CHAPTER

Thermal Analysis and Kinetics o f Degradation

--. ---

?hurts presenteS in tfjk cljapter Gave h e n communicateS to:

9.1

Introduction

hermogravimetry offers precise control of heating conditions, such as This analysis

variable temperature range and accurate heating rate.

needs only a sniall quantity of sample. It is also possible to quanhfy the amount of moisture and volatiles present in the composites, which have a deteriorating, effect on the properties.l.2 The thermogravimetric data

provides number of stages of thermal breakdown, weight loss of the material

in each stage, threshold temperature, etc.3 Both TG and DIG (differential

thermogravinietric) curves provide information about the nature and conditions of degradation of the material.
TGA can help in understanding the degradation mechanism and must

assist any effort to enhance the thermal stability of a polymeric material4. The threshold decomposition temperature of composite indicates the fabrication temperature. The thermal stability of individual polymers can be evaluated to a great extent by blending it with other polyniers or reinforcing with fibres. Composites usually have better thermal properties than corresponding components in the system5.6. This synergism is usuaUy attributed to the interface adhesion of the components. 'l'he thermal degradation of natural fibres has rcccivcd considerable attention in the past'8. The effects of crystallinity, orientation and

Chapter 9: Thermal and Kinet'c Degradation

260

crosslinking on the pyrolytic behaviour of cellulose fibre have already been described in considerable detail9-12. It is observed that the thermal breakdown of cellulose proceeds essentially through two types of reactions. At low

temperature@etween 120C and 250C), a gradual degradation, which includes depolymerization, hydrolysis, oxidation, dehydration and

decarboxylation.

At higher temperature, rapid volatilization occurs

accompanied by the formation of levoglucosan and a charred product. Decomposition leads to loss in fibre strength and a marked reduction in Initial n~olecular weight decrease is severe and degree of polyn~erisatiot~(l)I'). occurs via rupture of chains at the crystaLline/amorphous interfaceI3. The pyrolysis of lignin has been studied by Abet4. Thermal stability and moisture retention of coir fibre has been increased by the effect of mercerisationl5. Mohanty ct
nl1f1. have

studied the thermal analysis of PAN(po1y acrylonitrile)

grafted coir fibres. Thus TGA studies estimate the thermal stability of the fibresl7. Various researchers have previously studied the thermal behaviour of rubber blends and composites in detail'"l9. 'lhe storage stability of some

synthetic rubbers and ENR(epoxidised natural rubber) has been analysed through TGA by Chaki et alls. TGA has been used to determine the filler content of wood-based compositesl9.
DSC (differential scanning calorimetry) can explore the heterogeneous

nature of rubber composites. This mill give the Tg of the polymeric material and the fibre phases. Miscible system will show single, sharp transition

peak(T,) intcrrnediate between those of the components. Separate peaks will be obtained for heterogeneous phase separated systems. In this laboratory, Thomas and co-workers have already reported on
the- thrrmnl an,rlp.;is of rr~bl>er blencts and compositcs"'?2 irr detail. Very

recently Prasantha Kunrar and 'Ihomas have prepared cost-effective from styrene-butadiene rubber and sisal fibre ?'.IJ. composite n~aterials
Chapter 9. Thermal and Kinetic Degradation

26 1

In this cliaptrr, the thermal behaviour of the sisal fibre rcinforced SBR composites has hc.c.11 an'ilyscd by 'I'GA and USC as a tunction of fibre loading, chemical modification of fibres and incorporation of bonding agent. Attempts have also bccn made to corrclatc the properties with thc morphology of the system. Finally, the kinctic paramctcrs of thc thermal degradation wcrc aLso evaluated using ninc mechanistic equations.

9.2

Results and discussion

9.2.1 Thermogravimetric Analysis

(a)

'I'herma! analysis of fibres

The major constituents of sisal fibres are cellulose, hemicellulose, pectins, lignin, etc. Of these, cellulose is the main fraction reprtwnting 72% of the fibre followed by hemicellulose and pectins (10%)'6. The differences in the proportions of ccllulose, hemicellulose and pectins in untreated and treated sisal fibres contribute to the thermal characteristics of the sample. Scheme 9.1 shows the structure of cellulose backbone present in the fibre.

Sc!:cme 9.1.

Strucfure o f cellulose bnckhorte irr thejibre.

