I

of
Aim:

decomposition

of materials using Thermo gravimetric

Thermal Analysis anrl Differential Scanning Calorimetry. To determine the decomposition kinetics of materials and to determine the amount of
elements present in a mixture rtf calcium and magnesium carbonates using TGA analysis.

Procedure:
A rypic:rl lfCi cr-rr-v* trl-ir nrixtrrrr: r;l'cirlcitrrrr rtrrrl rrr:r.lrrcsittr.tr t'lrrlrrrrtrrles is sl:rrrtrt in [iig- 16, \"r:r"r cart rt<:t"icrl thitl :t sigrril-rearrt rtti:ss ]rrss Lrct:trrs t>.'l'r'r'c . ltl' (.'. This is rlue tr-r the ltroistrlrr: llru'st:nt irr the nriltur.-- -,\rrothcr rl'l:rss lrrss irl illrrrtrt -+SO" C is clut- to llrrl firlltrrt'i:rg: re*ctir.rll: : (s) -F C'(): r:r} ... L l(t.r'1 I'ig{.)r\) ;., . -.. .i! li ' Ir't.S!'$\ / 'i: -'('. Irr Fig. ldli *tutie*:serlr+uirlrkxietld:atf CaC(}.l cll'(-rlr)rl)rrses a{ nirotrt S(}(J

rrtirss loss

h{:l1.1.*-*11

dl:1]Lrr}-rFlLrs i t i (}

Por-tion (]i- t,l'l* (trLrrvc alr re-prt:sr:rlts ar r}}ixtr-rr-c of \,l.gO irrr<J C'irC'()r i1r)rl t.:(l represents n rcsitlrre of the rr rixtrrre of l\{S() arrd C:rC)- I}rtlr tlrr':e Jrlate;rtts lrh rrrrr-l t:(l r-e1>rilsilrlt l.ueight rz1 atrcl ,rr], respectieela'. I l: l-lrct tllitss lrr: is rltre tr: Clr(-'Clr -r tr''t=o

n crl' C ir CIC);. (-';rC'O. I s, Cl,O t s; + C'O - , :: 1 -,

irhr:L:t 6Ot-) '''C-:rrtrl (i()f) C c:rr-l lf.- irrt(:rl)r*lcrl !ltlL'1()

... r l().71

-1

-j-ernPerature

Fig- f-ODt 'l'(j ctrr-ve oJ'fltiNtLrre ol-c::rlcirrlrl iirxl llrirglrosiurrl rill l,{}rri}l(. 'l-lrrrs, tn1 rrr: is tlrr* loss uI'Cl{)1 tlctlvLrt:n -s()() C rrrrcl (){}(}" (,- rlrrc lo the crrrr'.- \-\!- cirn i-q'l;t{c tltc rtt.irss ol't.li l'tl'r'e nr dr-ccrrr:position crl'CltC-O3- I-ising-I'(i,\ conlglonents ftrrnretl during -[-CiA experi ]rrcr]t. -flrr: rrurss rrf-Cl*(J {rru r) forrlt.:tl cilrr hrt: crrlcttlrrl.Ll ,lxa:l-27{.rx1-trr7"r -fhi-s er1r"raltirI!"t (:ur! trc <rtrtrirr."tl as tirlIrrr'r,'s: -flre Clr(J i"s l{rrntt}d Llsirlrl lirllcx,irrg
l--t1. I l(}.S
r

...tlt).}i)

hy the. ar',.oltltir;rt fil- CO: .)!t I}t!- r1!-(:(}Dll)(rsilirrtt

-+-

irl'(":i(-'(')=.

CIC)C). l(s.) --+ Cl;rC}ts} r1f, I{}t}. 1

C()"r=1 -l-l

56, 1

,o-,\

, \\'
.o-o\t

.- t '-./1,r\' -

Frt:,n: tltr: ;rht-rv* *r.lttirtiott I trlole of CaCos gives

mt-rle of

CO: and l mole t:t

('rr( ). 'l-lrtrs. rr(,lL'\ t,l

^

Irttt ('( ). irr the si'err exirillples :;i,a=[1

trt s )

-rd this is *qual

lrr tttr.llr.'r r,[ ('lr( ) Iirt'ltrt=tl

-\r..-}
.

