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..-
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New Concepts in Polymer Science
Thermal Stability of Engineering
Heterochain Thermoresistant Polymers
New Concepts in Polymer Science
Previous titles in this book series:
The Concept of Micellar-Sponge Radiation Chemistry of Polymers
Nanophases in Chemical Physics of Polymers V.S. Ivanov
Yu.A. Mikheev, G.E. Zaikov
Polymeric Composites
Structure of the Polymer Amorphous State R.B. Seymour
G. V. Kozlov and G. E. Zaikov Reactive Oligomers
The Statistical Nature of Strength and Lifetime S.G. Entelis, V.V. EvreinovandA.I Kuzaev
in Polymer Films and Fibers Diffusion of Electrolytes in Polymers
B. Tsoi, E.M Kartashov and V.V. Shevelev
G.E. Zaikov, A.L. Iordanskii and V.S. Markin
Cyclolinear Organosilicon Copolymers:
Chemical Physics ofPolymer
Synthesis, Properties, Application
Degradation and Stabilization
0. V. Mukbaniani and G.E. Zaikov
N.M Emanuel and A.L. Buchachenko
Modem Polymer Flame Retardancy
S.M. Lomakin and G.E. Zaikov
Polymeric Biomaterials.
Part I. Polymer Implants
MI. Shtilman
Biodegradation and Durability of
Materials under the Effect of Microorganisms
S.A. Semenov, K.Z Gumargalieva
and G. E. Zaikov
Fire Resistant and Thermally Stable Materials
Derived from Chlorinated Polyethylene
A.A. Donskoi, M.A. Shashkina and G.E. Zaikov
Polymers and Polymeric Materials
for Fiber and Gradient Optics
N. Lekishvili, L. Nadareishvili,
G. Zaikov and L. Khananashvili
Polymers Derived from Isobutylene.
Synthesis, Properties, Application
Yu.A. Sangalov, K.S. Minsker and G. E. Zaikov
Ecological Aspects of Polymer
Flame Retardancy
S.M Lomakin and G.E. Zaikov
Molecular Dynamics of Additives in Polymers
A.L. Kovarski
Structure and Properties of
Conducting Polymer Composites
V.E. Gut'
Interaction of Polymers with
Bioactive and Corrosive Media
A.L. Iordanskii, T.E. Rudakova and G.E. Zaikov
Immobilization on Polymers
M.I. Shtilman
New Concepts in Polymer Science

Thermal Stability of
Engineering Heterochain
Thermoresistant Polymers

E. V. Kalugina, K.Z. Gumargalieva

and G.E. Zaikov

//IVSP/11
UTRECHT • BosTON - 2004
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2004 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Version Date: 20120727

International Standard Book Number-13: 978-9-04-741422-3 (eBook - PDF)

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 Thermal Stability of Engineering ...

CONTENTS

FOREWORD ................................................................................................. .
INTRODUCTION ........................................................................................... 1
Chapter 1. Degradation of aliphatic-aromatic polyimides - polyalkanimides
······························································································································ 6
POLYALKANIMIDE DEGRADATION IN MELT ...................................... 9
Thermal degradation ................................................................................... 9
Thermal oxidative degradation .................................................................. 21
Solid-phase oxidation ................................................................................. 39
Chapter 2. Degradation of aliphatic-aromatic polyamides .......................... 60
HIGH-TEMPERATURE DEGRADATION ................................................. 61
THERMAL OXIDATION IN THE SOLID PHASE- AGING ................... 80
Chapter 3. Degradation of poly(phenylquinoxaline) (PPQ) and co-
poly(imidophenylquinoxalines) ....................................................................... 88
Chapter 4. Degradation of polysulfones and polyesterimides ..................... 98
DEGRADATION IN MELT ......................................................................... 98
Polysulfones ............................................................................................... 98
Polyesterimides ........................................................................................ 126
On the mechanism ofPSF and P EI thermal oxidation ............................ 140
SOLID-PHASE OXIDATION .................................................................... 146
Polysulfone ............................................................................................... 146
Polyesterimide .......................................................................................... 15 0
Chapter 5. Degradation of aromatic co-polyesters derived from n-
oxybenzoic, tere- and isophthalic acids, and dioxydiphenyl ...................... 151
Heavy products of LCP degradation ....................................................... 158
Chapter 6. Fundamental regularities of thermal oxidation of heat-resistant
heterochain polymers ..................................................................................... 163
Chapter 7. Practical stabilization of heat resistant polymers .................... 178
LABILE STRUCTURES AND ADDITIVES ............................................. 178
Polysulfones ............................................................................................. 178
Polyesterimide .......................................................................................... 186
Polyphthalamides ..................................................................................... 188
Poly(alkane imide) ................................................................................... 192
STABILIZATION ....................................................................................... 196
Polysulfones ............................................................................................. 196
Polyesterimides ........................................................................................ 205
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov

Aliphatic-aromatic polyamides and glass-filled composite materials

derived from them .................................................................................... 205
Stabilization ofglass-filled composite materials derived from P PA ....... 207
Glass-filled composite materials derived from poly(alkane imide) ......... 218
On the mechanism of transition metal compounds .................................. 221
On the mechanism ofdegradation transformations in heat-resistant
heterochain polymers in the presence of stabilizers- phosphorus-
. containing compounds ............................................................................. 23 5
Chapter 8. Conclusion ................................................................................... 250
REFERENCES ............................................................................................ 254
ABBREVIATIONS ..................................................................................... 277
 Thermal Stability of Engineering ...

FOREWORD

In 1960, the laboratory on degradation and stabilization of polymers was

established in G.S. Petrov Scientific Research Institute of Polymeric Materials
on the initiative of Professor M.B. Neiman from Institute of Chemical Physics,
Academy of Sciences of the former USSR. At that time, development of
technologies for production of engineering polymers and composite materials
derived from them was the main objective of the Institute of Polymeric
Materials. High quality of the final product cannot be achieved without
understanding the features of thermal transformations in polymers, specifically
at the stage of material production (during polymer synthesis), then at
manufacture of articles, and so on. Therefore, very timely was establishment of
such division, directly related to process engineers who developed new
polymeric materials. Actually, in the early 1960's the problem of polymeric
material stabilization was of special interest both in Russia and abroad. Since
works by Soviet scientists had been published in different scientific magazines
during many years, in 1962 this brought up the question about publishing a
monograph about aging and stabilization of polymers. To speed up the process
of the book issue, a large group of specialists - the experts in stabilization of
polymers- was recruited for writing it. Fortunately, in 1964, the first Russian
monograph on this theme (Aging and Stabilization of Polymers, Ed. M.B.
Neiman) was published. Chapter 6 "Aging of polyamides" and Chapter 7
"Aging of some condensed polymers" were written by Doctor 1.1.
Levantovskaya, the senior scientific worker, and B.M. Kovarskaya, the Head of
Laboratory of degradation and stabilization of polymers, Institute of Polymeric
Materials.
That primary monograph initiated a series of publications on the above-
mentioned problems. One of the following monographs was "Thermal Stability
of Heterochain Polymers" which united results of investigations, carried out in
the laboratory of degradation and stabilization of polymers during next 15 years.
It was published in 1977, written by Doctors B.M. Kovarskaya, A.B.
Blumenfeld and 1.1. Levantovskaya.
In 1970's- the early 1990's a definite intensification was observed in
researches and development of new thermally stable polymers (polysulfones,
polyester sulfones, polyester ketones, polyester imides, aliphatic-aromatic
polyamides and polyimides, etc.). This outburst was induced by development of
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov

high technologies in the branch of aerospace industry, electronics and other

types of special engineering. Therefore, this naturally initiated development of
new directions in studies of heat-resistant polymer degradation in the mentioned
laboratory. The features of mechanisms of degradation transformations in these
polymers happened at high temperatures (during processing, for example)
required new, untraditional approaches to their stabilization. However, despite
the urgency of this problem, up to now it was shortly illustrated in generalizing
publications, which were mostly reviews and articles, published from time to
time in international and Russian scientific magazines and collections.
The present monograph is intended to pool the data, recently
accumulated in Russia and other countries in the branch of heat-resistant
heterochain polymers. The book shows investigation results of degradation
transformations in aliphatic-aromatic polyimides and polyamides, polysulfones
and polyester imides, liquid-crystal copolyesters and polyphenyl quinoxalines in
a wide temperature range, which includes temperature ranges of polymer
processing to articles and operation of the latter. High-temperature stabilization
of polymers is also discussed as an important applied task.
The authors of the book high appreciate the scientists of G.S. Petrov
Research Institute of Polymeric Materials from the laboratory of degradation
and stabilization of polymers, recently headed by Dr. A.B. Blumenfeld, the
leading specialists Drs. L.M. Bolotina, A.G. Chernov, M.E. Savina,
physicochemical and physicomechanical test departments, etc. for presented
materials and fruitful discussion of the monograph.

E.V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov

INTRODUCTION

The development of special machinery, aircraft and missile engineering,

and automotive industry brought up the task of creating heat-resistant polymeric
materials before chemistry of high-molecular compounds. By now
manufacturing of articles by press molding or extrusion is one of the most
effective and progressive methods. Therefore, polymeric materials must possess
thermoplastic property.
In recent decades, the achievements in chemistry of high-molecular
compounds are associated with creation of several polycondensation polymers,
which combine aromatic, carbo- and heterochain groups with aliphatic branches
in their structure. On the one hand, high softening temperatures which usually
fall above 250 - 350°C represent an important positive feature of these
compounds. It indicates the shape stability of even unfilled polymers in articles
up to 200 - 300°C or even higher. On the other hand, closeness of the melting
point and the start of degradation hamper processing of these materials.
Therefore, of importance becomes stabilization of heat-resistant polymers at
increased processing temperatures, usually falling in the range of 300 - 400°C.
Hence, the traditional task of polymer stabilization during long-term operation
(currently, also at increased temperatures) is actual still. Development of these
tasks requires implementation of a set of studies which include:

- Detection of thermally labile or defect structures in macromolecules;

Determination of acceptable content of primary and process additives in the
polymer;
- Setting the upper temperature border of processing, above which
degradation makes problems with the final product quality or abruptly
decreases sanitary-hygienic conditions of processing;
- A set of data for making sanitary-chemical passports for processing of
polymeric materials: identification and quantitative analysis of volatile
products extracted in the processing cycle;
- Estimation of operation property changes of polymeric materials at aging
and forecasting of temperature-time criteria of operation (durability).

