Group standard PV 3935

Issue 2023-01
Class. No.: 55104

Descriptors: EGA, Heart-Cut, HeartCut, Py-GC/MS, TD/Py-GC/MS, adhesive, aging process, anti-aging agent, anti-
static agent, coating, elastomer, mass spectrometry, multi-temperature range analysis, paint, plastic,
plasticizer, processing agent, pyrolysis, pyrolysis-gas chromatography, thermoplastic, thermoplastic
elastomer, thermoset material

Plastics and Elastomers

Py-GC/MS, TD/Py-GC/MS, Heart-Cut, EGA

Previous issues
PV 3935: 1998-05, 2017-03

Changes
The following changes have been made to PV 3935: 2017-03:
a) Section 4 „Designation“ updated and expanded
b) Standard edited and structure updated
c) Section 5.1.2.1 „Evolved gas analysis (EGA)“ expanded
d) Section 5.1.2.2 „Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS)“ expanded
e) Section 5.1.2.5 „Reactive pyrolysis“ added
f) Section 5.1.3.1 „Pyrolyzer“: Pyrolysis programs D and E in Table 1 expanded
g) Section 5.2 „Test procedure“ expanded
h) Section 6.2 „Qualitative evaluation“: Note on comparative evaluation expanded
i) Section 7 „Test report“: Changes in EGA thermogram expanded

Contents
Page
1 Scope ......................................................................................................................... 2
2 Definitions .................................................................................................................. 2
3 Abbreviations ............................................................................................................. 3
4 Designation ................................................................................................................ 4
5 Test ............................................................................................................................. 4
5.1 Test setup ................................................................................................................... 4
5.1.1 General ...................................................................................................................... 4
5.1.2 Analytical methods ..................................................................................................... 5
5.1.3 Analytical components ............................................................................................... 6
5.2 Test procedure ........................................................................................................... 9
6 Evaluation ................................................................................................................ 10
6.1 General .................................................................................................................... 10
6.2 Qualitative evaluation ............................................................................................... 10

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6.3 Semi-quantitative evaluation .................................................................................... 10

6.4 Quantitative evaluation ............................................................................................. 10
7 Test report ................................................................................................................ 11
8 Bibliography ............................................................................................................. 11
Appendix A Maintenance of the test fixture ................................................................................. 12
A.1 Tuning ...................................................................................................................... 12
A.2 Cleaning the analytical components ........................................................................ 12
A.3 Adapting the retention index .................................................................................... 12
Appendix B Measurement artifacts .............................................................................................. 13

1 Scope
This standard describes the analysis of polymers by means of pyrolysis-gas chromatography/mass
spectrometry (Py-GC/MS). This analytical method enables the evaluation of thermoplastics, elasto-
mers, thermoplastic elastomers, and thermoset materials (duromers), as well as any organic mate-
rials (deposits) and organic additives.
A big advantage of this method is that it makes it possible to analyze even insoluble, cross-linked
materials, for example, paints, adhesives, and coatings, which is not possible with other chemical
methods for structure determination. It also does not require complex specimen preparation. Infor-
mation about the materials and the organic additives, among other things, anti-aging agents, plasti-
cizers, anti-static agents, and processing agents, are obtained. In addition, comparative structural
changes due to aging processes or changes to materials can be determined.
Both a qualitative analysis and also, after calibration has been performed in advance, a quantita-
tive analysis are possible.

2 Definitions

Auto-tuning
Self-calibration of the mass spectrometry detector by means of a special standard substance
(here: PFTBA).

Chromatogram
Diagram with the detector intensity with respect to retention time.

Gas chromatograph
Device for separating evaporated and gaseous substances. Main components are injector, column,
detector, and oven.

Heart-Cut
Multi-temperature range analysis

Mass spectrometer
Universal detector in gas chromatography. Ionizes the substances in the ion source in a vacuum.
In the analyzer, the ions are separated and recorded in a changing electromagnetic field, e.g., a
quadropole field, as a function their ratio of mass to charge.
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Pyrolyzer
Device for the evaporation and thermal decomposition of predominantly organic compounds in in-
ert gas atmospheres.

Retention index
For the device-independent standardization of the retention times of the unknown analytes (Kovats
retention index) based on the relationship between carbon content and retention time.

Retention time
Dwell time of a substance in the gas chromatography system up to detection.

Split mode
Method for splitting the gas flow to be analyzed.