4-[ sr$a(1iD\'lrr.ts \{hr:re. Mr{(-'ufi} is th* rt-lative rnolar rnass t:f CaO.
intr-tttt) rttt: _r17:

th*,rrln,trrtt ot' {';to Intrst lre. lirr

Ittl' -ttt.l : Ji:____! x Il.{ , t CaO t

x -.,o9

rnt: l.17ltrtr - ,rz:, S \!'r: krrou, tlri: rltlrss l:l'l'tsirltte leti. i-e-. fltt, the mass of h'{g{}
citlt:t-tlatqlrl.
llil.1

{rrt+} can

Lre

171'

--

711,-

Here m: is l[tt-: ntirss r-r['CaO t-orrned. rvtric:h is equal to 1.27 {rrr1-frr2}. Thus

rrl: - rlrl - l.:7 (tt'y- ntll [.1ass +l'tl-r*: ('lr {ru1.,r) in the origin:rl sa::tplrr'cult also be rt:latedto rnl andrrltry tt':e- l'olIort itig l'nrt:-trtll rrtrr= t).r)I {rl: - ttt:l This call hc- itbtiritrecf :rs follo*-s:

Yru krlnu. iultot"tr:r r:f Cir in CaCO,i and CirLJ w=ill be c-quirl in moles- therefc'rrt: rur)ount ..,['Clr itt ,/ r'Arr Ca r : l'2J (li' I -rtt'lx. AxCa ) illcir: rrii*=]i* '^ iLl,(CtOl77 ' M'{CaO) - and relative nlL)lal' r,vhi:rr. Ar({-';r} unJ I\1r i(ludi'are ttre relative :rtorttic tr)AS\ '' Thtts. lr);rsc o1'(-'it trncl ['ir(). respec-tivell'. = I .3? (ntt - rnr) x +ty-56 : O.9l imr- rn=-)
Siltti lirrlv. nlilss
Lll-

ma:rnesitltr in the original sartrple r-an be related to rrrr atrtlrtrl:

irt rrriginul sunrple (rrt\r8)
,t

Thrrr. tire

rrrrrs< r''l' NIS

f{ r^.^crli'

Iliils\,ok-itlue -

^^ ^ ClrO,*ftO; l,tllss of
:
1

A.(fuIg)

v'i-

/rl\!o =
fll1,1,

A- rN,Is I ltll - - rrt.1 iX -r--l14. tlv-tg{)

{},{rL}

(nr.-m, lx 24.3 -

40--3

{rn:-

/.I-r-}

.,' I

Result:
The amount of calcium and magnesium present in the given sample is
......

'-.\

f^'r aL'

,o'
\ -!.

..

\':

,aJ

/' /";
\td

,.\\ \.}r'- -

'''af

q
/'.-> -.. (
Aim:
To determine Tg, T. and
Tn-.
)

using DSC curve of a Polymer sample (PEEK).

Principle: Differential scanning r:alorimetry or DSC is a thermoanalytical technique in which the

difference in the amount of heat required to increase the temperature of a sample and reference is
measured as a function

of tenrperature. Both the sample and reference are maintained at nearly

the same temperature througho",,,l:

The basic principle underly+ng this technique is that when the sample undergoes
ph1-sical transformation such as phase transitions. more or less heat

:iryii*f

*
a

will

need

to flow to it than

the reference to maintain both at the same temp-rerature. Whether less or more heat must flow to

the sample depends on whether the process is exothermic or endothermic. For example, as solid sample melts to a liquid

it will

require more heat flowing to the sample to increase its

temperature at the same rate as the reference. This is due to the absorption of heat by the sample as

it

undergoes the endothernric phase transiticn from solid to liquid. Likewise, as the sample

undergoes exothermic processes (such as cgstitllization) less heat is required to raise the sample

temperature.

By observing the difference in heat flow

between the sample and reference,

differential scanning calorim:ters are able to rneasure the amount of heat absorbed or released
during such transitions. DSC rnay also be used to observe more subtle physical changes, such
glass
as

transitions.-Itiswidely

+rsed

in industrial settings

as a

qu-dlitytontrol instrument dtrs to its

appiieability-in evaluating sanple purity and for studying polymer curinp

Instrumentation:
The main assembly o1'a typical heat-flur DSC cell is enclosed in a heating block (for
example Ag), which dissipates heat to the specimens (S and R) via a constantan disc attached to

the Ag block. The constantan disc has tu'o platforms on which the S (specimen) and R
(reference) pans are placed. A chromel disc and connecting wire are attached to the underside of

each platform: the resulting chromel-constantan thermocouples are used

to

determine the

differential temperatures of interest. Alumel u'ires are also attached to the chromel discs to

provide chromel-alumel junctions which measure the sample and reference temperatures
separately. Another thermocouple

is

embedded

in the Ag block and serves as temperature

controller for the programmed heating/cooling c1cle.