Thermal decomposition of each sample takes place in between a progrsamec! temperature range of 10 to 550'C. Most natural fibres lose their strength at about 1 6 K . Thermal analysis of cellulose fibres has been carried out and the cfffcts of cl-ystallinit)., orientation and crosslinking on the
' 1- 7 pyrolytic behaviour of cellulose have been reported2 -* -' .

Chapter 9 Thermal arid K ~ n e t ~ Uepradat~on c

202

Figure 9.1 shows the 7'G curves of untreated and chemically modified sisal fibre. Curve A represents untreated, B, mercerised, C, acetylated and D, benzoylated sisal fibre respectively. 7'he major source of stability in cellulose is due to hydrogen bonding, which allows thermal energy to be distributed over many bonds3L1. Between 75 to 1750C dehydration as well as degradation of lignin occurs and most of the cellulose is deconiposed at a temperature of
350C. 'l'he oxidative degradation of cellulose takes place in the aulorphous

region7. The decomposition of treated fibres occurs at a temperature range of

460-472"C, whereas the untreated fibre decou~posedat 45:;.7Y;;C.

'l'able 9.1

shows the mass losses (76) of untreated, mercerised, acetylated and benzoylated sisal fibre at various temperatures. On analysing the table, it is found that the decomposition temperature of the treated fibre is higher than that of untreated fibre.

100

200

3 m

un
' C I

sin

TEMPERATURE (

Figure 9.1.

7.G crrnVes o f untrenled, rrrerceri.~errince~~l(ired nrrri brrizo.~lnld sisnl

fibre
Chapter 9 Thermal and K ~ n e t ~ Degradation c

263

Table 9.1.

Ili~ighf lasses o f ttrtlreared, ntercerised, acefylafed artd berizo~lated sisal fibre af various temperatures,

Figure 9.2 shows the DTG curves of the untreated, rnercerised, acetylated and benzovlated fibre. The letter A corresponds to untreated, B, mercerised, C, acetylated and D, benzoylated sisal fibre respectively. The complete pyrolysis of the fibre sanlple takes place in t h e e stages showing a very small peak, a broad peak and a sharp peak. The thennogram of sisal fibre obtained by Chand et al?' have also revealed that its thermal

n the case of untreated fibre, the degradation follows three distinct stages. L
lirsl pmk L>C~M.C~-II h0 811d I O O ' C C ( I I . I . ( ' S ~ O I ~ ~ to S thr 11c.at ol vaporisalio~~ ot water in the sample. The second peak at about 325" is due to the thermal

depolymerisation of hrnlicellulose and the cleavage of glucosidic linkages of cellulose3'. The third peak in these thermograms was sharp and at about

450'C may be due to t h r further brcakogr of the d c c c i r ~ ~ ~ ~ o 1~roc1ucts siict of

stage 11, leading to the formation of tar through levoglucosan".

Chapter 9 Thermal and Kinetlc Degradat~on

264

Figure 9.2.

D I G cunqes c f l urtireared, ntercerised, nce!flnted nrtd benzojqlnIed

sisalJibre

The main dcconiposition temperatures of chen~ically modified fibre are shifted to the lugher side with respect to untreated fibre, i.e., the DTG peak temperature at 45PC in the case of untreated fibre is shifted to 465-472'C range in the case of t~eated fibre. I'he mass loss(%) of treated fibres at this step(combination of heniicellulose & a-cellulose) increases, whereas the char left(%) at 475'C showed a decrease. I'he percentage of char is higher in the case of untreated fibres ('I'able 9.2). 'The rate of thermal degradation between outer and inner layers of the cellulose fibrils it1 fibre particles present in samples may be significantly different. Consequently, complete pyrolysis takes placc in a relatively wider temperature band showil~g a broad decompositiori peaks. On degradation, ITI'G curves displace towards high temperature side depending on the alnount of residual non-cellulose

Chapter 9 Thermal and K~nebc Degradat~on

265

polysacharicies present with the cellulose fibre"'.

l'he physical differences

between the fibre c a n be clearly identified from their cross-sections and also

from their surface cl-lar-acteristics. For cxaniple, trcatcd fibres sl-tow a rough
surface topography compared t o untreated fibres. SEM Figure 9.321 shows the

morphology of the untreated fibre while the Figure 9.3b shows the fibre after
treatment. The size and shape of the test sample can also affect the pyrolysis patterns due to the diFferences in surface area and heat conductivity.3"

1
1

;rhble

9.2.