Such applied setting of the problem allows posing of definite

requirements to raw materials and production process, which provide the
2 Thermal Stability of Engineering ...

complex of properties or the "quality" of the polymeric material, and setting the
operational life of the articles. Hence, more detailed approach to the problem is
possible: thermal transformations are based on chemical reactions of
macromolecules initiated by heat and active chemical agents present in the
environment, mainly, air oxygen (a special case, the so-called physical aging).
The study of chemistry (the mechanism) of thermal transformations of
macromolecules is not the point of fundamental sciences. They are highly
applicable, because understanding of the mechanism defines the possibility of
effect or control - currently, deceleration (stabilization) or acceleration
(ecological self-elimination or industrial processing of polymeric waste) of
polymer destruction. Of high importance are hydrocarbon (carbochain) and
vinyl chloride derived polymers. The fundamental studies of degradation of
these polymers, developed in the framework of chemical kinetics [1 - 5] and
united in monographs [4 - 22], have indicated the methods of thermal and
thermal oxidative stabilization, mostly using additives. For the main elementary
reactions, the classical kinetic problem of the "structure - reactivity" type is
solved via additives inhibiting the radical-chain process. This created a wide
range of effective stabilizers for polyolefins and PVC in the world industrial
production scope equal hundred thousand tons at 5% annual increase of
production [23]. The modern stabilizing compositions have drastically
improved stability of carbochain polymers and PVC at processing that allowed
realization of highly effective processing modes and significant increase of the
operational life of polymeric materials in articles.
The new phase in studying degradation and stabilization of polymers
was started over 20 years ago. Primarily, it concerned the so-called engineering
or construction thermoplastic polymers (thermoplasts), the overwhelming
majority of which represent heterochain polymers. Since 1985 till 2000, the part
of these polymers in the total volume of materials, including metals, increased
from 5 to 20%, which may potentially increase to 40% [24]. The most rapid
development is observed for the so-called high-temperature or heat-resistant
polymers, the production scope of which in the period of 1986 - 2002 was
increased by 14%. The highest raise was observed for polyester ketones- 27%,
polyester sulfones, polysulfones and polyester imides - 21%, liquid-crystal
polymers - 25%, aromatic and aliphatic-aromatic polyamides - 7%. Up to 60%
of high-temperature engineering plastics are applied in hi-tech branches of
industry - electronics and aerospace industry. For instance, the Boeing
Company experts estimated reduction of the cost price by 90% weight of
articles by 30% as replacing aluminum by modern composites (the so-called
advanced polymer composites- APC) in the aircraft building industry.
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 3

Engineering polymers are subject to thermal impacts during their life:

short-term when synthesized and processed and long-term during operation.
Seemingly, the situation is similar to the well-known polyolefins, styrene,
acrylic and vinylchloride polymers. However, thermal loads on technological
polymers in both phases are much higher, which is illustrated in Figure 1. Here
the abscissa axis represents processing temperature of polymer molding or
extrusion, and the axis of ordinates gives temperature resource of polymer work
capacity, characterized by the known UL parameter (where UL is the
Temperature Index) [25]. Therefore, the following tendency is obvious:
polymers with higher UL-indices are usually processes at higher temperatures.
The formal tendency indicates the fundamental dependence of thermal stability
on structure: the more rigid aromatic structure of a polymer is, the higher its
thermal stability is. The fundamental experience obtained in the science
(chemical physics) on the polymer aging at the previous stage of studying
mostly hydrocarbon polymers prompts a complex of interrelated physical and
chemical mechanisms defining kinetics of degradation of solid and melted
aromatic polymers.
However, mechanical transfer of the known degradation schemes, for
example, thermal oxidation, on aromatic polymers is not unambiguous: 1r- and
n,1r-systems differ from a-systems in their electrical and magnetic properties,
and electron excitation levels in them are much lower. It is commonly known
from the classical kinetics [ 1] that differences in electron structures affect
reactivity of aromatic and aliphatic molecules both qualitatively (different
mechanisms) and quantitatively (kinetically). Therefore, further development of
science on degradation and stabilization requires experimental study of
degradation behavior of new polymeric structures. Naturally, there are also
purely applied reasons for such investigations.
Technological polymers may conditionally be divided into two groups.
The first group is represented by heterochain aliphatic and aromatic
polymers with relatively low processing and operation temperatures:
polyacetals, aliphatic polyamides, PET, poly(butylene terephthalate),
polycarbonate. The phenomenology of thermal and thermal oxidative
degradation of these polymers is studied quite well. The applied thermal
stabilization of these polymers is definitely different from classical antioxidant
compositions; therefore, its successful development is generally based on the
empirical experience rather than on the understanding of the degradation and
inhibition mechanism.
4 Thermal Stability ofEngineering ..•

250
PEC

PPS
u 200
0 • •
PEl, PES
-~
....l • •
--
::>
><
(!) 150
PAl, PSF, LCP, PPA
• •
·-"'"""
s:
0 PC
:::;,
.......
100 • PET, •
• PBT
~

s
0
0.
•• PAc • • PA•
•ABS
~ ----..PE
50 PMMA, PS

0~----~----~~----~----_.----~
150 200 250 300 350 400
Processing temperature, °C

Figure 1. The upper temperature boundary of long-term operation (according to

UL temperature indices [25]) and temperatures of polymer
processing (beside the known abbreviations PA, PMMA and PE, the
following are used: PSF - polysulfones; PPS - polyphenylene
sulfide; PEK - polyester ketone; PAl - polyalkanirnide; PEl -
polyester imide; PES - polyester sulfone; PBT - poly(butylene
terephthalate); PAr- polyarylates; PAc- polyacetals; LCP- liquid-
crystal polyesters; PPA- polyphthalarnides; etc.)

The second group is composed of the so-called heat resistant and high-
heat-resistant polymers - polysulfones, polyester ketones, liquid-crystal
aromatic polyesters, fatty-aromatic and aromatic polyimides and polyamides,
polyester irnides, and other polyheteroarylenes. These polymers are processed
under rigid temperature conditions (300 - 400°C) and long operated at 150 -
300°C with respect to the structure type. Intense studies of thermal behavior of
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 5

polyheteroarylenes were initiated in 1970's - the early 1980's [25 - 28].

Apparently, this was associated with intensive introduction of these polymers in
aerospace technologies. Though degradation transformation mechanisms in
aromatic systems are still ambiguous, high-temperature antioxidant stabilization
of some polyheteroarylenes was successfully realized [26, 29 - 32], and even
hypotheses were advanced about the stabilizing action mechanism, principally
different from the mechanism of non-chain inhibition [33] considered as the
universal mechanism of high-temperature stabilization.
However, degradation behavior of the group of thermoplasts, usually
named as heat-resistant engineering polymers (HRP) - polysulfones and
polyester sulfones, fatty-aromatic polyimides and polyester imides, polyester
ketones, and liquid-crystal polymers, etc. - is not well studied yet. These
polymers are designed as hi-tech construction materials, mostly for electronics,
energy and vehicle machine industry [34]. Though temperature boundary for
long-tern operation of these polymers (about 200 - 250°C) is not so high as for
fully aromatic polyheteroarylenes, increased thermal stability and other
properties, as well as relative (compared with polyheteroarylenes) economical
efficiency of manufacturing and processing form the optimal set of properties,
owing to which HRP are intensively developed at present and will being
developed in future. Nevertheless, problems of HRP thermal stability,
specifically during processing, when the material "quality" is established, are of
particular character due to developing technology of HRP manufacturing. This
circumstance as well as the deficiency of information about thermal
transformations of HRP in the literature stimulated writing of this monograph.
The book is intended to cover questions interesting to a wide range of
specialists working in the branch of synthesis, processing and application of
plastics.
6 Thermal Stability of Engineering ...

Chapter 1. Degradation of aliphatic-aromatic

polyimides - polyalkanimides

Polyalkanimides (PAl) are fatty-aromatic polymers derived from

aliphatic, usually linear diamines and tetracarboxylic aromatic acids.
For the first time PAl were synthesized in 1955 by polycondensation in
melt of pyromellitic acid and C7 and C9 diamines [36]. In the former USSR,
Academician V. V. Korshak et al. were the first who synthesized PAI by the
one-stage high-temperature polycondensation in solution [37]. The studies of
PAl properties, derived from 3,3'4,4'-diphenyl tetracarboxylic, 3,3'4,4'-
diphenyloxide tetracarboxylic, and 3,3 '4,4' -diphenylsulfone tetracarboxylic
acids, as well as on pyromellitic acid and C6 and Cs diamines indicated the
prospect of PAl application as heat-resistant construction fiber polymers and the
binder for abrasion tools.
Industrial development of PAI was determined by the increase of
industrial demand in heat-resistant wire insulation. Experts of Raychem
Company tested many polymers, including polycarbonate and polysulfone. The
results of these investigations gave raise to design of technology and
organization of manufacturing PAI derived from pyromellitic anhydride and
dodecamethylene diamines or tridecamethylene diamines. These PAl possess
high hardness number at room temperature, are strong at temperatures above
150°C, and may be effectively processed by extrusion. In 1970's, Raychem
Company already produced a great variety of wires with insulation from PAI
[38- 40], PAl-based films and fibers, and construction materials of Polyimidal
and Poly-X trademarks for the automobile industry. Rohm und Haas GmbH
produces PAl derived from dodecamethylene diamine under Kamax 201 and
Kamax 301 trademarks [43]. In Russia, pilot production of PAl and composite
glass-filled materials derived from them is also realized.
Chemical structure of PAI with variable fatty chain length is the
following:
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 7

It provides the variety of macromolecule packing in polymeric body; therefore,

homological sequences of PAl became the object of many X-ray diffraction
studies which, besides works on synthesis, gave a large volume of fundamental
publications on PAl also concerning degradation transformations [37, 44, 45, 47
-49].
From applied positions, in the PAl family polydodecamethylene
pyromellitimide (PAI-12) attracts attention due to its excellent physical and
mechanical, heat physical and dielectric properties [50- 52]. In the sequence of
engineering thermoplasts, PAI -12 is considered as material for electrotechnical
purposes, having the working temperature range of 150 - 200°C. As is indicated
by "UL - temperature indices", PAl are present in the same sequence with
polysulfones.
PAI-12 (hereinafter, PAl, if not compared with different
polyalkanimides) is synthesized in sequence by polycondensation of
dodecamethylene diamine and pyromellitic dianhydride in N-methylpyrrolidone
solutions at 40 - 50°C, further polyamidoacid cyclization at 150°C, separation
of precipitated polymer with the cyclization degree over 90% (IR-spectroscopy
data on the ratio of absorption bands at 1780 and 1720 cm" 1), and then powder
washing and drying.

HN-(CH2)l2-HNOCVCO-

HOOC~COOHn
8 Thermal Stability of Engineering ...

(CH2)12-~
oc:©J:co
oc
0 co
> n

Polycondensation in amide solvent proceeds through formation of

intermediate salts ofthe following structure:

+H +-ooc :=©(coo
3
N-(CH ) -NH
2 12 3 0
HOOC COOH
n

which was determined with the help of IR-spectra and potentiometric titration
technique [54]. Studies of condensation in model systems, for example, phthalic
anhydride - Iaury! amine or pyromellitic acid - lauryl amine ones, also
indicated possible formation of di-, tri- and tetrasalts at a single aromatic ring
which, in turn, indicated quite high reactivity of all carboxylic groups at the
aromatic ring. At polycondensation appropriate group reactions must lead to
branching of macrochains, which is the apparent reason for low gel-fraction
concentration (below 5 wt.%) in the marketable end PAL Low defectiveness of
the structure is also indicated by comparison of calculated ([C] = 69.1 %, [H] =
6.8%, [N] = 7.3%, [0] = 16.8%) and experimental ([C] = 69.0%, [H] = 7.5%,
[N] = 7.1%, [0] = 15.4%) ofPAI elemental composition.
End groups significantly affect thermal oxidative stability of PAl. In
PAI synthesis pyromellitic dianhydride is taken in some excess that defines
predominance of carboxylic end groups in macromolecules compared with
amine ones or blockade of amino groups by acetic anhydride. Marketable end
PAl are have the melt viscosity equal 103 - 5x105 P or 77sp = 0.8- 1.5 (0.5%
solution of m-cresol - tetrachloroethane mixture). According to X-ray
diffraction data [46, 4 7] P AI has 40 - 60% crystallinity degree, and the chain
conformation of the polymer extracted from the reaction mixture is coiled in the
amine component. At temperature about 270°C, resulting conformation
transformation, the chain is straightened and becomes bladed; PAI melting point
is 285°C with the maximum of appropriate endothermic DSC peak at 298°C.
 E. V. Ka/ugina, K.Z. Gumargalieva, and G.E. Zaikov 9

The following production phase - extrusion, is used either for powder

pelletization or obtaining composite materials (glass-, mineral-, etc. filled),
derived from PAL The temperature mode by zones is 270 - 330°C. The mass
was press molded at 330 ± 10°C to a mold, heated up to 150 - 180°C. These
stages are the most temperature aggressive for the polymer. That is why the
·study of degradation transformations in the melt is the urgent problem.

