Rubber and Plastic Materials Characterization Using

Micro-Furnace Multi-Mode Pyrolysis-GC/MS

1
Copyright © 2020 Frontier Laboratories Ltd.
 Why Pyrolysis-GC/MS?
Manufacturers are always seeking new technologies and developments that increase production efficiency and the
quality of the produced parts. Many analytical protocols used to analyze rubber and plastic components require
multi-step sample preparation prior to chromatographic analysis.
These procedures often include solvent extraction, filtration, and concentration. These traditional techniques are
cumbersome, time-consuming, and suffer from analyst-to-analyst variability while producing data of limited value.
Samples are analyzed “as is” when using the Frontier Micro-Furnace Pyrolyzer. No sample preparation is needed.
Eliminating the solvent extraction process enhances the precision of quantitative analysis while virtually prevent
sample contamination and improves analytical efficiency. These are three of the primary reasons many
manufacturing and polymer development laboratories utilize the Frontier Pyrolyzer.
The Multi-Shot Micro-Furnace Pyrolyzer can be configured in a number of different
ways, so that a sample can be characterized using various analytical techniques,
including evolved gas analysis, thermal desorption, flash pyrolysis, double-shot,
Heart-Cutting of individual EGA thermal zones, and reactive pyrolysis.
Initially, such diversity may be perceived as a
complicated decision process: what analytical
mode will give us the most insight into the nature
of the sample in the least amount of time? To
assist, Frontier scientists have created a “method
map” for material characterization. An overview
of the “method map” is provided on page 44.

FRONTIER LAB FRONTIER LAB 2

2
 Table of Contents
Use the bold numbers to bring you straight to the corresponding page.

A. Rubbers

A-1 Determination of Antioxidants in NBR Rubber A-7 Structural Characterization of Hydrogenated

A-2 Analysis of Compounded Rubber Acrylonitrile-Butadiene Rubbers
A-3 Compositional Analysis of Isoprene-Butadiene- A-8 Effect of Separation Conditions to Analysis
Styrene Blend Rubber Accuracy of a Blend Rubber
A-4 Identification of an unknown Antidegradant in A-9 Determination of Fatty Acids in Vulcanized SBR
Rubber Rubber Using Reactive Pyrolysis-GC/MS
A-5 Analysis of Rubber Composition with EGA and
EGA polymer MS Library
A-6 Analysis of Acrylonitrile Butadiene Rubber (NBR)

B. Plastics

B-1 Analysis of Brominated Flame Retardant in a B-10 Determination of Phthalates in PVC by Thermal
waste Plastics Desorption GC/MS- Part 2
B-2 Polyphenylene Ether Resins and Filaments B-11 Effects of Thermal Desorption Temperature for
B-3 Polycarbonate (PC) Plastic Resins Phthalates in PVC
B-4 Analysis of Gases Released from Heated Food B-12 Differentiation of DOTP and DNOP
Wrap Films B-13 Antioxidants (Irganox 1076 and Irganox
B-5 Analysis of Food Wrap Film using EGA-MS 1010) In Polyethylene- Part 1
B-6 Evaluation of The Aged Deterioration of PE Pipes B-14 Antioxidants (Irganox 1076 and Irganox 1010) In
B-7 Analysis of Thermoset Resin Polyethylene- Part 2
B-8 Analysis of Additives in Polybutylene Terephthalate B-15 Quantitative Analysis of Phthalate Bis(2-Ethylhexyl)
B-9 Determination of Phthalates in PVC by Thermal Phthalate (DEHP) in Heat Resistant PVC Sheath
Desorption GC/MS- Part 1

FRONTIER LAB 3
 A-1
Determination of Antioxidants in NBR Rubber
❖ PROBLEM: What is the best method to TIC Elution of Additives Decomposition of Polymer Backbone
quantitate additives in rubber? A B

❖ SOLUTION: A piece of an acrylonitrile- Mass Chromatogram

butadiene rubber sample (NBR) weighing about NOCRAC 810-NA
1 mg is placed in an inert sample cup. Using the m/z=226

micro-furnace multi-mode pyrolyzer directly NOCRAC 6C

interfaced to a GC/MS system, the sample was m/z=268

analyzed. EGA and thermal desorption-GC/MS 50 100 200 300 400 500 600 ºC
modes of operations were used.
Fig. 1. Evolved Gas Analysis of NBR

❖ RESULT: The EGA thermogram of the NBR Table 1. Reproducibility of Area Ratios (vs ISTD) of NBR additives ISTD
sample, containing various types of additives, is
shown in Fig. 1. This suggests that the volatile n NOCRAC 810-NA NOCRAC 6C

components are desorbed in zone A. Fig. 2 1 0.113 0.139

2 0.118 0.140
shows the (TD)-GC/MS chromatogram of zone 3 0.119 0.144
NOCRAC 6C
A fraction. Table 1 shows the results that the 4 0.122 0.143 NOCRAC 810-NA
5 0.124 0.140
reproducibility of the relative peak intensities for 6 0.123 0.144
two types of antioxidants is less than 2% RSD. 7 0.123 0.144
8 0.124 0.143
Aver. 0.122 0.143
RSD 1.98 % 1.27 %

0 5 10 15 min

Fig. 2 Chromatogram for Zone A by (TD)-GC/MS analysis

NOCRAC810-NA: N-Phenyl-N’-isopropyl-p-phenylenediamine
NOCRAC 6C: N-Phenyl-N’-(1,3-dimethylbutyl)-p-phenylenediamine

FRONTIER LAB 4
 A-2
Analysis of Compounded Rubber Polymer main chain

❖ PROBLEM: How can a compounded rubber be Volatile components

analyzed using Multi-Shot pyrolyzer? What
information can be obtained?
100 200 300 400 500 600 700 ºC
Fig. 1 Evolved Gas Curve of a Compounded Rubber
❖ SOLUTION: A compounded rubber is analyzed by Pyrolysis temp.: 100 - 700 ºC (20 ºC/min), Carrier gas : He 50 kPa, Split ratio : ca. 1/20
Multi-Shot pyrolyzer operating in double-shot mode, EGA capillary tube : 0.15 mm id, 2.5 m (UADTM-2.5N), GC oven temp.: 300 ºC
Injection temp.: 320 ºC, Sample : ca. 5 µg, Detector : MS (m/z 29 - 400)
Thermal Desorption (TD), followed by flash
pyrolysis (PY). Following the “Method Map”
methodology, Evolved Gas Analysis (EGA) was first
performed to obtain the sample’s thermal profile. Fig.2a. Thermal Desorption Chromatogram (100 - 300ºC (20 ºC/min)
n-C30H62
2-mercapto thiobenzothiazole

❖ RESULT: Fig. 1 shows an EGA thermogram of a 2-methyl thiobenzothiazole Nocrac 6C

C16 acid n-C31H64
compounded rubber. Weak peaks are observed in D4
DOP
100~300 ºC zone due to the thermal desorption of D3
X10 D6
additives. In 300~500 ºC zone, a broad peak due to
thermal decomposition of the rubber is observed.
Fig.2b. Pyrogram (550 ºC )
From this result, thermal desorption was performed
from 100 to 300 ºC (20 ºC/min), and then flash isoprene
Dimer (limonene)
pyrolysis was done at 550 ºC. Fig. 2 shows results trimer
of analysis. In the chromatogram of thermal Butadiene tetramer
desorption shown in Fig. 2a, cyclic siloxanes
(D3~D6) originated from silicon coupling agent, 6 8 10 12 14 16 18
2 4 20 min
benzothiazole (vulcanization accelerator), higher
aliphatic acid (vulcanizing agent), and waxes Fig. 2 GC/MS Analysis of Compounded Rubber by Double-Shot Technique
(antioxidants) were observed. Because isoprene Column flow rate : 1 ml/min (fixed flow rate), Split ratio : 1/20, Separation column: Ultra
and limonene were mainly observed in the ALLOY+-5 (5% diphenyl polysiloxane), 30 m, 0.25 mm id, Film thickness : 0.25 µm; GC oven
temp.: 40 - 300 ºC (20 ºC/min), Sample : 5 µg, Detector: MS (m/z 29 - 400, 2 scans/sec)
pyrogram shown in Fig. 2b, the major component of
this sample is natural rubber.

FRONTIER LAB 5
 A-3 Compositional Analysis of Isoprene-Butadiene-
Styrene Blend Rubber
❖ PROBLEM: Is there a simple method to analyze the Butadiene
chemical composition of a blended rubber sample? Isoprene Styrene
Isobutene

❖ SOLUTION: About 200 µg of a rubber mixture,

composed of polybutadiene(PB)- polyisoprene (PI)-
polystyrene (PS), is placed in an inert sample cup and 0 10 20 min
pyrolyzed at 550 ºC using the micro-furnace multi-shot
pyrolyzer. Fig. 1 Pyrogram of standard sample
Pyrolysis temp.: 550 ºC, detector: FID, sample: standard sample A
Separation column: Ultra ALLOY+-5 (5% diphenyl 95% dimethylpolysiloxane)
Length: 60 m, id: 0.25 mm, film thickness: 1.0 µm
❖ RESULT: Fig.1 shows the pyrogram for the blend rubber GC oven temp.: 50 ºC (7 min hold) – 280 ºC (10 ºC/min), carrier gas: He
sample. The monomers of each component, which are Injection port pressure: 175 kPa, split ratio: 1/60, sample size: ca.200 µg
butadiene, isoprene and styrene, are the main
pyrolyzates. The calibration curves between relative
peak intensities for the specific peaks and the ratio of PB
to total weight of the sample shows a fairly good linear

Relative peak area (%)

relationship with a correlation coefficient greater than 10

0.99. The calibration curve for the PB composition in the

blended sample is shown in Fig.2. Using this calibration
curve, a fairly accurate determination of the component 5
is possible within 3% of accuracy.
0
0 10 20 30 40 50
Starting composition ratio (wt. %)

Fig. 2 Calibration curve for PB composition

FRONTIER LAB 6
 A-4
Identification of an Unknown Antidegradant in Rubber
❖ PROBLEM: Is there any library search system that
allows for the identification of unknown antidegradants (a) Chromatogram of the volatile components in the unknown rubber sample
used in rubber?

