Microscopy

Easiest and most common method of characterization Limited to the pores at the surface Optical microscopy can be used for pore diameters down to 50uM. Smaller structures can be imaged using electron microscopy.

Comparison of the light and electron microscope

Light Microscope Electron Microscope

Cheap to purchase
Cheap to operate. Small and portable. Simple and easy sample preparation. Material rarely distorted by preparation.

Expensive to buy
Expensive to produce electron beam. Large and requires special rooms. Lengthy and complex sample prep. Preparation distorts material.

Vacuum is not required.

Natural color of sample maintained. Magnifies objects only up to 2000 times Specimens can be living or dead

Vacuum is required.
All images in black and white. Magnifies over 500 000 times. Specimens are dead, as they must be fixed in plastic and viewed in a vacuum The electron beam can damage specimens and they must be stained with an electrondense chemical (usually heavy metals like osmium, lead or gold).

Stains are often needed to make the cells visible

 Two main varieties or electron microscopy is in use.

Scanning Electron Microscope Usually uses a electron gun (hot tungsten filament) to raster an ebeam over the surface. Some of the incident electrons are scattered and can be detected. Scattering intensity is proportional to the surface area of the incident electron spot and the material type. A steep surface has a larger surface area and thus greater scattering signal. This gives topographic resolution. Resolution from 1nm to 20nm Can image relatively large area of sample Transmission Electron Microscope Angstrom level resolution (lattice resolution) Requires the sample to be transparent to electrons (very thin) Electrons either scatter off atoms in the sample or pass through.

Information is gathered in two ways:

1. Electron diffraction pattern in reciprocal space at the back-focal plane 2. Image in real space located at the image plane. Images only a relatively small area of the sample.

SEM Capabilities
Backscattered Imaging (BSI) Compositional Contrast Secondary Electron Imaging (SEI) Surface Topography, Morphology, Particle Sizes, etc.

Scanning Electron Microscope (SEM) Transmitted Electron Imaging (TEI) Internal ultrastructure Energy-Dispersive X-ray Spectrometry (EDS) Elemental composition, mapping and linescans Electron Backscattered Electron Diffraction (EBSD) Crystallographic Info

TEM Capabilities
Bright- and Dark-Field Imaging (BF/DF imaging) Internal ultrastructure Nanostructure dispersion Defect identification Electron Diffraction (ED) Crystallographic Info

High-Resolution Transmission Electron Microscopy (HR-TEM) Interface structure Defect structure

Transmission Electron Microscope (TEM) Electron Energy Loss Spectroscopy (EELS) Energy-Dispersive X-ray Spectrometry (EDS) Elemental composition, mapping and linescans Chemical composition Other Bonding info

TEM can obtain lattice resolution for microporous materials LTL zeolite is an example of a porous material with 3 different size pores. It has 6, 8, and 12 member rings. TEM has the ability to image each of these pores. The 12 member rings are only 7 Angstroms in diameter.
Karge and Weitkamp p.87

Zeolite-Y looking down [011] direction.

S. X. Wang, L. M. Wang and R. C. Ewing, " Electron irradiation of zeolites", Mat. Res. Soc. Symp. Proc. 540 (1998)

Layered Silicates (Nanoclay) and Polymer Nanocomposites

Improved properties related to the dispersion and nanostructure (aspect ratio, etc.) of the layered silicate in polymer The greatest improvement of these benefits often comes with exfoliated samples Intercalate: Organic component inserted between the layers of the clay Inter-layer spacing is expanded, but the layers still bear a well-defined spatial relationship to each other Exfoliated: Layers of the clay have been completely separated and the individual layers are distributed throughout the organic matrix Results from extensive polymer penetration and delamination of the silicate crystallites
http://www.azom.com/details.asp?ArticleID=936

Polymer-Layered Silicate Nanocomposites

TEM of Intercalated Nanoclay
Organoclay nanocomposite (10% in Novalac-Based Cyanate Ester)
XRD gives average interlayer d-spacing while TEM can give site specific morphology and d-spacing In this case, XRD gave no peaks Many factors such as concentration and order of the clay can influence the XRD patterns XRD often inconclusive when used alone

Alexander B. Morgan, and Jeffrey W. Gilman, Characterization of Polymer-Layered Silicate (Clay) Nanocomposites by Transmission Electron Microscopy and X-Ray Diffraction: A Comparative Study, J. Applied Polymer Science, 87 13291338 (2003).

Polymer-Layered Silicate Nanocomposites

In the authors own words: The majority of PLSNs that we investigated were best described as intercalated/exfoliated. By XRD, they would be simply defined as intercalated, in that there was an observed increase in the d-spacing as compared to the original clay dspacing. However, the TEM images showed that although there were indeed intercalated multilayer crystallites present, single exfoliated silicate layers were also prevalent, hence, the designation of an intercalated/exfoliated type of PLSNs.

TEM Image of an Intercalated/Exfoliated PS Nanocomposite

Small Intercalated Clay Layers

Exfoliated Single Layers

Alexander B. Morgan, and Jeffrey W. Gilman, Characterization of Polymer-Layered Silicate (Clay) Nanocomposites by Transmission Electron Microscopy and X-Ray Diffraction: A Comparative Study, J. Applied Polymer Science, 87 13291338 (2003).

Epoxy-Based Clay Nanocomposites

TEM Images of Clay/Epoxy Nanocomposites

Change of basal spacing of organo-clay nanocomposites during processing of epoxy/clay nanocomposites by the sonication technique TEM images of nanoclay in different epoxy systems showing intercalated(white arrows)/exfoliated (black arrows) nanocomposite hybrids Increase in basal d-spacings in nanoclay platelets observed by TEM and XRD In some cases from 1.8 nm up to 8.72 nm
Hiroaki Miyagawa, Lawrence T. Drzal, and Jerrold A. Carsello, Intercalation and Exfoliation of Clay Nanoplatelets in Epoxy-Based Nanocomposites: TEM and XRD Observations, Polymer Engineering and Science, 46(4) 452-463 (2006).

Alexander B. Morgan, and Jeffrey W. Gilman, Characterization of Polymer-Layered Silicate (Clay) Nanocomposites by Transmission Electron Microscopy and X-Ray Diffraction: A Comparative Study, J. Applied Polymer Science, 87 13291338 (2003).

CONCLUSIONS
We have shown several different PLSNs of varying nanoscale dispersions, comparing and contrasting the results by XRD and TEM. In light of these results, the definitions used to describe PLSNs should be modified to more accurately describe the dispersion at the nanoscale. Two of the definitions are still quite useful in describing the nature of the PLSN, namely, immiscible and exfoliated. To avoid confusion, immiscible systems should probably be described as microcomposites rather than as immiscible nanocomposites. The exfoliated systems do fall into two categories, exfoliated ordered (PS) and exfoliated disordered (PA-6). The greatest clarification is needed for the intercalated definition. Although some purely intercalated nanocomposites have been made, they are not very common. As exfoliated nanocomposites are generally the desired product of PLSN synthesis, attempts that do not achieve exfoliation often fall into this mixed morphology category. The most important observation determined from this study is that XRD results by themselves cannot be used to adequately describe the nanoscale dispersion of the layered silicate present in PLSNs. XRD results when properly interpreted and combined with TEM results give a much clearer picture of the actual nanoscale dispersion and overall global dispersion of the clay in the polymer. Further, these two techniques provide information to help derive meaningful relationships between the PLSN nanostructure and macroscale properties.