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STRUCTURE–PROPERTY RELATIONSHIP OF ORGANOSILICON MATERIALS: EVALUATION BASED ON THERMOGRAVIMETRIC ANALYSIS

Author: Tosheva Dilfuza Farxodovna; Siddikov Ikrom Iminjonovich; Rakhimov Firuz Fazlidinovich
Publisher: Zenodo
DOI: 10.5281/zenodo.17535044
Source: https://zenodo.org/records/17535044/files/4_Tosheva_Dilfuza_Farxodovna,_Siddikov_Ikrom_Iminjonovich,_Rakhimov.pdf
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CONTENTS
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CONTENTS
POVERTY AND DEVELOPMENT ...............................................................................................................................................14
Kholmi zaye Abdulhamid Khapizo ich
WAYS TO ACHIEVE ECONOMIC STABILITY THROUGH THE IMPLEMENTATION OF INNOVATIVE
TECHNOLOGIES IN INDUSTRIAL ENTERPRISES ..............................................................................................................23
Sad iddino Bakh iyo
STRUCTURE–PROPERTY RELATIONSHIP OF ORGANOSILICON MATERIALS: EVALUATION
BASED ON THERMOGRAVIMETRIC ANALYSIS ..................................................................................................................36
Toshe a Dil uza Fa xodo na, Siddiko Ik om Iminjono ich, Rakhimo Fi uz Fazlidino ich
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STRUCTURE–PROPERTY
RELATIONSHIP OF
ORGANOSILICON MATERIALS:
EVALUATION BASED ON
THERMOGRAVIMETRIC ANALYSIS
Toshe a Dil uza Fa xodo na
Doc o al candida e, Bukha a S a e Technical Uni e si y.
E-mail: [email p o ec ed]
Siddiko Ik om Iminjono ich
P o esso , Depa men o Cons uc ion and En i onmen al Enginee ing,
Tashken A chi ec u e Uni e si y.
Rakhimo Fi uz Fazlidino ich
PhD, Associa e P o esso ,
Depa men o Cons uc ion Enginee ing,
Bukha a S a e Technical Uni e si y.
Abs ac . This a icle p esen s a comp ehensi e scien i ic e alua ion o he s uc u e–p ope y ela ionships o
o ganosilicon ma e ials using he mog a ime ic analysis (TGA). Due o he high bond ene gy o he –Si–O– linkage,
polyo ganosiloxanes and hei de i a i es exhibi ema kable he mal s abili y a ele a ed empe a u es. By applying TGA
and DTG me hods, he decomposi ion s ages, onse and peak empe a u es, esidual mass, and decomposi ion a e o
he ma e ials we e accu a ely de e mined. Kine ic analyses based on he Kissinge and Flynn–Wall–Ozawa me hods we e
conduc ed o calcula e he ac i a ion ene gy and assess he in luence o s uc u al pa ame e s on he mal pe o mance.
The esul s con i m ha he he mal esis ance o o ganosilicon ma e ials di ec ly depends on he chemical na u e o side
g oups, he deg ee o molecula b anching, and he inco po a ion o nano ille s.
Key wo ds: o ganosilicon ma e ials, he mog a ime ic analysis, s uc u e–p ope y ela ionship, he mal s abili y,
ac i a ion ene gy, nano ille s.
Anno a siya. Mazku maqolada k emniyo ganik ma e ialla ning s uk u a–xossa bog‘liqligi e mog a ime ik ahlil (TGA)
asosida ilmiy jiha dan baholangan. –Si–O– bog‘la ining yuqo i ene giyasi u ayli polio ganosiloksanla a ula ning hosilala i
yuqo i ha o a la da yuqo i ba qa o likni namoyon e adi. TGA a DTG usulla i yo damida ma e ialla ning pa chalanish
bosqichla i, boshlanish a cho‘qqi ha o a la i, qoldiq massasi hamda pa chalanish ezligi aniqlangan. Kine ik ahlilning
Kissinge a Flynn–Wall–Ozawa usulla i asosida ak i a siya ene giyasi hisoblab chiqilib, s uk u a iy pa ame la ning
issiqlik xossala iga a’si i baholangan. Tadqiqo na ijala i k emniyo ganik ma e ialla ning issiqlikka chidamliligi ula ning
yon gu uhla abia i, a moqlanish da ajasi a nano o‘ldi gichla ning ma judligiga be osi a bog‘liqligini ko‘ sa adi.