RI:1989 RI:3331183
184

❖ SOLUTION: The additive library for F-Search (mass RI:1080 91

124
(B)
(C)
338
spectra library search engine) contains data for 80 107
[m/z]
91
[m/z]
commercially available 32 typical antidegradants. The (A) [m/z]

library consists of mass spectra of major peaks on 4 6 8 10 12 14 16 18 min

chromatograms obtained by thermal desorption (TD)-
GC/MS method, chemical names, and retention
indexes. Analysis of a rubber that contains ca. 1% of
(b) Chromatogram of p-(p-Toluene sulfonylamido) diphenylamine in the MS library.
unknown antidegradant is described here.
RI:3338
p-(p-Toluene sulfonylamido)
RI:1986 diphenylamine
N-phenyl-1,4-
❖ RESULT: Fig. 1(a) shows the chromatogram of a RI:1084
benzenediamine
H O
S
H
N NH
p-Toluenthiol N
rubber sample containing an unknown antidegradant SH H2N
O

obtained by (TD)-GC/MS and mass spectra for major

peaks A, B and C. Major peaks were identified by 4 6 8 10 12 14 16 18 min
comparison of mass spectra obtained by library search
with their similarity and retention indexes (RI) as
shown in Fig. 1(b). Further, from the chromatogram in Fig. 1 Chromatograms obtained by TD-GC/MS technique
the library shown in Fig. 1 (b), the antidegradant Furnace temp.: 340 ºC (1 min), GC oven temp.: 40 – 320 ºC (20 ºC/min, 10 min)
Column: Ultra ALLOY-5 (MS/HT) (30 m, 0.25 mm, film thickness 0.25 µm), sample amount: 1.0 mg
candidate related to these three compounds was
estimated to be p-(p-Toluene sulfonylamido)
diphenylamine.

FRONTIER LAB 7
 A-5 Analysis of Rubber Composition with EGA
and EGA Polymer MS Library
❖ PROBLEM: What analytical technique can be used to analyze 41
67
79 91

a rubber of unknown components?? 171 55

105
57 119 133
146
158
70 219 172
❖ SOLUTION: The EGA-MS technique is a combination of 112
m/z
evolved gas analysis (EGA) and mass spectroscopy (MS)
using Multi-Shot Pyrolyzer and is very useful as a primary m/z
Peak B
analytical tool for unknown polymeric samples.
Peak A

❖ RESULT: An example on the right is the analysis of a rubber

with unknown composition. Shown in Fig. 1 are the EGA
thermogram of the rubber and mass spectra of peaks A and B 50 100 200 300 400 500 600 ºC
observed. Peak A is considered to arise from additives due to
low elution temperatures. To obtain further information,
Fig. 1 Evolved Gas Curve of a Rubber and Averaged Mass Spectra
components in peak A need to be analyzed by GC/MS. Peak Pyrolysis temp.:50 - 600 ºC (10 ºC/min), Carrier gas : He 50 kPa, 60 ml/min, Split
B is originated from thermal decomposition of the polymer ratio :ca.1/50
backbone. Table 1 shows the result of library search on the EGA capillary tube : 0.15 mm id, 2.5 m (UADTM-2.5N), GC oven temp. : 300 ºC
Injection temp.: 320 ºC, Sample :ca. 0.5 mg, Detector : MS, Scan range : m/z 29 - 400,
average spectrum of peak B using EGA-MS Library. Scan speed: 0.1 scans/sec; PY-GC interface temp.: 320 ºC (AUTO mode)
Polynorbornene and acrylonitrile-butadiene rubber were found
as candidate polymers. EGA and library search with EGA-MS
Library provide information on the amounts and desorption Name Qual
1. Polynorbornene : 49
temperatures of the additives contained in a sample, and is 2. Polynorbornene : 43
very useful for analysis of unknown materials as a primary 3. Acrylonitrile-butadiene rubber : 43
technique
Table 1 Result of Library Search on Peak B

FRONTIER LAB 8
 A-6 Analysis of Acrylonitrile Butadiene Rubber (NBR)
by Double-Shot Technique
❖ PROBLEM: Because polymeric materials are generally
blend of basic polymers and additives, pyrograms obtained
by conventional single-shot technique (instant pyrolyis)
include both additives and thermal decomposition products
of the basic polymer, and this often makes analysis difficult.
Fig. 1. Pyrogram of NBR by Single-Shot Technique (Total ion chromatogram)
Pyrolysis temp.: 550 ºC, Carrier gas : He, Column flow rate : 1.0 ml/min, Carrier total flow rate : 100 mL/min
❖ SOLUTION: Double-shot technique is useful because Separation column : Ultra ALLOY-5 (5% phenyldimethylpolysiloxane), 30 m, 0.25 mm id, Film thickness : 0.25 µm
GC oven temp.: 40 ºC (3 min) → 10 ºC/min → 300 ºC (3 min), GC injection port temp.: 320 ºC, Sample : 0.31 mg,
volatile components are thermally desorbed at the first stage, Detector : MS, Scan range : m/z 29 - 400
then instant (flash) pyrolysis of the basic polymer follows.

DOA
❖ RESULT: Analysis of NBR is described here as an example. DOP
a. First stage : Thermal desorption (100 → 20 ºC/min → 300 ºC (5 min))
Fig 1 shows a pyrogram of NBR by single-shot method. DOS
Thermal decomposition products and additives are shown
on a single pyrogram, it is difficult to distinguish the peaks of
basic polymer from those of additives. In the double-shot
technique (Fig. 2); however, volatiles and additives are DOA : Dioctyladipate
b. Second stage : Pyrolysis (550 ºC)
eluted off in the first step, whereas thermal decomposition DOP : Dioctylphthalate
DOS : Dioctyl sebacate
products of basic polymer come off in the second step,
allowing much easier identification of peaks. Conditions for
thermal desorption and pyrolysis can be determined from
EGA curve obtained in evolved gas analysis technique.
Fig. 2. Pyrogram of NBR by Double-Shot Technique
Analytical conditions are the same as above (Fig. 1.)

FRONTIER LAB 9
 A-7 Structural Characterization of Hydrogenated Acrylonitrile-
Butadiene Rubbers
❖ PROBLEM: Acrylonitrile-butadiene rubbers (NBRs) have
relatively low thermal stability due to the presence of
double bonds from butadiene (BD). Hence, hydrogenation
is required to improve the thermal stability. It is therefore
important to characterize their microstructures and
hydrogenation mechanism. compound class abbreviation sequence

Butadiene BD B

❖ SOLUTION: Hydrogenated NBRs were prepared by Butadienen dimer

(4vinylcyclohexane)
VC BB

dissolving NBR in THF followed by hydrogenation in the

Acrylonitrile AN A
presence of Pd catalyst. About 70 µg each of samples Hydrocarbons HC EE
was pyrolyzed at 550 ºC under nitrogen carrier gas (50 EEE

mL/min). The identifications of peaks were done by a Mononitriles MN(A) EA

EEEA
directly coupled GC-MS with both EI and CI sources. MN(B) EA
EEA
MN(C) EAE
MN(D) BA

❖ RESULT: Figure 1 shows the pyrograms of NBR samples Dinitriles DN AEA

at 550 ºC before and after the hydrogenation that were
obtained using a fused silica capillary column with B = 1,4-butadiene unit; A = acrylonitrile; E = hydrogenated 1,4-butadiene unit

poly(dimethylsiloxane) stationary phase. Characteristic

peaks in the pyrogram of N-37(0) were butadiene (BD) Figure 1. Pyrograms of NBRs before and after hydrogenation at 550 ºC
monomer, BD dimer, and acrylonitrile (AN) monomer; separated by a poly(dimethylsiloxane) column: (a) N-37(0); (b) N-37(44);
whereas those of hydrogenated NBR consisted of a series (c) N-37(98). See Table 1 for abbreviations. Numbers indicate carbon
numbers of compounds.
of linear mononitriles (MN(A)s) up to C12, each of which
consisted of a doublet corresponding to an -olefinic
MN(A) (the former) and a saturated MN(A) (the latter).
Another series of mononitrile positional isomers (MN(B)s)
are also observed. HC peaks of each carbon number
consisted of a triplet corresponding to an ,-diolefine,
and -olefin, and a n-alkane.

FRONTIER LAB 10
 A-8 Effects of Separation Conditions for Analysis Accuracy
in Composition Analysis of A Blend Rubber
❖ PROBLEM: The Py-GC technique is a useful analytical tool which offers facile and prompt compositional analysis of
various blend polymers. With this technique, however, not only peaks due to constituent monomers, but peaks due to
various by- products are also observed on the pyrograms and those peaks often overlap, causing the analytical accuracy
to be deteriorated. For example, in analysis of a three-dimensional blend rubber such as polybutadiene(PB) -
polyisoprene(PI) - polystyrene(PS), depending on the analytical conditions, peaks for butadiene, the monomer of PB,
and isobutene, a pyrolysis by-product may not be well resolved on the pyrogram. Here, in this technical note such effects
to the analytical accuracy were studied.

❖ SOLUTION: In the Py-GC system, the Micro-Furnace Multi-Shot Pyrolyzer directly attached to the split/splitless injection
port of a GC was connected to an FID via a capillary separation column. The GC separation conditions used were
conditions recommended by ISO 7270 (Condition A) and those used to separate isobutene and butadiene in this study
(Condition B). Composition ratios of unknowns are determined using a calibration curve generated from three standard
samples of varied composition ratios.

❖ RESULT: Fig. 1 (next page) shows a pyrogram of the PB-PI-PS blend rubber obtained using
Condition A, while Fig. 2 shows a pyrogram obtained using Condition B. On both pyrograms,
peaks due to the constituent monomers of butadiene (BD), isoprene (IP), and styrene (ST)
are observed as major peaks, however, in the pyrogram obtained with Condition A, peaks for
IB and BD were not resolved, so it is difficult to obtain the peak area of each peak by
integration using a vertical drop line.