Heating

C0l

Fst,.rrcrdaHEiE=

i a

c
o

c
o o e o
Lrert-Cas +

= t
.-E

(Vccuuu)

:AT
lhenl,rcouples

T*Tr'raa=lt

In heat-flux DSC instruments, the difference in energy required to maintain both S and R at the same temperature is a measure of the energy changes in the test specimen S (relative to the inert
reference R). Tne thermocouples are usually not embedded

in neither S or R materials. The temperature difference DT that develops between S and R is proportional to the heat-flirw between the two. In order to detect such small temperature differences, it is essential to ensure
that both S and R are exposed to the same temperature programme. The measurements are
usually performed under vacuum or inert-gas flow: the flow rate (typically around 40 ml/min.) is maintained oonstant throughout the experiment.
Fi**e=s I Transithn
Sclid-sdid Eansition
Crystallizatiwr Melling

Exotlxlrtnl

End*iilerm*i

* *

!
I L

- Diflarential Scanning C*odmeter (OSG)

Potyethercth*etcne {PEECI
H=r$C

Vaporization Sublimation Adsorption Desorption

r
,/

* * * *
+

...t

C\:

Qn

rr

rtA* z

! ET

i 1',

!t
"-.r HH' E@lM!.{_'i
:

it
rernovd)

/
lr
--,J ,
)

t--/

Dryin g (sotvent

Decomposition Solid-state readioa Solid-liquid rcactiur

?r

crydrLrGil er' * er !r.lllrsI..ildr r.nr1d

il
I]
li

P..r

i 16!$

Solid4as

redion

* * * *
.F

* * * *

Folymerizatim
r*'",**_*;*d ldr@+t'S

Catalytic

readhrs

Inference:

propertiesofasaryple.Elsitgffinique-+ri@fusion,#crysta|1ization
e:*en+s.as--rirc$-as-glass transition temperatures

Differential scanning calorimetry can be used to measure a number of characteristic E") ' a-\

?,

fs. DSC can also be used to study oxidation,

as

well

as other chemical reactions- Glass transitions may occur as the temperature

of an amorphous

solid is increased. These transitions appear as a step in the baseline of the recorded DSC signal. This is due to the sample undergoing a change in heat capacity; no formal phase change occurs,

As the temperature increases, an amorphous solid will become less viscous. At some point the
molecules may obtain enough freedom of motion to spontaneously affange themselves into a

crystalline form. This is known as the crystallization temperature (2.). This transition from
amorphous solid to crystalline solid is an exothermic process, and results in a peak in the DSC signal. As the temperature increases the sample eventually reaches its melting temperature (7,,).

I,

depends on the molecular weight

of the poly'mer and thermal history, so lower grades may

have lower melting points than expected. The rnelting process results in an endothermic peak in

the DSC curve. The percent crystalline content of a polymer can be estimated from

the

crystalhzation/melting peaks of the DSC graph. The ability to determine transition temperatures and enthalpies makes DSC a valuable tool in producing phase diagrams for varicus chemical
systems.

Result:

u , The given sample has T*, T. and T, value to be ..lA:).":. , (6:% , 3j

/,,

u,

''l

'

Aim:
1., ,i ,,

,,

^ "1'

'

To&tetndas
Principle:

using DTA analysis.

The principle of the DTA technique resumes to heating (or cooling) a test sample (S) and
an inefi reference (R) under identical conditions while measuring the temperature difference DT

between S and R. In this technique it is the lreatflc.w to the sample and reference that remains the
same rather than the temperature. When the sample and reference are heated identically, phase changes and other thermal processes cause a difference

in temperature between the sample and

reference. Both DSC and DTA provide similar information. DSC measures the energy required

to keep both the reference and tire sample at the same temperature r,vhereas DTA measues the
difference in temperature bet\\'een the sample and the reference when they are both prrt under the
same heat.

The differential temperature DT is then plotted against time or against temperature.

Chemical, physical, structural and microstructural changes in the sample S lead to the absorption (endothermal event) or evolution of heat (exotherrnal event) relative to R. If the response of two

inert samples submirted to an applied heat-treatinent programme is not identical, differential

temperatures DT arise as well. Therefore. DTA can also be used to study thermal properties and
phase changes which do not necessarill lead to
a.

change

in enthalpy. The baseline of the DTA

DTA peak

curve exhibits discontinuities at transition temperatures and the slope of the cun'e at any point

will

depend on the microstructural constitution althat temperature. The area under a

can be related to the enthalpy change and is not affected b1-the heat capacitl'of the sample.