POLYALKANIMIDE DEGRADATION IN MELT

Thermal degradation

Chemical instability of PAl macromolecules in melt becomes noticeable

already at 300°C due to the increase of gel-fraction content and decrease of
specific viscosity in solution (Figure 2). The processes are speeded up with
temperature, and the effective activation energy of PAI gel formation in the
temperature range of 300- 450°C equals (50± 10) kJ/mol.
Judging by kinetics of mass losses and cl - c3 hydrocarbon extraction
(Figures 3 and 4), pyrolytic reactions in PAl are detected already at 300°C,
though after tens of hours of heating are required for detection. At the initial
stage, the seeming zero order of kinetics of mass losses and hydrocarbon
extraction is determined by transformations degrees, negligible even at 400°C.
The effective activation energy of mass losses, equal (232 ± 20) kJ/mol,
correlates with Ea values for release of methane, ethylene, ethane and propane
equal (192 ± 15), (160 ± 15), (238 ± 15) and (170 ± 15) kJ/mol, respectively.
PAl pyrolysis at 300°C proceeds with release of light (volatile)
hydrocarbons only; at 350°C or higher carbon oxides and low-volatile products
are also released from PAL The latter precipitate near the hot zone, shaped as
yellow-brown oil-like blushes and light crystals.
According to 13 C NMR-spectroscopic and mass-spectroscopic data, this
oil-like blush is formed by the following homologues of phthalamide, nitrile
phthalamide and pyromellite diimide:
10 Thermal Stability of Engineering ...

40 r - - - - - - - - - - - - - - - - - - - , 0.9

30 0.8
ci~
~

t:::
0
......
u
cct 20 0.7 ~-
~ 0
0
0
0 -·
cr.
q

lO 0.6

~-----~--------~-------~------J.------' 0.5
0 I00 200 300 400 500
Temperature, °C

Figure 2. Kinetics of gel-fraction accumulation (1) and sol fraction viscosity

variation (2) at PAI degradation in vacuum
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 11

p
©=~ >N- R' (R)
II
0

Homological sequences are traced well by mass-spectra of degradation

products measured at low ionization potential with sequences of molecular ions,
differed by 14 wt. units:

(CH2)- 217-231-245-259-273-267-301- 315;

201-215-229-243-257-271 -285-299-313-327- 341;
230-244-258-272-286-300-314-328-342- 356-370-384-398
-412-426-440-454-468-482-496-510-524- 538.

Natural fractionation of the products with respect to distance from the

hot zone and determination of mass-spectra at programmed heating allow
detection of the yield distribution in homological sequences. This distribution
indicates preferable breaks of methylene chains at their ends (a great amount of
methyl phthalimide is formed) or almost at the middle of them.
A low volatile product precipitating as crystals Gudging by IR-spectra of
crystals and ethanol [136]) represents ammonium bicarbonate, the formation of
which during PAl pyrolysis is possible at the interaction of primary products
(ammonia and C02) in the hot zone, i.e. NH4HC03 is the secondary product.
12 Thermal Stability of Engineering ...

100
- ,
..... .....

~0
' \
\
\
\
\1
\
?t 60 \
~
~
\
0 \
~

'f.
:;n
\
(';! \
::?: 40

20

0
200 400 600
l;;lllperatun:. °C

Figure 3. Thermogravimetric analysis (TGA) of PAl at the heating rate of 5

deg/min in air (1) and argon flow (2)

As the initial chemical structure and chemical structures of the products

are compared, it is indicated that pyrolytic transformations of PAl proceed in
two directions: by methylene chains and heterocycles. Being the most thermally
labile fragments of PAl macrostructure, ethylene chains begin degrading at a
noticeable rate when polymer melts, i.e. at 300°C, approximately, though even
at this temperature the pyrolysis rate is also negligibly low Gudging by total
yield of hydrocarbons): about 0.1% of methylene chains per hour are damaged.
At 350°C, products of heterocycle decomposition occur: carbon oxides,
phthalimide and nitrile phthalimidestructures, but the yield of these products is
very low yet. For example, the release rate of C0 2 - the main product (by yield)
of heterostructure degradation - is by one and half orders of magnitude lower
than hydrocarbon release rate, not even taking into account the release of
oligomeric fractures with residues of broken methylene chains. However,
heterocycle pyrolysis becomes clearer with temperature increase. At 400 -
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 13

=i' 0.8
0
:i
u"
; 0.4
:c
u

0 50 100 150
Time, h

Figure 4. Extraction kinetics of CH4 ( 1, 1',I"), C2H4 (2, 2', 2") and C2H6 (3, 3',
3") at 300, 350 and 450°C, respectively, and C3H 8 (4, 4') at 350 and
400°C at PAl degradation in vacuum

450°C IR-spectra display the progressive degradation of heterocycles, first, by a

decrease and then full disappearance of absorption bands at 1720 and 1780 cm- 1,
related to V5 (C=O) and Vas(C=O) of the imide cycle [137], respectively. One
more sign of this degradation is occurrence and intensification, and then full
dominance (at 450°C or higher) of v(C=N) absorption band of nitrile groups
[138]. Aliphatic structure degradation leads to the conjugation system increase
in pyrolyzate, detected by intensive coloring of the coke residue and
paramagnetic manifestations (ESR signal represents a singlet with g-factor
equal to free electron). The analysis of polymer degradation always implies two
points of view on this process. From practical positions, purely thermal
(pyrolytic) reactions must not make obstacles at normal cycle of PAl processing
lasting several minutes. However, thermally, PAl is not absolutely inert in the
temperature range of processing. Though the pyrolysis rate is still negligibly
low, at overheatings and long stay of the material in dead volumes pyrolytic
reactions will cause serious damages of chemical structure of macromolecules
and, correspondingly, a decrease of polymeric material quality.
14 Thermal Stability ofEngineering ...

Moreover, thermal transformations in PAl are of definite scientific

interest. The structure of PAl which represents (very simply) a hybrid of
polyethylene and polyimide has not ever been considered in terms of reactivity
in thermal reactions. Basing on the previous experience in the polymer science,
it might be instinctively forecasted that methylene chains are thermally stable
compared with cycloarylene structure, but the experiment is the only think that
may determine the features of flexible and rigid fragment reaction in the
chemical structure and, apparently, their interrelations.
Let us start from low temperatures (300°C), when methylene chains
break and heterocycle is stable still. Typical feature of this process is rather
narrow selection of C1-C3 hydrocarbons- the degradation products. Random
breaks would cause occurrence of wide selection of products from methane to
dodecane and release of alkylpyromellitimide oligomers. In the sensitivity range
of modern instrumental techniques of analysis (GLC, mass-spectroscopy) the
attempts to detect these substances failed. This means that either these
substances do not occur at all or, which is most probable, their synthesis rate is
negligibly low versus light hydrocarbons. As a consequence, methylene chain
breaks in PAI have some specificity.
It is common knowledge that similar to cracking of alkanes, pyrolysis of
PE and other hydrocarbon polymers is the radical-chain process [82]. The signs
of radical process are observed for pyrolysis of methylene chains in PAl, which
are high activation energies and synthesis of not single but several unitypical
products (hydrocarbons up to C3) with approximately similar yields. Finally, of
great importance is the similarity principle concluded in equal structure
(methylene chains) and equal chemistry. The chain type of the process is
determined directly by chain initiation and propagation rate changes. This was
made at the study of hydrocarbon cracking, when the origin of one product or
another in one elementary reaction or another may be simply determined. At
polymer pyrolysis direct proofs of the chain process proceeding are not
obtained. Indirect proofs are used: correlation of effective activation energies
with C-C bond strength and identification of products, which synthesis might be
explained as the consequence of the chain transfer reaction.
These signs are also displayed by pyrolysis of PAl methylene chains:
effective activation energies of C1-C3 hydrocarbon release fall within the range
of 160 - 240 kJ/mol, which is much lower than any estimations of C-C-bond
energy both in purely carbon surrounding (330 - 360 kJ/mol) and nearby the
heteroatom (290- 330 kJ/mol) [78]. Homolytical break of a-C-C-bond happens
simpler compared with more distant bonds. Single 0 and N atoms in the chain
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 15

reduce a-C-C-bond strength by 12- 20 kJ/mol [139]. High delocalizing ability

is displayed by aromatic ring: delocalization energy of benzene radical equals
30- 40 kJ/mol [115]. Following the additivity concept in chemistry, one would
expect an analogous effect for pyromellitimide fragment. The authors of the
current monograph have calculated molecular diagrams for methyl phthalimide
and dimethyl pyromellite diimide - compounds modeling the boundary
fragment of the elementary unit of PAI - by CND0/2 technique using the
software developed in L.Ya. Karpov Research Institute of Physical Chemistry.
The geometry of molecules is shown in [140]. Diagrams in Figure 5 show
charge distribution on atoms ofthe models.

(1) -0.2341
0.0209
W0.3109 -0.0017

8c~ -0.2738
N-C-H
f o.I05o

C o.3125 H
0.0097
I
11 -0.0017

0.0179 0
-0.2376
-0.3088
{?

c>
0.0079
(2) II o.3461
0.0266 o.o158 fc o.oo25
-o.o156H-
1 -0.0172 N-c· H 0947
-0.0085
-o.o156 H I
0.0267
-o.o169 i
-0.191

H
-0.0085

0.0079
0
-0.3071

Figure 5. Molecular diagrams of PAl model compounds: dimethyl pyromellite

diimide (1) and methylphthalimide (2)
16 Thermal Stability of Engineering ...

The calculations show development of Jr-electron system in the model,

which also affects alkyl substituting groups, to higher extent at a-C atom rather
than at a distant one. Valent Jr-electron released from a-C atom at homolytical
break of C-C and C-H bond is engaged in the 1r-system of arimide cycle, e.g.
delocalization energy is released, by the value of which the strength of a-C
atom bonding in alkyl substituting group is reduced.
Therefore, since strength of aliphatic C-H-bonds is much higher than
that of C-C-bonds [78], the most probable initiation act is the weakest a-C-C
bond break in the methylene chain:

r P
"""-N<»~ /N-CH 2
II I
0 0
I

Though the end alkyl macroradical I is stabilized by the arimide

structure, it dies eventually, most likely, by detachment of H-atom and
sequential formation of methyl pyromellitimide end group. End macroradical II
of quite long methylene chain is quite reactive, especially in the polymer melt.
Actually, macroradical II is identical to corresponded macroradical of
methylene chain in PE.
The situation becomes more similar due to close viscosities of the melts
of marketable end PAl and common PE trademarks (up to 105 P). This
definitely indicates equal molecular mobility in melts. The probability of two
subsequent breaks in the same methylene chain of limited length is low.
Therefore, long hydrocarbons are not detected in products of PAl pyrolysis at
300°C. More probable is depolymerization of macroradical II with ethylene
detachment, which is the main product by output at 300 - 350°C.
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 17

Ethylene polymerization heat known from the literature [141] equals 121
kJ/mol, which correlates well with experimentally determined activation energy
of ethylene release at PAl pyrolysis (158 ± 12 kJ/mol). End macroradicals of
type II are capable of realizing the chain transfer by detaching H atom from
CH2-group in intermolecular or intramolecular reactions. Intramolecular
detachment of H atom as a monomolecular reaction is kinetically more
profitable than the interchain exchange [1], if nonstressed transition complexes
are synthesized. This possibility of macroradical II isomerization through six-
term transition complex formation leads to detachment of C3H7 radical then
formation of C3Hs and end allyl groups:
0
II
P
I /C~" r /CH2'-.,..
CH
...,.,... N(~
~c
C )N- CH
2
CH -CH ---- C
2 2
2 _____..
1,,
I II H ',, /CH2
0 0 CH 2

Compared to other hydrocarbons, besides ethylene, relatively low

effective activation energy of propane release which equals (170 ± 14) kJ/mol
correlates with suggested mechanism of its formation in specific reaction of
radical isomerization. As temperature increases, differences in the reaction
energy becomes smoother, and already at 350°C products of PAl pyrolysis
possess compounds of oligomeric type with full selection of lengths of
methylene chains.
Thermal instability of the imide cycle is observed already at 350°C,
when products of its decomposition - carbon oxides, phthalimide and nitrile
18 Thermal Stability of Engineering ...

phthalimide structures- are primarily detected (formed). Schemes of pyrolytic

reactions of polymellitimide cycle are widely discussed in the literature, devoted
to degradation problems of classical aromatic polyimides [28]. Generally, these
schemes are unambiguous, but some reactions - imide-isoimide regrouping, in
particular, which leads to formation of a "crude" for C02 (one of the main
products)- are unique:

This reaction explains the occurrence of both C0 2 and nitrile

phthalimide homologues in PAl pyrolysis products with some molecular ions in
the following mass-spectrum: 201-215-229-257-271 - 285.
The only way for CO formation is direct break of isoimide cycle and its
decomposition. Besides molecular hydrogen release, some products may be
hydrogenated at high temperature in hydrogen-fertile systems (which are PAl)
with active transfer of H atoms from methylene chains. This is confirmed
experimentally by detection of ammonium bicarbonate (the "witness" of
ammonia presence in the system) in the pyrolysis products:

i p ,'
I c ,'
c '
,>N- CH2"""
H
.. NH
3
+
:II \
0 .