FRONTIER LAB 11
 Therefore, in calculation of a triplet corresponding to an IB+BD IP
,-diolefine, and -olefin, and a n-alkane of composition ST
ratio, peak area was obtained from two peak areas
combined and was used as peak area for BD.
2 3min
0 5 10 min

On the other hand, in the pyrogram obtained with Figure 1. Pyrogram of a blend rubber obtained with conditions recommended by ISO7270 (Condition A)
Condition B, peaks for IB and BD are marginally resolved, Pyrolysis temp. : 550 ºC, Detector : FID, Separation column : Ultra ALLOY+-5 (5%-diphenyl-95%-
thus the peak area of each was obtained by integration diphenyl-95%-dimethylpolysiloxane); Length 30 m, 0.25 mm id, Film thickness 1.0 µm; GC oven temp. :
using a vertical drop line. 50 ºC (2 min hold) – 280 ºC (10 ºC/min), Injection port pressure : 175 kPa, Split ratio : 1/60, Sample
size : ca.200 µg

Table 1 shows starting composition ratios and IB

BD IP
composition ratios obtained with both conditions. In the
results obtained with Condition A, composition ratios were ST
obtained with fairly good accuracy, but with regard to PB,
relatively large error of -0.8 wt% are shown. 4.5 6.5min

0 10 20 min

On the other hand, composition ratios obtained with Figure 2. Pyrogram of a blend rubber obtained with conditions used in this study (Condition B)
Condition B gave a good accuracy and even the largest Separation column : Ultra ALLOY+-5 (5%-diphenyl-95%-dimethylpolysiloxane), Length 60 m,
error made was mere +0.2 wt% for PS. 0.25 mm id, Film thickness 1.0 µm; GC oven temp. : 50 ºC (7 min hold) – 280 ºC (10 ºC/min),
Other conditions are the same as those in Fig. 1.

PB PI PS
Starting composition ratio 37.2 25.0 37.8
With Condition A 36.4 25.2 38.4
(error) (-0.8) (+0.2) (+0.6)
With Condition B 37.1 24.9 38.0
(error) (-0.1) (-0.1) (+0.2)

Table 1. Composition ratios for unknowns and starting material (wt%)

FRONTIER LAB 12
 A-9 Determination of Fatty Acids in Vulcanized SBR
using Reactive Pyrolysis GC/MS
❖ PROBLEM: Various additive packages are added to SBR to vary the chemical and physical properties of the polymer.
The qualitative and quantitative analysis of these additives generally requires sample pretreatment, such as solvent
extraction, to isolate or concentrate the additives of interest.
For example, when analyzing SBR for the total amount of fatty acids, the sample is first extracted using ethanol/toluene
followed by titration (ISO 7781 and JIS-K6237); however, this method requires large amounts of solvent, excessive
analyst time, and is prone to contamination. The result of this additional ‘sample handling’ reduces laboratory productivity
and results often exhibit poor precision and accuracy.

❖ SOLUTION: Fatty acids are reactive; the GC peak tails which degrades the
accuracy and precision of the peak integration. For this reason, fatty acids are
analyzed as methyl esters. Methyl esters are inert, and the GC peaks are
symmetrical.
The most efficient method to determine fatty acids in a complex mixture like
rubber is reactive-pyrolysis using an organic alkali like tetramethylammonium
hydroxide (TMAH).

TMAH hydrolyses the acid and forms the ester at temperatures beyond 250 ºC.
This technical note demonstrates reactive pyrolysis-GC/MS using TMAH to
determine the fatty acids (stearic acid, and palmitic acid) in vulcanized SBR.

FRONTIER LAB 13
 Methyldehydroabietate

a) TIC
❖ EXPERIMENTAL: The analysis of the rubber was done Methyl stearate
2-(methylmercapto)
using a micro-furnace multi-shot Pyrolyzer (EGA/PY- benzothiazole
Methyl palmitate

3030D) directly interfaced to the injector of a GC/MS. The

analysis was automated using an Auto-Shot Sampler (AS-
1020E). The separation column was an Ultra ALLOY-5 8 9 10 11 min
metal capillary column. A Micro Puncher (2 mm) was used
to cut a plug of sample (200 µg) which was placed in a b) M+ (m/z 270)
sample cup. Next, 2 µL of 25 wt% TMAH was added to the Methyl palmitate

cup and the cup was placed in the Auto-Shot carousel. The
sample cup was subsequently dropped into the hot zone
(350 ºC) of the quartz liner. The derivatized fatty acids were c) M+ (m/z 298) Methyl stearate

swept though the GC splitter and focused at the separation

column inlet.
8 9 10 11 min

Fig. 1 Chromatogram of vulcanized SBR obtained by reactive pyrolysis-GC/MS

❖ RESULT: The total ion chromatogram of the products Pyrolysis temp.: 350 ºC, GC oven temp.: 70 – 280 ºC (20 ºC/min, 2 min hold), GC inj temp.: 300 ºC
formed using reactive pyrolysis have peaks for the methyl Separation column: Ultra ALLOY+-5 (5% diphenyl 95% dimethylpolysiloxane), L=30 m, i.d.=0.25 mm,
df=0.25 µm; Column flow rate: 1 mL/min (He), split ratio: 1/100, sample weight: approx. 200 µg
esters of palmitic (C16:0) and stearic acid (C18:0) - Fig. 1a.
No peak tailing is observed in the extracted ion
Quantitated values (wt%) of fatty acids in
chromatograms of the M+ ions - Fig.1b and Fig.1c. The vulcanized SBR
concentration of each acid was determined to be 0.16 wt% < formulation concentration 0.6 wt% >
(C16:0) and 0.46 wt% (C18:0) using the peak area of the
M+ ions and a single point external standard calibration. Sample wt. (μg) Palmitic acid Stearic acid
Total fatty acid
Total fatty acid concentration is 0.62 wt% which is in good contents

agreement with the original formulation concentration of 0.6 197 0.160 0.456 0.616
wt%. The precision (n=5) of the individual fatty acids 194 0.155 0.441 0.596
determinations is 2.1 and 3.8 % RSD 203 0.152 0.449 0.601
202 0.156 0.479 0.635
204 0.159 0.479 0.639
Average 0.156 0.461 0.617
RSD (%) 2.12 3.84 3.16

Table 1 Quantitation of total amount of fatty acids in vulcanized SBR and reproducibility (n=5)

FRONTIER LAB 14
 B-1 Analysis of Brominated Flame Retardant in a Waste
Plastics
❖ PROBLEM: In the analysis of brominated flame retardants, to be controlled
under the Restriction of Hazardous Substances (RoHS directive), GC analysis
is generally conducted after solvent extraction, although, it involves
cumbersome operations. Therefore, simpler analytical technique needed to
be developed. Here, the analysis of decabromodiphenyl ether (DeBDE), a
most commonly used brominated flame retardant is achieved by thermal
desorption (TD)-GC/MS technique.

❖ SOLUTION: A TD-GC system in which a micro-furnace multi-shot pyrolyzer

was directly attached to the split/splitless injection port of a GC was used. A
polystyrene (PS) based waste plastic containing brominated flame retardants
was used as a sample, and an aliquot (5 µL) of THF solution (10 µg/µL) was
placed in a sample cup for analysis. The temperature of the PY-GC interface
and the GC injection port was set to 320 ºC, at which temperature no
absorption or thermal decomposition of DeBDE has been reported. A metal
capillary column specifically designed for brominated flame retardants [Ultra
ALLOY-PBDE] with highly deactivated inner wall was used.

FRONTIER LAB 15
 400 799
232
299
❖ RESULT: Fig. 1 shows evolved gas analysis (EGA) 459 719
640 959
Thermal decomposition of PS
curves of waste plastic, which was obtained in order to x 106
0 200 400 600 800 1000 m/z

find optimum thermal desorption conditions. The major 4 (a) TIC

Desorption of DeBDE
peak between 400 and 500 ºC proved to be derived 3 Residual solvents and oligomers x5
from thermal decomposition of the base polymer PS. 2
Also a small peak observed between 250 and 350 ºC 1
0
showed m/z 799 and m/z 959 (molecular ion) on the 100 200 300 400 500 ºC
x 103
average mass spectrum, hence it was considered to be 2 (b) m/z 959
due to thermally desorbed DeBDE. 1
0
100 200 300 400 500 ºC
From this result, the optimal thermal desorption
temperature for DeBDE was determined to be 200~400 Figure 1 EGA curve of waste plastic
Pyrolysis temp.: 50 - 550 ºC (20 ºC/min), GC oven temp.: 300 ºC, Column flow rate: 1 mL/min,
ºC (20 ºC/min). With this thermal desorption condition, split ratio: 1/50, GC/MS ITF temp.: 320 ºC; MS ion source temp.: 250 ºC, scan range: 29-1000 (m/z),
the quantitative analysis of DeBDE in the waste plastic scan rate: 0.2 scan/sec, sample size: 50 µg

was performed by the TD-GC/MS technique.

Peak area of DeBDE

Fig 2. shows a chromatogram obtained, giving well- (x 106, m/z 799)
Quantity determined: 7.1%
resolved peaks without interferences from coexisting 1 17.05
species. By this method, it was confirmed that the 2
3
18.15
18.78
DeBDE
Styrene trimer
waste plastic contained 7.1 wt% of DeBDE, with a good 4 19.07
reproducibility (RSD=3.5%). 5 18.30
Average 18.27
RSD (n=5) 3.5 % NoBDE

5 10 15 min

Figure 2 Chromatogram of waste plastic obtained by TD-GC/MS

Pyrolysis temp.: 200 - 400 ºC (20 ºC/min), Separation column: UA-PBDE (polydimethylsiloxane, length 15 m,
0.25 mm id, film thickness 0.05 µm), Sample size: 50 µg; Column flow rate: 1 mL/min, Split ratio: 1/50,
GC/MS ITF temp.: 320 ºC, MS ion source temp.: 230 ºC, Scan range: 29 - 1000 (m/z), Scan rate: 3 scans/sec

FRONTIER LAB 16
 B-2
Polyphenylene Ether (PPE) Resins and Filaments
❖ BACKGROUND: Poly(p-phenylene oxide)(PPO) or poly(p-phenylene ether) (PPE) is a high-temperature thermoplastic. It is rarely
used in its pure form due to difficulties in processing. It is mainly used as a blend with polystyrene, high impact styrene-butadiene
copolymer or polyamide. PPO is a registered trademark of a commercial Innovative Plastics and is commercially known as Noryl.
There is a high interest in using PPO or PPE for 3D Printing. PPE blends are used for structural parts, electronics, household and
automotive items that depend on high heat resistance, dimensional stability, and accuracy. They are also used in medicine for
sterilizable instruments made of plastic. This plastic is processed by injection molding or extrusion; depending on the type, the
processing temperature is 260-300 ºC. The surface can be printed, hot-stamped, painted or metalized. Welds are possible by
means of heating element, friction or ultrasonic welding. It can be glued with halogenated solvents or various adhesives.

