Rapid integrated rheo-optical and polarized Fourier-transform infrared spectrometry measurement system for polymer films undergoing chemo-mechanical changes

摘要

The design and performance of a multisensory instrument to track physical and chemical changes of thin polymer films (typically 5 μm < thickness < 100 μm) subjected to thermal and mechanical treatments are described in this paper. For the first time, real-time measurements of spectral birefringence, true stress, true strain, and temperature are integrated together with ultra-rapid-scan polarized FT-IR spectrometer (URS-FT-IR) to investigate the relationships between true mechanical measures and structural features at different length scales. The rheo-optical properties (birefringence-true stress-true strain) are collected at a rate of 10 data points/s and URS-FT-IR data are collected at a rate of 300 complete spectra/s. The IR dichroism measurement is performed by exposing the sample to non-polarized IR beam in transmission mode with two mutually perpendicular polarizations, parallel and perpendicular to the stretching direction, received by detector unit. This design allows to analyze both polarizations simultaneously wavenumbers in the range of 500 cm-1–4000 cm-1. Controlled processing parameters include air speed, air temperature, stretching rate, stretching ratio, stretch cycling, and holding times; while simultaneously measuring optical retardation, sample width, temperature, load cell, and both parallel and perpendicular IR spectra. Calibration and performance of this instrument is demonstrated with several film samples. These are: A polystyrene standard, an atactic polystyrene (homo-polymer), a polyurethane (consists of hard and soft segments) for physical changes during uniaxial deformation, and a polyamic acid during imidization reaction. This measurement system is particularly useful in unraveling molecular level details of complex physical and chemical events that take place during very fast deformation schemes (uniaxial stretching, retraction, relaxation, annealing, etc.) relevant to industrial process- s. These include specific orientation behavior of each phase, block or filler, crystallization, relaxation and orientation state. It is also suited to track reaction rates and products in polymers undergoing thermal or photo curing.