Results of derivntive rhernzogravinlctric nttaZysis of sisn L n ~ t d treated

sisal fibre.

Sisal fibre

1
1

Jegradation) temperature ttC) (at cliff.-Peaks

1
1

Weight loss(%) (Peak temp) - - . -- -

I
1

Residual mass at 47S0C (%)

9.228

1
1

Untreated fibre

335.49

51.82

hlercerised
-

Acetylated
-- -

Renzoylated

342.46 465.32 45.8 343.72 468.59 47.41 345.45 471.85

48.15 9.25 68.27

4 .(A

48.65 6.63 66.2

49.52 2.72

3.076
.-

2.307

Figure 9.3.

SEII~ pltorugrplrs shotuirrg the scrrficr ntorphology of fibre arid (6) b e n z ~ ~ l n t e d f i b r c .

(4 raw s i s ~ l

Chapter 9:Thermal and Kinetic Degradation

266

The chemical treatment on sisal fibres reduces the pyrolysis

temperature, decreases the weight loss during pyrolysis facilitating the formation of a lower percentage of flammable volatiles. Table 9.2 also shows

the results of DTG runs of untreated and treated sisal fibre. The differences in
ash left in the crucible at the end of the DTG runs have shown that the inorganic content of each of the three treated samples of fibre was not
significant. Maxittiurn ash was detected in the case of untreated fibresxi. In

general, alkali treatment and mercerisation of natural fibres reduce the cementing material followed by the removal of volahle products with rupture of bonds. It is well estabkhed that thermal behaviour of cellulose fibres is largely influenced by alkali treatment, which also affects their mechanical proper ties's. Treated sisal fibres would have more surface area compared with untreated fibres for the same weight assuming that density of these fibres is similar. ?'he pyrolysis would advance rapidly in treated fibres and the rate of

decomposition may be xelated to mean radius of the fibre. This conclusion is

further supported by the parameters determined by 1)'I'G. Differential

Thermogravimetric Analysis not only provides a thermal spectrum of the sample but may also be able to relate to the treatment of the fibre. Using

TGA, Kokta et a l . 5 have studied the effect of grafting of various polyacrylates

on to cellulose and its influence on temperature and heat of degradation.

DTG therrnograms of untreated and treated fibre show initial moisture

loss peak between 60 and 100C and a main deconlposition peak at 325'C for
untreated fibre, 342.6OC for mercerised, 343.720C for acetylated and 345.45C for benzoylatecl fibre. In the case of treated fibre, the decomposition step due

Chapter 9:Thermal and Kinetic Degradation

267

to the hemicellulose, which is observed in the case of untreated fibre, is almost merged with a-cellulose degradation. The weight losses of these treated and untreated sisal fibres at various temperatures are given in Table 9.1 In the case of untreated cellulose fibres, lignin degradationHsets in at around 200cC, and other polysacharides mainly cellulose are oxiciised and degraded at higher temperatures?2. From the data, it is clear that benzoylated sisal fibre exhibits a higher thermal stability con~pared to other treated fibres. This may be attributed to substitution of bulky phenyl group in the fibre that restricts the segmental mobility, thereby increasing the stiffness of the cellulose backbone. It is also partially due to the fact that some of the components of the fibre, such as LignocelIulose, that degrade at a lower ten~peraturemay be extracted during alkali treatment. The improvement in the thermal stability of the fibre will lead to the better service perfornlance of the composites at elevated temperatures.

(b)

Thermal analysis of composites 'Ihe formulation of the mixes are given in Table 9.3. Figure 9.4 shows

the thermal degradation of gum SBR sample. On analysing the TG curve of thc sample, it is found that the dc,composition of Sllli occurs at a temperature of 445.17C. The Sf3li starts degrading at 414.09.C and only 2.889%remains at
60OC. I'he decomposition temperature of SUR gun1 is higher than that of the

fibre. DTG curve of the sample showed two peaks. l'he degradation of SBR started from the minor peak and followed by a broad decomposition peak.