❖ PROBLEM: Although PPE is a commonly

used high performance polymer resin, their
properties and formulation chemistry vary
with different formulators and manufacturers.
While IR spectroscopy can be used for
screening, it is not sufficient for composition
determination or distinguishing the presence
of PPO resins or sources.

❖ SOLUTION: Perform EGA followed by a

single shot analysis to confirm the presence
of the PPE or its other polymer contents and
the general presence of other additives of a
commercial filament.

FRONTIER LAB FRONTIER LAB 17

17
 ❖ EXPERIMENTAL: Around 100 μg of an extruded filament from commercial pellet was cut into an inert Eco-Cup and placed
in the auto sampler. To perform EGA, the micro-furnace was then programmed from 100 to 800 ºC (20 ºC/min). The GC
oven was kept isothermal at 320 ºC. A single shot analysis was done at 600 ºC, determined from EGA thermogram. The
oven temperature is programed to equilibrium at 40 ºC for 2 min, increase to 320 ºC by 20 ºC/min and hold 320 ºC for 10
minutes. The result was analyzed by F-search library of component.

❖ RESULT: The EGA chromatogram demonstrated the PPE filament starts to degrade at 440 ºC and will be totally degraded at
600 ºC. The EGA-MS was created by summarize the spectra from 440 ºC to 600 ºC. Library search is done by F-search,
which fits well with the EGA-MS of sample.
[%] 110 121
100
EGA-MS of PPE filament
90
80 107
70
60
50 77 91 135 242

40
[%] 110 30 362
228 256
100 20 376
39 51 65 165
90 211 348
10 496
80 288 430 540 602
0
70 m/z --> 0 100 200 300 400 500 600
60
[%] 110
50 121
100 Library search of PPE
40
90
30
20 80
70 107
10
0 60 135 242
100 300 500 700
50
Temperature (oC) 40 77 91 362
30 228
376
20 348 482
39 51 65 165 211
10
0 588
m/z --> 0 100 200 300 400 500 600

FRONTIER LAB 18
 By utilizing pyrolysis at 600 ºC, the fragments of PPE filament can be studied. o-Cresol, dimethylphenol and
trimethylphenol were detected which suggested the presence of monomer. Dimers were also detected from 10 min to
15 min, while trimers were observed at 17 min. These results proved the presence of PPE polymer.

[%] 110

100
90
80
70
60
50
40
30
20
10
0
min --> 0 5 10 15 20 25

Polyphenylene ether(PPE)

FRONTIER LAB 19
 Thermal Desorption (TD) mode of operation was also used
to confirm the presence of two additives. TD was [%] 100 TIC
performed from 100 - 380 ºC. The Total Ion Chromatogram
(TIC) is shown on the right-hand side. Below are the
50
Extracted Ion Chromatograms (EICs) of m/z 84 and m/z
149 indicates N-Butylidenebutylamine and Dibutyle
Phthalate (DBP), respectively. 0
min --> 0 5 10 15 20 25

EIC EIC
[%] 100 [%] 100
m/z 84 m/z 149

50 50

0 0
min --> 0 5 10 15 20 25 min --> 0 5 10 15 20 25

[%] 110 [%] 110 149

100
84 100
90 Mass Spectrum of PPE @6.308 min 90 Mass Spectrum of PPE @13.405 min
80 80
70 70
60 57 60
50 50
40 41 40
30 70 30
20 20
10 30
99 112 10 41
57 76 93
104 121 205 223
160 184 255 281 295 315 341 355 377 401 432445 470 488 508 535
0 126 147 167 207 255 267 327 341 429 0
m/z --> 0 100 200 300 400 500
m/z --> 0 100 200 300 400
[%] 110 [%] 110 149
100
84 100
90 Reference of N-Butylidenebutylamine 90 Reference of Dibutyl phthalate (DBP)
80 80
70 70
60 60
50 57 50
40 40
30
42
70 30
20 29 20
10
99 112 10 41 65 76 93104 121 205 223 278
0
126 209 0
m/z --> 0 100 200 300 400 500
m/z --> 0 100 200 300 400

FRONTIER LAB 20
 B-3
Polycarbonate (PC) Plastic Resins
❖ BACKGROUND: Polycarbonates (PC) are a group of thermoplastic polymers containing carbonate groups in their
chemical structures. Polycarbonates used in engineering are strong, tough materials, and some grades are optically
transparent. They are easily worked, molded, and thermoformed. Because of these properties, polycarbonates find many
applications. Unlike most thermoplastics, polycarbonate can undergo large plastic deformations without cracking or
breaking. As a result, it can be processed and formed at room temperature using sheet metal techniques, such as
bending on a brake. Even for sharp angle bends with a tight radius, heating may not be necessary. This makes it valuable
in prototyping applications where transparent or electrically non-conductive parts are needed, which cannot be made from
sheet metal. This highly desirable engineering polymer material offers excellent chemical resistance and ductile properties
suitable for various applications.

❖ PROBLEM: Although PC is a highly desirable resin, their properties and formulation chemistry vary with different
formulators and manufacturers. While IR spectroscopy and be used for screening, it is not sufficient for composition
determination or distinguishing the presence of PC resins or sources.

❖ SOLUTION: Perform EGA followed by a single shot analysis using the Micro-
Furnace Pyrolyzer to confirm the presence of the PC or its other polymer contents
and the general presence of other additives.

FRONTIER LAB 21
 ❖ EXPERIMENTAL: About 100 µg of commercial PC filament was cut from a commercial PC filament to perform EGA from
100 to 800 ºC (20 ºC/min). The GC oven was kept isothermal at 320 ºC. Flash pyrolysis technique was done using single
shot mode at a 620 ºC. The oven temperature is programed to equilibrium at 40 ºC for 2 min, increase to 320 ºC by 20
ºC/min and hold 320 ºC for 10 minutes.

❖ RESULT: The EGA thermogram demonstrated

that the PC filament start to degrade at 320 ºC
and will be totally degraded at 600 ºC. Library 110
[%]
search is done by F-search, which fits well with 100 213

the EGA-MS of sample, giving a result of good 90

Unknown Mass Spectrum of EGA-MS result
80
fitting with PC reference.
70 (11.986 to 23.026 min)
60
50
40
30
[%] 110 119
20 228
100 39 65 77 91
90 10 55 107 239
29 134 165 197 506 543 567
80 0 282 301 332 369 390 418 445
70 m/z --> 0 100 200 300 400 500 600
60 [%] 110
50 100 213
40
90
30
Reference of Polycarbonate(solution method) ; SM-PC
20 80
10 70 (F-search Library reference)
0 60
min -->100 300 500 700
Temperature (oC) 50
40
30
20 119 228
91
10 39 65 77 107
165 197
181 303 329
0 389 407
m/z --> 0 100 200 300 400 500 600

FRONTIER LAB 22
 The single shot GC/MS was analyzed by F-search compound library. A major peak of bisphenol A is detected,
demonstrating the breaking of ester bonds. Phenol, cresol and isopropylphenol were detected which
demonstrate the C-C breaking at higher temperature. This result proves the presence of PC.

[%]110

100
90
80
70
60
50
40
30
20
10
0
min --> 0 5 10 15 20 25

FRONTIER LAB 23
 B-4 Analysis of Gases Released from Heated Food
Wrap Films
❖ PROBLEM: How can gases released Table 1 Additives of Food Wrap Films
Basic polymer Organic additives labeled on the package
from food wrap films at high temperatures tributyl aconitate tributyl acetylcitrate
PVDC Fatty acid derivatives, Epoxidized vegetable oil
be analyzed?
PVC Chlorinated fatty acid esters, Epoxidized vegetable oil O
O
O
O
O
O
PE None O
O
O
O
O
O
O
O
PP+Nylon Olefinic hydrocarbons, fatty acid derivatives
❖ SOLUTION: Using Micro-furnace Multi-
Shot Pyrolyzer, evolved gases from
triethylene glycol fatty acid ester
various food wrap films that were exposed O
O
O
H
H
O
●
adipic acid ester
● ●
to 100 ºC for 10 min were analyzed.

❖ RESULT: Table 1 shows basic polymers n-C14

of the food wrap films analyzed and

organic additives labeled on the package. n-C12 n-C16

Fig. 1 shows chromatograms obtained by

(TD)-GC/MS analysis of evolved gases fatty acid ester
collected with MicroJet Cryo-Trap. Upon caprolactam
●
quantitative analysis, it was found that acetic acid
triacetin

levels of each component were 100 ppm ●

or less.
0 5 10 15 min

Fig. 1 Chromatograms of Evolved Gases from Food Wrap Films Exposed to 100 ºC for 10 min
Pyrolysis temp: 100 ºC, Carrier gas: He, column flow rate: 1.0 mL/min, carrier gas total flow rate: 60 mL/min,Cryo trap: 10 min,
separation column: Ultra ALLOY+-5 (5% diphenyl dimethyl polysiloxane), length: 30 m, id: 0.25 mm, film thickness: 0.25 µm, GC oven
temp: 40 - 320 ºC (20 ºC/min), GC injection port temp: 320 ºC, sample: 9 cm2, MS scan rage: m/z 29 - 400, scan rate: 2 scans/sec

FRONTIER LAB 24
 B-5 Analysis of a Food Wrap Film (Polypropylene
and Nylon) using EGA-GC/MS
Zone A Zone B
❖ PROBLEM: When heated, volatiles are released
from food wrap film (polypropylene + nylon). How
can the analysis be performed?

