The Application of High Resolution Chemical Imaging Techniques for Butyl Rubber Blends

2008 ◽  
Vol 81 (2) ◽  
pp. 265-275 ◽  
Author(s):  
Donald A. Winesett ◽  
Andy H. Tsou

Abstract Atomic Force Microscopy (AFM), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) imaging, and Scanning Transmission X-ray Microscopy (STXM) are applied to identical series of elastomeric blends to evaluate the relative strengths and weaknesses of each imaging technique. AFM is a high resolution, high contrast technique with straight forward sample preparation that derives contrast through elastic modulus variations, but, when used in a conventional mode, has limited chemical specificity. ToF-SIMS imaging can map phases, detect trace levels (ppm) of additives and other chemical species based on relatively straight forward sample preparation, but has poorer spatial resolution and the instrumentation is expensive. STXM has excellent chemical specificity and good spatial resolution but is only available at a beamline and requires more advanced sample preparation. Each technique will be overviewed briefly and relative merits of each will be compared based on evaluations of some commercially relevant rubber blend materials.


Author(s):  
C. Barry Carter

This paper will review the current state of understanding of interface structure and highlight some of the future needs and problems which must be overcome. The study of this subject can be separated into three different topics: 1) the fundamental electron microscopy aspects, 2) material-specific features of the study and 3) the characteristics of the particular interfaces. The two topics which are relevant to most studies are the choice of imaging techniques and sample preparation. The techniques used to study interfaces in the TEM include high-resolution imaging, conventional diffraction-contrast imaging, and phase-contrast imaging (Fresnel fringe images, diffuse scattering). The material studied affects not only the characteristics of the interfaces (through changes in bonding, etc.) but also the method used for sample preparation which may in turn have a significant affect on the resulting image. Finally, the actual nature and geometry of the interface must be considered. For example, it has become increasingly clear that the plane of the interface is particularly important whenever at least one of the adjoining grains is crystalline.A particularly productive approach to the study of interfaces is to combine different imaging techniques as illustrated in the study of grain boundaries in alumina. In this case, the conventional imaging approach showed that most grain boundaries in ion-thinned samples are grooved at the grain boundary although the extent of this grooving clearly depends on the crystallography of the surface. The use of diffuse scattering (from amorphous regions) gives invaluable information here since it can be used to confirm directly that surface grooving does occur and that the grooves can fill with amorphous material during sample preparation (see Fig. 1). Extensive use of image simulation has shown that, although information concerning the interface can be obtained from Fresnel-fringe images, the introduction of artifacts through sample preparation cannot be lightly ignored. The Fresnel-fringe simulation has been carried out using a commercial multislice program (TEMPAS) which was intended for simulation of high-resolution images.



The assessment of drug permeation into/across the skin is traditionally accomplished using Franz diffusion cells with subsequent analysis by conventional chromatographic methods such as HPLC and more recently using advanced imaging techniques. In this context, time of flight-secondary ion mass spectrometry (ToF-SIMS) offers distinctive advantages in mapping drugs within skin with high sensitivity and chemical specificity without the need for fluorescent tags or radiolabels. The work in this paper uses the combination of conventional and advanced methods to evaluate imiquimod permeation into the skin. This approach provides complementary and detailed information regarding the permeated mass, the permeation depth and the spatial distribution and localisation of drugs within skin. Imiquimod is an immune modulator drug approved by the FDA for the treatment of superficial basal cell carcinoma (BCC) but not the nodular lesions. As other studies have reported that Aldara™ cream (imiquimod 5% w/w) has some limitations in the treatment of nodular BCC lesions due to the cream’s inability to deliver imiquimod into the deeper more invasive nodular lesions, an enhancement of imiquimod permeation is thought to be useful to overcome these limitations. Therefore, an attempt to improve delivery of imiquimod into the deeper skin layers using microemulsions was investigated. Imiquimod microemulsions were formulated and characterised in our previous work are now tested for skin permeation enhancement. However, the assessment of imiquimod permeation from the formulated microemulsions using HPLC and ToF-SIMS demonstrated a limited ability of the microemulsions to improve delivery of imiquimod over Aldara™ cream. This was attributed to the poor release of imiquimod from the microemulsion formulas due to the high affinity of imiquimod for the oil phase and the encapsulation of the oil droplets by the S/Co-S mixture. This is thought to be, the first time that ToF-SIMS has been used to assess permeation of imiquimod from a microemulsion dosage form.



2019 ◽  
Vol 34 (6) ◽  
pp. 1098-1108 ◽  
Author(s):  
Pietro Benettoni ◽  
Hryhoriy Stryhanyuk ◽  
Stephan Wagner ◽  
Felix Kollmer ◽  
Jairo H. Moreno Osorio ◽  
...  

ToF-SIMS boundaries were pushed to enhance lateral resolution and mass resolving power for chemical imaging of nanoparticles in biological systems.





