METHODS FOR ANALYSIS OF PLASTICS
1. Wet Chemistry Techniques
2. Spectroscopic Techniques
3. Chromatographic Techniques
4. Thermal Techniques
5. Elemental Techniques
6. Microscopy Techniques
7. Miscellaneous Techniques
WET CHEMISTRY TECHNIQUE
- Used to determine information such as generic polymer type of a material.
- Used in PVC products, determines amount of PVC in the formulation by quantifying of chlorine.
Ex. Oxygen Flask method
SPECTROSCOPIC TECHNIQUE
- Used for identifying, quantifying composition of a material including water, residual solvents
and monomers.
- For quality assurance, measuring raw material purity and analyzing moisture content.
- used for troubleshooting in failure analysis. It can determine chemical compositions even those
of the smallest structures.
Ex. A) Infrared Spectroscopy (IR) – for plasticized plastics, this method requires extraction with the
use of solvent such as methanol, to remove plasticizers, which can interfere with the infrared data.
(i.e. ATR or Attenuated Total Reflectance Spectroscopy, a surface technique)
Ex. B) Ultraviolet Light Spectroscopy (UV) – used in the qualitative and quantitative analysis of
additives, particularly antioxidants and UV stabilizers.
Ex. C) Nuclear Magnetic Resonance Spectroscopy (NMR)- determines polymer structure
i. Solid state NMR- used to analyze insoluble polymers or those that do not melt.
ii. High temperature NMR- applied to studies of molten polymers or materials in special
high temp. solvents
iii. HR-MAS-NMR (High Resolution Magic Angle Spinning)- can provide detailed information
of polymers in solvent swollen or rigid-states.
Ex. D) Atomic Absorption Spectroscopy (AAS)- This technique, and the related inductively coupled
plasma (ICP), are used where it is necessary to quantify metals in a plastic compound. Although not
often required it can be of use in the analysis of flame retardant systems, where additives such as
antimony trioxide and zinc borate have been used.
Ex. E) X-Ray Fluorescence Spectroscopy- used to obtain semi- quantitative elemental data from
plastics and their ashes. It is also useful in identifying inorganic fillers and pigments in samples.
- Usually in conjunction with Infrared Spectroscopy (IR)
- In scanning contaminants, small scale samples, SEM/XRF, or scanning electron microscope/X-ray
Fluorescence, can be used.
- “energy dispersive analysis (Edax)”
Ex. F) Raman Spectroscopy- used for identification of polymer types and analysis of contaminants
within polymer samples.
CHROMATOGRAPHIC TECHNIQUE
Ex. A) Gas Chromatography- Mass Spectrometry (GC-MS) - a powerful and versatile technique that
can provide a significant amount of compositional information on plastic samples.
- It is used to identify minor components of the sample such as stabilizers, flame retardants, anti-
static agents and the crosslinking system.
- can also be used to investigate the polymer fraction within a sample when the instrument is
fitted with a pyrolysis unit set at around 600 °C.
- can also be used for failure analysis. This can identify odours and organic contaminants that may
cause degradation on the sample.
- There are a variety of ways that the sample or fractions of the sample (e.g., an extract) can be
analysed by GCMS. These include static headspace, dynamic headspace, solution injection and
pyrolysis.
Ex. B) Gas Chromatography- can identify polymer type via Pyrolysis.
- less powerful than GC with Mass Spectrometry. It also requires a “Pyrogram” fingerprint and a
library of known standards for comparison.
- used for the identification and quantification of additives such as antioxidants and, where
sufficient volatility exists, plasticisers and organic flame retardants.
Ex. C) High Performance Liquid Chromatography (HPLC)- used to identify and quantify additives that
are either too involatile or insufficiently stable to be determined by GC/GC-MS.
- also comes into its own in the quantification of plasticisers such as dioctyl phthalate (DOP).
Ex. D) Liquid Chromatography- Mass Spectrometry (LC-MS)-
- Particle Beam Interface: used to generate Electron Ionization Spectra (EI)
very good for qualitative work because the 70 eV spectra contain a significant amount of
structural information and can be searched against conventional mass spectra libraries.
However, in the full scan mode the sensitivity is restricted to the low nanogram levels.
- Atmospheric Pressure Ionization Interface: used to generate either electrospray (ESI) or
atmospheric pressure chemical ionisation (APCI) spectra and can generate either positive (i.e.,
molecular ion plus one hydrogen) spectra or negative (i.e., molecular ion minus one hydrogen)
spectra.
