growth step is applied after BEN, these domains develop into islands of identical shape consisting of epitaxial diamond with a high local area density of oriented grains. Outside the domains the nucleation density is either orders of magnitude lower or the grains are completely non-oriented. The diamond nuclei or precursors which are formed during the BEN step proved to be very stable: They still yielded oriented diamond islands when the samples were stored in air for 1 year before the growth step. Electron backscatter diffraction (EBSD) patterns taken from inside and outside the domains immediately after BEN did not show any significant difference. This allows the conclusion that the modification of the iridium crystal lattice accompanied with diamond nucleation is either very faint or only restricted to a very thin layer at the surface. Kelvin probe force microscopy (KPFM) measurements indicate a reduced work function within the domains.     

Miscibility, crystallization and morphologies of syndiotactic polystyrene blends with isotactic polystyrene and with atactic polystyrene

Two-component blends of differing polystyrene (PS), one syndiotactic (sPS) and the other isotactic (iPS) or atactic (aPS), were discussed. The phase behavior, crystallization and microstructure of binary polystyrene blends of sPS/iPS and sPS/aPS with a specific composition of 5/5 weight ratio were investigated using optical microscopy (OM), differential scanning calorimetry, wide-angle X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM). Based on the kinetics of enthalpy recovery, complete miscibility was found for the sPS/aPS blends where a single recovery peak was obtained, whereas phase separation was concluded for the sPS/iPS blends due to the presence of an additional recovery shoulder indicating the heterogeneity in the molten state. These findings were consistent with OM and SEM observations; sPS/iPS exhibits the dual interconnectivity of phase-separated phases resulting from spinodal decomposition.Both iPS and aPS have the same influence on the sPS crystal structure, i.e., dominant β-form sPS and mixed α-/β-form sPS obtained for melt-crystallization at high and low temperatures respectively, but imperfect α-form sPS developed when cold-crystallized at 175 °C. Co-crystallization of iPS and sPS into the common lattice was not observed regardless the thermal treatments, either cold or melt crystallization. Due to its slow process, crystallization of iPS was found to commence always after the completion of sPS crystallization in one-step crystallization kinetics. Segregation of rejected iPS component during sPS crystallization was extensively observed from TEM and SEM images which showed iPS pockets located between sPS lamellar stacks within spherulites, leading to the interfibrillar segregation, which was similar with that observed in the sPS/aPS blends. The addition of iPS (or aPS) component will reduce the overall crystallization rate of the sPS component and the retardation of crystal growth rates can be simply accounted by a dilution effect, keeping the surface nucleation intact. The phase-separated structure in the sPS/iPS blend shows a negligible effect on sPS crystallization and the signature of phase separation disappears after sPS crystallization. Depending on the relative dimensions of the segregated domains and iPS lamellar nucleus, subsequent crystallization of iPS can proceed to result in a crystalline/crystalline blend, or be inhibited to give a crystalline/amorphous blend morphology similar with that of sPS/aPS blends.