3 Abbreviations
DMC Dimethyl carbonate
EGA Evolved gas analysis
EI Electron impact ionization
EIC Extracted ion monitoring
GC Gas chromatography
HDMS Hexamethyldisilazane
MIC Characteristic mass traces in the chromatogram
MS Mass spectrometry
Py Pyrolysis
Py-GC/MS Pyrolysis-gas chromatography/mass spectrometry
S/N Signal-to-noise ratio
SIM Selected ion monitoring
TD/Py-GC/MS Pyrolysis-gas chromatography/mass spectrometry with preceding thermal
desorption (method used by default)
TIC Total ion current
TMAH Tetramethylammonium hydroxide
m/z ratio Mass/charge ratio
u Atomic mass unit; 1 u ≈ 1,66 × 10-27 kg
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4 Designation
Py-GC/MS as per PV 3935
or
TD/Py-GC/MS as per PV 3935
or
Heart-Cut-GC/MS as per PV 3935
or
EGA-MS as per PV 3935
or
Reactive pyrolysis-GC/MS as per PV 3935

5 Test

5.1 Test setup

5.1.1 General
The Py-GC/MS method combines three different processes:
1. The pyrolysis, which is performed first and in which the solid specimen is split into small frag-
ments under inert conditions and thus made available for the gas chromatography.
2. The second step is the gas chromatography separation of the resulting fragments.
3. The third step involves the detection and characterization of these fragments by means of a
mass spectrometer.
Figure 1 shows a schematic representation of a Py-GC/MS device with the individual components.
The stainless steel pan in which the specimens are located are moved into the pyrolyzer oven by
means of the optional autosampler.
The resulting gaseous substances are flushed by an inert gas flow (e.g., helium or nitrogen) via the
injector onto the gas-chromatography column that is located in a temperature-programmable oven.
At the start of the column, the substances from an optional upstream desorption process are fo-
cused with the help of a cryopump. Separation occurs on the column due to different boiling points
and interactions with the column coating.
At the end of the gas chromatography column, the substances are moved into the mass spectrom-
eter, where they are fragmented and ionized with an electron beam. The loaded fragments are se-
lected and then detected by a quadrupole analyzer. The data recording and the control of all com-
ponents are performed with the help of a computer.
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Legend
1 Autosampler (automatic sample- 6 Reversible flow unit (selective sam-
taking device) pler)
2 Pyrolyzer 7 Cryopump
3 Computer for data recording and 8 Gas chromatography column with
control of all components column coating
4 Selection unit for the carrier gas 9 Quadrupole analyzer
(carrier gas selector)
5 Inert gas and air supply
Figure 1 – Schematic representation of a Py-GC/MS device

5.1.2 Analytical methods

Different analytical methods can be performed with reference to the system described in
section 5.1.

5.1.2.1 Evolved gas analysis (EGA)

EGA uses a short, deactivated gas chromatography column without stationary phase. The outgas-
sing substances are moved directly to the detector without gas-chromatic separation. A thermo-
gram is obtained, which is similar to a thermogravimetric analysis (1st derivative) with an averaged
mass spectrum over all masses.
EGA can be used to examine the thermal decomposition behavior of polymers. This serves as a
starting method for the appropriate selection of temperatures for the methods in section 5.1.2.2,
section 5.1.2.3, and section 5.1.2.4. The pyrolysis temperature can provide information on the poly-
mer type.
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5.1.2.2 Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS)

The pan is moved into the oven that is preheated to the pyrolysis temperature, where the specimen
is instantly pyrolyzed and the fragments produced are moved into the gas chromatography column.
A pyrogram is produced and its fragmentation pattern can be used to draw conclusions on the pol-
ymer.

5.1.2.3 Pyrolysis-gas chromatography/mass spectrometry with preceding thermal

desorption (TD/Py-GC/MS) (default method)
This method provides information on volatile components and the polymer simultaneously. To do
this, in the first step, the sample is heated in a temperature range in order to out-gas the volatile
components (thermal desorption). These volatile components are trapped and analyzed by means
of GC/MS. In the second step, the remaining specimen is pyrolyzed and the polymer composition
is determined.

5.1.2.4 Multi-temperature range analysis (Heart-Cut)

This enables a multi-component system to be analyzed. With the Heart-Cut method, multiple tem-
perature ranges can be tested one after the other in order to determine the composition of the
components in the temperature range of interest.