In the case of the API interface, both the electrospray and APCI modes are soft ionisation
techniques which leave the molecular ion (or pseudomolecular ion) intact without much
fragmentation. The interface therefore offers more sensitivity and is ideal for quantitative work
at low levels (e.g., contamination of drug and food matrices by polymer additives/ breakdown
products).
Ex. E) Gel Permeation Chromatography (GPC)- this technique requires the sample to be readily
soluble in an organic solvent.
- It is possible to obtain molecular weight data on both amorphous plastics and semi-crystalline
plastics.
** In the amorphous case (e.g., polystyrene), the system used is set around ambient
temperature (30 °C) and solvents such as THF, chloroform and toluene are used. With semi-
crystalline plastics (e.g., polyolefins), more aggressive solvents such as orthodichlorobenzene
and meta-cresol are used at elevated (140 °C) temperatures.
Ex. F) Thin Layer Chromatography (TLC)- a relatively simple technique that can be used for
both the separation and identification of additives such as antioxidants and UV stabilisers.
- can be used in a preparative way for the isolation of sample fractions for subsequent
chromatographic or spectroscopic analysis
- old- fashioned technique
THERMAL TECHNIQUE
Ex. A) Differential Scanning Calorimetry (DSC)- used extensively in the analysis of plastics, particularly
those that are semi-crystalline - polyolefins, nylons, polyesters, etc.
- it is sensitive enough to differentiate between different polyethylenes (i.e., LDPE, LLDPE, HDPE,
etc.) from their melting points and the appearance of their melting endotherms as well as being
able to detect and, with appropriate standard materials, quantify plastic blends, e.g., PP/PE and
nylon 6/nylon 6,6.
- It is also possible for providing quality control fingerprint thermograms from which deviations in
the composition of a plastic compound can be detected. One reason for this is that although the
technique is not capable of determining the molecular weight of a plastic, differences in
molecular weight will be apparent in the melting endotherm region.
- It can also determine the quantity of certain level of additives in a sample.
- can also be used in thermal stability studies of the plastic compound, and to investigate the
effectiveness of anti-degradants and fire retardants.
Ex. B) Dynamic Mechanical Thermal Analysis (DMTA) - very useful for generating modulus versus
temperature data on plastic compounds. The effects of temperature on this important material property
can be obtained over a wide temperature range (typically –150 °C to +200 °C), along with the glass
transition temperature and information on thermal stability.
- The sensitivity of DMTA to glass transition temperatures (approximately 1,000 times greater
than DSC which measures heat capacity changes rather than modulus) is very useful in the
analysis of plastics and their blends
Ex. C) Thermogravimetric Analysis (TGA)- useful in the analysis of compounded plastic samples. It is
possible to obtain accurate quantifications of the principal compound constituents such as plasticiser,
polymer and inorganic species. This data can be obtained on small (e.g., 10 mg) samples in a relatively
short time (around 45 minutes). By the use of the temperature maxima at which weight events occur it
is also possible to use the technique to obtain some qualitative assignments for the plasticiser and
polymer.
- Also for production of compositional fingerprints for quality control purposes and the
investigation of thermal stability and the effects that additives such as flame retardants and
antioxidants have on it.
ELEMENTAL TECHNIQUE
- Determination of concentration of elements.
- Amounts of nitrogen and halogens are necessary to be determined.
MICROSCOPY TECHNIQUE
- High magnification (e.g., 150x) optical microscopy can be used to examine the dispersion of
fillers within the plastic matrix.
- Transmission electron microscopy (TEM) can be used to investigate the phase morphology of
polymer blends and the dispersion of fillers.
MISCELLANEOUS TECHNIQUE
- X-ray diffraction (XRD) to identify between different crystalline forms of inorganic additives
(e.g., rutile and anatase forms of titanium dioxide) and direct probe mass spectroscopy (for the
determination of high molecular weight antioxidants).
- Surface analysis techniques such as secondary ion mass spectrometry (SIMS), laser induced
mass analysis (LIMA) and X-ray photoelectron spectroscopy (XPS) are used for failure diagnosis
work associated with such things as poor bonding to substrates and for surface characterisation
work.
- supercritical fluid chromatography (SFC). This is essentially a liquid chromatography technique
that uses similar analytical columns to HPLC but where the mobile phase is a substance (e.g.,
carbon dioxide) that is kept in a supercritical state by a suitable combination of temperature and
pressure. One of the benefits of the technique is that the analytes can be easily separated from
the mobile phase once the chromatography has taken place so, for example, they can be
deposited on infrared transparent substrates for analysis using an infrared microscope