The set of heterocycle pyrolysis products in PAl conforms to that of

polypyromellitimide derived from 4,4'-diaminodiphenyl ester of the Kapton
type - the representative of aromatic polyimide family, most well known and
studied.
Of interest is another thing: if the radical process of methylene chain
degradation in PAI affects stability of heterocycles in its structure compared
with classical polyimides, in which chain type of the process is rather
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 19

0
E
~ 00?
.-
""c:s
.e
0
s
8'
8 0.01

0 50 100 150
Time,h

Figure 6. Kinetic curves of CO (1) and C02 (2) release at PAl degradation in
vacuum at 350°C

ambiguous at low temperatures, when direct detachment of H atom from the

ring is thermally hampered still. Among organic compounds, the strength of
Caromatic-H-bonds is maximal [78]. Figure 6 shows kinetic curves of carbon
oxides release during PAl thermal degradation at 350°C. There are no data in
the literature on transformations of aromatic polyimides under current
conditions. Therefore, these products obtained at pyrolysis of fatty-aromatic and
fully aromatic polyimides may not be accurately compared. It has been shown
[142] that thermal processing of aromatic polyimide PM proceeding during 2
hours at 485°C in the oxygen-free environment releases 0.15 and 0.3 mol/base-
mol of C02 and CO, respectively. Even a rough comparison of total yields of
these products shows much lower stability of the heterocycle in fatty-aromatic
polyimide. Apparently, chemical structure of PAl represents one more example
of interrelation and agreement of structural components, absolutely different in
their structure. Elementary unit of the macromolecule is presented by an entire
construction. Some elements of the structure are displayed under some
conditions, and the rest elements - under other conditions, but signs of
20 Thermal Stability of Engineering ...

nonadditivity will always be found in the behavior, indicating the interaction of

elements. The concept of additivity is a suitable tool of investigation, which
gives an opportunity to assess the system response. Therefore, real deviations
from additivity create a broad palette of reactivity and properties observed for
polymers, which macromolecules are "built up" from the same "bricks".
Thus, in the temperature range of PAl processing, its pyrolytic
transformations, generally associated with degradation of methylene chains, is
possible. Since high-temperature inhibition of alkyl radicals, for instance, such
radical "traps" as conjugation systems or stable radicals, is low effective, the
processing mode must be strictly observed and overheatings avoided.
Heating in air is of greater danger for PAl, because its degradation is
sharply intensified due to oxidation.

100

?;':. 60
u:··
ttl
...9
'f)

""
~
2: 40

20

0 100 200 300 400 500 600 700

Temperature, "C

Figure 7. TGA curves for PE (1), PA-12 (2), PA-6 (3), PAl (4), and PI (5), in
air at 5 deg/min heating rate
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 21

Thermal oxidative degradation

The formal assessment by TGA technique in air (Figure 7) shows that

among other polymers with one or another PAl fragments in the structure
(namely, aliphatic polyamide derived from dodecalactam (PA-12) and
polypyromellitimide derived from 4,4 '-diaminodiphenyl ester (polyimide PM-1
or Kapton), thermal oxidative stability of PAl is medium. Figure 7 also shows
TGA curves for high density polyethylene (HDPE), which structure models
very long methylene chain (3 - 6 branches and 0.6- 0.8 unsaturated bonds per
1000 C atoms in the methylene chain) [143], and polycaproamide (PA-6)- the
polymer with relatively short methylene chain.
It is clear why thermal stability of PAl in air is lower compared with
aromatic polyimide. The whole experimental experience in questions of
oxidation of hydrocarbons, hydrocarbon and heterochain polymers [ 1, 8]
testifies about higher reactivity of aliphatic structures in thermal oxidation
reactions, which confirmed by well-developed theory of gas- and liquid-phase
oxidation [2, 8]. This theory associates kinetics of oxidative reactions with C-H
bond strength, chain process specificity, and the presence of intermediate
products which branch the kinetic chain. Apriori thermal oxidative degradation
of PAl is developed in the aliphatic chain. PAl possesses higher thermal
oxidative stability compared with other polymers of similar structure,
specifically with the closest analogue- PA-12. Judging by kinetics of H atom
detachment by nitroxyl radical in heptane, pentane and linear PE [144], the
strength of C-C and C-H-bonds changes weakly along the methylene chain. The
energy of middle C-C-bond breaks in C12H26 and C6H 14 equal 334 kJ/mol.
approximately [78]. The bond strength in alkanes increases by 10% approaching
the chain end [78]. On the contrary, C-C- and C-H-bond strengths in nitrogen-
containing aliphatic compounds are reduced by 8 - 20 kJ/mol compared with
methylene groups more remote from the heteroatom [139]. Similar effect of
another heteroatom (oxygen) on thermal oxidation kinetics of polyethers and
strengths of appropriate bonds was shown before [139]. Calculations and
experimental determination of C-H-bond strengths in individual compounds are
confirmed by studies of thermal oxidative degradation of aliphatic polyamides,
for which the primary attack of oxygen on a-methylene group was shown [26].
The above-shown results of quantum-chemical calculations of the models
indicate delocalizing ability of the arimide fragment even in relation to valent a-
electrons of methylene C atom. Therefore, from positions of pure chemistry,
one would hardly expect any advantage in thermal oxidative stability, which
really exists in PAl compared with the analogues- aliphatic polyamides.
22 Thermal Stability of Engineering ...
400~------------------------------------------~
PAI-6
0

350

300

250

200

!50 ~----~----~------~----~----~~----~----~
100 150 200 250 300 350 400 450
Melting temperature, <>c
Figure 8. Dependencies of melting point and initial degradation temperature
(To) according to TGA data on PE, PA-12, PA-6, PAl (1) and
polyalkanimides (2) at the heating rate 5°/min in air

The modern concept of solid-phase degradation reactions [9] is

illustrated by the dependence of almost all elementary reactions of chain
oxidation, 0 2 and degradation product transport due to molecular movements in
the polymeric body. Even the initial mass loss temperature (To) - the gross
parameter of thermal oxidative stability - in the sequence of polymers having
similar chemical structure of the elementary unit is bound to macrochain
mobility, estimated by melting points of the polymers. The polymers in the
following sequence: PE, PA-12, PA-6 and PAl, possess melting points equal
125, 181, 215 and 298°C and To equal 60, 240, 270 and 320°C, respectively. As
is obvious, both parameters display almost linear dependence (Figure 8).
Similar dependence was also observed for some polyalkanimides with
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 23

methylene chain from 6 to 13 carbon atoms long: PAI-6, PAI-8, ... , PAI-13,
correspondingly (Figure 9).

.,....,...,
/'"
I
I
I

0 100 200 300 400 500 600 700 800

Temperature, °C

Figure 9. DTA curves for PAl in air (1) and argon flow (2). The heating rate is
5°/min

The thermogram of PAl in air (Figure 9) possesses high intensity

exothermal DTA peak with the maximum at 290°C and two less intensive
exothermal peaks with maximums at 350 and 450°C. The first peak corresponds
to temperatures approaching the initial mass loss temperature, whereas other
peaks correspond to advanced PAl degradation. A thermogram, recorded in the
absence of 02, possesses a split up endothermic peak, related [47] to the phase
transition of PAI (279°C), at the place of the first exothermal DTA peak
location.
The exothermal effect associated with 02 presence fully masks
endothermic effects of both phase transitions.
Similar situation is observed for other polyalkane pyromellitimides -
PAI-6, PAI-8, PAI-9, PAI-10, PAI-II, and PAI-13 - for which the intensive
24 Thermal Stability of Engineering ...

exothermal peak masks endothermic peaks of phase transitions and melting. The
dependence of PAl chain conformation features on the evenness (the number of
C atoms) of the methylene chain is considered [47]. It is proved that contrary to
PAl with even number of methylene groups (except for PAI-6), a spiral twofold
axis is typical of uneven aliphatic chains of PAl and PAI-6. In the case of
massive framing (heterocycle), this axis prevents chain packing e.g.
crystallization. P AI with even chains are highly crystalline polymers, and
uneven ones are liquid-crystal with the long-range order along the chain and
short-range order in the chain location plane [47]. The phase transition of
primarily coiled structure to more stretched one is absent in uneven PAI and
PAI -6, whereas in even P AI it is prior to melting.

Table 1
T emperat ure t rans1·rIons and h eaeecsm
t fti t . PAl
DTA effect*, kJibase-mol
Melting Exoeffect
Phase point, °C Initial correction
Polymer transition (byDTA Phase oxidation with
temperature, peak transitions (lstDTA respect to
oc [47] maximum) (total) exopeak) phase
[47] transition
heats
PAI-6 - 430 10.3 139.1 149.4
PAI-9 - 303 23.3 76.1 99.4
PAI-11 - 292 23.4 77.0 100.4
PAI-13 - 263 24.6 107.9 132.5
PAI-8 349 362 18.5 190.3 208.8
PAI-10 308 318 26.9 191.9 218.8
PAI-12 279 298 31.0 203.5 234.5
Note: * According to known data from the literature, thermoanalyzer is
calibrated by NaN0 3 and AgN03 standard substances, which melting
temperatures fall within the range of PAl phase transition
temperatures. Calibration check of PET melting heat gave (40.6 ± 4)
kJ/mol, which correlated well with literary data [145]- 47.3 kJ/mol.

Therefore, the connection of exothermal DTA peak in the presence of 0 2

in the system and its location near the initial mass loss (intensive PAI
degradation) in the temperature field indicates its oxidative origin. Putting the
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 25

mechanism of P AI interaction with 02 aside, note that the process in even PAl
is characterized by almost twice higher hear release rather than in uneven PAI
and PAI-6 (Table 1). This shows obvious correlation between thermal oxidation
kinetics and morphological features of PAI structure.
Since the rate of heat release correlates with thermal oxidation rate, at
molecular mobility defrost (1st phase transition) and further melting the
oxidation rate of even, highly crystalline PAl is twice higher compared with
uneven, liquid-crystal PAI. NMR wide bands of uneven PAl also display a
narrow component indicating the presence of non-crystalline domains. For more
details on the liquid-crystal structure formation in uneven PAl, refer to X-ray
diffraction analysis results [4 7].
At dynamic heating, a rigid, low mobile structure of even PAl somewhat
stabilizes the polymer. Methylene chains in PAl, thermodynamically labile at
high temperatures (in PE, these methylene chains are intensively oxidized and
break at these temperatures), are kinetically unable to overcome the activation
barrier of unfavorable (possibly for propagation and kinetic chain branching
reactions) morphological structures. The polymer is somewhat "overheated",
which promotes similarity with the idea of "explosive" depolymerization, put
forward [146] in the analysis of TGA data on depolymerizing polymers at
extremely high heating rates (over 200°/s). The authors [146] suggested
characterize degradation by critical temperature, at which intermolecular links
preventing emission of products - backbone fractures somewhat break at ones,
and the polymer "explosion-like" degrades.
In PAl hydrogen bonds are absent [47]. Therefore, thermal oxidation
kinetics is limited by dormancy of molecular motions in macrochains. We are
not to discuss the mechanism of morphology effect on kinetics of PAl thermal
oxidation in the radical-chain process. One may refer to the famous monograph
written by Buchachenko and Emanuel [9], where this question is thoroughly
discussed on the example of solid polyolefins. The oxidation chemistry of these
substances and their low-molecular analogues - liquid hydrocarbons, is studied
quite well. The following different thing is of importance in the context of the
current monograph. The intense oxidation during a short time (within the 1st
exothermal peak at the thermogram - 10 min or less) leads to noticeable
degradation-induced changes, increasing in the polymer symbate with oxidation
proceeding (traced by the DTA curve run, Figure 10). The gel-fraction content
in PAl within exothermal peak of oxidation is auto-excited accelerated up to
15%, and specific viscosity ofthe sol-fraction decreases from 0.88 to 0.52 dl/g.
26 Thermal Stability of Engineering ...