Chapter 9 Thermal and K~net~c Oegradat~on

2(>8

Table 9.3.
Mixes hgredients

Fornrulatior~ of miresfrom A to S@lrr)

-

Synaprene Sulphur Stearic Acid Zinc Oxide

loo

B C D E F G H L Q R S 100 100 1 0 0 ~ 0 0100 1 0 0 ~ ~ 0 100 0 loo 100 100

2.2 2.2 2.2 2 2 2

2.2 2.2 2.2 2.2 2 2 2 2

2.2 2 2 2 2

2.2 2

2.2 2.2 2 2

Hexa*

2.5

Sisal fibre(Fibre length,mrn) Sisal Fibre (Untreated)

1 0 6

35

35

35

10 15

20 35

(Acetylated)

35

Ilexamethylene Tetramine N-cyclo hexyl benzothiazole sulphenamide '" 2,2,PTrimethy 1,2-di hydroxy quinoline polymerised.
+

*f

Chapter 9. Thermal and Ktnetic Degradation

269

Figure 9.4.

TGA attd DTG curves of vuicarrized SBR (Mix A)

The degradation of SBR occurs in two steps. It is stable u p to 250C and after that degradation occurs rapidly. ?he degradation starts at about
414.0YoCand at 5 5 K almost 92% degradation is completed. Above 7 5 0 C no

residue remains. In the D'I'G of SBR, a major peak is observed at 501.370C, which indicates the degradation of saturated and unsaturated carbon atoms
UI

S U R . l'his corresponds to the chain scission to give volatile monomer along

with some amount of impurities.

The mechanism of random scission of

polymer chains that occurs at high temperature is shown in Scheme 9.2.

Chapter 9: Thermal and Kinetic Degradation

270

+c

Schente 9.2. Degradation sites o f SBR.

The TG and DI'G curves for the fibre filled(17.7%) mix C is shown in Figure 9.5. The degradation temperature of fibre reinforced composites is greater than the vulcanized SBR matrix. The fibre filled SBR starts degrading

al

n )+~~~-"+=-=c~--F*a-

at 300C and 6-7% remains at 600c.C. About 80% of the material gets degraded
in the temperature range of 400-60O.C.

lliis is evident from the

thermogravimetric scan that the thermal stability of fibre reinforced composite is increased. DTG curves also supports this fact.

Ts*oll"*T""E

.C,

Figure 9.5.

TGA and DTG curves o f n~iv C(35PIir)

Chapter 9 Thermal and K~netic Degradation

27 1

In sisal/SUR composites, generally two peaks are obtained. In the case of untreated fibre reidorced SBli composites(Mix C), the degradation is characterised by three peaks. The minor peak at 386.36'C corresponds to the degradation peak of SBR and the major peak at 494.09"C corresponds to the degradation of sisal/SBR composite. The third peak at 610.82indicates the It is

conversion of volatile mass and impurities to the tany products.

interesting to note that, in the composite, the major peak is shifted to higher temperature region compared to sisal and SUR peaks, i.e., thermal stability is marginally increased in the composite compared to pure SBR due to improved fibre-matrix interaction. I h i s can be further understood from the weight losses at a definite temperature (Table 9.4). In most temperatures, the weight losses are lower in the case of composite samples. Table 9.4. 7fiernral degradation temperatures.
of

sisaUSBR

conrposites

at

diJferent

Chapter 9 Thermal and Kinetic Degradation

272

9.2-2 Thermal decomposition as a function of fibre loading

Figures 9.5-9.9 show the 'l'G/Ul'G curves of mix C, E, F, G and H respectively. On comparing these thermograms, it is understood that the increase in the volume percent of short sisal fibres has a retarding effect on the extent of degradation of sisal/SBR composites. On increasing the volume percent of fibres in the composite, the degradation temperature also increases as indicated by the 1;igures 9.6-9.9. L he resistance to degradation is caused due to the presence of increased fibre content and increased interaction between the fibre and the rubber matrix. Our earlier studies indicated that the interaction between fibre and rubber increases with the increase of fibre concentration23.

-..................

+ .........

71

* E:
Y
50

\\
,..
\ .,

. . . . . . . . . . . . . . . . . . . . . . . . . .

i ,

,, , ,
5

, :
,
,
I :

: , 4

.
,

, ,
2,

:'
I

40

,no

>m

I I,"

3%"

,cr:\ii--;,674r--.l,

Figure 9.6.