40 100 200 300 400 500 600ºC

❖ SOLUTION: The analysis can be performed using
a Multi-Shot Pyrolyzer. Using EGA-MS technique,
EGA profile is obtained by programmed pyrolysis Fig. 1 EGA Profile of Polypropylene + Nylon
Pyrolysis temp: 40 – 600 ºC (30 ºC/min), carrier gas: He
from 40 to 600 ºC at a ramp rate of 30 ºC/min. Then, Interface: deactivated metal capillary column (length: 2.5 m, id: 0.15 mm)
Zone A and Zone B of the EGA profile are analyzed Injection port pressure: 50 kPa

by (TD)-GC/MS using MicroJet Cryo-Trap.

●：fatty acid ester
●
❖ RESULT: Fig. 1 shows the EGA profile acquired -caprolactam
using EGA-MS technique. The results of (TD)- Zone A acetic acid
● ●
(100~320ºC ) ●
GC/MS analysis of Zones A and B obtained utilizing
● ●
MicroJet Cryo-Trap are shown in Fig. 2. In Zone A,
volatile acetic acid, and fatty acids and their
derivatives as plasticizer were found. In Zone B, Zone B n-C’6
olefinic hydrocarbons of C6 , C9 , C12, and C15 (320~600ºC)
derived from pyrolysis of polypropylene, and ɛ-
caprolactam, monomer of nylon-6, were observed. 0 5 10 15 min

Fig. 2 Analysis Results of Zones A, B, and C of Polypropylene + Nylon

Carrier gas: He, column flow rate: 1 mL/min, total carrier gas flow rate: 40 mL/min, separation column: Ultra
ALLOY-5 (5% diphenyl dimethyl polysiloxane), length: 30 m, id: 0.25 mm, film thickness: 0.25 µm, GC oven
temp: 40 ºC (1 min hold) - 320 ºC (20 ºC/min), injection port temp: 320 ºC, Cryo trap temp: -196 ºC, sample:
0.25 cm2

FRONTIER LAB 25
 B-6 Evaluation of The Aged Deterioration of PE Pipes
Used for a Hot-Water Heating System
❖ BACKGROUND: A variety of additives are added to
polymeric materials to suppress the aged deterioration.
Information on the degradation of additives over time is
useful to evaluate the life of polymer products. Thermal
desorption (TD)-GC/MS has been widely used for
polymer additive analysis, because cumbersome
pretreatments, such as solvent extraction, are not
necessary. This note describes the results of TD-GC/MS
analysis of the additives contained in cross-linked
polyethylene (PE-Xb) pipes which have been exposed to
hot water.

❖ EXPERIMENTAL: TD-GC/MS analysis was carried out

using a Py-GC/MS system which consisted of a Multi-
Shot Pyrolyzer (EGA/PY-3030D) interfaced directly to the
split injection port of a GC/MS system. TD maximum
temperature was based on the EGA-MS thermogram.
PE-Xb samples were collected by scraping the inner wall
surfaces of “new” and “used” pipes, and 1 mg of the
sample was placed in a deactivated stainless sample cup.

FRONTIER LAB 26
 ❖ RESULT: The chromatograms of the “new” and “used” PE-Xb samples obtained by TD-GC/MS are shown in Fig. 1. In the
“new” PE-Xb pipe, Irgafos 168 (including the oxidized Irgafos 168, phosphate form) and Irganox 1076 are observed,
whereas Irgafos 168 and Irganox 1076 are not observed in the chromatogram of the “used” pipe. These results suggest
that the additives in PE-Xb pipes are either oxidized or hydrolyzed when exposed to hot water and oxygen over time.

O C18H37
* Linear-hydrocarbons HO
from PE-Xb P O
New 3

Irganox 1076

Irgafos 168

Irganox 1076

Irgafos 168
Irgafos 168

Di-tert-butylphenol

Oxidized
*C26

*C28

*C30
*C24
*C22

*C32
O P O

*C20
3

*C34
*C18
Oxidized Irgafos 168

*C16

*C36

*C38
*C14

1-Octadecanol
acid
acid
Palmitic acid

Stearicacid
Palmitic
Used

Stearic

*
*

*
*

*
*

*
*

*
*

*
8 12 16 20 [min]

Fig.1 Chromatograms of new and used PE-Xb samples obtained by TD-GC/MS

Furnace temp.: 40 - 350 ºC (40 ºC/min, 1 min hold), GC oven temp.: 40 (2 min) - 340 ºC (20 ºC/min, 13 min hold),
separation column: Ultra ALLOY+-5 (5 % diphenyl 95 % dimethylpolysiloxane), L=30 m, i.d.=0.25 mm, df=0.25 µm,
column flow rate: 1 mL/min He, split ratio: 1/10, sample: 1 mg

FRONTIER LAB 27
 B-7
Analysis of Thermoset Resin
Table 1 EGA-MS Library Search for Regions B and C

❖ BACKGROUND: The EGA-MS library search is a Region B

Name Ref No. Qual
combination of Evolved Gas Analysis, a thermal 1. Cresol formaldehyde resin (Novolak) #165 53
analysis technique using multi-mode micro- 2. Cresol formaldehyde resin (Novolak) #163 53
furnace Pyrolyzer, and mass spectrometry. It is 3. Phenol formaldehyde resin (Novolak) : PF #156 32

very useful as a primary search technique for Region C

unknowns. Name Ref No. Qual
1. Cresol formaldehyde resin (Novolak) #165 38
2. Poly-m-phenyleneisophthalamide #195 16
3. Poly(phenylene oxide) : PPO #210 10
❖ EXPERIMENTAL: Described here is an analysis
example of a thermoset resin. Fig. 1 shows the
EGA curve of the thermoset resin and averaged Triphenylphosphineoxide
spectra obtained from regions A, B, and C. The P O
result of library search on these spectra using 277
43
107
107

EGA-MS LIB is shown in Table 1. 77

121 7794
94 43 121
183 201
77
228

50 100 150 200 250 m/z 50 100 150 200 250 m/z
❖ RESULT: Cresol and phenol resins were found in 50 100 150 200 250 m/z

region B, and a cresol resin was found in region

B
C with high quality. Because of low elution
temperature of region A, therefore low boiling
C
species, a library search was done using
A
Wiley275, a commonly used MS library and
Triphenylphosphineoxide, a reaction catalyst, was 100 200 300 400 500 600ºC
found. As described here, EGA-MS technique
and library search using EGA-MS LIB are
extremely useful for composition analysis of Fig. 1 EGA Curve of a Flame-Retardant Resin
unknown polymer materials as a primary search Furnace temp: 100 - 600 ºC (20 ºC/min), Carrier gas : He 50 kPa, Split ratio : ca. 1/50; EGA capillary
method. tube : 0.15 mm id, 2.5 m (UADTM-2.5N), GC oven temp.: 300 ºC; Injection temp.: 320 ºC, Sample : ca.
0.5 mg, Detector : MS (m/z 10 - 400, 0.1 scans/sec); PY-GC interface temp.: 320 ºC (AUTO mode)

FRONTIER LAB 28
 A B C
If more than one peak are observed in an
evolved gas (EGA) curve, EGA-GC/MS is a
useful technique to determine the composition of
each peak observed. In this technique, 100 200 300 400 500 600 ºC

components in each temperature region are

introduced into a GC column and temporary Fig. 1 EGA Curve of a Flame-Retardant Resin
trapped at the front of the column using
Selective Sampler (SS-1010E) and MicroJet
Cryo-Trap (MJT-1030E). They are then
separated by GC and finally analyzed by MS.
P O

Using this technique, analysis of components in A

each peak allows detailed characterization of
polymers.

2,6-dimethyl phenol
Fig. 2 shows chromatograms of three

2,4-dimethyl phenol
p-cresol

2,4,6-trimethyl phenol
temperature regions, A, B, and C observed in
the EGA curve of a thermoset resin.

o-cresol
styrene
Triphenylphosphineoxide, a reaction catalyst, dimer

was found in peak A, while various phenols, trimer

phenol
thermal decomposition products of phenol resin,
and styrene monomer, thermal decomposition B
product from polystyrene, were found in peaks B

toluene
benzene
and C.
As shown here, analysis of each temperature C
region of an EGA Curve offers detailed 0 10 20 min

information on polymers. Fig. 2 Chromatogram of Each Temperature Region of EGA Curve

Separation column : Ultra ALLOY+-5 (5% diphenyl polysiloxane) 30 m, 0.25 mm id,
Film thickness : 0.25 µm; Sample : 500 µg, Detector : MS (m/z 10 - 400, 2 scans/sec)

FRONTIER LAB 29
 B-8
Analysis of Additives in Polybutylene Terephthalate (PBT)
❖ BACKGROUND: For electronic applications,
polyolefin modifier is often added to Polybutylene H 3CO O CH 3

terephthalate (PBT) resin to improve hydrolysis and 1,4-Dimethoxybutane

thermal shock resistances. It is of importance to
Dimethyl terephtalate
analyze additives in PBT resin in order to ascertain 1-Butyleneglycolmonomethyl ether
H CO C
3 2
CO C H
2 3
First step
its performance. H3 CO OH Reactive pyrolysis temp: 400 ºC
Sample size: 0.1 mg
THF Reagent: 2 µL of 25% methanol solution of TMAH

❖ EXPERIMENTAL: Here, a new analysis technique,

which is a combination of Double-Shot and reactive
pyrolysis, is described. In the first step, a pyrogram
was obtained by reactive pyrolysis of PBT at 400 ºC 0 5 10 15 20 25 30 min.

in the presence of tetra-methyl ammonium hydroxide Fig. 1 Pyrogram Obtained by Reactive Pyrolysis of PBT
(TMAH) (Fig. 1). In the second step, a pyrogram was
obtained by instant pyrolysis of residual polyolefin
modifiers at 550 ºC (Fig. 2). Second step
Olefin chains
Pyrolysis temp: 550 ºC

❖ RESULT: A methyl derivative of terephthalic acid, a

constituent monomer of PBT, was observed in the
first step; and sets of 3 peaks for straight chain
hydrocarbons of diolefins, olefins, and paraffin were
0 5 10 15 20 25 30 min.
observed in the second step. These results
Fig. 2 Pyrogram of Residue (550 ºC)
demonstrated that polyolefin additives in the PBT
Analytical conditions: carrier gas: He, Injection port pressure: 103 kPa, Split ratio: 1/60, Separation
resin could be separated and identified using this column: Ultra ALLOY+-5 (5% diphenyldimethylpolysiloxane); Length: 30 m, Id: 0.25 mm, Film
technique. thickness: 0.25 µm, GC oven temp: 38 ºC - 300 ºC(20 ºC/min), GC injection port temp: 320 ºC

FRONTIER LAB 30
 B-9 Determination of Phthalates in PVC by
Thermal Desorption-GC/MS
Part 1: Determination of the thermal desorption temperature zone by EGA

❖ BACKGROUND: Phthalates are widely used in the plastic industry;

the six phthalates listed in Table 1 are regulated by the EU and the
US when used in toys and other childcare products. In Japan, the
Health, Labor and Welfare Ministry guideline No.336 issued on
September 6, 2010 regulates the six phthalates listed in Table 1;
consequently, the analysis of phthalates is becoming commonplace
and there is a near universal interest in a simple, accurate method
for analyzing phthalates in polyvinyl chloride (PVC).

