1960 polymers and 590 additives are stored in libraries

F-Search System
Search software F-Search (Ver. 3.8) that supports polymer analysis, and varied types of libraries:
Evolved gas (polymers), thermal desorption (additives), and pyrolysis (polymers)

Additives

Polymers
HCL< EGA info >

100

200

300

400

500 O

600°C
C9 H19

Temp.

O
O C H
9 19

Additives< Additive info >

O

DBP

DEHP

HCL

Polymers< Polymer info >

x10
Time

Multi-functional
Pyrolyzer

GC

MS

Multi-functional Pyrolysis System

F-Search System

“F-Search System” (Search program for polymers and additives)
The qualitative analysis of unknown polymericmaterials is performed using a variety of methods suchas IR, NMR, thermal analysis, and pyrolysis (Py)-GC.
Polymeric material containing cross-linked or network
polymers, or with complex additive packages, are best
characterized using the Multi-functional pyrolyzer thatallows you to use techniques such as Py-GC, thermal
desorption (TD)-GC and evolved gas analysis (EGA).

However, interpretation of the pyrogram or EGA
thermogram is a difficult task, requiring professional
intuition and experience. Frontier Laboratories has now
upgraded F-Search (Ver. 3.8). Approximately 650
polymers, including natural products, textiles, fats, oils,
adhesives, and more, have been newly added. Thissignificantly broadens its applications, making it useful
not only for general analysis but also for foreign matter
analysis.

Eight Unique Advantages of F-Search System (Patents: 3801355 Japan, 6444979 US)
1. F-Search system consists of search software and four unique libraries andallows users to select among them for specific purposes.
 Search software: F-Search Libraries
Polymer analysis

Pyrogram library
EGA library
Pyrolyzates library

Additives analysis --- Additive library

UA-5 Column
UA-WAX Column

The reliability of analysis results is greatly improved by evaluating data obtained by different analytical techniques. Search
results such as mass spectra, pyrograms and thermograms of candidate compounds can be displayed side-by-side for easy
visual comparison. Further, the system allows users to effortlessly construct their own libraries.

2. The search software F-Search allows you to quickly search different types of datasuch as pyrograms and EGA data. It can also accommodate various GC/MS data
formats for your convenience.
Compatible with major
GC/MS systems

Because the unique search algorithm is used to compare mass spectra,
candidate compounds are instantly displayed. Also, the search can be
simultaneously performed across multiple libraries.
GC/MS data formats of Agilent, Shimadzu, and JEOL can be directly read
without any translation or conversion, while other data formats can also beread upon converting to AIA format (NetCDF) files using software from theirown companies.

1 : What is Py-GC?

Furnace Temp.:
600 ºC

monomer

ColumnMS

Py-GC is a method used to obtain apyrogram. In this method, thesample is placed in a sample cup. It
is kept at the ambient temperature
until it is introduced into the center ofthe pyrolysis furnace, which is hot
enough to thermally degrade thesample. The sample is instantly
pyrolyzed and the pyrolyzates are
rapidly transferred to a separation
column. A plot of detector response
vs. retention time is called apyrogram.

2 : What is EGA?

Furnace Temp:
40 – 700 ºC (20 ºC/min)

EGA TubeMS

EGA is a simple thermal analysis
method where the temperature of
the sample is continuously raised,
and the evolved gases are directly
measured. A plot of detector
response vs. sample temperature
is called a thermogram. As shownin the figure, the pyrolyzer and the
MS are connected by a short 2.5
m deactivated EGA tube (0.15mm i.d.) in the oven where thetemperature is maintained at 300ºC.