1'GA atui DI'G cunvesofrrrir E(5Pltr).

Chapter 9 Thermal and Ktnet~c Degradat~on

273

.~1*,.11111111"~,

I .C,

Figure 9.7.

TCA and DTG cunreso f ntiv F(I0Pllr).

Figure 9.8.

TCA arrd D7% curves o f miu G(I5Plrr).

Chapter 9: Thermal and Kinetk Degradai~on

274

Figure 9.9.

TGA arrd DTG curves of nriv H(20P11r).

The parameters evaluated from the thermograms and their derivatives of sisal/Sl3Ii composites are tabulated and shown in 'l'able 9.5. 'I'he initial temperature for 50% decomposition ('150)and decomposition temperature ('1'4, the final decomposition temperature (TI) were plotted against volume percent of fibres (Figure 9.10a). It is seen that fibres increase the initial degradation temperature. As the fibre content increases from the mix E to H, the stiffness and strength of the composite also increase as observed from the mechanical property measurements. The increase in the decon~positiontemperature is due to the increased fibre-matrix interaction in the composite, which enhances the overall thermal stability of the composites. Figure 9.10b shows the effect of different treatments on the degradation temperature of samples. ?'he increase of degradation temperature is attributed to the strong interface created through chemical modification of fibres. Among these samples, it is evident that benzoylated sample has the maximum thermal stability than others.

Chapter 9 Thermal and Ktnetc Oegradatlon

275

Table 9.5.

Pnranceters evaluated from tlre tlternwgrams o f conlposiles.

tlte sisaVSBR

Volume

Final

Temp.
place('C).

486.664
~~

--

5.779 8.425

358.53 406.79

376.61 498.184 488.838 386.359

503.29 558.21 588.13 494.0875 635.53

.- -

487.047

VOLUME OF FIBRES( % )

k'igure 9. I Oa. /'lots o f Tb I;" attd

Tfversus voluttte percetrt offibres.

Chaplet 9 Thermal and K~netc Degiadat~on

276

Untreated Bondg Agt

Mercerised Acetylated Benzoylated

TYPES OF TREATMENT

Figure 9.10b. l'lols of T;, Tsoarrd TI versus drferertt cl~emical treatment.

The weight loss uf con~posites at different temperatures is tabulated in

'Table 9.4. It is obvious that thermal stability increases in the fibre fdled
systems on increasing the fibre content due to the belter fibre-matrix
interaction. It is also understood that the modiEication of fibres by chemical
treatment has also helped in the iuiyrovenlent of inlel.facia1 adhesion wluc11

paved the way for the better thermal stabdity .

9.2.3 Effect of chemical treatment 8 bonding agent

The effect of chemical treatment on fibres and incorporation of bonding

agent on the system affect the thermal degradation of sisal/SHli composites.

'l'his is well explained in the '17G/LY1'G curves of mixes C, Q, I< and S, which
are shown in Figures '3.5, 9.11-9.13respectively. 'l'he cxtcnt of degradation of

Chapter 9: Thermal and Kinetic Degradation

277

sisal/SBR composites treated with mercerised, acetylated and benzoylated fibres are less than that of untreated fibre composites. When comparing the weight losses a t 450C the values are 45.01% for the untreated composite,
39.29%, 30.72%, 26.71% for mercerised, acetylated and benzoylated fibre

composites, respectively (Table 9.4). ?he slightly higher thermal stability of treated fibre composite can be explained by the additional intermolecular bonding between fibre and matrix induced due to the treatment. The

benzoylation of the fibre makes the composites thermally more stable than the untreated one. This is associated with the better interaction between fibre and matrix, due to the formation of covalent bonds between GHs-CO- group of benzoyl chloride and -OH gtoup of cellulose. The schematic model of the interface of the benzoylated fibre con~posites is represellled in Schentc 4.3

Chapter 9: Thermal and Kinet'tc Degradation

278

TUYPII."TII"II

I .CI

Figure 9.12.

TCA arrd DTC cunvesof nliv R.

,,,H,~,z,,hr,,",,

,.,,

Figure 9.13.

7%A and 177% cunveso f n ~ i v S.