50 .-----------------------------------------~

40 0.8
"0
-:>'
t:
0
·.:::

0
0
~
~.:.:
<:,)
30 - 0.6
tI+
20 0.4 i",./1

10 0.2

-----·-'------'------'-----'----'-------·-_l____.....__ ____.0
0 50 100 !50 200 250 300 350 400
Temperature, "'C

Figure 10. Gel-fraction content (1) and sol-fraction viscosity (2) in exothermal
DTA peak for PAl (3) in air (the heating rate so/min)

The first stage of PAI-12 powder processing (extrusion, compounding)

is similar to thermal analysis, and the sample is subject to dynamic heating in
both cases. At initial stages of vacuum extruder the residual pressure equals 30
- 50 mm, e.g. oxygen is always present in the system, even not taking into
account oxygen dissolved in the polymer. The gross heat release corresponded
to the 1st exothermal DTA peak increases from 203.5 to 277.8 kJ/mol with the
heating rate of S0 /min. As a consequence, in contrast with the extremely short
range of dynamic heating (320 - 350°C) at vacuum extrusion of the powder,
danger of PAI-12 thermal oxidation is significant at polymer melting. This is
confirmed by difficulties in its processing into articles and problems with
granular material quality.
Hindered P AI oxidation at low temperatures (below 250°C) does not
show its full absence. For example, PAl heated in air at 200°C during 100 hours
absorbs more than 1 02 mol/base-mol. The 1st exothermal peak is absent on the
thermogram. It is replaced by an endothermic peak associated with melting of
the polymer. On the thermogram of oxidized sample the first exothermal peak is
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 27

absent, and an endothermic peak associated with the polymer melting occurs at
its place. The first exothermal peak is a suitable index of PAI-12 oxidation
degree, if 02 diffusion into the sample is free. For example, if a bulky sample
melted in air is grinded, the powder thermogram possesses oxidation exotherm
at the place of endotherm of melting.

b.H

100 150 200 250 300

Temperature, °C

Figure 11. DTA curves for PA-6 (1), PA-12 (2), PBT (3), PET (4), and PAI-12
(5) heated in air (heating rate 5°/min)

The phase transition effect on exothermal DTA peak, similar to PAI, is

observed for PET and specifically for poly(butylene terephthalate) (PBT). These
are crystalline polymers with chemical structure affined to PAl, namely, by
combined methylene chains and aromatic rings (Figure 11). Judging by
significant intensity of exothermal peaks preceding endothermic melting peaks
28 Thermal Stability of Engineering ...

on DTA curves, oxidation processes, primarily hindered due to the structure

rigidity, are sharply intensified at pre-melting of these polyolefins. On the
contrary, oxidation of aliphatic PA is described by a fuzzy exothermal peak. As
shown in the thermogram, it begins at temperatures much below P A melting
point (Figure 11 ). Exothermal PA peaks are symbate to weight increment due to
atmospheric oxygen binding. No weight increments at PAl, PET and PBT
heating are observed. DTA curves illustrate the difference in thermal oxidation
kinetics for crystalline polymers having methylene chains in their structure.
Purely aliphatic polymers with highly developed molecular motion in the solid
phase are simply oxidized at dynamic heating at temperatures much below their
melting points. Solid oxidation of fatty aromatic polymers is hindered, but
becomes intensive at phase transition temperatures. DTA data is sufficient for
thermal stabilization of engineering polymers. For example, for aliphatic PA,
these data currently indicate the necessity in protection of polymers both at
processing and operation, whereas PAl and aromatic polyester should be
stabilized at processing only. However, the final decision about thermal
stabilization at particular stages of polymer "life" may be made on basis of
comprehensive study of polymer features concerning its thermal behavior in
temperature intervals of material processing and operation.
When heated, PAl absorb 0 2 and release carbon oxides, water and
formaldehyde (Figure 12). Thermal oxidation kinetics (with eliminated
diffusion hindrances) is at first glance of the breakthrough type typical of high
temperature oxidation of hydrocarbon polymers [147]. At 250 - 300°C during
initial 5 - 20 hours, PAl absorb up to 8 0 2 mol/base-mol. Further on, the process
is abruptly slowed down, but the polymer manages to absorb more 2 0 2
mol/base-mol during next 100 - 200 hours. The two-stage type of thermal
oxidation process is clearly observed at 350°C, when the first fast stage is
finished by absorption of 8 02 mol/base-mol during last 2 hours, and then the
second, slow stage with almost linear dependence of 0 2 absorption rate lasts for
hours. At low temperature oxidation of PAl (250°C or lower) the second stage
is not observed. As transferred to semi-logarithmic coordinates, corresponded
kinetic curves of 0 2 absorption and those describing the first stage of high-
temperature oxidation are transferred to lines that formally indicate the first
kinetic order. The Arrhenius temperature dependence of 0 2 absorption initial
rate constants does not fit a straight line, but displays a break in the temperature
range of phase transitions in PAl (Figure 13).
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 29

12 r--------------------------------------------------.

10
2
3

........-- ---------------
5
---------
__..!!..-------
__ ......... _.....------ --
/
/

"
2
I
I ,......._________ ___.
...,.,...-----
-----
7

0 20 40 60 80 100 120 140 160 180 200

Timc.h

Figure 12. Kinetics of 02 absorption (1 - 4), C02 (5 - 8) and CO (9 - 12)

release at thermal oxidation of PAl in air at 350, 300, 250 and
200°C, respectively

Kinetics of carbon oxide release is identical to 0 2 absorption kinetics.

Effective activation energies of CO and 02 release at PAl thermal oxidation in
melt equal (163 ± 10) and (135 ± 10) kJ/mol.
The two stage kinetics of high temperature oxidation of aromatic
polybenzoxazole containing the methylene bridge in the diamine component is
described in the literature [148]. The first, fast stage is associated with aliphatic
fragment oxidation, and the second, slow one - with oxidation of the aromatic
structure. The case is similar for PAL The below IR-spectroscopy and mass-
spectrometry data indicate that methylene chains are primarily oxidized both at
low temperature of PAl oxidation (the operation temperature range and close
temperatures) and high temperature oxidation (temperature of processing)with
exposures correlating with the processing cycle duration. Therefore, aromatic
30 Thermal Stability of Engineering ...

structure is not practically touched. At processing temperature the rate of

aromatic structure oxidative degradation is, at least, two orders of magnitude
lower than the methylene chain oxidation rate, i.e. choosing the way of PAI
thermal stabilization one may neglect oxidation of the aromatic structure.

0.16

0.14
~
..E:_IJ

0.12

0.1

0.08 ..___ _ _ _ _ _ _...}._.__ _ _ _ _ _ ___,__ _ _ _ _ _ __...,

l.5 1.7 1.9 2.l
1/T, K

Figure 13. The Arrhenius dependence of initial rate constants K 0 of 0 2

absorption on temperature of PAI thermal oxidation in air

The quantity of oxygen released from PAI at thermal oxidation (at the 1st
stage), totally with carbon oxides, water and formaldehyde equals a half (molar)
of 02 absorbed by the polymer from the gas phase (Table 2).
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 31

Table 2
0 x_yg_en b a Iance at PAl t h erma I ox1"d atmn
.
Total oxygen amount
Exposure conditions* 0 2 absorption, mol/base- released with C02, CO,
mol H20, CH20, mol/base-
mol
350°C, 1 h 2.4 1.1
300°C, 2 h 3.3 1.5
250°C, 5 h 1.4 0.7
200°C, soh 0.9 0.5
Note: * Different exposure times are caused by the process kinetics at the
mentioned temperatures. The data relate to the 1st oxidation stage.

Though the release of carbon oxides possesses quite high temperature

coefficient: Ea = (134- 163) ± 10 kJ/mol, temperature increase to 350°C leads
to a noticeable reduction of the part of these products in the oxygen balance.
Moreover, the release ratio of C02 and CO changes with temperature: it is 10:1
(molar) at temperature below 300°C, and 6:1 at 350°C. The increase of CO
release is associated with heterocycle decay. As shown above, heterocycles
participate in PAl pyrolysis at 350°C. The rate of these decays is low compared
with methylene chain breaks. Moreover, as observed from mass losses, the
gross rate of PAl pyrolysis at 350°C is by an order of magnitude lower than
thermal oxidation rate. Therefore, a noticeable increase of CO output is
explained by oxidative pyrolysis of heterocycles. Previously, using an isotope
label in 0 2, it is shown [ 149] that at temperatures of full thermal stability of
imide cycles oxygen activates purely thermal reactions of heterocycles in
aromatic polyimide.
As PAl oxidizes, relatively low amount of H 2 0 is released (2 - 5% of
C02 release), whereas H20 is the main product released at hydrocarbon polymer
thermal oxidation, but in another temperature range (up to 200- 220°C) [4, 28].
The variety of oxygen-containing organic oxidation products (aldehydes,
ketones, alcohols, ethers, acids) is typical of thermal oxidation of polyolefins
generally and methylene chain in PE specifically. Total output of these
substances exceeds the release of carbon oxides [110]. The variety and output of
these products at thermal oxidation of aliphatic PA is lower [26]. At
temperatures up to 300°C, thermal oxidation of methylene chain in PAI leads to
formaldehyde release and trace amounts of other aldehydes. At high
temperatures, oxidative degradation of methylene chain in PAl in melt is clearly
32 Thermal Stability of Engineering ...