trimerdimer
Polystyrene 300 µg

Polystyrene 20 µg

～
～

5

10
15
Retention time / min(40)100

20
2

200

300
400
Furnace temp / ºC

500

600

700

3. Search results obtained by the unique search algorithm employed in F-Search areunaffected by changes in analytical conditions.
Generally, retention times are greatly influenced bychanges in analytical conditions and separation columns;
however, due to the unique patented search algorithm, thesearch results are not affected by the use of different
separation columns or analytical conditions. Data 1 andData 2 are mass spectra from the same unknown polymer.
The mass spectra derived by this algorithm are very similareven though they were obtained using different GC
analytical conditions. In both cases, the unknown polymer
is identified as “BT resin.” Data 1 compares the search

results from Case 1 and Case 2. In both Cases 1 and 2, BT
resin was the first candidate. The library contains three setsof mass spectra for the retention times of C1 - C10, C1 C20, and C1 - C40, so even if a compound with a highboiling point is missing, as in Case 2, equivalent results canbe obtained. As these results show, F-Search can be used
to reliably identify polymers using data obtained under
different analytical conditions.

Data 1 and Data 2 are pyrograms of the same unknown polymer obtained using different GC conditions.

Data 1Case 1 (mass spectrum of the peaks detected from 0 to 45 min)

Furnace temp.: 600 ºC, Col: UA-5 (MS/HT) (L=30 m, i.d.=0.25 mm,
df=0.25 µm)

GC Oven: 60 - 170ºC (20ºC/min)Case 1 (stop run at 45 min)Case 2 (stop run at 20 min)Phenol
(M+:94)50

Bis-phenol A(M+:228)

10

20

30

100

150

200

250 [m/z]

Case 2 (mass spectrum of the peaks detected from 0 to 20 min)40

Retention time / min

50

150 [m/z]

100

Data 2
Furnace temp.: 600 ºC, Col: UA-5 (MS/HT) (L=30 m, i.d.=0.25 mm, df=0.25 µm)

GC Oven: 40 - 140 (10ºC/min) - 320ºC(20ºC/min) Mass spectrum created from all the peaks detected

Bis-phenol A(M+:228)

Phenol
(M+:94)
Aniline(M+:93)50
1020

Retention time / min

3

100

150

200

250 [m/z]

4. Two-dimensional multi-ion chromatograms allow you to obtain high quality mass
spectra from overlapping peaks.
Pyrograms generally consist of complex pyrolyzates; therefore,
it is very important to obtain high quality mass spectra of thetargeted peak. F-Search displays TIC and mass
chromatogram on a single screen, and also allows you tosubtract surrounding peaks from the targeted peak to obtain ahigh-quality mass spectrum. An example is shown below toillustrate this feature.
To identify the compound of the peak marked with an arrow
shown in the TIC, a search was made on the average
spectrum between (a) and (c). The search result obtained was
acetic acid with 65% match quality and benzene with 44%
match quality. Then, a two-dimensional multi-ion mass

chromatograms were generated as shown below
suggesting overlap of the multiple peaks.
Now, to obtain a high-quality mass spectrum for thecompound drawn in red, the mass spectrum (c) was
subtracted from one at (b), then the resulting mass
spectrum was searched to obtain acetic acid as a candidate
with 98% match quality. Similarly, focusing the compound
shown in black line, the mass spectrum at (a) was
subtracted from one at (c) to obtain a mass spectrum. Thena search was performed on the mass spectrum. Now,
benzene was shown as a candidate with 98% match quality.

(a) (b) (c)

m/z

TIC
Selecting m/z in window above
is shown in red line.

Mass chromatogram

Acetic acid : 65 %Benzene : 44 %

20

40

60

[m/z]

80

Average mass spectrum from (a) to (c)Acetic acid : 98 %

O

OH
20

40

60

80

[m/z]

Mass spectrum obtained by subtracting mass spectrum (c) from (b)Benzene : 98 %

20

40

60

80

Mass spectrum obtained by subtracting mass spectrum (a) from (c)

4

[m/z]

5. Overlay of multiple TICs or EICs
Up to a maximum of seven TICs or EICs can be displayed separately or overlaid in the same window.

Separate display of TICs

Overlay display of TICs

6. Subtracting a mass spectrum from a TIC
A specific mass spectrum can be subtracted from each spectrum in the TIC. This eliminates background or interfering ions fromthe TIC.

