Poster Presentation on Sponsor’s Day at University of Akron, October 2011
1. Real-Time Characterization (True Stress-True Strain-Birefringence-IR Spectroscopy) of
Multicomponent Functional Thin Polymer Films During High-Speed Uniaxial Deformation:
Ultra-Rapid-Scan FTIR Coupled with Uniaxial Stretching Machine
E. Unsal, M. Cakmak
University of Akron, Polymer Engineering Department
Introduction Real-time Measurement System Dichroic Ratio
Load cell – for stress Uniaxial Stretching
The physical properties of polymers can be altered by post- measurements during uniaxial URS-FTIR
processing techniques to improve certain properties such as stretching of polymer films Machine Detector unit of the URS-FTIR. It
gas permeability and modulus. Uniaxial stretching is one of consists of two separate detectors
Heating chamber – allows us to for each polarization.
the common methods, which can affect the molecular stretch materials at different
orientation, crystallinity and morphology of polymer films. temperatures up to 200°C (heated Visible wavelength range light
The physical properties are generally characterized by off- by hot air flow) source for the real-time in-plane
line methods after the morphological changes already took birefringence measurements
Sample position during uniaxial stretching
place. The real-time measurement of such properties is Spectral Birefringence is
challenging, due to high rates of production and non-contact measured at the center of sample Interferometer unit of the URS
measurement requirements for the industrial environments. FTIR. This interferometer 3 cos 2 1 D 1 D0 2
Thermocouples and pyrometer – generates two IR beams (parallel
f
2 D 2 D0 1
Located inside the chamber, to and perpendicular polarized with
We developed a uniaxial stretching machine which is Ai ( M i E) 2 (Mi E)2 cos2
measure the surface temperature respect to the stretching direction) A||
capable of measuring real-time true stress-true strain- D D0 2 cot2
of film and ambient temperature simultaneously A
birefringence of polymer films during deformations. 1 This
stretching instrument is modified by adding an Ultra-rapid- Laser micrometer is used to Solid framework is designed to Figure 8 Polymer chain axis and dipole moment of the
measure the width of the sample mount the URS-FTIR instrument chemical groups with respect to the draw direction and
scan FTIR (URS-FTIR) spectrometer, which can reach data during stretching and the data is around the stretching machine. corresponding equations8-10
acquisition speeds of 200 scans/second. URS-FTIR is used to calculate the real-time
capable of generating simultaneous parallel and thickness Figure 4 – Sensors and capabilities of for f=0 random orientation
perpendicular polarized (with respect to stretching direction) stretching machine and URS-FTIR f=-0.5 orientation perpendicular to the stretching direction
infrared spectra that gives us ability to track orientation of f=1 parallel orientation to the stretching direction
each component separately for multi-component systems
such as; crystalline polymers, polymer nanocomposites,
blends, copolymers and films including spun fibers. 2 Among
Figure 9 Orientation functions
these physical changes, this instrument can also detect any of functional groups in
chemical changes happening during the heating/stretching polyurethane samples 11
of polymer films (e.g. imidization process).
Polymer-clay nanocomposites 5 Fiber spun films 7
Interferometer Conclusions
The design of a stretching machine coupled with a URS-
FTIR is explained, to measure real-time true stress-true
strain-birefringence and spectroscopy of multicomponent
films during uniaxial deformations. Preliminary raw data is
represented. This instrument will allows us to track chemical
Block copolymers 6 Films containing solvent
and physical changes of each component independently for
Figure 5 – Real-time measurement system that is capable of tracking true stress-true strain-birefringence and the multicomponent functional polymer films during very high
Figure 1 – Classical interferometer 3
spectroscopy of multi-component polymer systems. These systems include, clay nanocomposites5, block speed deformations which the industry requires. The
Figure 1 above shows the interferometer of an FTIR copolymers6, polymer blends, films containing fibers7 and solvents. Real-time spectroscopic measurements instrument will be updated for scan rates of 1000
instrument . It consists of a stationary mirror and a linear will reveal information on the orientation of each component separately during stretching and this data will be
scans/second and the two data sets will be synchronized. .
synchronized with the mechano-optical data generated from the stretching machine.
moving mirror to create a optical path difference (OPD). The
linear motion of the moving mirror limits the rate of scanning
of spectrometer. Manning 4 created the OPD by using Preliminary Results References
wedged rotating mirrors, which can achieve scanning rates 3
1T.Z. Sen, PhD Dissertation, The University of Akron, 2003.
of 1000 scans/second. Bench-top FTIR instrument
URS-FTIR Horizontal Spectra
2Pellerin, C. et. al. Macromolecules, (2003), 36, 4838.