Kali soʻzla : k emniyo ganik ma e ialla , e mog a ime ik ahlil, s uk u a–xossa bog‘liqligi, issiqlikka chidamlilik,
ak i a siya ene giyasi, nano o‘ldi gich.
Аннотация. В данной статье представлена научно обоснованная оценка взаимосвязи «структура–свойства»
кремнийорганических материалов на основе термогравиметрического анализа (ТГА). Благодаря высокой энергии
связи –Si–O– полиорганосилоксаны и их производные демонстрируют высокую термостабильность при повышенных
температурах. С использованием методов ТГА и ДТГ были определены стадии разложения, температуры начала
и пика, остаточная масса и скорость разложения материалов. Кинетический анализ, выполненный по методам
Киссингера и Флинна–Уолла–Озава, позволил рассчитать энергию активации и определить влияние структурных
параметров на термические свойства. Полученные результаты показывают, что термостойкость кремнийорганических
материалов напрямую зависит от природы боковых групп, степени разветвления и наличия нанонаполнителей.
Ключевые слова: кремнийорганические материалы, термогравиметрический анализ, взаимосвязь «структура–
свойства», термостойкость, энергия активации, нанонаполнители.
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INTRODUCTION
In ecen yea s, o ganosilicon (siloxane-based) ma e ials ha e ound b oad applica ion in ae ospace,
mic oelec onics, biomedicine, cons uc ion composi es, and p o ec i e coa ings owing o hei high he mal
s abili y, hyd ophobici y, dielec ic eliabili y, and chemical ine ness. The p ac ical pe o mance and du abili y o
hese ma e ials a e p edominan ly de e mined by he in insic ela ionship be ween hei molecula s uc u e and
ope a ional p ope ies. Speci ically, pa ame e s such as he leng h and angles o he –Si–O–Si– backbone, he
s e ic and pola cha ac e is ics o o ganic side g oups, he deg ee o molecula b anching, and he c osslinking
densi y di ec ly in luence c i ical ac o s including he mal s abili y, oxida ion and ca boniza ion beha io , mass
loss s ages, and esidual cha yield.
This s udy sys ema ically e alua es he in e dependence be ween s uc u al pa ame e s and
physicochemical p ope ies o o ganosilicon ma e ials h ough he mog a ime ic analysis (TGA) and di e en ial
he mog a ime y (DTG). TGA eco ds eal- ime changes in sample mass unde a con olled empe a u e
egime, allowing o p ecise iden i ica ion o he mal decomposi ion s ages, elease o ola ile componen s,
oxida ion–decomposi ion ansi ions, and he amoun o esidual mass (ash o ce amic ac ion). DTG, in u n,
illus a es he mass-loss a e e sus empe a u e p o ile, p o iding clea di e en ia ion o he onse and peak
empe a u es (T_onse , T_max) o each decomposi ion s age and enabling a kine ic in e p e a ion o hese
p ocesses.
In ce ain cases, TGA is supplemen ed by di e en ial he mal analysis (DTA) o di e en ial scanning
calo ime y (DSC) o de ec hea e ec s such as endo he mic and exo he mic eac ions, as well as by TGA–
FTIR o GC–MS coupling sys ems o iden i y he gaseous p oduc s o he mal deg ada ion. Consequen ly, he
in luence o s uc u al modi ica ions—including he p esence o me hyl, phenyl, o i luo op opyl subs i uen s,
silsesquioxane segmen s, and nano ille s—on he he mal beha io o he ma e ials is quan i a i ely es ablished.
The high bond ene gy o he Si–O linkage (≈444 kJ/mol) se es as a key ac o ensu ing excep ional he mal
esis ance in o ganosilicon sys ems. Howe e , a ia ions in he chemical na u e o side chains and he deg ee
o mac omolecula b anching subs an ially a ec he decomposi ion pa hways and esul ing s abili y.