Background Subtraction

32

40
m/z

7. Displaying peak area and height
TIC and EIC peaks can be integrated under specified conditions, and the area and height can be displayed. Peak integrationlines can be adjusted manually by dragging with the mouse in the detailed view screen.

8. Using NIST library directly from within F-Search.
If NIST/EPA/NIH Mass spectral Library (National Institute of Standards and Technology) and its search software
have been installed in your PC, you can use it from within F-Search.

5

Example of an unknown polymer analyzed by EGA-MS and Py-GC/MS
A: Evolved Gas Analysis

B: Py-GC Analysis(with EGA-MS24B library)This method allows simple thermal analysis of a sample. The
thermogram provides the thermal property of the entire sample.

(with PyGC-MS24B library)This technique offers detailed and advanced analysis of eachpeak on the pyrogram through analysis of mass spectra.

A thermogram obtained using EGA-MS

A pyrogram obtained using Py-GC/MS

Furnace temp.: 100 - 600 ºC(20 ºC/min)
ITF Tube: UA-DTM (L=2.5 m, i.d.=0.15 mm)
GC Oven: 300 ºC

Furnace temp.: 600 ºC
Col: UA-5(MS/HT) (L=30 m, i.d.=0.25 mm, df=0.25 µm)
GC Oven: 40 (2 min) - 320 ºC(20 ºC/min)
C10H20C30H60C41H82

Searching the PyGC-MS24B library

Searching the EGA-MS24B library

F-Search automatically detects all peaks in the pyrogramand prepares a mass spectrum. This spectrum is thensearched. The following results indicate that theunknown polymer is a form of PE. However, there areseveral polymers with match qualities greater than 90%.
This suggests that further searches may not be of value.

First, the mass spectrum at the apex of the EGA peak ofinterest is displayed and searched. The unknown sample
appears to be PE. However, there are several polymers
with match qualities greater than 90%. This suggests thatfurther searches may not be of value.

Unknown

Unknown

Candidate No.1: PE(HDPE)

Candidate No.1： PE(HDPE)

Candidate No.17: E/EA/MAH

Candidate No.12： Montan wax#

Polymer/Additive

Qual [%]Start [C]Top [C]End [C]

Entry ID#

Polymer/Additive

Qual [%]

Entry ID

1

PE(HDPE)

99.3

436

486

534

FLT-001

1

PE(HDPE)

99.4

FLT-001…

…

17 E/EA/MAH

97.8

365

455

540

FLK-437

12Montan wax

98.1

FLK-856

18 L-LDPE

97.7

422

479

550

FLK-031

13

Oxidized HDPE

97.7

FLK-871

Comparing the thermogram of the unknown
polymer with those of the candidate polymers

Comparing the pyrogram of the unknown polymer
with those of the candidate polymers

Comparing the thermograms of the possible candidates, itshows that candidate No. 17: E/EA/MAH does not match withthat of the unknown and can be eliminated from consideration.

The distribution of the high boiling peaks in the pyrogram ofcandidate No.12: Montan wax differs from that of theunknown sample and can be eliminated from consideration.

Unknown

Unknown

Conclusion :Candidate No.1: PE(HDPE)

1st candidate : PE(HDPE)

Candidate No.17: E/EA/MAH

12th candidate: Montan wax

Based on the search results of both thermograms and pyrograms, the unknown
sample was narrowed down from the candidate polymers to PE.
6Analysis of vulcanization accelerator in rubber (ADD-MS22B library used)
The example below is the analysis of unknown vulcanization
accelerator in a compounded rubber sample using TDGC/MS technique. ADD-MS22B library for additives was
searched for peaks (A) - (D) in Fig. 1. They were identified bycomparing the mass spectra and the associated retention

indexes (RI) to be compounds shown in Fig. 1. In addition, thesimilarity of the chromatogram for 1,3-Diphenylguanidine tothat of the unknown further supports the identification of thevulcanization accelerator.

Chromatogram of volatile compounds in an unknown rubber sample
Furnace temp.: 100-340 ºC (20 ºC/min), Col: UA-5 (MS/HT) (L=30 m, i.d.=0.25 mm, df=0.25 µm) , GC Oven: 40 (2 min) - 320 ºC (20 ºC/min, 10 min)(D)
(RI : 2168)(C) (RI : 1788)(A)(RI : 973)

(B)
(RI : 1407)121412.5 [min]14.3[min]

Chromatogram of 1,3-Diphenylguanidine in the additive library
Furnace temp.: 400 ºC, Col: UA-5 (MS/HT) (L=30 m, i.d.=0.25 mm, df=0.25 µm) , GC Oven: 40 (2 min) - 320 ºC (20 ºC/min, 10 min)Aniline(RI : 980)

1-Phenyltetrazole(RI : 1423)

NH2

C
N

N N
N

1,3-Diphenylguanidine(RI : 2169)

N

NH

N

Diphenylcarbodiimide(RI : 1803)
5

N
H

N
H

15 [min]10

Search results of peak (D)Fig. 1 Library search of volatile compound from rubber sample

Library-search of methyl derivatives of a polymer obtained bythermally assisted hydrolysis and methylation (THM)-GC/MS(Pyrolyzate-MS22B and PyGC-MS24B libraries used)
An example shown below is the chromatogram of a polymer
obtained by THM-GC/MS. A library-search against threepeaks in Fig. 2 using F-Search and Pyrolyzate-MS22B
library permitted identification of each methyl derivative.
The data set stored for each methylated compound
includes information of polymer from which it is derived
from; therefore, it is very useful. Peak (C) is of unique in thislibrary because it is not in the NIST library.

Using PyGC-MS24B library, a library-search against the mass
spectrum obtained by the summation-integration of the mass
spectra of three major peaks revealed that the original polymer
was found to be poly(ether ether ketone), PEEK.
PEEK
O

O

CO

n

Furnace temp.: 400 ºC, TMAH(25 wt%): 2 µL
Col: UA-5(MS/HT) (L = 30 m, i.d.= 0.25 mm, df = 0.25 µm)
GC Oven: 40 (2 min) - 320 ºC (20 ºC/min, 14 min)

(B)
O

O

(C)

O
O

(A)
O

O

O

O
O

10

15
Retention time / min20

Fig. 2 Library-search of methyl derivatives formedby THM using Pyrolyzate-MS22B libraryFig. 3 Polymer search results obtained using integration-summation
mass spectrum and PyGC-MS24B library
7

Polymer search using pyrolyzates of pyrogram (Pyrolyzate-MS22B library used)
Using mass chromatograms, unknown polymers can be
identified by searching the polymer library (PyGC-MS24B);
however, search can be accomplished utilizing chemical
information of pyrolyzates. In the example shown below, an
unknown polymer is identified through compound search foreach peak. First, from the pyrogram shown in Fig. 4, major

peaks (A) through (E) are selected. Then using NIST library,peaks (A) and (B) were identified as acrylonitrile and styrene,
respectively; however, there were no candidates for peaks (C)and (D). Using Pyrolyzates MS22B library, peak (E) was identified,
and the result is shown in Fig. 4. Candidate polymers can befurther narrowed down as shown in Fig. 5.

Pyrogram of unknown polymer

Search result for peak (E)(A) and (B) below were identified by library search on NIST
library; however, (C) and (E) could not be identified.
Styrene

N

N

N

(B)

Pyrolyzate-MS22B library was searched for the mass spectrum
for peak (E), and using the mass spectrum and its retention
index (RI), it was estimated to be 2-Phenethyl-4-phenylpent-4enenitrile. However, there were many polymer candidates ofwhich pyrograms contain the compound. Then candidates
must be narrowed down as shown in Fig. D3.

(RI : 1902)(RI : 2260)

N

(D)

(E)

12

14

Acrylonitrile(RI : 1384)

(C)
(A)

2

4

6

8

10

[min]

Furnace temp.: 600 ºC, Col: UA-5(MS/HT) (L=30 m, i.d.=0.25 mm, df= 0.25 µm), GC Oven: 40 (2 min) - 320 ºC (20 ºC/min)Fig. 4 Pyrogram of unknown polymer
Pyrolyzate candidates
generated upon library
search.