displayed by sharp increase of formaldehyde output which, besides C02,

becomes the basic volatile degradation product. According to 1H NMR-spectra,
PAl oxidation in melt gives various degradation products. The main
contribution to the spectrum is belonged to aliphatic chain protons: signals with
chemical shifts of 0.85 - 86 ppm correspond to end CH 3-groups; y- and more
remote CHz-groups - 1.23-1.28 ppm; a- and ~-CHz-groups - 3.6 and 1.6-1.7
ppm, respectively; N-CH 3-groups- 3.2 ppm. Signal intensity integrals show the
length of methylene chains in thermal oxidation products equal C5-C6 and,
basing on the contributions from protons in N-CH 2-groups, about 20% of
methylene chains are linked to imide cycles or other nitrogen-containing groups,
amino groups, for example. The rest methylene chains (R) are distributed
between the following structures: R-CH20C(O) - 4.0 - 4. I ppm, and R-
CH2C(O)- 2.2-2.3 ppm. Signals with chemical shifts of7.69 -7.82, 7.93 and
8.24 ppm relate to phthalimide, nitrile phthalimide and pyromellitimide
structures, respectively. In C NMR-spectrum, chemical shifts ranged within
132.3 - 133.8, 123.9 - 126.6 and 1 I 7.2 ppm correspond to the mentioned
structures. Here, methylene chains are observed at 38.7 - I4.08 ppm at
corresponded distance from nitrogen atom: for example, chemical shift of 3 8. 7 -
38.1 ppm corresponds to a-CH2 group, 27.0-26.8 ppm to ~-CH2 group, etc.
A lower amount of absorbed oxygen is released with volatile products.
The rest oxygen is accumulated in the polymer (refer to Figure 14 showing
temperature dynamics of changes in PAI elemental composition, induced by
thermal oxidation at different temperatures). At 200°C, a noticeable oxygen
accumulation in PAI takes about 1000 hours, whereas at 350°C change of the
initial elemental composition C- 69.0%, H- 7.5%, N- 6.7%, 0- 16.8% to 66.4,
6.0, 5.9 and 21.7%, respectively, takes 1 hour only.
Degradation changes in PAI are reflected by IR-spectra. The Fourier
distribution IR-spectrum of initial PAl has the following absorption bands: a
doublet at vcc-H)arom = 3038 and 3 I 01 cm' 1; a doublet at V(C-H)aliph = 2848 and
2921 cm· 1; a doublet at Vs = 1720 cm- 1 and Vas(C=O) = 1780 cm· 1 of imide cycle,
respectively [137]; and deformation oscillations of imide cycle at 728 cm- 1
[138]. Intensive bands at 1122, 1157, 1367, 1397 and 1563 cm- 1 are related to
valence and deformation oscillations of bonds which form skeleton (backbone)
ofthe macromolecule.
Compared with IR-spectrum of the initial polymer, spectra of PAl
oxidized at high temperatures, but at low exposure at first glance display no
significant differences, except for consecutive increase of the absorption band at
 E. V. Kalugina, K..Z. Gumargalieva, and G.E. Zaikov 33

70

60 c

50
0~

.
:i' 40
~

OJo
rJ 0
20
- -
10 -
.- -
- - -- N
H
0 50 100 150 200 250 300 350
Temperature. °C

Figure 14. The change of PAl elemental composition at thermal oxidation in

air: at 200, 250, 300 and 350°C and 500, 200, 10 and 1 hour
exposure, respectively

3470 cm- 1, which relates to associated t.toH) [138], as well as broadening ofthe
lon~-wave wing at 1720 cm- 1 band base and occurrence of a bending at 1620
em- . Computer treatment of degraded PAl spectrum and its comparison with
the library of Fourier distribution IR-spectra, measured on Perkin-Elmer 1710
FTIR spectrophotometer has given a formal evidence of possible presence of the
following structures: aromatic imide, for example, phthalimide, maleimide or
glutimide, ureal and carbamate, and various linear or cyclic carbonyl groups.
Obviously the first evidence of aromatic imides, currently pyromellitimide
group, is unambiguous. Therefore, since computer searches by the most
intensive bands in decodable spectrum, the rest structures suggested should be
taken into consideration, and new evidences of their occurrence must be
searched for.
Quantitatively, changes in optical densities of basic spectrum bands
were estimated using the band of 728 cm- 1 (Table 3).
34 Thermal Stability of Engineering ...

Table 3
D
Relative optical densities __x_ of absorption bands in IR-spectra of
Dns
oxidized PAl (at 1 h exposure)
D
__x_ at x equal:
Temperature, °C Dns
2921 cm- 1 2848 cm- 1 1720 cm- 1 1780 cm- 1
Before oxidation 1.2 0.9 2.5 1.1
275 1.1 0.8 2.6 1.1
300 1.0 0.8 3.8 1.1
350 1.3 0.9 4.7 1.3

The band intensity at 1720 cm- 1 regularly increases with thermal

oxidation which is illustrated by differential IR-spectra. No regularity is
observed in changes of other bands. These IR-spectroscopy data contradict to
the hypothesis of primary oxidation of methylene chains in PAl. Actually,
thermal oxidation of PAl at 300 and 350°C during 1 hour results in absorption
of 1.6 and 2.4 mol 02/base-mol and release of 0.1 and 0.5 mol C0 2/base-mol
(dominant output product), respectively. Thus resulting oxidation, the oxygen
content in PAl becomes nearly twice higher, whereas methylene chain damages
calculated by C0 2 as the degradation index in the carbon balance give 2%,
approximately. One may make a different suggestion: in oxidized structures one
oxygen atom substitutes two (ketone) or, most frequently, one (aldehydes,
alcohol, ether) hydrogen atom. As a consequence, the mentioned level of 0 2
absorption induces the loss of hydrogen from methylene groups equal 10 -
20%. The lower level falls within the error of IR-spectrum quantitative
assessments, where 20% difference would be noticeable. IR-spectra do not
allow methylene chain oxidation assessment, but clearly indicate the increase of
carbony I group content.
The Fourier IR-spectra in the range of 1650 - 1750 cm- 1 observed at
high resolutions (2 cm- 1) indicated identity of the band shape at 1720 cm- 1 with
the maximum at 1713 crn- 1, detected at sensitivity increase for the initial and
oxidized PAl (Figure 15). Propagation of a new carbonyl band somehow from
inside (to say "from the same root") of the initial one related to V(C=O) of the
imide cycle. This may be dually explained. Primarily, thermal oxidation and
degradation of methylene chains intensify symmetrical oscillations of the cycle
by means of asymmetrical oscillations. This explanation is obeyed by the
 E. V. Kalugina, K.Z. Gumargalieva, and G. E. Zaikov 35

above-mentioned increase of negligibly small damage of methylene chains,

detected at the moment of spectrum record. Moreover, if judged by the area of
bands within 1,650- 1,800 cm-I, at 1,720 and 1,790 cm- 1 both the relation of
optical densities changes and carbonyl absorption significantly increases.
Secondly, it may be explained by occurrence of new C=O-groups as the
oxidation product.

,---~---------------------.31.4

I
I 30.4
I
1 29.4
\ I
\ I
\ I 27.4
\ I
'' ' /
/
/ 26.4

''
'' __ / /
/
/ 25.4

24.4

1660 1680
'
'-----1..--...1-----l--'-_;_-~...-.:;_..
_
1700
_...__ _...~.-_--t___..__
1720 1740
___..j 23.4

v,cm·'

Figure 15. High resolution (2 cm- 1) Fourier IR-spectrum for PAl before (1) and
after (2) thermal oxidation in air at 350°C during 1 hour

The literature shows investigations of aliphatic PA thermal oxidation by

IR-spectroscopy [150]. The occurrence of new C=O-groups, resulted by low-
temperature oxidation of PA-6, PA-66, PA-11, PA-12, and the so-called
"soluble" N-methoxymethylated PA-6 is displayed in absorption increase in the
range of 1700- 1750 cm- 1 at the short-wave wing of the initial amide band.
The authors have not performed the band separation, but, anyway,
consider that the bending contains two maximums at 1715 - 1719 and 1731 -
1736 cm- 1, which they relate to a new imide structure, synthesized by a-CH2-
group oxidation.
36 Thermal Stability of Engineering ...

For N-methoxymethylated PA-6, the most intensive, new carbonyl band

in IR-spectrum is observed at 1719 cm- 1• As shown in the literature, the feature
of oxidized PAl IR-spectra may be explained by occurrence of new a-C=O-
group in the methylene chain. The alternative attack of molecular oxygen and
preferable oxidation of internal methylene groups would form a situation similar
to thermal oxidation of PE backbone, when a broad, multi-structural band
occurs in the range of 1700- 1800 cm- 1 in IR-spectra of oxidized PE. Analysis
of this multi-structural band has detected the contribution of aldehydes< ketone,
ether, and carboxylic groups into \1C;:Q) [161].
Besides gaseous and polymeric products, PAl thermal oxidation
produces low-volatile substances condensed near the hot zone. Natural
fractioning of these products by the reaction chamber and programmed heating
in the mass-spectrometric analysis with direct injection to the source of ions
make mass-spectra, measured at low ionizing stress (12- 20 eV) with mostly
molecular ions fixed, simpler. These mass-spectra simply trace series of
molecular ions with mass step of 14 mass units: 216-230-244-258-272-286-300-
314-328-342-356-370-384-398-412 etc. to 552; 231-345-259-273-287-301-315;
243-257-271-285-299-313-327-341-355; 371-385-399-413-427-441-455-469-
483-511-525-539; 543-557-571-585-599-613-641-655-669-683-698. Moreover,
mass-spectra possess separate molecular ions either interfering into homological
sequences, but being more intensive rather than the neighboring ones and all
sequence members (for example, peaks with 160, 230 and 543 m.u.), or singles
outside the sequence (for example, 73, 82, 214, 109 m.u.), or inside the
sequence, not occupying a sequence member place (for example, 460 m.u.).
These peaks belong to substances with somewhat "economic" structure,
e.g. the structure with no breaks of the methylene backbone with mostly arylene
and heterocyclic end groups, as well as methylene or ethynyl products of
heterocycle degradation. In mass-spectra of thermal oxidation products,
homological sequences of molecular ions mainly correspond to analogous
sequences in mass-spectra of PAl pyrolysis products. Initial two sequences with
uneven values for molecular ions correspond to mass-spectra of pyrolysis
products by both distribution and multiplicity (ions-satellites of sequence
members with mass numbers ±(1 - 3)). E.g. they respond to methylene
backbone fractures having phthalimide end group, alkane phthalimides with end
methyl or ethyl group. The rest two uneven sequences include higher order
oligomers than these formed in pyrolysis. For example, molecular ion with 543
m.u. starts the following homological sequence:
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 37

r P r
(R)H-N<~~ )N- (C~12N~
I 1 I
0 0 0

It is traced up to the last member of R = C12H2 5 sequence with the molecular

weight 711. Therefore, thermal oxidation gives high yield of products
representing the elementary unit fragment or fractures without methylene
backbone fragments, or preserving it in full by means of end blockade similar to
the above-mentioned product with molecular weight 543. Pyromellitimide and
dodecamethylen diphthalimide are among these products.

~ p
HN<»~>NH
I I
0 0

This molecular ion sharply interferes between alkane pyromellitimides. At

thermal oxidation, homological sequence with even molecular ions is much
longer than at pyrolysis. Tracing the intensity distribution and multiplicity, the
second part of the sequence with molecular weights of 370 or higher is found
analogous to some molecular ions of alkane pyromellitimide sequence formed
at pyrolysis. The beginning of the even sequence of thermal oxidation products
from 244 and 216 m.u. is not shown in mass-spectra of pyrolysis products. The
intensity distribution in this half of the even sequence possesses the maximum
at 230 m.u. Molecular ions in the first and the second half of the even sequence
possess different multiplicities. Obviously, the even sequence is not a single
homological sequence, but is formed by two independent sequences, one of
which is represented by alkane pyromellitimides. Another sequence might be
formed by oxidation products, containing C=O groups in the methylene
backbone, for example:
38 Thermal Stability ofEngineering ...