❖ PROBLEM: Traditional (e.g. solvent extraction, filtration, etc.)

sample preparation techniques are cumbersome, time consuming
and suffer from analyst-to-analyst variability.

❖ SOLUTION: Thermal desorption (TD)-GC/MS is a simple, one-step

technique which is suited for the analysis of phthalates in PVC. PVC
often contains a large amount of other plasticizers (several tens of
percent) which co-elute with the phthalates of interest. This so-
called matrix interference many lead to either false positives or false
negatives. In addition, matrix interference makes an accurate
determination of the co-eluting phthalates problematic, at best. This
technical note describes how Evolved Gas Analysis (EGA) – MS is
used to define the optimal thermal desorption temperature zone for
the phthalates of interest.

FRONTIER LAB FRONTIER LAB 31

31
 ❖ EXPERIMENTAL: A sheet of PVC containing DINCH at 40% (Fig. 1) and six restricted phthalates at 0.1% each was
analyzed. Small pieces (~ 20 mg) sampled from several different locations were dissolved in 1 mL of THF (20 mg/mL). 10 µL
of the solution was placed in a sample cup and the solvent evaporated leaving a thin film of the sample on the surface of the
cup. EGA-MS analysis was performed on this sample using a Multi-shot pyrolyzer: EGA/PY-3030D.

❖ RESULT: The EGA thermogram of the PVC sheet is shown in Fig. 2. It contains peaks originating from the plasticizers, HCl
(thermal decomposition of PVC), and aromatic compounds (which are attributed to the thermal decomposition of polyenes
upon the dehydro-chlorination of PVC). Characteristic ions for DINCH, HCl, and the phthalates of interest are used to define
the optimal thermal desorption temperature zone: 100 - 320 ºC.

DINCH / Phthalates
Table 1. Restricted phthalates
1,000,000
(0.1 % upper limit by Directive 2005/84/EC)
Di(2-ethylhexyl)phthalate (DEHP) PVC
Dibutylphthalate (DBP)
Butylbenzylphthalate (BBP)
2 4 6 8 10 12 14 16 18 20 22 24 min
Diisononylphthalate (DINP)
Diisodecylphthalate (DIDP) 100 200 300 400 500 600 ºC
200,000 Sample Temperature
Di(n-octyl)phthalate (DNOP) m/z 155: DINCH

20,000

O m/z 36: HCl

155
O C9H19 6,000
O C9H19 m/z 149: Phthalates

71 O
127 2 4 6 8 10 12 14 16 18 20 22 24 min
57 85
109 281
252 299
97 173
100 200 300 m/z
Thermal desorption zone: 100 – 320 ºC (20 ºC/min, 5 min hold)

Fig 1. DINCH: 1,2-Cyclohexane dicarboxylic acid di-isononyl ester Fig. 2 EGA thermogram and mass fragmentgrams of PVC sample

FRONTIER LAB 32
 B-10 Determination of Phthalates in PVC by Thermal
Desorption-GC/MS
Part 2: Calibration using absolute calibration method and standard addition

❖ BACKGROUND: Using the thermal desorption temperature zone described in the previous page, two different calibration
methods (absolute calibration and standard addition) were evaluated in order to determine which method most effectively reduces
or eliminates the matrix effects caused by the presence of a large amount of plasticizers in the sample.

❖ EXPERIMENTAL: The thermal desorption (TD)-GC/MS system consisted of a Multi-shot Micro-furnace pyrolyzer (EGA/PY-
3030D) interfaced directly to the split/splitless injection port of a GC/MS. A thin film (0.2 mg) of the PVC-DINCH sample was
prepared as described in the previous page. The thermal desorption temperature zone was 100 – 320 ºC. A calibration standard
(Ph-Mix) containing 0.1% of each phthalates was used. Identification was based on the retention time of each phthalate’s
characteristic ion and the common m/z 149 ion. Quantitation was based on the peak area of the characteristic ion.

❖ RESULT: No DINCH interferences were observed for DBP, BBP, and DEHP, and both methods gave similar results – Fig.1.
However, DNOP, DINP, and DIDP co-elute with the DINCH peak envelop which potentially will degrade the accuracy of the
phthalate concentration determination. Specifically, if there is no DINCH in the sample, the retention time of DNOP shifts and the
peak width at half-height is double what it is when the sample contains DINCH. In addition, the peak height is 60% lower when
DINCH is present; consequently, when the absolute calibration method is used, the concentrations of DNOP, DINP, and DIDP are
higher than the true value of 0.1% On the other hand, the concentration of the phthalates obtained using the standard addition
method are very close to the true value of 0.1%. The results show that standard addition is the preferred method when
quantitating phthalates in PVC using TD-GC/MS. Standard addition minimizes the interference when high concentrations of
plasticizers which co-elute with the phthalates of interest are present.

FRONTIER LAB FRONTIER LAB 33

33
 DINCH

DEHP
DNOP
1.0e+07

DEHP

DBP
1.0e+07

DBP

BBP

BBP

DNOP

DINP
DINP

DIDP
DIDP
TIC TIC
7 8 9 10 11 12 13 14 min 7 8 9 10 11 12 13 14 min
60,000 60,000
m/z 223: DBP m/z 223: DBP

100,000 100,000
m/z 206: BBP m/z 206: BBP

60,000 60,000

m/z 279: DEHP, DNOP m/z 279: DEHP, DNOP

6,000
2,000 m/z 293: DINP
m/z 293: DINP

2,000 4,000
m/z 307: DIDP m/z 307: DIDP
7 8 9 10 11 12 13 14 min 7 8 9 10 11 12 13 14 min

(a) Ph-Mix (0.1% each) (b) PVC-DINCH (Contains 0.1% each Ph)

Fig.1 TD chromatograms of samples and effects of DINCH interference to phthalates (TD: 100 - 320 ºC/min, 5 min hold)

Phthalate: 0.1% each DBP BBP DEHP DNOP DINP DIDP

%RSD (n=5) 0.79 0.85 0.69 1.59 1.59 0.98

Absolute calibration 0.122 0.117 0.121 0.029 0.126 0.193

Quantified
value (%)
Standard addition 0.115 0.093 0.096 0.098 0.103 0.088

FRONTIER LAB 34
 B-11 Effects of Thermal Desorption Temperature for
Phthalates in PVC
DBP(dibutyl phthalate) DEHP (di-2-ethylhexyl phthalate) O

O C9H19

❖ PROBLEM: When phthalates in plastic toys are analyzed : ca. 50 ppm : ca. 300 ppm
O
O C9H19

149 O

using thermal desorption (TD)-GC/MS, does the sample x 107

149
O O iso C8H17 1,2-Cyclohexane
O iso C8H17
dicarboxylic acid di-
form influence the reproducibility? 1.5 O C4H9
O C4H9 O
isononyl ester (DINCH)
167
O

1.0 41
57
41 71 113
279 Non-phthalate
223
❖ EXPERIMENTAL: Solid samples were milled to 45 mesh, 100 200 300 m/z
100 200 300 m/z
plasticizer

and thin films were prepared by solvent casting, and were 0.5

analyzed by (TD)-GC/MS. The thermal desorption zone TIC

for the phthalates was determined to be 100 - 350 ºC. 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 min

m/z 149:
400000
The levels of the phthalates were calculated using an Phthalates
absolute area calibration. (common ion)
20000
m/z 223: DBP
❖ RESULT: Fig. 1 shows a TIC chromatogram obtained by
(TD)-GC/MS. DINCH, a non-phthalate plasticizer, was 60000

m/z 279: DEHP

identified as the major component in the 17 - 18 minutes
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 min
retention window. Compounds having fragment ions m/z
149, 223, 273 were found at 11 and 16 min, and based Fig. 1 TIC and extracted ion chromatograms of a PVC sample obtained by TD-GC/MS
on the mass spectra and retention times, these peaks are Thermal desorption temp: 100 - 350 ºC (40 ºC/min, 3 min), GC oven temp: 80 - 320 ºC (10 ºC /min, 6 min),
identified as DBP and DEHP. The concentrations of these Separation column*: Ultra ALLOY+-1 (polydimethylsiloxane, L=30 m, i.d.= 0.25 mm, df=0.05 µm), Column
flow rate: 1 mL/min He, Split ratio: 1/20
phthalates are ca. 50 and ca. 300 ppm, respectively. The
* For separation column, please use Ultra ALLOY+-5 (5% diphenyl 95% dimethylpolysiloxane, L=30 m,
reproducibility (n=5) of the DEHP concentration was 5% i.d.=0.25 mm, df=0.25µm).
RSD for the powder, and 1% for the thin film. The
difference between the two can be attributed to the lack
of homogeneity of the solid sample.