Polymer candidates which generate 2-Phenethyl4-phenylpent-4-enenitrile by pyrolysis.

Fig. 5 Search result for peak (E)Narrowing down from multiple polymer candidates (Visual comparison of pyrograms of polymers stored in the library)To narrow down candidate polymers, the comparative
display capability of F-Search is used. Shown below is
the comparison of the pyrograms of candidate
polymers obtained in Fig. 6 with the unknown polymer.
Candidate 1 can be eliminated by comparing peaks inGroup A, and candidate 2 can also be eliminated due to thepresence of 1-butene and butanol. Comparing peaks inGroup B, the unknown polymer can be narrowed down to beacrylonitrile-EPDM-styrene copolymer through comparison ofrelative peak heights.

Monomer

Dimer

TrimerStyreneUnknown polymer
Acrylonitrile
2

Group B

12

14

12

14

▼

Toluene4

Group A

6

8

10

▼

Candidate 1: Acrylonitrile-styrene alternating copolymer

Candidate 2: Acrylonitrile-acrylate-styrene copolymer
1-Butene

Butanol▼Candidate 3: Acrylonitrile-EPDM-styrene copolymer▼

Candidate 4: Acrylonitrile styrene copolymer

2

4

6

8

10

Retention time / minFig. 6 Visual comparison of pyrograms of polymers stored in the library
8

[min]

UA-5 column and UA-WAX column (Pyrolyzate-MS22B library used)

C10 RI : 1000

pyrolyzates of polymers are the same as those obtainedusing the UA-5 column, the elution order of the pyrolyzates
differs significantly due to the high polarity of the stationary
phase. Therefore, even when the target compounds areoverlapping with other compounds in a chromatogram
obtained using a UA-5 column, they may be separated witha UA-WAX column. Fig. 7 shows examples of polyethylene
and cellulose acetate-butyrate.

C10’

C14’
C20’

Furnace temp.: 600 ºC, Col: UA-5(MS/HT) (L = 30 m, i.d.= 0.25 mm, df = 0.25 µm), GC Oven: 40 (2 min) - 320 ºC (20 ºC/min)

C10’’ RI : 1089

UA-WAX

C10 RI : 1000

UA-5

C10’
RI : 991

Polyethylene

C10’
RI : 1045

C10’’ RI : 983

The low-polarity UA-5 column with 5 % diphenyl – 95 %dimethyl polysiloxane as stationary phase is commonly used
for GC/MS analysis. However, free acids and alcohols cancause peak shape deterioration, resulting in leading or
tailing peaks. Accordingly, a polar UA-WAX column with
polyethylene glycol as stationary phase is used. In Ver 3.8,
the pyrolyzates library contains additional 165 polymers
measured using the UA-WAX column. Although the

C14’
C20’

C10’

4

6

8

10

12

14

Retention time / min
Furnace temp.: 600 ºC, Col: UA-WAX (L= 30 m, i.d.= 0.25 mm, df = 0.25 µm), GC Oven: 40 (2 min) - 240 ºC (20 ºC/min)

n-Butanoic acid
RI : 829

UA-5

2-Hydroxyethyl acetate
RI : 766

Cellulose acetate-butyrate

Acetic acid
RI : 608

With a UA-5 column, compounds elute in order of boiling point, whereas with a WAX columns, compounds elutein order of polarity, i.e., from low to high polarity. Therefore, the RI of unsaturated hydrocarbons is different.

