Experimental and Modeling

Techniques to Assess and

Quantify Polymer Degradation
Molecular Properties Characterization, Morphology Characterization
and Material Properties Characterization
Degradation analysis
 Molecular Properties Characterization
• Chromatography
• Size exclusion chromatography (SEC)
• Rheometry and Viscometry
• Rheometry
• Melt flow index (MFI)
• Spectoscopy
• NMR
• FTIR
• Raman
FTIR and NMR can be ineffective at defining small structural changes
 Chromatography
• Size exclusion chromatography (SEC)
Size exclusion chromatography
(SEC)

The average molar The molar masses

Dispersity
masses distribution

the average molar mass

Degradation
decrease

Chemistry, Learning. “Size Exclusion Chromatography - Column, Principle, Procedure.” Learning Chemistry (blog), February 23, 2022. https://www.priyamstudycentre.com/2022/02/size-exclusion-
chromatography.html.
 Rheometry and Viscometry
Rheometry MFI (Melt flow index)

rheometer allow to obtain flow curves,

which via extrapolation allow the If there is a decrease in
determination of the zero-shear melt the average molar mass
viscosity (η0). This viscosity parameter of the material, the
may be correlated with Mm, for linear tendency is that it will
polymers often expressed by an flow easily, increasing
empirical power law the MFI.

the average molar the average molar

Degradation Viscosity decrease Degradation MFI increase
mass decrease mass decrease
 Spectoscopy
FTIR NMR
• The different types of interatomic bond vibrations existing • NMR may resolve the structure of the polymer, and
in organic molecules, polymers, and composites have been has therefore been used to probe the chemical
investigated variations during their degradation.
• carbonyl (>C=O) located around 1600 –1800 cm−1 • the detection of new functional groups formed due
• hydroxyl (-O-H) located around 3200 – 3600 cm−1 to degradation can be evaluated

Chang et al 2017.
Liu, Tuan, Xiaolong Guo, Wangcheng Liu, Cheng Hao, Liwei Wang, William Hiscox, Chengyun Liu, Can Jin, Junna Xin, and Jinwen Zhang. “Selective Cleavage of Ester Linkages of Anhydride-Cured Epoxy Using a
Benign Method and Reuse of the Decomposed Polymer in New Epoxy Preparation.” Green Chem. 19 (August 2, 2017). https://doi.org/10.1039/C7GC01737E.
 Morphology Characterization
Microscopy Crystallography
It can detect variations on the morphology of polymers X-ray diffraction techniques may
because of degradation with microscopic techniques be used to resolve morphological
such as optical microscopy (OM), scanning electron features such as size, distribution,
microscopy (SEM), and atomic force microscopy (AFM) and orientation of crystallites and
lamellae of polymers,
contributing to the study of their
degradation

processing at 190 C and 100 rpm processing at 270 C and 100 rpm
Chatterjee et al. 1995
Bai et al. 2007
Material Properties Characterization
• Thermal analysis
• TGA
• DSC
• Spectoscopy
• UV-Vis
• Mechanical properties
• Contact angle
Thermal analysis
TGA
Thermogravimetric analysis (TGA) allows
tracking variations on the thermal stability of
polymers and the onset of degradation either in
the absence or in the presence of oxygen
Rimez et al. 2008
DSC
Differential scanning calorimetry (DSC) is
commonly used to monitor variations of Tg, Tm,
and crystallization temperature (Tc).
Ioannis M. Kalogeras. 2016
 Spectoscopy
• UV-Vis
• ultraviolet-visible (UV-Vis) spectrophotometry is a technique commonly employed to
measure color variations of polymers which underwent degradation.
• Yellowing is an usual degradation outcome for manufactured polymer parts and the color
properties obtained via UV-Vis may be translated into a Yellowness Index (YI), which supports
the assessment of degradation of the material.