FRONTIER LAB 35
 B-12 Differentiation of DOTP and DNOP in Analysis of Restricted
Phthalate Esters Using Thermal Desorption GC/MS
❖ BACKGROUND: Thermal desorption (TD)-GC/MS is a simple analytical method for the determination of restricted phthalates
in polymers. ASTM D7823-18 utilizes TD-GC/MS to determine six restricted phthalates in PVC. D7823-18 uses retention
times and mass spectra for the identification of phthalates; therefore, attention must be given to similar compounds having
similar retention indices and mass spectra. Miss-identification will result in a false positive and an elevated concentration for
the target phthalate. One such example is the possible miss-identification of di-(n-octyl) phthalate (DNOP, CAS: 117-84-0)
and bis (2-ethylhexyl) terephthalate (DOTP, CAS: 6422-86-2). Both have m/z 149 and 279 - ions that are used to identify and
quantitate DNOP. This technical note shows that these two phthalates are differentiated using the standard GC method
described in ASTM 7823-18.

❖ EXPERIMENTAL: 70 µg of PVC containing tens of % of DINCH and hundreds of ppm of DNOP and DOTP was placed in a
sample cup and analyzed using the conditions described in ASTM D7823-18. The Multi-Shot Micro-Furnace Pyrolyzer
(EGA/PY-3030D) was directly interfaced to the injection port of the GC/MS system.

❖ RESULT: DNOP and DOTP co-elute with DINCH (see Fig. 1) which precludes the positive identification and quantitation of
either phthalate using the TIC. The mass spectra of both DNOP and DOTP have 149 and 279 ions – see Fig. 2, and therefore
extracted ions chromatograms (EIC) cannot be used to differential DNOP and DOTP. On the other hand, m/z 261 is a
significant ion in the DOTP mass spectrum. As demonstrated here, the retention time and the presence or absence of m/z
261 ion can be used to differentiate between DNOP and DOTP.

FRONTIER LAB 36
 149
1 x106 DINCH DNOP
O
0.5 O
O
TIC
08 O
9 10 11 min

x104 DOTP 279

DNOP 43 57
5
167 261 390
m/z: 149 100 200 300 400 m/z
0
8 9 10 11 min
261
70 112
x104
5 DOTP O
O
m/z: 261 149 O
0
8 9 10 11 min
O

2 x104 167 279

57 83
1
m/z: 279 361
0
8 9 10 11 min 100 200 300 400 m/z

Fig. 1 Chromatograms of a PVC which contains various Fig. 2 Mass spectra of DNOP and DOTP
plasticizers obtained by TD-GC/MS

TD: 100 - 320 ºC (20 ºC/min, 5min hold), GC oven: 80 - 200 ºC (50 ºC/min) - 320 ºC (15 ºC/min, 2 min hold)
Separation column: Ultra ALLOY+-5 (5% diphenyl 95% dimethylpolysiloxane)
L=30 m, i.d.=0.25 mm, df=0.25 µm, split ratio: 1/100, sample wt.: approx. 70 µg

FRONTIER LAB 37
 B-13 Determination of Antioxidants (Irganox 1076 and Irganox
1010) in Polyethylene – Part 1
❖ BACKGROUND: Plastic products often contain a number of additives which give the products desirable physical and chemical
properties. Irganox 1076 and 1010 are sterically hindered phenolic antioxidants and are widely used in the formulations of
plastics, lubricants, adhesives and car parts. Irganox 1076 in polyethylene (PE) is determined using thermal desorption (TD)-
GC/MS. Irganox 1010 in PE can be hydrolyzed and methylated using tetramethyl ammonium hydroxide (TMAH). The methyl
derivative has a much lower boiling point and it can be easily vaporized and determined using GC/MS.

❖ EXPERIMENTAL: PE-pellets, spiked with either Irganox 1076 a

Irganox 1076
(340 ppm) or Irganox 1010 (470 ppm), were pulverized. The Residual hydrocarbons
530
515
spiked PE samples containing Irganox 1076 and Irganox 1010 in PE 219

were respectively analyzed by TD-GC/MS and reactive

C25
pyrolysis (RxPy)-GC/MS. In RxPy-GC/MS, TMAH was added C18 C20

to the sample cup containing the spiked PE prior to analysis. 16 20 24 28 min

Standard addition method was used to generate calibration
curves. The analysis was done using a Multi-Shot Pyrolyzer b
(EGA/PY-3030D) which was directly interfaced to the split Product of TMAH reactive pyrolysis of Irganox 1010
injector of a GC/MS system. TMAH origin
291
306

❖ RESULT: TD chromatogram of PE containing Irganox 1076 is

shown in Fig. 1a. The large peak at 26.8 min is assigned as
Irganox 1076. Figure 1b shows the total ion chromatogram of
PE containing Irganox 1010 treated by hydrolysis and 10 15 min 20 min

methylation using TMAH. The large peak at 17.9 min is Fig. 1 a: Chromatogram of PE with Irganox 1076 obtained by thermal desorption
assigned as the methyl derivative of Irganox 1010. Using the b: Pyrogram of PE with Irganox 1010 obtained by reactive pyrolysis
standard addition method, the concentrations of Irganox 1076 Furnace temp.: 260 ºC (reactive pyrolysis), 320 ºC (thermal desorption); GC oven: 40 - 150 ºC (10 ºC/min) - 320 ºC
(20 ºC/min, 3 min hold); Separation column: Ultra ALLOY+-5 (5% diphenyl 95% dimethylsiloxane), L=30 m, i.d.=0.25
and Irganox 1010 were respectively determined to be 374 mm, df=0.25 µm; Split ratio: 1/30, Sample wt.: approx. 100 µg, 25 wt% TMAH methanol solution: 20 µL
ppm (10% error) and 429 ppm (9% error).

FRONTIER LAB 38
 B-14
Determination of Antioxidants (Irganox 1076 and Irganox
1010) in Polyethylene – Part 2
❖ BACKGROUND: 1010 (MW 1178) and Irganox 1076 (MW 530) have
been used as an antioxidant in polymeric materials. Determination of
each antioxidant in polyethylene (PE) was reported previously, where
Irganox 1076 (MW 530)
Irganox 1010 was determined by reactive pyrolysis (RxPy)-GC/MS TD-GC/MS
with tetramethylammonium hydroxide (TMAH) and Irganox 1076, by
thermal desorption (TD)-GC/MS. Both of these antioxidants are
sometimes co-added in polymeric materials, and it is not easy to
determine each antioxidant in such polymeric materials because both
antioxidants give the same reaction product by RxPy-GC/MS with
Irganox 1010 (MW 1178)
TMAH as shown in Fig. 1. Individual concentration of antioxidants in
a PE sample containing both antioxidants can be determined
according to the analytical protocol given in Protocol part 1.
Identical methyl derivative is
❖ EXPERIMENTAL: The analytical data was obtained using a Multi- formed from Irganox 1010 and
Irganox 1076
Shot Pyrolyzer (EGA/PY-3030D) interfaced directly to the injection
port of a GC/MS system. Analytical conditions including amounts of
sample and reagent used are identical to those described in the Fig. 1 Methyl derivative of Irganox 1010 and Irganox 1076

previous page.

❖ RESULT: The concentrations of Irganox 1010 and Irganox 1076

contained in the PE sample was determined to be 1406 ppm
(formulated as 1000 - 1500 ppm) and Irganox 1076 was 476 ppm
(formulated as 450 - 550 ppm), respectively.

FRONTIER LAB 39
 ❖ PROTOCOL 1: Analytical protocol for the determination of Irganox 1076 and Irganox 1010 co-added in PE.

1. TD-GC/MS is used to determine Irganox 1076 in a PE sample containing both antioxidants.

PE

Irganox 1076 Determination of Irganox

1076 by TD-GC/MS
Irganox 1010

2. The methyl derivative of Irganox 1076 produced by RxPy with TMAH is determined by the standard addition of Irganox 1076
to the PE sample containing Irganox 1076 only (Fig. 2), and the determined value is correlated with the concentration of
Irganox 1076 obtained in the step 1.

3. By the standard addition of Irganox 1010 to the PE sample containing both antioxidants, concentration of the methyl derivative
produced by RxPy with TMAH is determined (Fig. 2). The determined concentration corresponds to the sum of concentrations
of Irganox 1010 and Irganox 1076.

4. By subtracting the concentration of Irganox 1076 determined in the step 2 from the sum of concentrations determined in the
step 3, the concentration of Irgaox 1010 can be determined.

PA (1010) Me ＝ PA (1010 + 1076) Me － PA (1076) Me 1.5E+06

PA (1076) Me

Peak area
1.0E+06

PA： Peak area

5.0E+05 PA (1010) Me
PAMe： Peak area of the methyl derivative PA (1010 + 1076) Me

0.0E+00
-280 -180 -80 20 120 220
-152 Amount added (ng)

Fig. 2 Calibration curves for the methyl derivative of Irganox 1010

FRONTIER LAB 40
 B-15 Quantitative Analysis of Phthalate Bis(2 - Ethylhexyl)
Phthalate (DEHP) in Heat Resistant PVC Sheath
❖ BACKGROUND: Phthalate esters are added to PVC formulations to improve the processability and the performance of the
PVC. Recently many of these phthalates have been found to adversely affect human health and their use has been restricted
or in some cases banned. Bis(2-ethylhexyl) phthalate (DEHP) is among the first six compounds that the EU is phasing out
under its REACH program. There are more than 17 analytical methods currently being used to measure DEHP in PVC. With
two exceptions, the analysis begins with a cumbersome, time consuming liquid/ liquid extraction. This technical note uses the
ASTM Method: D-7823-18 which utilizes thermal desorption (TD)-GC/MS. The method is simple to use and has proven to
yield superior precision and accuracy values when compared to those obtained using solvent extraction. This note describes
the quantitative TD-GC/MS analysis of DEHP in the outside sheath of commercial-grade cable.

❖ EXPERIMENTAL: TD-GC/MS system consisted of a Micro-Furnace Multi-Shot pyrolyzer (EGA/PY-3030D) interfaced directly
to a GC/MS split injection port. 500 μg of a PVC thin film was placed in an inert SS sample cup. The TD was done as
described in the ASTM method. The concentration of DEHP was calculated using an absolute area calibration curve method
(m/z 279). The ASTM method requires that quantization to be done using standard addition because of the possible
interference from other plasticizers (e.g., DINCH) in the PVC. In this case the plasticizers were trimellitate and adipates and
there was no interference with the DEHP ions.