0

2

4

6

8

n-Butanoic acid
RI : 1620

UA-WAX

Acetic acid
RI : 1440

2-Hydroxyethyl acetate
RI : 1367

Furnace temp.: 600 ºC, Col: UA-5(MS/HT) (L = 30 m, i.d.= 0.25 mm, df = 0.25 µm), GC Oven: 40 (2 min) - 320 ºC (20 ºC/min)

10

12

14

Retention time / min
Furnace temp.: 600 ºC, Col: UA-WAX(L=30 m, i.d.=0.25 mm, df=0.25 µm), GC Oven: 40 (2 min) - 240 ºC (20 ºC/min)

Carboxylic acids with COOH groups, such as acetic acid and n-butanoic acid, with a UA-5 column give leading peaks due to their low
compatibility with the stationary phase. On the other hand, these compounds give sharp peaks with a UA-WAX column.

Fig. 7 Comparison of pyrograms using separation columns of different polarities

8

Analysis targets, Analytical Techniques, and Libraries for F-Search System<Local / detailed analysis with GC/MS>

Unknown sample
Double-Shot GC/MS analysis<Simple thermal analysis>

Analysis targets
Volatiles and non-volatiles

Additives (volatile)

Polymers (non-volatile) Polymer pyrolyzates (non-volatile)

Thermal desorption (TD)/ Pyrolysis (Py)

Pyrolysis (Py) / Thermally assisted hydrolysis andmethylation (THM)

Analytical techniques
Evolved gas analysis (EGA)

Data types (libraries)
Thermogram(EGA-MS24B)

Chromatogram(ADD-MS22B)

Pyrogram(PyGC-MS24B)

Pyrogram(Pyrolyzate-MS22B)

Specifications for F-Search System (Japanese patent 3801355, US patent 6444979)

Product name
(P/N)

F-Search“All-In-One”(PY-1110E-241)

Analytical technique

Number ofpolymers/additives

Packagecontains
Stored chromatogram F-Search (Ver. 3.8)
and all four
Number of mass
libraries
spectraOther

Optional libraries (search software F-Search (Ver. 3.8) (PY-1111E-241) required)

EGA-MS24B

PyGC-MS24B

Pyrolyzate-MS22B

ADD-MS22B(PY-1112E-241)(PY-1113E-241)(PY-1115E-221)(PY-1114E-221)

Pyrolysis-GC/MS(Py-GC/MS)

Pyrolysis-GC/MS(Py-GC/MS)

Pyrolysis-GC/MSand methylation-GC/MS(THM-GC/MS)

and methylation-GC/MS(THM-GC/MS)(TD-GC/MS)

268 polymers

590 additives(Py-GC/MS)
Evolved gas analysis
and
and
and
Thermally
assistedhydrolysis
Thermally
assistedhydrolysis(EGA-MS)
Thermal desorption-GC/MS

1,960 polymers

1,960 polymers(THM data in 33 polymers)

Thermogram(containing165 polymer data (Py and TD data in 200 additives)
obtained using UA-WAX
column)Pyrogram/chromatogram

c.a. 3,800

c.a. 5,800

c.a. 8,900

Contains all polymers listed in “Pyrolysis - GC/MS Data Book ofSynthetic Polymers -Pyrograms, Thermograms and MS of
Pyrolyzates-” S. Tsuge , H.Ohtani and C. Watanabe, 2011, Elsevier Inc.

c.a. 5,800
Contains 321 additives recorded
in “Standard Spectral Databasefor Polymer Additives ‘94/95”, S.
Tsuge, S. Takayama, 1994,
Nihon Kagaku Johosha, in
addition to 37 major additives forrubbers.

Compatible GC/MS(Available software)

Agilent (MassHunter, ChemStation), Shimadzu (GCMSsolution, LabSolutions), andJEOL (Novaspec, Escrime)
Thermo, Varian, PerkinElmer, and LECO require conversion to AIA format.

PC system required

OS : Windows 11, 10, 8.1 (64 bit or 32 bit) CPU: Intel or AMD, minimum storage space ： 600 MB• The complete lists of polymers and additives contained in the libraries are available on Frontier Laboratories’ website.
• F-Search can be installed on up to two PCs per single serial number.

4-16-20 Saikon, Koriyama, Japan, 963-8862
TEL:81(24)935-5100 FAX:81(24)935-5102
www.frontier-lab.com

10V240827E