~ p
(H) R-N<G-r()rC / N - C - R (H)
~W II
0 0 0

This oxygen-containing structure (possibly, an alternative of OH-

containing structure) allows composing a sequence of homologues
corresponded to experimentally obtained one. Enumeration of other alternatives
does not give positive results, for example, nitrilephthalimide alkanes, which
also form an even sequence. 1H and 13 C NMR-spectroscopy data indicate the
presence of carbonyl-containing aliphatic structures in thermal oxidation
products.
Single, intensive molecular ions with 57, 73, 97 and 109 m.u. belong to
nitrogen-containing products of pyromellitimide structure degradation.
Comparison with the mass-spectra library shows that amides and pyrrolidone
derivatives are most grobable.
Judging by 3C NMR-spectroscopy data, the part of polymelliiimide
oligomers decreases with temperature in thermal oxidation products; vice versa,
the contribution of phthalimide and substituted phthalimide oligomers, for
example, nitrilephthalimide oligomers increases (Figure 16). These data allowed
assessment of the mean molecular mass of thermal oxidation oligomeric
products: 1,200- 2,000 at 300 - 350°C and 350- 700 at 400- 450°C. Hence,
the average length of methylene backbone twice decreases.
Finally, as PAI are subject to high-temperature thermal oxidation, the
main degradation changes proceed in both methylene backbone and aromatic
fragment, which is the imide cycle.
The unique property of PAl which differs it from the known polymeric
materials, is high resistance to short-term (up to 30 s) thermal impact (260-
2800C) without meltbacks and deformations that allows flow soldering of metal
reinforcement [52].
Thermal aging (during 90 days) at 100- 200°C [56] shows decrease of
blow viscosity, stress at break and relative elongation of PAl at simultaneous
change of polymer morphology (X-ray analysis and electron microscopy data).
Thermal aging ( 1,000 hours at 170°C) and cycles of heating from -60 to + 170°C
 E. V. Kalugina, KZ. Gumargalieva, and G.E. Zaikov 39

do not change the dielectric loss tangent and permeability, but an abrupt (almost
by an order of magnitude)· decrease of surface and volumetric electrical
resistance is observed [52].
8()r-------------------------------------------------~

0~------------~------------~~------------~
300 350 400 450
Temperature, ''C

Figure 16. Changes in the ratio of structural fragments in oligomers at thermal

oxidation of PAl (according to 13 C NMR-spectroscopy data)

Obviously, the mentioned macroscopic changes in PAI processing and

operation temperatures are induced by definite changes in chemical structure of
the polymer due to heat and oxygen effect.

Solid-phase oxidation

As obvious from IR-spectra of PAl subject to thermal oxidation at 200 -

250°C during 1,000 hours, the polymer, though slowly, is oxidized in the solid
phase in the temperature range of operation: concentration of C=O-groups
increases and methylene groups are clearly exhausted ( 11C-H) bands at 2,800 -
40 Thermal Stability of Engineering .•.

2,900 cm- 1). Thermal oxidation during 1,000 hours at 250°C, i.e. under rigid
operation conditions, leads to full burn off of methylene backbone and partial
destruction of imide cycles (the occurrence and extension of 'iC-H) band at 1,620
cm- 1). Similar observations were made [30, 32] at thermal oxidation of aromatic
polypyromellitimide PM-1.
It is found that slow oxidation of aromatic nuclei happens already at
250°C. After several thousand hours, this process causes destruction of
cycloarylene structure and the loss of macroscopic properties. Kinetics of 02
absorption at 250°C (Figure 17) shows that thermal oxidation rate of fatty
aromatic polyimide PAI is an order of magnitude higher than the oxidation rate
of aromatic polyimide. Though in this case the main contribution is made by
fatty chains, high reactivity is displayed by cycloaromatic structure in PAl
should also be taken into account.

9
1
8
-7
0
E
~6
tf.l
(IS
;gs
0
E4
""
~3
2

~-L---·----------'---- .L_______________---..,J,....___ _ _ _ _ _J._____ _

0 50 100 150 200 250 300

Time, h

Figure 17. Kinetics of 0 2 oxidation at thermal oxidation of PAI (1) and PM-1
(2) in air at 250°C
 E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov 41

1.6.-------------·--------------------------------~

-E
0

0 1.2
.e""
:a

0
E
. 0.8
~6

X
2
::c
0
0 0.4
0::

-·-----.L .J.._________l _ ___._ _..J.. ______ _ l _ _ _

0 l 00 200 300 400 500 600 700 800

Time. h

Figure 18. Kinetics of ROOH hydroperoxide accumulation (1) and decay (2) at
PAI thermal oxidation at 200°C in air

As known in kinetics of liquid-phase reactions, oxidation of purely

aromatic substances is induced by hydrocarbon additives as the source of
peroxy radicals [8].
Predominant oxidation and degradation of fatty chains during thermal-
induced aging noticeably exhausts the C and H element concentration in PAI
(refer to Figure 14). As shown in experiments, 500 hour thermal oxidation at
200°C decreases C and H contents from 69.0 and 7.5 to 65.0 and 6.0%,
respectively, with corresponded increase of oxygen concentration. Hydrogen is
reliably detected during 800 hours of thermal oxidation. Hydrogen release
kinetics correlates with the gel formation kinetics (Figure 19).
Thermal aging causes formation and accumulation of hydroperoxides
(the iodimetric technique) in PAl (Figure 16). The kinetics of hydroperoxide
ROOH accumulation is extreme. Accumulated ROOH concentrations (-1.5xl02
mmol/base-mol) are negligibly small (by five orders of magnitude lower) than
absorbed amounts of 02. Nevertheless, these negligible amounts are reliably
detected during initial 800 hours ofthermal oxidation. Meanwhile, ROOH is not
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whether we reached the top of Everest or not. A good instance of
this altered attitude of mind is provided by the fact that Finch and
Bruce took a camera with them on their ascent, and forgot to take
any photographs of their last day’s climbing.
I have mentioned the deleterious effect of altitude on the appetite
of some of our older members; but the same was to some extent
true of us all. I have the most vivid recollection of distaste for food
during our first few days at Camp III, and especially of the way one
had almost to push a prune down one’s throat on the way up to the
North Col; but with the majority of us this distaste for food
(especially for meat and the slowly-digested foods) diminished
during our sojourn at great heights, though our appetites never
became quite normal until we reached one of the lower camps.
Those who had oxygen reported that they had large appetites above
the North Col; and there is no doubt that it is the rarefaction of the
air that causes this alteration of the appetite. One may perhaps be
justified in assuming that the secretion of gastric juice is diminished
while air that is poor in oxygen is inhaled, though it is rather hard to
understand how this is brought about.
Although acclimatisation is not entirely connected with the actual
increase in the number of blood corpuscles (as has been proved by
Barcroft in 1922), yet this is still recognised as one of the important
factors in its production. But this increase in the concentration of the
blood must be associated with a great increase in its viscosity, and
when that is combined with intense cold with its accompanying
constriction of all the smaller blood-vessels, there are present all the
conditions necessary for the production of frostbite. Therefore
acclimatisation with all its benefits probably increases the risk of
frostbite; hence one who is acclimatised must be especially careful
of feet and hands and their coverings. It is hard to put on too many
clothes at a great altitude, and very easy to put on too few.
The chief point still remaining to be mentioned concerns the after-
effects of the climbing of Everest; but these varied so much that
they give us little or no scientific information. Some of us were tired
for twenty-four hours only, some for many days; some were
reported to have enlarged hearts, while in some the heart was
normal; some were incapacitated by frostbite, though their general
physical condition was very probably good. One therefore cannot
generalise about after-effects, but as a medical man I felt strongly
(by observation on myself and my companions on the Expedition)
that if one is to “live to fight another day” and to require the
minimum recuperation period after an attempt on the mountain, it is
essential during the attempt to keep oneself well within one’s
powers. One is tempted to go too hard, and to exert one’s strength
to its limits; but it is just the last few ounces of strength which call
forth the greatest effort and make the maximum demands on one’s
resources; and if these resources are to be used to their full extent
they should be continuously conserved by an avoidance of definite
hurry. Personally I am of opinion that exercise before the climbing
begins is of great value. Mallory and I were the only ones whom
Longstaff allowed to make two attempts on Everest; and we were
probably rendered fit in this way by the subsidiary expeditions we
had made on the way to Mount Everest and by our preliminary work
in getting the camp ready on the North Col. It is, however, hard to
generalise on a point like this, but each man knows the
idiosyncrasies of his own constitution, and it should be left to
individuals to a great extent to see that their condition on arrival at
the foot of the mountain is the best that is possible.
 CHAPTER XIII

COLOUR IN TIBET

In order to bring before the reader a vivid picture of Tibet, and

especially of the region around Mount Everest, a comparison
between Tibet and other better-known countries is almost inevitable.
The Expedition of 1922 took with them no official artist, or no doubt
he would have been deputed to write this section of the book; there
were, however, two people who tried to paint pictures of the
country, Major Norton and myself; and though I realise how
inadequate our efforts were, perhaps those of an official artist might
have been almost as bad. However, as one who looks on the world
with an eye for its beauty, although lacking the ability to transfer
that beauty to canvas, one may perhaps be pardoned for
endeavouring to describe certain general impressions of the scenery
encountered by the Expedition.
In the course of our journey we passed through a great variety of
landscape; in Sikkim, for instance, we found a land of steep slopes
and dense forests, while Tibet is almost a desert country. We
experienced the clear air of the winter, and the mists and storm-
clouds of the monsoon. While we were on the rolling plains of the
Tibetan Plateau, only a few miles away were the snow-covered
summits of the highest mountains in the world.
Sikkim is a country of deep valleys and of luxurious vegetation;
the air is generally damp and the skies cloudy, and there is often a
beautiful blue haze that gives atmosphere to the distance. Sikkim is
not unlike the Italian side of the Alps, in many ways. True, its scale
is larger, and it possesses some of the most beautiful and impressive
peaks in the world (for no Alpine peak can vie with Siniolchum or
Pandim for sheer beauty of form and surface), but on the whole the
scenery of Sikkim is of the same general build as the valleys and
peaks of Northern Italy. In this sense Sikkim did not offer to the
new-comer anything entirely different from what he had seen
before. But Tibet and Everest certainly did; and the difference
between Sikkim and Tibet is twofold—first, Tibet is almost uniformly
over 13,000 feet above sea-level, and therefore bears no trees at all;
second, Tibet is almost free from rainfall and is, in consequence, a
desert country. One’s eye travelled, for mile after mile, over red-
brown sand and red-brown limestone hills, finally to rest on the blue
and white of the distant snows. The air, before the monsoon
commences, is almost always clear—clear to an extent unimagined
by a European, clearer even than the air of an Alpine winter. So
peaks and ridges 30 or 40 miles away are often almost in the same
visual plane as the foreground of the landscape. In some extensive
views, such as we had from the hills above Tinki Dzong, one came to
look upon hills 30 miles away as the middle distance of one’s picture,
while the background was formed of mountains a hundred miles
from the point of view. It is this lack of atmosphere which makes
pictorial representation of these Tibetan scenes so very difficult; the
pictures I made on the course of the Expedition have all had one
criticism from many different people—“there is no atmosphere.”
Many as are the demerits of these pictures, this is the one merit they
have; and if they had an “atmosphere” they would cease to be
truthful. In the Alps one has often seen mountains with extreme
clearness at a great distance, but I never remember having viewed
an Alpine landscape in which there was practically no effect of
distance, and practicably no blueness of the more distant shadows.
Yet that is precisely what obtains in Tibet before the month of June.
And then, with startling suddenness, comes the monsoon, with its
damp air; for some months the landscape is entirely altered, and
also much beautified. The blue haze of the monsoon converts the
distant shadows from their crude purple-brown to the most
magnificent and sometimes brilliant blue. Once or twice one looked
in vain on one’s palette for a blue of sufficient brilliance and intensity
to reproduce the colour of the shadows 20 or 30 miles away. Then
the monsoon brings clouds and rain-storms, all of which tend to give
variety to the scene, and to endue the distant peaks with that effect
of mystery which renders them so alluring and so beautiful.
As far as the scenery among the higher mountains is concerned,
the comparison of photographs of the Everest group of peaks with
those of the Alps will give one more idea of the differences between
the two districts than can a mere verbal description, save in the
matter of scale and colour. In colour, the Alps are more varied and
the rock is, as a rule, a darker brown; the snow-shadows are more
blue and the outlines less clear; while Alpine foregrounds so often
contain trees which are totally absent from the foregrounds of Tibet.
There both rocks and stones, scree and valley-bed are of a light
reddish-brown, almost uniform in tone from near foreground to
extreme distance; Makalu, for example, is a colossal rock-pyramid of
quite a light ochre colour; the rocks of Everest are of a light amber
brown relieved in the neighbourhood of 27,000 feet by a lighter
yellowish band of quartzite. The snow of the range on its northern
side resembles that of Alpine peaks, but on the southern face the
festoons and grooves of ice, so well known to many from
photographs of Himalayan mountains, decorate the much steeper
and more uncompromising slopes. Most of the higher peaks are
swept by continual gusts of wind which whirl clouds of snow from
the topmost ridges into the sky.
 CHAPTER XIV