Chapter 9: Thermal and Kinetic Degradation

279

Figure '9.14 shows the thermogram of bonding agent incorporated composite (Mix L). On analysing the two-stage decomposition as shown by IXG, it is seen that the rubber phase started decomposition at 338C while the composite decomposes at a higher temperature shown by the degradation peak at 525.86"C. liere, the incorporation of bonding agent shows little

enhancement on thermal stability. This is due to the easy degradation of the interface of bonding agent added composite. ?his is also evident from the values of weight loss reported in Iable 9.4. The formation of the ln sihc resin formed during vulcanization is also depicted in Scheme 4.6. Among these mixes, benzoylated fibre reinforced SnR composite(Mix S) showed maximum thermal stability.

l'7glcre 9.14.

TG,? arrd DTG' cunvs c ~ r r r i u I*.

Chapter 9: Thermal and Kinetic Deqradaion

280

9.2.4 Kinetic parameters from thermal degradation

Nowadays, tliermoanalytical techniques are extensively used for the evaluation of kinetic ynrameters, viz., rate constant(k), energy of activation(E), order of reaction(n), pre-exponential factor(A), etc., of heterogeneous reactions. Mass measurement has higher accuracy and precision as compared to the measurement of bT(DTA) or dH/dt(DSC), and therefore, 'I'G is preferred in many studies. The general approach in kinetic analysis is to obtain an equation to express the rate of reaction in terms of the degree of transformation, a , and a temperature dependent function k(T). If the reaction is proven as iso-kinetic over the range of temperature, the second term becomes the rate constant governed by the Arrhenius law. Mechanism-noninvoking method is a simple extension of homogeneous kinetics, assuming g(u) = (I-up. A plot of Ln[g(a)/T*] against 1 / T gives a straight lime with slope as

E/R and intercept as in AR/$E as shown in Figure 9.15.

Figure 9.15.

Plots of lrr 1,y(a)/Id 1versrrs In:

Chapter 9: Thermal and Kinetic Degradation

28 l

Different authors have derived several equations based on the integral method for the deterinination of the decomposition kinetics. Using the

integral method explained by Ninan2 on the above rate equation, the kinetic parameters for thernial decomposition of sisal/SBI< composites were analysed by the least square technique. ?'hisfits well with the first order kinetics. 'lhe mechanisms of kinetic equations are based on the assumption that the form of g(a) depends on the reaction mechanism. 'The heterogeneous processes are classified into three broad categories governed by (1)transport of matter(diffusion), (2) nucleation and growth of nuclei and (3) phase boundary reactions. l h e most prominent rate controlling process operating in a particular case is chosen and used for deriving the rate equation. Different ic of authors basrd on the integral method to determine thc, k i ~ ~ e tparalnelcrs thermal decon~positionhave derived several mechanistic equations. Satwa has chosen 9 equations based on 9 possible mechanisms [9 different forms of g(a11~~. 'l'he equations and the rate controlling process in each case are shown in Table 9.6 and were used to analyse all TG data. 'lhe form of g(a) which best represents the experimental data gives the proper mechanism. ?he

results of the analysis have revealed that the highest correlation coefficient and hence best linear fit of the experimental data was obtained from Manlpell equation irrespective of the composition and method of preparation of the composites. The analysis of thermal decomposition data showed that the best-fit curve was obtained from Mampell equation irrespective of fibre loading and treatment. ?his leads to the conclusion that the degradation of sisal/SBR composites is based on random nucleation meclianisrn, which is the rate controlling process

Chapter 9 Thermal and K ~ n e t ~ Oegradat~on c

282

Table 9.6.
I
I

Conrtrmr~ly used ~ ( a /o ) m s for solids state rmclions.

1

-. . -. -

Equation

Rate controlling Process

--.~

Random nucleation- one nucleus on each particle- Mampell equation. l-(l-a)1/2 Phase boundary reaction, cylindrical symmetry.
. . . . .~. ..

I 3 l
~-

l-(l-a)1/3

T'hase boundary reaction, spherical symmetry. Two-dimensional diffusion.

-~

1
I
.. . . ~

n + (1-a) ln(1-a)
1 - ) - ( - a )

Three-dinlensional diffusion, spherical symmetry- Ginsthing-Brounshtein equation.

~ ~

.. .--

1
.