LITERATURE REVIEW
The s udy o he s uc u e–p ope y ela ionship o o ganosilicon ma e ials based on he mog a ime ic
analysis (TGA) ep esen s a highly ele an and dynamically e ol ing esea ch di ec ion bo h globally and
wi hin Uzbekis an. Due o hei excep ional he mal s abili y, chemical ine ness, and mechanical du abili y,
o ganosilicon polyme s ha e gained widesp ead applica ion in elec onics, ae ospace, cons uc ion, and
p o ec i e coa ings.
The pe o mance cha ac e is ics o hese ma e ials a e di ec ly de e mined by hei molecula a chi ec u e,
and TGA se es as a p ecise analy ical me hod o quan i ying he co ela ion be ween s uc u e and unc ional
p ope ies. In e na ional s udies ha e la gely concen a ed on elucida ing he he mal s abili y and deg ada ion
beha io o polyo ganosiloxanes a ele a ed empe a u es.
In Uzbekis an, a numbe o no ewo hy in es iga ions ha e been conduc ed in his ield. Sh. Sha ipo and
co-au ho s (2021) examined he he mal esis ance o o ganosilicon esins employed in cons uc ion ma e ials
using TGA, con i ming hei high s abili y and en i onmen al ad an ages. M. Rasulo (2020) expe imen ally
demons a ed ha he p esence o a ious o ganic subs i uen s in polyo ganosiloxanes—such as me hyl,
phenyl, and luo ina ed g oups—exe s a signi ican in luence on hei he mal endu ance. Resea che s a
Bukha a S a e Technical Uni e si y (2019–2023) sys ema ically analyzed he he mal s abili y o o ganosilicon-
based composi es in ended o cons uc ion applica ions, highligh ing hei p ac ical pe o mance bene i s.
Fu he mo e, A. Tu aye (2022) es ablished ha he inco po a ion o nano ille s e ec i ely delays decomposi ion
s ages and enhances he o e all he mal esis ance o o ganosilicon sys ems.
RESEARCH METHODOLOGY
A comp ehensi e and sys ema ic app oach was employed o e alua e he s uc u e–p ope y ela ionship
o o ganosilicon ma e ials. Ini ially, he molecula s uc u e o he samples was de e mined using ad anced
spec oscopic and analy ical echniques, including Fou ie T ans o m In a ed Spec oscopy (FTIR), Nuclea
Magne ic Resonance (NMR), and Gel Pe mea ion Ch oma og aphy (GPC). These me hods allowed o he
p ecise iden i ica ion o he chemical composi ion, molecula weigh dis ibu ion, and s uc u al con igu a ion o
he polyme s.

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In he subsequen s age, he mog a ime ic analysis (TGA) and di e en ial he mog a ime y (DTG) we e
applied as he p incipal me hods o eco d he mass-loss beha io o he samples, de e mine he onse (T_
onse ) and peak (T_max) empe a u es, and quan i y he esidual mass a e he mal deg ada ion. The ob ained
he mog a ime ic da a we e p ocessed using kine ic analysis models—speci ically he Kissinge , Flynn–Wall–
Ozawa (FWO), and Kissinge –Akahi a–Sunose (KAS) me hods— o calcula e he ac i a ion ene gy (Eₐ) and o
in e p e he decomposi ion mechanisms o he ma e ials.
In addi ion, Di e en ial Scanning Calo ime y (DSC) was u ilized o examine endo he mic and exo he mic
ansi ions, p o iding complemen a y in o ma ion abou phase changes and eac ion ene ge ics. The TGA–
FTIR/MS coupling echnique was u he applied o iden i y he gaseous decomposi ion p oduc s, he eby
elucida ing he de ailed he mal deg ada ion pa hways o he o ganosilicon sys ems.