URS-FTIR Vertical Spectra
3Scientific, T.F. FT-IR vs. Dispersive Infrared. Technical Note: 00128 2010 [cited 2010 5-
2
11-2010]
Absorbance
4Manning, C. J., US Patent 5898495
1 5Alexandre, M. and P. Dubois, Polymer-layered silicate nanocomposites: preparation,
properties and uses of a new class of materials. Mater. Sci. Eng., R, 2000. R28(1-2): p.
1-63.
0 6S. Förster, T. Plantenberg, Angew. Chem. Int. Ed. (2002), 41, 688.
7Cakmak, M. et.al. US Patent 20090020921
8SChalmers, J.M., Everall, N. J., ed. Qualitative and Quantitative Analysis of Plastics,
-1
4000 3000 2000 1000 Polymers and Rubbers by Vibrational Spectroscopy. Vibrational Spectroscopy of
Wavenumber (cm-1) Polymers, ed. C.J.M.
9Everall N. J., Griffiths P. R. 2007, John Wiley & Sons Ltd.: West Sussex
Figure 2 – Interferometer design with rotating wedged mirrors (on Figure 6 Real-time raw data collected from the Figure 7 Left- Poly amic acid sample and IR light with two polarizations 10Everall N. J., C.J.M., Griffiths P. R., ed. Vibrational Spectroscopy of Polymers. 2007,
the left). 4 Top view of actual URS-FTIR interferometer equipped uniaxial stretching machine during the imidization (representative image). Right- Comparison of bench-top FTIR (Thermo John Wiley & Sons Ltd.: West Sussex.
11Versteegen, R. M., et. al., Macromolecules (2006), 39, 772
on the stretching machine (on the right). of Poly amic acid/NMP (10 wt%) film Scientific-Nicolet 380) with URS-FTIR
www.postersession.com
![Real-Time Characterization (True Stress-True Strain-Birefringence-IR Spectroscopy) of
Multicomponent Functional Thin Polymer Films During High-Speed Uniaxial Deformation:
Ultra-Rapid-Scan FTIR Coupled with Uniaxial Stretching Machine
E. Unsal, M. Cakmak
University of Akron, Polymer Engineering Department
Introduction Real-time Measurement System Dichroic Ratio
Load cell – for stress Uniaxial Stretching
The physical properties of polymers can be altered by post- measurements during uniaxial URS-FTIR
processing techniques to improve certain properties such as stretching of polymer films Machine Detector unit of the URS-FTIR. It
gas permeability and modulus. Uniaxial stretching is one of consists of two separate detectors
Heating chamber – allows us to for each polarization.
the common methods, which can affect the molecular stretch materials at different
orientation, crystallinity and morphology of polymer films. temperatures up to 200°C (heated Visible wavelength range light
The physical properties are generally characterized by off- by hot air flow) source for the real-time in-plane
line methods after the morphological changes already took birefringence measurements
Sample position during uniaxial stretching
place. The real-time measurement of such properties is Spectral Birefringence is
challenging, due to high rates of production and non-contact measured at the center of sample Interferometer unit of the URS
measurement requirements for the industrial environments. FTIR. This interferometer 3 cos 2 1 D 1 D0 2
Thermocouples and pyrometer – generates two IR beams (parallel
f
2 D 2 D0 1
Located inside the chamber, to and perpendicular polarized with
We developed a uniaxial stretching machine which is Ai ( M i E) 2 (Mi E)2 cos2
measure the surface temperature respect to the stretching direction) A||
capable of measuring real-time true stress-true strain- D D0 2 cot2
of film and ambient temperature simultaneously A
birefringence of polymer films during deformations. 1 This
stretching instrument is modified by adding an Ultra-rapid- Laser micrometer is used to Solid framework is designed to Figure 8 Polymer chain axis and dipole moment of the
measure the width of the sample mount the URS-FTIR instrument chemical groups with respect to the draw direction and
scan FTIR (URS-FTIR) spectrometer, which can reach data during stretching and the data is around the stretching machine. corresponding equations8-10
acquisition speeds of 200 scans/second. URS-FTIR is used to calculate the real-time
capable of generating simultaneous parallel and thickness Figure 4 – Sensors and capabilities of for f=0 random orientation
perpendicular polarized (with respect to stretching direction) stretching machine and URS-FTIR f=-0.5 orientation perpendicular to the stretching direction
infrared spectra that gives us ability to track orientation of f=1 parallel orientation to the stretching direction
each component separately for multi-component systems
such as; crystalline polymers, polymer nanocomposites,
blends, copolymers and films including spun fibers. 2 Among
Figure 9 Orientation functions
these physical changes, this instrument can also detect any of functional groups in
chemical changes happening during the heating/stretching polyurethane samples 11
of polymer films (e.g. imidization process).