1997 ◽  
Vol 3 (S2) ◽  
pp. 817-818
Author(s):  
Fran Adar ◽  
Roussel Bernard ◽  
Alian Wang ◽  
Shari Hawi ◽  
Kasem Nithipathikom

Chemical imaging of complex multi-component materials has important potential for the analyst in many fields of research. Raman imaging is of particular interest for several reasons. The Raman spectra contain detailed information on chemical species and crystalline phase. Because the Raman effect is excited by optical radiation, the spatial resolution, which is proportional to the wavelength of the light, is better than 1 μm. and with near field optical techniques currently under development, there is potential for even higher spatial resolution in the chemical image.The methods used to produce an image fall into essentially two categories - global imaging and confocal mapping. When creating global images, a large area of the sample is bathed in laser light. The light scattered by the sample is filtered to select a Raman band, and then that light is used to create an image of the sample on a two-dimensional detector.



Author(s):  
Steven J. Pachuta

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) has in recent years become a useful tool for surface analysis in industrial laboratories. All elements and isotopes, as well as many molecular entities, can be detected by SIMS, with most of the signal coming from the outer 10 - 20 Å of the surface. The initial penetration of TOF-SIMS into industry was as an improvement over existing quadrupole instruments, with higher mass range, mass resolution, and sensitivity. The coupling of TOF-SIMS with high brightness liquid metal ion sources greatly expanded the applicability of the technique, making chemical imaging of the outermost monolayers of a surface a routine experiment.Several examples will be presented of TOF-SIMS imaging applied to real-world materials encountered in an industrial analytical laboratory. All results were obtained from a PHI-Evans TFS series instrument equipped with an FEI two-lens 69Ga+ liquid metal ion gun (LMIG). When operated at 25 keV beam energy, a primary ion beam diameter of 2500 Å in continuous mode, and 1-2 μm in pulsed mode, can routinely be obtained.



2020 ◽  
Vol 19 (6) ◽  
pp. 960-970 ◽  
Author(s):  
Samvel K. Gularyan ◽  
Alexander A. Gulin ◽  
Ksenia S. Anufrieva ◽  
Victoria O. Shender ◽  
Michail I. Shakhparonov ◽  
...  

Glioblastoma (GBM) is one of the most aggressive human cancers with a median survival of less than two years. A distinguishing pathological feature of GBM is a high degree of inter- and intratumoral heterogeneity. Intertumoral heterogeneity of GBM has been extensively investigated on genomic, methylomic, transcriptomic, proteomic and metabolomics levels, however only a few studies describe intratumoral heterogeneity because of the lack of methods allowing to analyze GBM samples with high spatial resolution. Here, we applied TOF-SIMS (Time-of-flight secondary ion mass spectrometry) for the analysis of single cells and clinical samples such as paraffin and frozen tumor sections obtained from 57 patients. We developed a technique that allows us to simultaneously detect the distribution of proteins and metabolites in glioma tissue with 800 nm spatial resolution. Our results demonstrate that according to TOF-SIMS data glioma samples can be subdivided into clinically relevant groups and distinguished from the normal brain tissue. In addition, TOF-SIMS was able to elucidate differences between morphologically distinct regions of GBM within the same tumor. By staining GBM sections with gold-conjugated antibodies against Caveolin-1 we could visualize border between zones of necrotic and cellular tumor and subdivide glioma samples into groups characterized by different survival of the patients. Finally, we demonstrated that GBM contains cells that are characterized by high levels of Caveolin-1 protein and cholesterol. This population may partly represent a glioma stem cells. Collectively, our results show that the technique described here allows to analyze glioma tissues with a spatial resolution beyond reach of most of other omics approaches and the obtained data may be used to predict clinical behavior of the tumor.



2021 ◽  
Vol 5 (1) ◽  
Author(s):  
Meicheng Li ◽  
Antoine Seyeux ◽  
Frédéric Wiame ◽  
Philippe Marcus ◽  
Jolanta Światowska

AbstractThree-dimensional (3D) time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging is a promising tool in the analysis of surface modifications of alloy matrix and intermetallic particles induced by localized corrosion due to its good spatial resolution and very high sensitivity to chemical identification especially involving light mass elements like Li. In this paper, ToF-SIMS 3D chemical mapping combined with scanning electron microscopy was performed to study the localized corrosion of Al-Cu-Li alloy (AA2050-T8) in a region around an Al-Cu-Fe-Mn intermetallic particles (IMPs) in 0. 1 M NaCl solution. Initiation of corrosion was locally observed on the IMPs and between IMPs and matrix substrate. Moreover, a modified oxide/hydroxide layer was observed over IMPs compared to the matrix. This new corrosion layer was enriched with chlorides and Cu hydroxides. ToF-SIMS 3D imaging revealed that Li was present over the alloy matrix, while no Li was present over the IMPs in regions where localized corrosion occurred.



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