ANALYSIS AND RESULTS
O ganosilicon ma e ials a e polyme s cha ac e ized by a dis inc i e chemical s uc u e in which he main
backbone is composed o silicon–oxygen–silicon (Si–O–Si) bonds. The high bond ene gy o his backbone,
along wi h i s capabili y o inco po a e a a ie y o o ganic side g oups, endows hese ma e ials wi h excep ional
physicochemical p ope ies. Consequen ly, o ganosilicon polyme s demons a e high he mal s abili y,
ema kable chemical ine ness, p onounced hyd ophobici y, and excellen dielec ic s eng h. The ex en o
hese p ope ies, howe e , is s ongly in luenced by he molecula a chi ec u e—speci ically, he chemical
na u e o he side g oups, he deg ee o molecula b anching, and he inco po a ion o modi ying addi i es o
ille s.
The mog a ime ic analysis (TGA) se es as he p incipal scien i ic me hod o elucida ing he
in e dependence be ween s uc u e and unc ional p ope ies o o ganosilicon sys ems. This analy ical
echnique con inuously eco ds he mass change o a ma e ial as a unc ion o empe a u e, enabling de ailed
de e mina ion o decomposi ion s ages, onse and peak empe a u es (T_onse and T_max), as well as he
esidual mass ollowing he mal exposu e. Complemen a y o his, di e en ial he mog a ime y (DTG) allows
o a clea e s ep-by-s ep dis inc ion o he he mal decomposi ion p ocesses, quan i ying he a e o mass loss
a each s age and e ealing kine ic cha ac e is ics o deg ada ion.
Compa a i e esul s demons a e ha me hyl-subs i u ed siloxanes end o elease ola ile deg ada ion
p oduc s a ela i ely lowe empe a u es, while phenyl-subs i u ed siloxanes main ain s uc u al s abili y o e
a wide empe a u e ange and yield a la ge amoun o solid esidue upon oxida ion. These indings con i m
ha o ganosilicon ma e ials con aining phenyl g oups possess enhanced he mal esis ance and imp o ed
oxida i e s abili y compa ed o hei me hyl analogues. This he mal beha io highligh s he c i ical ole o side-
g oup chemis y in de e mining he o e all hea esis ance and s uc u al in eg i y o o ganosilicon polyme s
(Figu e1).
Figu e 1. De i a og am o an o ganosilicon oligome syn hesized om me asilicic acid, phenol, and o maldehyde:
1 – dynamic he mog a ime ic analysis (DTA) cu e;
2 – he mog a ime ic analysis (TGA) cu e.
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The he mal analysis o he ob ained polyme coa ing e eals ha he p ima y mass loss occu s du ing
he i s s age o decomposi ion, wi hin he empe a u e ange o 26.20–242.89 °C, co esponding o a 3.977%
educ ion in he ini ial sample mass. This s age is p ima ily associa ed wi h he e apo a ion o physically
adso bed mois u e and he elease o low-molecula -weigh ola ile compounds.
The second decomposi ion s age, aking place o e he empe a u e ange o 242.89–438.38 °C, is
cha ac e ized by a 36.525% mass loss, which ep esen s he mos in ensi e s age o he mal deg ada ion.
This p ocess is mainly a ibu ed o he b eakdown o o ganic agmen s and pa ial oxida ion o he siloxane
ne wo k.
The hi d s age o decomposi ion, obse ed wi hin he empe a u e in e al o 438.38–801.12 °C, accoun s
o an addi ional 16.267% mass educ ion, co esponding o he g adual emo al o esidual o ganic componen s
and he o ma ion o a he mally s able ino ganic esidue.
Abo e 450 °C, he sample demons a es no signi ican change in mass, which con i ms he o ma ion o
a s able, hea - esis an s uc u e and indica es he comple ion o decomposi ion eac ions. Acco ding o he
analysis, he p incipal weigh loss o he polyme coa ing occu s in he second he mal in e al, du ing which
he mos ac i e decomposi ion p ocesses a e concen a ed, accoun ing o 36.525% o he o al mass loss.
A de ailed in e p e a ion o he Dynamic The mog a ime ic Analysis (DTA) and The mog a ime ic Analysis
(TGA) cu es is p o ided in below (Table 1).