Instrumentation

The samples are placed in P1rex. silica, Ni or Pt crucibles (according to the temperature

programme and purpose

of the experiment). Thermocouples should not be placed in

direct

contact with the sample to avoid contamination and degradation, even though sensitivity may be compromised. 'fhe sample assemblJ' is isolated against electrical interference with the wiring of

the oven with an earthed metallic or Pt-coated ceramic sheath. For heating experiments up to about 500oC, an uniform transfer of heat away fiom the sample may be difficult. Disc-shaped
thermocouples must then be used to ensure optimum thermal contact with the bottom-side of the
sample container

(Al or Pt foil). The fumace should provide

a stable, large enough hot-area and a

7-

fast response to the temperature-controller commands. Data acquisition and/or the real-time
displa,v is handled by a computer system or an analog device (plotter).

Experimental details: potential sources of error.

Experimental parameters such as specimen environment, chemical composition. size. surface-to-volume ratio must carefully be selccted, since they might modif,v fr:r example the
thermal decomposition of pou der materials even though their solid-state phase transitions are not

affected. The packing state reactions and may lead

of pou'der samplc's is important in these thermal

decomposition

to significant differences in thermal behaviour

between otherwise

identical samples. Moreover, DTA measurements on powder materials do not always correctly illustrate the thermal behaviour of bulk specimens, for which most phase transitions exhibit the influence of built-in strain energy.
The heat flow rate ma;r sometimes satulate the response capability of the DTA system. It

will

also

is then advisable to dilute the specimen with a thermally-inert material. For the detection of
phase transition temperatures, one must also check that the peak temperature

T,

does not vary

with sample size. The shape of DTA peaks depends on sample weight and on the heating rate
employed. Low heating rates or small sample rveights lead to better resolved (sharper) DTA
peaks, but the signal-to-noise ratio might hou'eler be compromised. Reducing the specimen size

or the heating rate is also important in kinetic analysis (isothermal) experiments, where thermal
gradients should be minimized.

Data Analvsis:
The heat capacity and thermal conductir itv of the test specimen (S) and reference sample

(R) are usually not identical. fhis gives rise to a certain displacement between their response in

absorption of the linear regions of the DTA trace. The DTA peaks correspond to evolution or (S) under analysis. The detection of heat following physical or chemicai changes in the specimen phase transition temperatures using

DTA is not verl- accurate. The onset of the DTA

peak

are likely to indicates the start of the phase transition, but temperature shifts from the true values reference or occur depending on the location of the thermocouples riith respect to the specimen, block. Therefore. the temperatur:e calibration of the DTA instrument using

to the heating

standard materials with known melting points is necessan"

change

The area (A) enclosed betseen the DTA peak and the baseline is related to the enthalpy (e) of the specimen during the phase transition. \\-hen the thermocouples are in thermal

the (but not in physical) contact riith the specimen and reference materials, it can be shown that peak alea

A is given

bY
r??

'tl
q:
enthalpy change

s.fi
Where

m:

sample mass

(ueighl:

Q:

enthalpy change of the specimen;

per unit rnass; g

(ureasuredl geometrical shape iactor; K

thetmal conductivitl' of sample )

Errors in estimating the correct DTA peak areas are likel1'to occur for porvder materials pores or which and compacted'samples which rerain some degree of porosity'. The gas filling the cell eventually evolves frorn the specimen itself. aiters the thermal conductivitl' of the DTA

environrnent (compared to calibration e\periments), leading to rather large errors in the DTA
peak areas.

Enthalpv calibration:
The energy scale of the DTA instrument must also be calibrated to absolute enthalpy values by measuring peak areas on standard samples over specified temperature ra11ges. The enthalpy calibration implies measuring at least 2 different samples for which both heating and cooling experiments must be perfo.tmed. lt is then possible to measure the constant pressure heat capacity
(CP) using the DTA method
:

L - -7- lt'-

T. : -T,I
nt.

If

calibration constant and)t'iaT2 are the 2frKeenthalpy differential temperatures generate d Wgan initial 'empty' run (witho ,y&*land during the
k

where H is the heating rate emploved,,

qte{:i,q' ESjt "i

:=e75=

*i3ss*:,.

*9_SE= r.

x
::!i&* t.1ttr ,=rC
t: S!*
rC

,|s . :-0 r:rl

B*at+-gf, HffiEilJH.E.L4ist[CrFiro.

rc
x
z
r

7a

,.

r {}

Cv{* t.-z

t-

femperalure ('C)

lls

i?c * '!E 'tr .t0; :.ls ; lrt S ;:.1 *

,r* tr ,E
\
Et1 ,,4 * ,t.2
+1**'.@-#-----T----*"* 1f;?B

{73

6tt
Tf i{

Er3

lqir+

:@s&

:0
t?7f;

.S

Result: