KULIAH KE V

Thermal Analysis
 Basic Principles of Thermal Analysis
 Modern instrumentation used for thermal analysis
usually consists of the following parts:
 sample holder/compartment for the sample
 sensors to detect/measure a property of the sample and the
temperature
 an enclosure within which the experimental parameters
(temperature, speed, environment) may be controlled
 a computer to control data collection and processing

temperature sample
PC
control (furnace)
sensors
Differential Scanning Calorimetry (DSC)
 Most popular thermal technique
 DSC measures the heat absorbed or liberated during the
various transitions in the sample due to temperature
treatment
 Differential: sample relative to reference
 Scanning: temperature is ramped
 Calorimeter: measures heat
 DSC measurements are both qualitative and
quantitative and provide information about physical and
chemical changes involving:
 Endothermic processes – sample absorbs energy
 Exothermic processes – sample releases energy
 Changes in heat capacity
Principles of DSC Analysis
 Power Compensation DSC

 High resolution / high sensitivity research studies

 Absolute specific heat measurement
 Very sensitive to contamination of sample holders
 Heat Flux DSC

 Routine applications
 Near / at line testing in harsh environments
 Automated operation
 Cost-sensitive laboratories
Summary Of Derived from DSC Analysis
 Melting points – crystalline materials
 Desolvation – adsorbed and bound solvents
 Glass transitions – amorphous materials
 Heats of transitions – melting, crystallisation
 Enthalphy Analysis
 Purity determination – contamination, crystalline/amorphous
phase quantification
 Polymorphic transitions – polymorphs and pseudopolymorphs
 Processing conditions – environmental factors
 Compatibility – interactions between components
 Decomposition kinetics – chemical and thermal stability
Typical Features of a DSC Trace
^exo Exothermic upwards
Endothermic downwards

MELTING
CRYSTALLISATION
GLASS TRANSITION
DESOLVATION

20 H2O
mW
DECOMPOSITION

Y-axis – heat flow

X-axis – temperature (and time)

40 60 80 100 120 140 160 180 200 220 240 260 280 300
o
temperature [ C]
Melting Point
Onset = melting point (mp)
^exo

MELTING
20
mW

Heat of fusion (melting) = integration of peak

40 60 80 100 120 140 160 180 200 220 240 260 280 300
o
temperature [ C]

DSC scan of a crystalline material – one polymorphic form

Purity Determination

Source: TA Instruments, Cassel RB,

Purity of phenacetin Purity Determination and DSC Tzero™ Technology
 THERMOGAVIMETRIC ANALYSIS
(TGA)

14
Thermogravimetric Analysis (TGA)
 Principle: TGA measures the amount and the rate of
weight change of a material with respect to
temperature or time in controlled environments.

 A TGA consists of three major parts a furnace,

1. A microgram balance,
2. An auto sampler and
3. A thermocouple.

15
GENERAL PRINCIPLES INVOLVED IN
THERMOGRAVIMETRY
 PRINCIPLE : Thermogravimetry is a technique in which
a change in the weight of a substance is recorded as a
function of temperature or time.

 Instrument: Instrument used for thermogravimetry is

“Thermobalance”. Data recorded in form of curve known
as ‘Thermogram’.

16 Goa College of cy, Goa. 02 January 2013

Thermogravimetric Analysis (TGA)
 The furnace can raise the temperature as high as 1000°C
which is made of quartz.
 The auto sampler helps to load the samples on to the
microbalance.
 The thermocouple sits right above the sample.
 Care should be taken at all times that the thermocouple is
not in touch with the sample which is in a platinum pan.

17
Thermogravimetric Analysis
(TGA)
• A technique that permits the
continuous weighing of a sample
as a function of temperature and/or
as a function of time at a desired
temperature

18
Thermogravimetric Analysis
(TGA)

19
Interpretation of TG and DTG curves
i. The sample undergoes no decomposition with loss of volatile
products over the temperature range shown but solid phase
transformation, melting ,etc can not be detected by TG,
ii. The rapid initial mass loss is characteristic of desorption or drying.
If it is true, then re-run the sample should result in type (i) curves,
iii. Single stage decomposition,

iv. Multi-stage decomposition with relatively stable intermediates :

provide information on the temperature limit of stability of
reactants and intermediate products and also stoichiometry,

v. Multi-stage decomposition with no stable intermediate product.