Table 1. Analysis o he DTA and TGA Resul s o he Polyme Coa ing Ob ained on he Basis o Mic osilica, Ammonium
Polyphospha e, and Epoxy Resin
№Tempe a u e, °C Mass Loss, mg (7.22) Mass Loss, %
1 100 0.141 1.95
2 200 0.216 2.99
3 300 0.552 7.65
4 400 2.566 35.56
5 500 2.96 41.03
6 600 3.204 44.4
7 700 3.504 48.56
8 800 4.071 56.41
In conclusion, he s udy demons a es ha o enhance he mechanical s eng h and i e esis ance o
wooden s uc u es, polyme coa ings o mula ed on he basis o mic osilica, ammonium polyphospha e, and
epoxy esin we e e ec i ely u ilized. Acco ding o he de i a og am o he syn hesized polyme coa ings, an
inc ease in empe a u e co esponds di ec ly o a g adual dec ease in sample mass, as he coa ing unde goes
con olled endo he mic and exo he mic ans o ma ions. This beha io e lec s he sequen ial decomposi ion
and s abiliza ion s ages cha ac e is ic o hea - esis an polyme sys ems.
To ob ain a 3% hea - esis an composi e based on he syn hesized o ganosilicon oligome , ammonium
polyphospha e and liquid glass we e inco po a ed as unc ional addi i es. These componen s signi ican ly
imp o e he mal insula ion, adhesion s eng h, and i e- e a dan pe o mance, p o iding an op imized balance
be ween mechanical du abili y and he mal s abili y o he p o ec i e coa ing.
The composi ion o he hea - esis an composi e con aining 3% o ganosilicon oligome is p esen ed below
(Table 2).
Table 2. Composi ion o he hea - esis an composi e con aining 3% oligome
№Composi ion name O ganosilicon oligome ,
gLiquid glass, g Ammonium polyphospha e, g
1 KSA 5/1 3 80 17
2 KSA 1/5 3 17 80
3 KSA 1/1 3 48,5 48,5
Acco ding o he esul s o he de i a og aphic analysis, an inc ease in he liquid glass con en wi hin he
composi ion con aining 3% o ganosilicon oligome leads o a no able enhancemen in he ma e ial’s he mal
pe o mance. Expe imen al es s we e conduc ed on he KSA 5/1 composi e, syn hesized on he basis o he
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de eloped o ganosilicon oligome , and comp ehensi e The mog a ime ic Analysis (TGA) and Di e en ial
The mal Analysis (DTA) we e pe o med ac oss a empe a u e ange ex ending up o 950 °C.
The de i a og am o he he mally ea ed oligome -based composi e consis s o wo dis inc cu es,
clea ly e lec ing he he mal beha io o he ma e ial unde con olled hea ing condi ions. The TGA cu e
(cu e 1) demons a es ha decomposi ion p oceeds p edominan ly h ough h ee main empe a u e in e als,
each co esponding o cha ac e is ic s ages o he mal deg ada ion. The i s decomposi ion s age occu s
wi hin he ange o 27.84–255.70 °C, p ima ily associa ed wi h he elease o physically adso bed mois u e
and low-molecula -weigh ola iles. The second s age, ex ending om 255.70–553.27 °C, ep esen s he majo
decomposi ion phase, du ing which he o ganic and polyme ic componen s unde go oxida i e deg ada ion and
pa ial c osslink scission. The hi d decomposi ion s age, obse ed be ween 553.27–901.50 °C, is cha ac e ized
by he g adual emo al o esidual o ganic s uc u es and he o ma ion o a he mally s able ino ganic esidue
(Figu e 2).
Figu e 2. De i a og am o he KSA 5/1 Composi e:
1 – The mog a ime ic Analysis (TGA) cu e;
2 – Di e en ial The mal Analysis (DTA) cu e.
The analy ical esul s indica e ha an in ensi e decomposi ion p ocess occu s du ing he hi d s age o
he mal deg ada ion, whe e he ex en o decomposi ion eaches 11.455%. Based on he expe imen al da a
ob ained om he DTA and TGA analyses, he kine ic pa ame e s o he he mal deg ada ion p ocess we e
calcula ed o di e en empe a u e in e als. This analy ical app oach o e s a dis inc ad an age, as i enables
he de e mina ion o eac ion kine ics ac oss he en i e empe a u e ange by pe o ming mul iple measu emen s
on a single expe imen al sample, ensu ing high accu acy and ep oducibili y.