Randonl nucleatio~l-Avrami equation 1

~

[ - h ( ~ - ~ : , ] ~ /Random ~ nucleation-Avrami equation I1 . . ~Three-dimensional diffusion, spherical symmetry- Jander ecluation.

~ ~ ~ ~ ~ ~ ~

.~. ..

One-djmei~sior~al diffusion.

'I'he kinetic parameters such as E, energy of activation(kJ/mol), A, Arrhenius parameter(S'), and AS ,entropy of activationu/deg/mol) for the two-stage thermal decomposition of sisal/SHlZ co~nposite san~pleswith different volumc c ~ f fibres are sun~tnarised in 'lablrs 9.7 anci 9.8. 'l'he

activation energy, defined as the amount of energy required to decompose one-gram mole of the substance, also reveals information about thermal stability. The larger the activation energy, the more stable is the material. 'I'he activation energy of material is dependent on the order of reaction and temperature range of pyrolysis. But no absolute value of activation energy can be expected in the composites due to its heterogeneous nature.

Chapter 9 Thermal and Klnettc Degradation

283

Table 9.7.

EJSrct of ~~ulume of Jibres (%) on kittetic paranleters for tlte ilterntal decot~tpositiort(for the bestfil equation).

Table 9.7 shows the effect of volume of fibres on the kinetic parameters while Table 9.8 shows the effect of treahnent on the kinetic parameters of thermal degradation. In a l l cases, the activation energy of the first stage is lower than that of second stage. I h e activation energies increase gra~iually in both stages as the fibre content increases. In the first stage the activation energy itlcreases from 204-221 kJ/mol as the fibre content increases from 5-35phr. Similarly, the second stage, the activation energy increases from

221-284 kJ/mol as the fibre content increases. This shows that the increase in
fibre content makes the system more resistant and less temperature sensitive during thermal degradation. 'Ihe kinet~cstudy of thermal decomposition showed the presence of two activation energy values for each composite indicating phase separation. Each phase decouiposes separately at two different teniperatures. 'I he low activation energy of first stage of decomposition compared to that of second stage shows that S15K degrades at lower temperature and fibre degrades at a higher temperature. The low value of pre-exponential factor indicates relatively few degradation sites for the compound.

Chapter 9: Thermal and Kinetic Degradation

284

Table 9.8.
7

Effect of chemical treatment and bonding agent in sisaL/SBR composites on kirtetic parameters for tlte tltermal decompositiort (for tlte best fit equation).

Tvpes of treatments

Activation energy, B (kJ/moi)

Ia , Stage I11 Stage I Stage I1

221.92 223.31 284.41 287.45 307.67 336.78 299.36 283.57 210.82 180.02 332.51

1
1
1
I

Arrhenius parameter, A ( ~ ~ 1 ) Stage I

2.6x1W 1.12~10' 1.89~10' 4.73~108 1.19~10'

Entropy of activation, A S (J/deg/mol)

Stage I1
4.51xlW 6.06x10h 2.39~107 9.23~107 1.03xlW

Stage I11
3.89x10j 2.33x107 3.97x102 5.39~106

I
/

Stage I
-225 -209 -194 -100

Stage U
-125

Stage 1 1 1
-145 -188 -202 -124

C-Untreated(N) Q-hfercerised(C) R-Ac.etvlate~l(G) S-Renzoviated(1) L-Bondg.lgent(L)

-111

,1

242.52 307.63 253.46

-122
-86

-175

-117

All values of entropy of activation have negative values. The negative values suggest that the segments undergo some chain alignment in elevated temperatures forming the activated complex. It is also observed that the magnitude of the entropy change is lower in the second stage of degradation. 'l'he effrct of treatment on kinetic paramctc.rs is made clear from Table 9.8. It is seen that treated co~nposites show three-stage decomposition showing t h e e different peaks in the DI'G run. l'he first one is a small peak showing the initial degradation and the second is a broad one showing main decomposition peak while the last one shows the deterioration of composite interface. From the first stage to the second stage the activation energy increases from 223.31 to 336.78 kJ/mr)l as the fibre treatment varies from mercerisation to benzoylation. Similarly, in the third stage, the activation energy increases from 210.82 to 332.51 kJ/mol as the as the fibre treatment reaches to benzoylation. When the samples were compared, it was observed that fibre treatment increases the interface bonding, which makes the system more thermally stable. tt is important to notice that the increase in activation energy from stage I to It1 points to the fact that fibre filled Sl3R is more thermally stable than neat SBR. From Table 9.7, it is clear that the entropy of activation have negative values. 'Ihe magnitude of entropy is lower in the second stage in all cases.

