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FTIR

> How does it work ?

FTIR stands short for Fourier transform infrared spectroscopy.

As we explained before, FTIR measures the spectral fingerprint of a material when irradiated with infrared light. Light interacts with molecules, and it is possible to extract molecular information from theses interactions. Indeed, low energy photons, which can be associated to infrared light, may induce vibrational excitation of covalently bonded atoms and groups. To understand how this happens, one needs to picture the covalent bond as a stiff spring that can stretch, bend and twist once excited. The vibrational excitations will cause the light to be absorbed at very specific frequencies, depending on the mass of the atoms, the strength of the bonds and the environment around the molecule [1,7].


The principle of FTIR is thus that a sample is irradiated with a beam containing many frequencies of light. Part of these frequency of light are absorbed depending on the presence of vibrationally excited covalent bonds. The transmitted part of the IR radiation is gathered by a detector. Several measurements are performed in order to raster the entire frequency range (which is fixed before the experiment). Once all signals are collected, a Fourier transform is applied in order to turn the raw data into the desired results. These results are the light absorption versus the wavelength. Peaks of absorbed light at specific frequency can be correlated to specific bonds. It is therefore possible to identity a material, as each one a particular set of peaks, also called their “spectral fingerprint” [1].

> Results

The first block of the thermoplastic copolyester (TPC) was quite easy to identify. It could either be poly(ethylene terephthalate) (PET) or poly(butylene terephthalate) (PBT), as those two materials share the same characteristic peaks. After going through the literature, we found that PBT was more likely used to make this TPC because this is the go-to hard block in thermoplatic copolyester..

Identifying the second material was a bit more tricky and required a lot of research. We were however able to find a

copoly(ether-esters) based on PBT and polytetramethyleneglycol (PTMEG, or also called Polytetrahydrofuran, PTHF) with a very similar IR spectrum [2].

[2]

The obtained spectrum is represented below over a range of 4000 to 500 cm⁻¹, followed by a zoom over the 2000 to 500 cm¹ range. The peaks that can be attributed to each block are listed below the spectrum.

PBT in red [3, 4]

  • 727 cm⁻¹: aromatic C-H bending

  • 1018 cm⁻¹: C–H out-plane deformation vibration of paradisplacement benzene ring

  • 1119 and 1101 cm⁻¹: ester functionality (O-CH2)

  • 1250 cm⁻¹: ester functionality (CO-O stretch)

  • 1267 cm⁻¹: C–O–C asymmetric stretching vibration

  • 1458 cm⁻¹: C=C stretching vibration of the phenyl group

  • 1412 cm⁻¹: aromatic ring

  • 1504 cm⁻¹: C=C stretching vibration of the phenyl group

  • 1579 cm⁻¹: aromatic ring

  • 1612 cm⁻¹: aromatic ring

  • 1716 cm⁻¹: C=O stretching vibration of the terephthalate units

  • 2852 cm⁻¹: –CH2– symmetric stretching vibration

  • 2958 cm⁻¹: –CH2– asymmetric stretching vibration

PTMEG or PTHF [5, 6]

  • 750 cm⁻¹: rocking of -CH2-

  • 812 cm⁻¹: out-of-plane bending C-H (benzene ring)

  • 916 cm⁻¹: out-of-plane bending C-H

  • 985 cm⁻¹: symmetric stretching C-O-C

  • 1119 cm⁻¹: antisymetric stretching C-O-C

  • 1207 cm⁻¹: twisting CH2

  • 1250 cm⁻¹: wagging CH2

  • 1458 cm⁻¹: out-of-plane bending CH2

[1] ThermoFischer Scientific, Introduction to FTIR spectroscopy, https://www.thermofisher.com/be/en/home/industrial/spectroscopy-elemental-isotope-analysis/spectroscopy-elemental-isotope-analysis-learning-center/molecular-spectroscopy-information/ftir-information/ftir-basics.html, consulted April 2017

[2] Yasutaka Nagai, Takahiro Ogawa, Liu Yu Zhen, Yuko Nishimoto & Fuji Ohishi,  Analysis of weathering of thermoplastic polyester elastomers-I. Polyether-polyester elastomer,  Polymer Degradation and Stability, 56, (1997), 115-12

[3] Pereira, Guilherme Cybis, Rzatki, Felipe Darabas, Mazzaferro, Luca, Forin, Daniel Maldonado, & Barra, Guilherme Mariz de Oliveira. (2016). Mechanical and Thermo-Physical Properties of Short Glass Fiber Reinforced Polybutylene Terephthalate upon Aging in Lubricant/Refrigerant Mixture. Materials Research, 19(6), 1310-1318. https://dx.doi.org/10.1590/1980-5373-mr-2016-0339

[4] Hubert Lobo, Jose V. Bonilla, Handbook of Plastics Analysis: Volume 68 of Plastics engineering, CRC Press, 2003, 270-274

[5] K. Nakayama , T. Ino & I. Matsubara (1969) Infrared Spectra and Structure of Polyurethane Elastomers from Polytetrahydrofuran, Diphenylmethane-4, 4′-diisocyanate, and Ethylenediamine, Journal of Macromolecular Science: Part A - Chemistry, 3:5, 1005-1020, DOI: 10.1080/10601326908051929

[6] Feng Liu, Meng Yao, and Ming-tao Run, “Synthesis and Characterizations of Poly(trimethylene terephthalate)-b-poly(tetramethylene glycol) Copolymers,” International Journal of Polymer Science, vol. 2013, Article ID 156289, 10 pages, 2013. doi:10.1155/2013/156289

[7] William Reusch, Infrared Spectroscopy, 05/05/2013, https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/Spectrpy/InfraRed/infrared.htm

> Bibliography

By Roselien

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