5.1.2.5 Reactive pyrolysis

Some polymers that contain hydroxyl groups, carboxyl groups, or amino groups fragment into po-
lar, thermally unstable components. For example, a polyester forms very polar carboxylic acids.
For better detection, these components must be derivatized before GC/MS is used to detect them.
Typically, such components can be converted into less polar, stable derivatives by means of silyla-
tion or methylation. Hexamethyldisilazane (HMDS), dimethyl carbonate (DMC), and quaternary
ammonium salts, e.g., tetramethylammonium hydroxide (TMAH), can be used as reagents for the
derivatization.

5.1.3 Analytical components

5.1.3.1 Pyrolyzer
Different variants are available for carrying out the pyrolysis. Ideally, an oven pyrolyzer is used. Al-
ternatively, filament or Curie-point pyrolyzers could also be used.
A high heating rate and a precise end temperature are important in order to prevent undesired
fragmentation and to guarantee good reproducibility.
The pyrolysis program must be adapted to the respective specimen. For unknown specimens, by
default pyrolysis program A is applied.
Table 1 shows the pyrolysis programs, their use, and their parameters.
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Table 1 – Pyrolysis programs

Pyrolysis
Use Parameters
program

Polyolefins, polyamides, polyethers, polyethylene Thermal desorption: 100 °C to 300 °C at 15 K/min,

A terephtalate, acrylate polymers, polyvinyls with 10 min isotherm
styrene units, elastomers Pyrolysis: 700 °C, 2 min
Thermal desorption: 100 °C to 200 °C at 15 K/min,
B Polyurethanes, polyoxymethylene 10 min isotherm
Pyrolysis: 550 °C, 2 min
Thermal desorption: 100 °C to 400 °C at 15 K/min,
C For determining the retention index
10 min isotherm
D Evolved gas analysis 50 °C to 900 °C at 20 K/min
E Reactive pyrolysis 400 °C, 2 min

5.1.3.2 Gas chromatograph

The gas chromatographic separation is based on different migration rates of the substances to be
examined in a two-phase system. The stationary phases are coated metal or quartz glass columns
with lengths between 10 m and 200 m. The diameter of the gas chromatography columns is usual-
ly between 0,25 mm and 0,50 mm; the film thickness of the coating is ≤ 1 µm. The coating is often
a polysiloxane whose polarity can be adapted by means of organic groups to the substances to be
examined. If a very high polarity is needed, coatings based on polyalkylene glycol can be used. For
the analysis of polymers that contain halogens, such as PVC, PTFE, FVMQ, or FKM, it must be
ensured that hydrogen halide has been separated. This can otherwise lead to accelerated aging of
the GC/MS system and destruction of the gas chromatography column. An inert gas, such as heli-
um or nitrogen, functions as the mobile phase.
In addition to the interaction with the column coating and the solubility in the carrier gas, the tem-
perature at which the substances transition into the gas phase also has a large effect on the result-
ing retention times. Therefore, with a suitable oven temperature program for the gas chromatogra-
phy device, even very complex substance mixtures can be split. In addition, a two-dimensional
separation can be performed with two different columns connected in series.
To prevent the gas chromatography column from overloading and the detector from saturating, split
mode is selected for the gas chromatography program. Split ratios between 1 : 2 and 1 : 400 can
be used. This means that approximately 50% to 0,25% of the produced molecules are analyzed.
The rest of the specimen is removed via the split outlet. The split ratio must be adapted to the
specimen quantity. The smaller the specimen quantity is, the smaller the split ratio must be. It must
be selected such that the signal-to-noise ratio (S/N) is between 220 and 270 (average value deter-
mined using the standards benzo(a)pyrene-d12 and styrene-d8).
By default, the gas chromatography program uses the following basic parameters, with possible
deviations due to analytical reasons:
Temperature program: – 35 °C, 4 min isotherm
– 35 °C to 380 °C, 15 K/min, 10 min isotherm
– 380 °C to 320 °C, -20 K/min
– 320 °C to 35 °C, -100 K/min, 11 min isotherm
Injector temperature: 345 °C
Split: 1 : 40, 1 : 60
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Column: High temperature column with 5% diphenyl compo-

nent;
30 m; 0,25 mm inner diameter (ID); 0,25 µm film thick-
ness (df)
Column flow: 1 ml/min „linear velocity“

