AFM for Polymer Science
by Joan Horwitz
AFM is a powerful characterization tool for polymer science, capable of revealing surface structures with unprecedented spatial resolution. It is extremely useful for studying the local surface molecular composition and mechanical properties of a broad range of polymer materials, including block copolymers, bulk polymers, thin-film polymers, polymer composites, and polymer blends.
In addition to remarkably high spatial resolution, another key advantage of AFM is simultaneous multichannel data acquisition. In acoustic AC mode, tip-sample force interactions cause changes in the amplitude, phase, and resonance frequency of the oscillating cantilever. The spatial variation of the change can be presented in height (topography) or interaction (amplitude or phase) images. A feedback system monitors the oscillating amplitude of the cantilever at each sample location and tries to maintain a set value (set-point) by moving the scanner up or down based on the surface morphology.
While the vertical motions of the scanner are used to generate a topographic image, the actual oscillation amplitudes and the phase lag between the AC drive input and the cantilever oscillation output can also be collected simultaneously to produce the corresponding amplitude and phase image, respectively. It has been demonstrated by many research groups that phase contrast is very sensitive to differences in material properties, such as variation of mechanical and adhesive properties.
The visualization of different components of heterogeneous polymer materials via AFM phase imaging has been demonstrated in numerous studies of block copolymers, semicrystalline polymers, and mesomorphic polymers. For instance, compositional mapping with AFM is often used for observations of microphase separation of block copolymers, which occurs at the sub-100 nm scale. In addition to the compositional imaging of multicomponent polymer samples, visualization of amorphous and crystalline components is an important application of phase imaging. Besides amorphous and crystalline forms, many liquid crystalline polymers such as poly(diethylsiloxane) (PDES) usually exist in a partially ordered or mesomorphic form, which can also be characterized by phase imaging.
Polymer or plastic materials can be divided into two major groups, thermoplastic or thermosetting, based on their response to heat. Therefore, knowledge of polymer behavior at different temperatures is essential for many practical applications. Although quite a few macroscopic techniques, such as differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermal mechanical analysis (TMA), are usually employed to probe the temperature changes of polymers, direct nanometer-scale visualization of polymers at different temperatures is still highly desired. With the development of both heating and cooling accessories, the use of AFM on polymer materials can be extended from ambient temperature to temperatures where polymer phase transitions occur. High-resolution AFM temperature studies can provide unique microscopic insight into polymer thermal behavior.
We have documented many examples of the imaging of different polymer samples with the Agilent 5400 atomic force microscope that demonstrate its capabilities for visualizing important polymer nanostructures and monitoring structural changes caused by thermal transitions. The 5400’s outstanding thermal control is a rare feature for economically priced microscopes and the additional advantage of MAC Mode compatibility provides direct drive imaging in oscillatory mode in liquid and air.
Please refer to the polymer-related application notes posted on our website. Detailed information about the 5400 atomic force microscope, thermal control, and MAC Mode can also be found on our website.