❖ RESULT: A typical total ion chromatogram (TIC) and extracted ion chromatograms (EICs) of the PVC sample are shown in
Fig.1. m/z 149 and 279 are used to confirm the presence of DEHP. Two positional isomers of DEHP (regioisomers), tris(2-
ethylhexyl) trimellitate (TOTM) and TOTM anhydride are also present. Quantification was performed using the calibration
curve shown in Fig.2. The concentration of DEHP in this PVC sample was found to be 245 ppm (n=3, RSD=0.7%).

FRONTIER LAB 41
 Abundance
O O TOTM
3000000 O
H17C8 O O C8H17
～
～

anhydride
O C8H17
O

*: Adipates O

TOTM
H17C8 O
O
O 100000
R O
O O R y = 376.15x - 9553.5
O R² = 0.9979
80000

Peak area (m/z: 279)

* * R2 = 0.998
*
* * 60000
* * ** *
** *** ** * * TIC
**** 40000
0
DEHP
60000 O
DEHP regioisomers
O
20000
O

m/z 149
0 0
0 100 200 300
9000
DEHP amount [ng]
Peak area: 37000
m/z 279
0 Fig.2 Calibration curve of DEHP
6 7 8 9 10 11 12 13 14 15 [min]

Fig.1 TD-GC/MS chromatogram and extracted ion chromatograms

of heat resistant PVC

TD temp.: 100 - 320 ºC (20 ºC/min, 1 min hold), GC oven temp.: 80 (2 min) - 200 ºC (40 ºC/min) - 320 ºC (15 ºC/min, 3 min hold)
Separation column: Ultra ALLOY+-5 (5 % diphenyl 95 % dimethylpolysiloxane, L=30 m, i.d.=0.25 mm, df=0.25 µm)
Column flow rate: 1.2 mL/min He, Split ratio: 1/50, Sample wt: ca. 500 µg

42

FRONTIER LAB 42
 What is Pyrolysis GC/MS Technique?
Pyrolysis GCMS is a powerful and straightforward technique The Frontier Pyrolyzer is interfaced directly to the GC inlet.
that utilizes a Frontier Micro-Furnace Pyrolyzer as a The sample is placed in a small deactivated cup which is, in
programmable temperature inlet to a Gas Chromatography- turn, positioned in a micro-furnace. The temperature of the
Mass Spectrometer (GCMS) system. The material of interest sample is carefully controlled (±0.1 °C) to ensure that the
(liquid or solid) is uniformly heated in an inert atmosphere. sample-to-sample thermal profile is identical. Frontier’s well-
Volatile organics evolve at temperatures below 300 °C. At engineered technology ensures that the sample is
higher temperatures, covalent bonds break, and the complex maintained at ambient temperature, in an inert atmosphere,
structure is degraded into smaller (stable and volatile) prior to pyrolysis; thus eliminating evaporation, thermal
molecules which are referred to as pyrolyzates. The degradation, and thermosetting before analysis.
pyrolyzates formed and their relative intensities provide insight
into the structure of the original material.

The technical data in this monograph were

obtained using one or more of the listed
accessories. Each accessory is described in
more detail in the system configuration
section.

FRONTIER LAB 43
 “Method Map” for Material Characterization
Frontier Lab has developed a sequence of tests referred to as The “method map” provides scientists with two simple steps
the “method map” to chemically characterize samples using for determining the organic composition of any unknown
the EGA/PY-3030D Multi-Functional Pyrolyzer System in material:
conjunction with a benchtop GC/MS. This sequence is
applicable when characterizing virtually any organic
material from volatiles to high molecular weight polymers.

i. The first step is to perform an Evolved Gas ii. The second step is to use the EGA thermogram and
Analysis (EGA). In this technique, the sample is selected ion chromatograms (EIC) to define the thermal
dropped into the furnace which is at a relatively low zones of interest and then perform one or a combination
temperature (ca. 40 - 100 ˚C). The furnace is then of the following techniques:
programmed to a much higher temperature (ca. 600 - Use the links below for more information.
800 ˚C). Compounds “evolve” continuously from the
sample as the temperature increases. A plot of detector Thermal Desorption (TD)
response versus furnace temperature is obtained.
Flash Pyrolysis (Py)

Heart Cutting (HC)

Reactive Pyrolysis (RxPy)

FRONTIER LAB 44
EGA & “Method Map”
EGA Configuration: No column is used; a short, small diameter (1.5m X 0.15mm id) deactivated tube connects the injection port
to the detector. All thermal zones (interface temperature, GC injection port, column oven and detector cross-over) are held at elevated
temperatures to prevent condensation. The figure below shows the EGA-MS configuration and a typical EGA thermogram.
Following EGA, the instrument is re-configured. The EGA tube is replaced by an analytical column. The Frontier Vent-Free GC/MS
Adaptor enables this to be done easily and quickly; there is no need to vent the MS. MS vacuum equilibrium is re-established within a
few minutes, and the exposure of the ion source to oxygen is minimized.
In this example, a double-shot analysis (TD of the thermally stable and the volatile components followed by Py of the residual
sample in the cup) was performed to characterize the two thermal zones shown on the EGA thermogram. One sample is
analyzed two times; the sequence is fully automated.

TD-GC/MS
He He
Py-GC/MS As shown in the Figure, information about the organic ‘volatiles’ in
100 ˚C – 700 ˚C @ 20 ˚C/min
the sample is generated by simply introducing the sample at 300 ˚C,
only the compounds evolving below 300 ˚C will evolve from the
Vent-Free
Adaptor sample and be transported to the head of the column. If there is
Micro-Jet
Cryo Trap interest in both the volatile fraction and the higher boiling
EGA tube Separation column
MS MS compounds, this can be done in two steps, and it may be necessary
GC Oven : 320 ºC GC Oven: Temperature Program to add a micro-cryo trap. Thermal desorption is performed over time,
e.g., 100 to 250 ˚C at 20 ˚C /min takes 7.5 minutes. The micro-cryo
trap re-focuses the volatile analytes of interest at the head of the
Thermogram (EGA-MS) column so that the full separating power of the column can be
TD Chromatogram (TD-GC/MS) utilized.
(100 ˚C – 300 ˚C @ 20˚C/min)

If there are more than two zones in the obtained EGA thermogram,
Pyrogram (Py-GC/MS) at 600 ˚C
Heart-cutting (HC) technique, which utilizes an accessory called a
Selective Sampler, slices the thermal zones out of the sample and
100 200 300 400 500 600 separate the components chromatographically with detection by MS.
Temperature ºC 10 20 30 40 min Time

FRONTIER LAB 45
F-Search Engine

SIMPLIFYING AND IMPROVING THE ACCURACY OF DATA INTERPRETATION

Polymeric materials often contain a variety of additives such as antioxidants, UV absorbers, etc. to assist during
the production phase and determine the physical and chemical characteristics of the final product. These
compounds are identified using commercial mass spectral (MS) libraries; however, these general-purpose MS
libraries contain very few entries for pyrolyzates and additives which severely limits their utility for polymer
characterization.

Frontier Laboratories developed a search engine

and libraries called F-Search. The ions associated
with hundreds of polymers, their degradation
products (i.e., pyrolyzates) and hundred of
additives are used to identify and thus
characterize the sample as it is heated in the Py.
The libraries include both chromatographic and
mass spectral data. There are four unique libraries
which allow users to select among them for
specific purposes. The ability to create in-house
specialty libraries is incorporated into the standard
software. Updating these libraries is
straightforward.

FRONTIER LAB 46
 Easy Sample Preparation
This technology allows multiple analysis on a single sample. There is no need for solvent and
sample preparation as the sample is simply introduced into the GCMS by the Frontier Pyrolyzer.

Step 1 Step 2 Step 3

Knife Pyrolyzer
Weigh the sample
into the inert sample cup Sample cup

Micro Syringe

100-200 µg MS GC

Micro Puncher Ready for

No Solvent Extraction
Analysis !!

FRONTIER LAB 47
 Use these links for more information.

Pyrolysis-GC/MS
System Configuration

1. Auto-Shot Sampler (AS-1020E) 2. Carrier Gas Selector (CGS-1050Ex)

Up to 48 samples can be automatically analyzed using The device allows switching of the gas, e.g., He and air,
any of the analytical modes (e.g., TD, Py, Double-Shot, surrounding the sample during analysis.
Heart-Cutting. Etc) with enhanced reliability.

FRONTIER LAB 48
 Use the links below formore information.
3. Selective Sampler (SS-1010E)
Any temperature zone as defined by the EGA
thermogram, that is Heart-Cutting either m anually or
automatically, can be introduced to a separation
colum n.

4. MicroJet Cryo-Trap (MJT-1035E) 5. Ultra ALLOY® Metal Capillary Column

By blowing liquid nitrogen jet to the front of separation By multi-layer gradient deactivation treatment, these
column, volatile compounds are cryo-trapped while separation columns have high flexibility, high
maintaining the temperature at -196ºC using only one temperature, and contamination resistances.
third of the amount of liquid nitrogen required for
competitors products. It supports automated analysis.

FRONTIER LAB 49
 Use the links below formore information.
6. Vent-free GC/MS Adapter
W ithout venting MS, separation column and/or EGA tube
can be switched.

7. F-Search System (Libraries and Search 8. Micro-UV Irradiator (UV-1047Xe)

Engine) W ith a strong Xe UV light source, photo, thermal, and
oxidative degradation of polymers can rapidly be
This software system supports identification of polymers evaluated.
and additives from data obtained by evolved gas
analysis, thermal desorption, or pyrolysis GC/MS
analysis.

FRONTIER LAB 50
 PLEASE VISIT OUR WEB SITE FOR OTHER APPLICATION AREAS

Visit Frontier Lab web site at www.frontier-lab.com

https://frontier-lab-sea.com/ to find more materials
categorized by the following application areas:

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FRONTIER LAB 51
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FRONTIER LAB 52