5.1.3.3 Mass spectrometer

A mass spectrometer is used to determine the masses of atoms and molecules. These are ionized,
and separated and detected as a function of the mass-charge ratio (m/z ratio).
The most frequent method for ionization is electron impact ionization (EI). The emitted electrons
usually have a higher energy than would be necessary for ionization, which leads to fragmentation.
The fragmentation pattern is characteristic for each substance, so that identification is possible us-
ing a database comparison.
The sum of all intensities in the mass spectrum represents the total ion current (TIC). The TIC is
measured in scan mode. If only the intensities of one or some m/z ratios are selected for display in
a measurement performed in scan mode, this is referred to as extracted ion monitoring (EIC). In
selected ion monitoring (SIM), only certain m/z ratios are detected during the measurement.
The mass spectrometer uses the following parameters:
Interface: ≥ 300 °C
Ion source: ≥ 250 °C
Scan range: At least 10 u up to 800 u
Scan rate: ≥ 5 000 u/s
Measurement start: 1 min
Measurement end: 37 min

5.1.3.4 Microbalance
A microbalance is used to determine the original weight of the specimen.
Tolerance: ≤ ±1 µg
Tare weight: At least specimen carrier mass
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5.2 Test procedure

For statistical quality validation, each specimen must be analyzed multiple times (at least twice).
The required number of specimen pans is provided in a pan holder.
The solutions of the internal standards (2,5 µl benzo(a)pyrene-d12 and benzo(g,h,i)perylene-d12 in
cyclohexane; 100 ng/µl for the desorption run and 2,5 µl polystyrene-d8 in polymethylstyrene-d10
methyl ethyl ketone; 100 ng/µl for the pyrolysis run) are sprayed into each pan by means of a mi-
croliter spray device, and the solvent is evaporated at room temperature as per Volkswagen stand-
ard VW 50554 – 2 until a constant weight has been reached.
If a different internal standard is used, it must be ensured in the selection that both for the desorp-
tion and also for the pyrolysis only one peak results in the mass spectrum.
From the specimen to be examined, a homogeneous part must be prepared and the mass must be
determined with a precision of ±1 µg. This specimen mass is selected so that the pure polymer
component, minus all of the components that cannot be pyrolyzed, is (150 ±10) µg. If this speci-
men quantity is not sufficient, the split ratio can be adapted accordingly.
For the properties and conditions of the specimen, such as water content, the same restrictions as
for GC/MS analyses with liquid injection apply to Py-GC/MS analyses. It must be ensured that a
sufficient quantity of liquid nitrogen is available if a cryopump is being used.
One of the methods described in section 5.1.2.1 to section 5.1.2.4 is performed on the specimens.
A modified preparation is prepared for the method described in section 5.1.2.5. Here, the polymer
to be studied is ground by means of cryogenic grinding. Of this ground polymer, a specimen of
100 µg mass (pure polymer content) is weighed into the specimen pan and a derivatization reagent
suitable for the polymer is pipetted into the pan.
Soluble polymers can be dissolved in a suitable solvent. A volume of the dissolved polymer equiva-
lent to 100 µg is pipetted into the pan and the derivatization reagent is added after the solvent has
evaporated.
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6 Evaluation

6.1 General
The method of evaluation must reflect whether qualitative and/or quantitative evaluation is re-
quired.

6.2 Qualitative evaluation

For a qualitative comparison, the chromatograms (with TIC) are laid one on top of the other. The
internal standards are used as fixed points (not for EGA).
The peaks that are determined to be distinguishing features during inspection of the chromato-
grams are characterized with the help of the MS databases (as well as proprietary libraries).
The analysis of an unknown substance will characterize all of the formed pyrolysis fragments or all
of the substances that can be desorbed, in order to be able to draw conclusions on the materials
being used or the origin of contaminants or deposits.
The fragmentation pattern of the unknown specimen must be compared with reference information,
e.g., [1], [2], or using software, e.g., F-Search 1).
For the analysis of known substances, the characteristic mass traces can be displayed in the chro-
matogram (MIC).
For the comparative evaluation, the thermograms are laid one on top of the other and the differen-
ces in the thermal decomposition are analyzed.

