Microstructural investigation of light elements and highly beam sensitive polymer materials using electron microscopy is attractive for elucidating nanostructure but presents numerous challenges. In particular, heavy element staining, often used to obtain image contrast, may obscure or degrade the structure of interest and the acquisition of detailed and spatially resolved information must be balanced with damage of the specimen. Here, scanning electron diffraction (SED) has been used to analyse the crystalline microstructure of unstained polyethylene, overcoming these challenges. SED involves scanning the electron beam across the specimen and recording a diffraction pattern at each position [1] at a high frame rate to enable the data to be acquired before severe degradation of the structure has occurred. In this way, electron diffraction patterns were obtained from an unstained polyethylene sample in 5 nm steps, over areas of a few microns squared and with a 10 ms dwell time. Radiation damage was further minimised by using a high electron acceleration voltage (300kV) to minimise radiolysis and cooling the sample with liquid nitrogen [2]. The diffraction patterns, acquired at every position in the scan, were indexed and analysed by plotting the intensity of a particular reflection as a function of electron probe position to form ‘virtual’ dark field (VDF) images. VDF imaging is much more effective than conventional imaging for visualizing the microstructure of polyethylene. Clear contrast is obtained without staining and the versatile post-facto nature of VDF image formation enables multiple complementary images to to be produced from a single acquisition.
Two novel observations from our SED experiments on polyethylene are highlighted here. The sample of polyethylene was extruded from a melt so as to form ‘shish-kebab’ structures confirmed through BF images of stained microtomed sections. For our experiments, again the samples were microtomed but now unstained to avoid any influence of the stain on the diffraction patterns. The first experiment highlights a lamella-like fragment of polyethylene crystal (likely to be a part of the ‘kebab’ structure). Fig 1 shows a ‘virtual’ BF image and a sample of diffraction patterns that can only be indexed assuming the orthorhombic crystal structure of polyethylene and that the lamella is twisting about a single axis almost parallel to the vertical axis of the image. Moreover, forming consecutive VDF images made it possible to visualize each region of the crystal having a particular orientation in the twisted lamella (Fig 2). In the second experiment, we found that the sample had several micron sized islands of hexagonal polyethylene first seen as a high pressure phase [3]. However, here the patterns reveal a √3 superstructure with weak spots at the 1/3[110]* position (Fig 3). VDF images (Fig 3(b-d)) formed by these supercell reflections revealed domains within which ‘striped’ contrast can be seen; these stripes run at an orientation of approximately 120° to one another. This work demonstrates the applicability of the SED technique to highly beam sensitive materials like polyethylene and the potential for new microstructural insights to be made in this way.

[1] Moeck P. et al., Cryst. Res. Technol., 2011, 46, 586-606
[2] Egerton R. F. et al., Micron, 2004, 35, 399-409
[3] Bassett D. C., et al., Journal of Applied Physics, 1974, 4146-415

PAM and SJK would like to acknowledge funding under ERC Advanced Grant 291522-3DIMAGE. DNJ receives a Vice Chancellor’s award from the University of Cambridge. HJ and HT thank Ms. Makiko Ito for her help in microtoming the polyethylene samples. The authors would like to thanks Anton Jan Bons (ExxonMobil) for initiating this research and stimulating discussions.

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