TIBETAN CULTURE

The Tibetans are a very simple folk, though not without a very
definite civilisation of their own. Art and music exist in all nations, if
the art be merely the fashioning of utensils, and the music be the
crudest of rhythms played on a tom-tom. Yet in Tibet the
rudimentary music and art associated with so many Eastern races is
carried a stage farther, and what is in wilder people merely natural
instinct has become in Tibet a definite culture. For I presume that
culture is merely organised art, and certainly on that criterion the
Tibetan is to some extent cultured.
He is a fine architect, and many of his houses have a simple
stateliness which raises them in artistic value high above the average
dwelling-house of most other Oriental countries, to say nothing of
our own garden suburbs. The Monasteries of Tibet are still more
imposing, and some of them are real objects of beauty, for the
dignified simplicity of the buildings themselves is combined with an
elaborate and often beautiful decoration of windows and cornices.
The Tibetans have learned the true principles of decoration—they do
not cover the surfaces of their buildings with unnecessary ornament,
but reserve the wooden parts alone for elaboration. The cornices are
often intricate in workmanship, but throughout the great principle of
design is carried to perfection—the principle that all ornament should
be founded on utility. Thus economy in the use of scrolls is combined
with the multiplication of brackets, supports, and rafter-ends, so that
the whole is satisfying to the eye as being beautiful, rather than
useless. Considerable Chinese influence is shown in their decorative
art, but the Tibetans have a personal, or rather national, touch
which distinguishes their work in all branches of art from the
Chinese. In painting, too, the influence of China, and very
occasionally of India, is felt: though through it all the refined
austerity of the better-class Tibetan shines unmistakably. The older
pictures, nearly always of sacred subjects, are drawn with
consummate skill, coloured with great taste, and in the matter of
design rank much higher than the contemporary art of India. But,
alas! the story of painting in Tibet is the same as it is everywhere in
this commercial world of ours; the modern Tibetan picture is
worthless, careless and meretricious. No doubt the demand for
“native art” at the bazaars of Darjeeling and other places around has
caused this deterioration of what was once a fine and noble art;
pictures which used to be the life-work of devoted lamas and
conscientious hermits are now “dashed off” to satisfy the capacious
maw of the tasteless traveller. Though Tibet is still in measure “The
Forbidden Land,” yet the tentacles of commercialism cannot but
penetrate between its bars, and the same thing is now happening to
Tibet as happened to Europe last century and produced oleographs
and official artists. It seems almost as if man by nature does bad
work only when he is working for reward.
 Religious Banners in Shekar Monastery.

This is a mere flashlight sketch of the art of Tibet, for details of

which other books must be consulted; but the music of Tibet will be
described more fully, for two reasons—first, that no accurate record
of it has to my knowledge been obtained until now, and second, that
the writer is himself particularly fond of music, which he believes to
be the highest of the arts.
Just as in Europe to-day we have both the traditional folk-song
and the highly organised orchestral music, so in Tibet both these
forms of the art exist. The two are also more or less interdependent
in Tibet, while in Western nations each often goes its own way
without the other.
The airs sung by the Tibetan people are usually simple, short, and
oft-repeated. They are nearly always in the pentatonic scale,
represented best to the general reader by the black notes of the
piano. Most isolated races evolve this scale at some time during their
history, and the tunes of the Highlands of Scotland, the Forests of
Central Africa, the Appalachians of America, and the Tibetans are all
in this scale.[8]
8. Sir Walford Davies has pointed out that, starting (on the black notes) from A
flat, and using only the perfect fifth, this scale is very soon developed. From
A flat one gets E flat and D flat, each a fifth away; from D flat one obtains G
flat, a fifth down, and from E flat a fifth upwards gives us B flat. Thus we get
the five notes of the scale by a simple series of fifths, the fifth being the
most perfect interval in music, and the one which will appeal most readily to
a primitive people.
A typical well-known pentatonic tune is “Over the Sea to Skye.”
Those who know, for instance, the songs of the Western Highlands,
will be able to appreciate the cheerful and non-Oriental character of
the tunes of Tibet, which are more akin to those of Russia and
Eastern Europe than to the music of China or India. This general
spirit of the music which the Tibetans play or sing points to a
common origin of the folk-tunes of Tibet and Russia. It seems
probable that in Turkestan was the real origin of this music, which
very likely spread eastwards into Tibet and westwards into Russia; or
if Turkestan is not the country of origin of the music, it may be the
musical link between Russia and Tibet. The tunes of Nepal, as sung
by our coolies, are many of them of a similar nature to those of
Tibet, though more often the whole major or minor scale is used,
giving them often a strangely European sound; some of the
Nepalese airs have a jolly lilt and swing; others in the minor key
have quite a haunting beauty; and they too are quite unlike the
music of the plains of India with its rather pointless wailing
characteristics.[9]
9. A more technical article on the subject of Tibetan Music, with musical
quotations, will be found in the Musical Times for February 1, 1923.
In Tibet, then, the folk-tunes are simple, short, and emphatically
not such “good tunes” as the airs of Nepal. But, in addition to the
songs of the peasants and beggars, there is the more highly-
organised and orchestrated music of the monasteries. This is usually
played with three groups of instruments—first and foremost the
percussion; drums of all sizes from those made of a human skull to
others 3 and 4 feet in diameter, and cymbals of great resonance and
good tone, coming often from China. The cymbals are taken very
seriously, and each different way of clashing them has a special
name and a special religious significance. The hard-worked
percussion department keeps up a continuous rhythm throughout
the performance of a devil-dance or other musical festival; and to its
strenuous and often sinister efforts are added from time to time the
sounds of the two groups of wind instruments. The first of these,
playing airs which often possess great charm, are the double-reed
oboes, about twice as long as our European oboe, and very often
provided with equidistant holes, rendering them incapable of playing
save in the scale of whole tones (or a close approximation to it). The
second and larger wind instrument is the long straight trumpet, 8 to
12 feet long, of which the fundamental note is almost continuously
blown. Most monasteries have two of these, about one tone apart in
pitch; but as the longer of the two is blown so as to play its first
overtone, while the fundamental note is played on the other, a drone
bass of a minor seventh is the resulting sound. This adds to the
sinister impressiveness of the music, and provides an effective
accompaniment to the quaint tunes of the oboe-like instruments. At
a devil-dance performance, the orchestra plays for a whole day, or
perhaps two, almost without rest either for itself or for its listeners.
In addition to these instruments, a fairly civilised violin is used in
Tibet, especially by wandering beggar minstrels. This is about two-
thirds as long as our violin, and has four strings, tuned A,D,A,D, in
that order. The bow has two hanks of hair, one of which passes
between the first and second strings, while the other goes between
the third and fourth. Thus, by pressing the bow in one direction the
two A strings are sounded, producing a reinforced note (i.e. two
notes in unison); by pressing the bow in the other direction the
sound of the D strings is obtained. The strings converge towards the
top of the instrument, so that they can all be fingered at once. The
Tibetans become very agile with their fingers, and I have heard very
skilful performances of rapid, jolly dance-tunes by wandering
minstrels; these tunes, like the songs of the peasants, are usually in
the pentatonic scale.
One more instrument must be mentioned—the trumpet made
from a human thigh-bone. This is not very commonly used in the
larger monasteries, but occasionally sounds a note in the ritual of
the worship of smaller villages.
NATURAL HISTORY
By
T. G. LONGSTAFF, M.D.
 CHAPTER XV

NATURAL HISTORY

Previous experience of the conditions of Tibetan travel had taught

me that collection and observation was a task requiring complete
immunity from other duties; but to the doctor of such an Expedition
this condition was not attainable. In the collection of specimens we
were, however, fortunate in obtaining the assistance of several other
members of the Expedition. But it is especially to Major Norton that
the thanks of the Everest Committee are due, for in addition to his
other duties, he took over the whole of the botanical work and
worked equally with myself in all other branches of Zoology. His gift
of painting was particularly valuable in leading to the certain
identification of birds in districts where collecting was prohibited. At
the time of writing he is on duty at Chanak, and the following notes
lose half their value through lack of his promised collaboration,
which I had anticipated with particular pleasure.
In his absence I must omit all reference to botany, for personally,
owing to the wintry conditions during our outward march and to the
speed of my journey back with the invalids, I saw nothing that has
not been already better described by Wollaston. But Norton, with our
Lepcha collector Rumoo, obtained some 350 flowering plants in
Kharta, and we also sent back samples of agricultural seeds.
It must be remembered that it was the constant aim of General
Bruce to render it easier for any subsequent party to pass through
the country. The objection of the Tibetans to the taking of any wild
life is almost universal amongst the clerics and is devoutly shared by
the lay population in certain localities. These considerations
unfortunately applied particularly to the districts of Tengkye, Shelkar
Dzong and Rombuk, where the killing of even domestic animals is
prohibited.
There are, however, other parts of Tibet where the same restraint
is unnecessary, and even where hunting is habitually practised by
the semi-nomadic population. This immunity in our case applied
especially to the Chumbi Valley and the country round Phari, and in
consequence we have been able to bring back some material which
it is hoped will add to the value of the larger collections brought
back last year by Dr. Wollaston.
That portion of Tibet visited by the Expedition, and indeed it is
typical of most of its provinces, is a region of bare uplands and
naked mountains. Such physical conditions combine with a violent
type of radiation in the thin dry air to evolve a daily strife of winds,
ceaselessly seeking to rectify the balance of atmospheric stability;
this continual wind is indeed the foundation of the traveller’s
discomfort and the worst enemy of the mountaineer.
Romoo, the Lepcha Collector, who assisted
Dr. Longstaff and Major Norton.
 Karma Paul, the Expedition’s Interpreter.

Owing to its aridity, due to the intervention of the rain-catching

Himalaya, the country is practically treeless. Distant open views
prevail over vast landscapes, lit by strong lights in an atmosphere
devoid of fogs or softening mist effects. Usually nothing can move
without being visible from a great distance. Hence, though it is not a
region particularly rich in life, yet those forms which do prevail are
not easily overlooked. Concealment is only to be obtained by
burrowing underground, or by immobility combined with protective
coloration.
Nowhere is this more obtrusively shown than on the great stony
uplands, at an altitude of from 14,000 to 17,000 feet East and South
of Khamba Dzong. Here we were in constant sight of bands of wild
asses, gazelle, and sheep: from a distance of a couple of miles a
prowling wolf was easily discerned. The ground is nowhere here
covered by a continuous carpet of grass or herbs, but each plant is
several yards from the next. Hence even a small herd of game will
cover the ground with innumerable tracks, suggesting to the
uninitiated a far greater number of individuals than really exist. To
watch a flock of Tibetan sheep or goats grazing seems like watching
a migration, for the herd moves at a smart walk, often breaking into
a run, each individual racing for the next mouthful a few yards
ahead. They move on a wide front, with the shepherd and his wolf-
dog well in evidence. On one occasion we came on a wolf devouring
a lamb: 50 yards away lay the guardian dog, waiting apparently for
any scraps the robber might leave.
It might be supposed that as in the Arctic the birds and animals
would turn white in winter. But two sufficient reasons against this
necessity have already been indicated. Firstly, the snow line is so
high, probably between 19,000 and 20,000 feet, that vegetation
does not extend up to it: even the predatory beasts are dependent
on vegetation for the pasture of their prey. Secondly, evaporation is
so rapid that the country is never snow-clad for long even during the
winter season.
But some modification of habit to meet the hostility of winter,
under conditions of life already so severe, is to be looked for. Of
Marmots we saw nothing during the journey to Everest; probably
they were still hibernating. Norton found them later in Kharta and
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