Polymer-clay nanocomposites 5 Fiber spun films 7
Interferometer Conclusions
The design of a stretching machine coupled with a URS-
FTIR is explained, to measure real-time true stress-true
strain-birefringence and spectroscopy of multicomponent
films during uniaxial deformations. Preliminary raw data is
represented. This instrument will allows us to track chemical
Block copolymers 6 Films containing solvent
and physical changes of each component independently for
Figure 5 – Real-time measurement system that is capable of tracking true stress-true strain-birefringence and the multicomponent functional polymer films during very high
Figure 1 – Classical interferometer 3
spectroscopy of multi-component polymer systems. These systems include, clay nanocomposites5, block speed deformations which the industry requires. The
Figure 1 above shows the interferometer of an FTIR copolymers6, polymer blends, films containing fibers7 and solvents. Real-time spectroscopic measurements instrument will be updated for scan rates of 1000
instrument . It consists of a stationary mirror and a linear will reveal information on the orientation of each component separately during stretching and this data will be
scans/second and the two data sets will be synchronized. .
synchronized with the mechano-optical data generated from the stretching machine.
moving mirror to create a optical path difference (OPD). The
linear motion of the moving mirror limits the rate of scanning
of spectrometer. Manning 4 created the OPD by using Preliminary Results References
wedged rotating mirrors, which can achieve scanning rates 3
1T.Z. Sen, PhD Dissertation, The University of Akron, 2003.
of 1000 scans/second. Bench-top FTIR instrument
URS-FTIR Horizontal Spectra
2Pellerin, C. et. al. Macromolecules, (2003), 36, 4838.
URS-FTIR Vertical Spectra
3Scientific, T.F. FT-IR vs. Dispersive Infrared. Technical Note: 00128 2010 [cited 2010 5-
2
11-2010]
Absorbance
4Manning, C. J., US Patent 5898495
1 5Alexandre, M. and P. Dubois, Polymer-layered silicate nanocomposites: preparation,
properties and uses of a new class of materials. Mater. Sci. Eng., R, 2000. R28(1-2): p.
1-63.
0 6S. Förster, T. Plantenberg, Angew. Chem. Int. Ed. (2002), 41, 688.
7Cakmak, M. et.al. US Patent 20090020921
8SChalmers, J.M., Everall, N. J., ed. Qualitative and Quantitative Analysis of Plastics,
-1
4000 3000 2000 1000 Polymers and Rubbers by Vibrational Spectroscopy. Vibrational Spectroscopy of
Wavenumber (cm-1) Polymers, ed. C.J.M.
9Everall N. J., Griffiths P. R. 2007, John Wiley & Sons Ltd.: West Sussex
Figure 2 – Interferometer design with rotating wedged mirrors (on Figure 6 Real-time raw data collected from the Figure 7 Left- Poly amic acid sample and IR light with two polarizations 10Everall N. J., C.J.M., Griffiths P. R., ed. Vibrational Spectroscopy of Polymers. 2007,
the left). 4 Top view of actual URS-FTIR interferometer equipped uniaxial stretching machine during the imidization (representative image). Right- Comparison of bench-top FTIR (Thermo John Wiley & Sons Ltd.: West Sussex.
11Versteegen, R. M., et. al., Macromolecules (2006), 39, 772
on the stretching machine (on the right). of Poly amic acid/NMP (10 wt%) film Scientific-Nicolet 380) with URS-FTIR
www.postersession.com](https://image.slidesharecdn.com/e2-v2-120122022400-phpapp01/85/Poster-Presentation-on-Sponsor-s-Day-at-University-of-Akron-October-2011-1-320.jpg)