9.2.5 DSC studies

In DSC, the heat flow rate associated with a thermal event can be measured as a function of time and temperature and it allows one to obtain quantitative information about melting and phase transition of the system. 'lhey can yicld insight into various aspects of ~n~~tc~ri'il structure, and can provide a convenient measure of 'I,,: and may influence other in~portant properties.

Chapter 9 Thermal and K~net~c Degradat~on

786

'I'he thermal behaviour of sisal fibre, Sllli, sisal/SBR composites with and without bonding agent was analysed by DSC. Figure 9.16 shows the DSC curve of raw sisal fibre. Figure 9.17 shows the DSC trace of the SBR compound. The transition temperatures of composites observed are tabulated

in Table 9.9 along with those of component materials such as sisal and SBR.
Table 9.9 showed the effect of volume of fibres and bonding agent on T,. T,s of sisal fibre and SUR gun1 compound are found to be 49 and -52.25'C respectively. The T, value of SBR gum compound is found to be very close to the already reported value irrespective of the method of preparation of mixes. Figure 9.18 shows the DSC trace of fibre filled composite (Mix E) containing 5phr of fibres while Figure 9.19 shows the DSC traces of mix C containing 35phr of short fibres. These DSC traces of composites show two endothermic peaks indicating two different transitions. Conlpositc~s show two 'I',:. due to the presence of fibres and rubber matrix.

-20

r#)

60

m im

TEMPERATURE ( O C )

f raw sisal$bre. Figure 9.16. DSC curve o

Chapter 9 Thermal and K~nelc Degradation

287

-100 -80 -60 -40 -20

20 40

TEMPERATURE ( OC)

Figure 9.1 7. DSC curve ofgum conlpourtd (SBR).

Table 9.9.

Effect of variatiort of volume of fibres ($6) and irlcorporatiorl of bonding agent oft the glass transition tenrperature.
Fibre length
(mm)

Miwes
A

Fibre content (%)

0

'1'6

rc)

of SBR
-52.25

o f sisal
-

L (with bonding agent)

17.674

-24.6

76.5

I
288

Chapter 9: Thetmal and Kinetic Degradation

3
5 0 J
[r.

I:

2 4 E !

u , - a j - 4 0 - a , o m

4 o m m

TEMPERATURE ( OC)

Figure 9.18. DSC curve oflibrefilled coniposite(mk E).

L
I:
0 cl

a
: 1
W

I d

,
~ - l o ' - a , 0

a , 40 TEMPERATURE ( OC)

a ,

Figure 9.19. DSC curve of miu C coritainiizg 35pBr offbres.

289

Chapter 9: Thermal and Kinet~c Degradation

Scvc-rnl rt-srnrrhcrs hilvc rc-portrd tlie chanp,c-s in 'I',: of the comyositcs upon the incorporation of fillers like fibres, particulate fillers, flakes, e t ~ " ~ ' ~ . On the addition of aramid, glass and carbon fibres to the polyphenylene sulphide, T, of the matrix was depressed by 5-3" 'Ihe incorporation of lowering of

1 , of 1%'" e. benzylated wood in polystyrene(PS) decreases the '

the polymer matrix.

'I', is due to the plasticisation effect of the fibre that diffuses or dissolves into

Figure 9.20 shows the USC trace of the coniposite containing the 35phr of fibres and bonding agent. The two transitions are also noted from these endothermic peaks indicating two different T,s of the composite, i.e., -24.6 and +76.5. But here, the l',s show higher values compared with other composites. 'The high interfacial interaction between the fibre and matrix, which is created by the resin of the bonding agent, stiffens the composite and hence the TK value increase. ?'he hypothetical niechanisni showing tlie reaction of the components with the bonding agent is depicted in Scheme 4.6.

a,-40-a,

mito

m m 1 m
(
OC)

TEMPERATURE

Figure 9.20. -DSC curve o f mir L cotifairtirig bortdirig agerif.

Chapter 9: Thermal and Kinetic Degradation

290

9.3

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Chapter 9 Thermal and K~nettc Oegradat~on

292