6.3 Semi-quantitative evaluation

For the semi-quantitative determination of a substance, the respective peak is integrated, the area
based on the peak area of the internal standard and on the original weight. The quantity (mg stand-
ard equivalent/g specimen) of the substance of interest is obtained.
It must be ensured that the resulting quantities do not involve results concerning the calibration of
individual substances, which would mean that the quantities of different substances could not be
compared with each other.

6.4 Quantitative evaluation

For the quantitative analysis of a substance (see literature reference [3]), a calibration must first be
performed in an appropriate concentration range of this substance. At least three, but preferably
five to ten calibration points must be selected.
From the peak areas of the substance to be examined, a concentration can be calculated using the
highlighted calibration function (in most cases, this is a linear regression).

1) F-Search is the manufacturer's identification of the product produced by Frontier Laboratories Ltd.
This information is only intended for informational purposes for the users of this in-house standard. This does not signify an en-
dorsement of the mentioned product by the Volkswagen Group. Equivalent products may be used if it can be verified that they lead
to the same results.
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7 Test report
The test report must include the test methods that were used. These include:
– the pyrolysis and the gas chromatography oven program
– the gas chromatography column that was used, and
– the scan range and the scan speed of the mass spectrometer
Depending on the stated problem,
– the interpretation of the characteristic substances,
– changes in the chromatogram, or
– the semi-quantitatively determined quantity of the detected substances,
– changes in the EGA thermogram (curve profile, shift of temperature maximum)
must be specified.
Raw data and chromatograms do not have to be included.

8 Bibliography
[1] Analytical Pyrolysis of Synthetic Organic Polymers, S.C. Moldoveanu, 2005
[2] Pyrolysis-GC/MS Data Book of Synthetic Polymers; Tsuge Shin, Ohtani Hajime, Wata-
nabe Chuichi, 2011
[3] Quantitative Pyrolysis - Gas Chromatography – Mass Spectrometry to Study Polymer
Dissolution and Solubility, Chojnacka, A., Dissertation University of Amsterdam, 2015
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Appendix A (normative) Maintenance of the test fixture

A.1 Tuning
Due to contaminants forming in the mass spectrometer, the detector voltage must be adjusted as
the number of measurements increases in order to maintain constant intensity values. This is ach-
ieved bu using automatic autotuning of a standard substance (PFTBA). Here, the intensities of cer-
tain mass traces are compared with a reference spectrum and the detector voltage is changed ac-
cordingly. We recommended performing autotuning before starting each new batch.

A.2 Cleaning the analytical components

Due to contaminants forming within the system, with an increasing number of measurements, the
analytical components must be cleaned at regular intervals.
Cleaning at an interval of every four weeks has proven effective for high measurement volumes.
In the case of the system from Frontier Laboratories, the cooled pyrolyzer is removed and the pyro-
lyzer tube is cleaned with a long cotton swab dipped in solvent. The septum, the injector needle,
and, if necessary, also the liner are replaced. If aging of the gas chromatography column is deter-
mined due to pronounced tailing or „column bleeding“, the column must also be replaced. The ion
source is removed and taken apart, and coarse contaminants are removed with a polishing pin, if
necessary with the help of a multi-purpose tool. Then it is cleaned in an ultrasonic bath in three
solvents of decreasing polarity (e.g., deionized water, ethanol, acetone, n-heptane). After it dries,
the ion source can be inserted again. The same procedure must be performed with the lens sys-
tem if the lens voltages increase (optionally by the service technician).

A.3 Adapting the retention index

To correct the retention time shift due to column aging, the retention indices in the methods being
used are adapted at regular intervals (e.g., four weeks). To do this, the retention times of a series
of straight (unbranched) aliphatic compounds (e.g., C5 to C44) are determined. Because their reten-
tion indices are known (nonane: 900; decane: 1 000; undecane: 1 100; etc.), the retention indices
for unknown substances can be calculated based on the measured retention times.
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Appendix B (normative) Measurement artifacts

If high molecular weight pyrolysis products do not elute completely from the gas chromatography
column, they appear as so-called memory effects in subsequent analyses and lead to incorrect in-
terpretations. To prevent memory effects, the GC software includes a heating phase. In unknown
specimens, memory effects can be identified and eliminated by an analysis without specimens.
Due to leaks in the system, the sensitivity of the detector is reduced and the aging process is ac-
celerated. Leaks can occur, among other things, when the temperature of components with threa-
ded connections changes. Leaks can be detected with the help of argon test gas (m/z = 40) and/or
with a leak detector based on a thermal conductivity detector.