ABS films Wavelength 350 nm

Photo-oxidized
Wavelength 410 nm
samples 15 h

Jouan, X., and J. L. Gardette. “Photo-Oxidation of ABS: Part 2—Origin of the Photodiscoloration on Irradiation at Long Wavelengths.” Polymer Degradation and Stability 36, no. 1 (January 1, 1992): 91–96.
https://doi.org/10.1016/0141-3910(92)90054-9.
 Mechanical properties
• The influence of degradation on the mechanical properties is usually
assessed via impact and tensile tests, tracking the impact resistance,
tensile strength, tensile modulus, and elongation at break of the
polymer

Spinacé, M. A. Silva, and M. A. De Paoli. “Characterization of Poly(Ethylene Terephtalate) after Multiple Processing Cycles.” Journal of Applied Polymer Science 80, no. 1 (2001): 20–25.
https://doi.org/10.1002/1097-4628(20010404)80:1<20::AID-APP1069>3.0.CO;2-S.
 Contact angle
• Higher contact angles indicate that the material has a higher
hydrophobic character. Oxygenated functional groups formed due to
degradation may alter this character and the material becomes more
hydrophilic, exhibiting smaller contact angles

Hurley, Claire R., and Graham J. Leggett. “Quantitative Investigation of the Photodegradation of Polyethylene Terephthalate Film by Friction Force Microscopy, Contact-Angle Goniometry, and X-Ray Photoelectron
Spectroscopy.” ACS Applied Materials & Interfaces 1, no. 8 (August 26, 2009): 1688–97. https://doi.org/10.1021/am900250q.
Manufacturing Case Studies
to Assess Degradability
polyesters, styrene-based materials, polyolefins and additive
manufacturing.
The influence of processing parameters on
the degradation of polymers
 Polyesters
210 C 240 C

a higher level of degradation in cases when elevated the increased residence time of the material in the
temperatures and low screw speeds were employed. extruder and the activated nature of degradation reactions.

Taubner, V., and R. Shishoo. “Influence of Processing Parameters on the Degradation of Poly(L-Lactide) during Extrusion.” Journal of Applied Polymer Science 79, no. 12 (2001): 2128–35.
https://doi.org/10.1002/1097-4628(20010321)79:12<2128::AID-APP1020>3.0.CO;2-#.
 Polyesters

Processing Tensile strengh Yellowing Index

MFI increase COOH increase
cycles number increase increase

A higher level of degradation in cases when high processing cycles number

Spinacé, M. A. Silva, and M. A. De Paoli. “Characterization of Poly(Ethylene Terephtalate) after Multiple Processing Cycles.” Journal of Applied Polymer Science 80, no. 1 (2001): 20–25.
https://doi.org/10.1002/1097-4628(20010404)80:1<20::AID-APP1069>3.0.CO;2-S.
 Styrene-based materials

a higher level of degradation in cases when elevated A higher level of degradation in cases when high residence
temperatures time

La Mantia, F. P., and A. Valenza. “Long-Term Thermomechanical Degradation of Molten Polystyrene.” Polymer Degradation and Stability 13, no. 2 (January 1, 1985): 105–11. https://doi.org/10.1016/0141-
3910(85)90059-X.
 Polyolefins

a higher level of degradation in cases when elevated A higher level of degradation in cases when high processing
temperatures and high processing cycles number were cycles number
employed.

González-González, V.A., G. Neira-Velázquez, and J.L. Angulo-Sánchez. “Polypropylene Chain Scissions and Molecular Weight Changes in Multiple Extrusion.” Polymer Degradation and Stability 60,
no. 1 (April 1998): 33–42. https://doi.org/10.1016/S0141-3910(96)00233-9.
 Additive manufacturing

DPP is higher level of

(a) Fused Filament Fabrication (FFF) (b) Direct Pellet Printing (DPP) degradation than FFF

Gradwohl, Marion, Feng Chai, Julien Payen, Pierre Guerreschi, Philippe Marchetti, and Nicolas Blanchemain. “Effects of Two Melt Extrusion Based Additive Manufacturing Technologies and Common Sterilization
Methods on the Properties of a Medical Grade PLGA Copolymer.” Polymers 13, no. 4 (February 14, 2021): 572. https://doi.org/10.3390/polym13040572.
Conclusions
• Special attention should be paid to chromatography and rheometry,
as they can be seen as sensitive techniques to capture molecular
changes, even at initial stages of degradation.
• Among these parameters,the most important are the processing
temperature, processing speed, feed rate, screw type and screw
elements. Overall, it can be stated that parameters which increase the
residence time will induce a higher degree of degradation of the
material.