The mass-loss a e ( ₘ) was de e mined using he g aphical di e en ia ion me hod applied o he TGA
cu e, as exp essed by he ollowing equa ion:
whe e:
Δm – mass loss, mg;
Δ – ime in e al, min.
A de ailed analysis o he he mog a ime ic analysis (TGA) cu e and di e en ial he mal analysis (DTA)
cu e is p esen ed in he ollowing able (Table 3).
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Table 3. The ela ionship be ween empe a u e and mass loss o he KSA 5/1 composi e.
№dw 9,48 1/T dw/d M.g Min T0+K
1 9,37 0,0026 0,0139 0,11 7,9 373
2 9,18 0,0021 0,0167 0,3 17,88 473
3 9,04 0,0017 0,0157 0,44 27,9 573
4 8,87 0,0014 0,0160 0,61 37,9 673
58,64 0,0012 0,0175 0,84 47,91 773
68,47 0,0011 0,0174 1,01 57,85 873
7 7,98 0,0010 0,0221 1,5 67,85 973
8 7,91 0,00093 0,0201 1,57 77,81 1073
97,63 0,00085 0,0210 1,85 87,76 1173
10 7,48 0,00083 0,0220 2 90,75 1202
The ac i a ion ene gy (Eₐ) alues o he he mal decomposi ion p ocess o he KSA 5/1 composi e we e
de e mined based on he esul s o he mal-oxida ion analysis, as summa ized in (Table 4).
Table 4. The he mal-oxida ion analysis esul s o he KSA 5/1 composi e
№Dw 9,48 Ln(W1/W2) 1/T *10-3
1 9,37 0,0116 2,6
2 9,18 0,0321 2,1
3 9,04 0,0475 1,7
4 8,87 0,0665 1,4
58,64 0,0927 1,2
68,47 0,1126 1,1
7 7,98 0,1722 1,0
8 7,91 0,1810 0,9
97,63 0,2170 0,8
10 7,48 0,2369 0,8
Based on he esul s o he de i a og aphic s udies, i was es ablished ha he main mass loss occu s
du ing he i s s age o he mal decomposi ion, wi hin he empe a u e ange o 27.84–255.70 °C, whe e 6.186%
o he o al mass is los . The second decomposi ion s age, obse ed be ween 255.70–553.27 °C, co esponds
o an addi ional 6.091% mass loss, indica ing he p og essi e deg ada ion o o ganic componen s. The hi d
s age, ex ending o e he empe a u e ange o 553.27–901.50 °C, esul s in a u he 11.455% mass educ ion,
which e lec s he comple ion o he mal oxida ion p ocesses and he o ma ion o a s able ino ganic amewo k.
Acco ding o he expe imen al da a ob ained o he kine ic beha io o he KSA 5/1 composi e wi hin he
empe a u e ange o 293–943 K, he ma e ial exhibi s dis inc he mal-oxida ion deg ada ion cha ac e is ics,
associa ed wi h i s sequen ial decomposi ion and subsequen o ma ion o he mally s able silicon dioxide (SiO₂)
as a esidual phase.
These esul s demons a e ha he syn hesized o ganosilicon oligome possesses high he mal s abili y
and esis ance o oxida i e deg ada ion, making i a p omising componen o he p oduc ion o ad anced i e-
esis an and hea -p o ec i e ma e ials.
CONCLUSION AND RECOMMENDATIONS
O ganosilicon ma e ials possess signi ican scien i ic and indus ial alue due o hei unique physicochemical
cha ac e is ics, including excep ional he mal s abili y, chemical ine ness, hyd ophobici y, and dielec ic
s eng h, all o which a e p ima ily de e mined by hei molecula s uc u e. Resea ch has shown ha he high
bond ene gy o he –Si–O– linkage ensu es he s abili y o he main polyme backbone, while he chemical
na u e o he side g oups—such as me hyl, phenyl, and luo ina ed subs i uen s—and he deg ee o molecula
b anching play c ucial oles in de ining he ma e ial’s he mal beha io . Fo ins ance, polyme s con aining