However heating-rate effect must be considered. At low heating
rate, type (v) resemble type (iv). At high heating rate, type (iv)
and (v) resemble type (iii) and lose all the details,
vi. Gain in mass due to reaction with atmosphere, e.g. oxidation of
metals,
vii. Oxidation product decompose again at higher temperature; this
is not often encountered.

20
TGA Curve of Calcium Oxalate

21
Examples of TGA Curves

22
Examples of TGA Curve of Calcium oxalate
 Constant Heating Rate
 Initial Temp
 Final Temp
 Heating Rate (°C/min)
 Data
 Weight vs Time
 Weight vs Temp.
 Differential This Data (DTG)

 Heating a sample of Calcium oxalate

 Ca(C204)*xH2O  Ca(C204) *H2O + x-1 H2O
 Ca(C204)*H2O Ca(C204) + H2O
 Ca(C204)  CaCO3 + CO or (CO2)
 CaCO3  CaO + CO2
We have TGA - only
 Heating a sample of Calcium oxalate

 Ca(C204)*xH2O  Ca(C204) *H2O + x-1 H2O

 Ca(C204)*H2O Ca(C204) + H2O
 Ca(C204)  CaCO3 + CO
 CaCO3  CaO + CO2
TGA – Ca(C204)*xH2O
Precipitated Zr5O8(SO4)2*15 H2O

This sample was dried fro 48 hrs at 110C before TGA analysis.
What is going on?
 Analysis of Filtrate from Precipitation
15 H2O Water Loss Wt. Loss % loss
 Precipitation 1 18.0152 1.721573
 5ZrOCl2 + 2H2SO4 + xH2O  2
3
36.0304
54.0456
3.443146
5.164719
Zr5O8(SO4)2*15 H2O (s) + 10 HCl 4 72.0608 6.886292
5 90.076 8.607865
6 108.0912 10.32944
7 126.1064 12.05101
 Decomposition 8 144.1216 13.77258
9 162.1368 15.49416
 Zr5O8(SO4)2*15 H2O (s)  10 180.152 17.21573
Zr5O8(SO4)2*14 H2O (s) + H2O (v) 11 198.1672 18.9373
12 216.1824 20.65887
13 234.1976 22.38045
14 252.2128 24.10202
 Zr5O8(SO4)2  5 15 270.228 25.82359
ZrO2 (s) +2 SO2 (v) SO2 1 64.0588 31.9452
2 128.1176 38.0668
Sample Preparation

 Sample preparation has a significant effect in obtaining good data.

 It is suggested that maximizing the surface area of the sample in a
TGA pan improves resolution and reproducibility of weight loss
temperatures.
 The sample weight affects the accuracy of weight loss
measurements.
 Typically 10-20 mg of sample is preferred in most applications.
 Whereas, if the sample has volatiles 50-100mg of sample is
considered adequate.
 It is to be noted that most TGA instruments have baseline drift of
±0.025 mg which is ±0.25% of a 10mg sample
 Heating Rate
 Purge gas .
28
Experimental Conditions -Heating Rate
 Samples are heated at a rate of 10 or 20°C/min in
most cases.
 Lowering the heating rates is known to improve the
resolution of overlapping weight losses.
 Advances in the technology have made it possible for
variable heating rates (High Resolution TGA) to
improve resolution by automatically reducing the
heating rate during periods of weight loss.

29
Experimental Conditions -Purge gas
 Nitrogen is the most common gas used to purge samples
in TGA due to its inert nature.
 Whereas, helium provides the best baseline.
 Air is known to improve resolution because of a
difference in the oxidative stability of components in the
sample.
 Vacuum may be used where the sample contains volatile
components, which helps improve separation from the
onset of decomposition since the volatiles come off at
lower temperatures in vacuum.
 e.g. oil in a rubber tire product.

30
Miscellaneous

31
Calibration
 Blank test
 Calibration of mass changes
 Calibration of temperature

32
Calibration- Blank test
 Without sample, air is passed at 20 ml/mm, and the
temperature is raised up to 1000 °C at heating rate of 10°C
min-1.

 By this blank test, the general condition of the apparatus

can be known.

 The TGA curve can drift slightly as the temperature is

increased.

 This is owing to the changes in the buoyancy and

convection.
33
Calibration- Blank test
 When noise appears in the TG curve, the possible
cause may include contact between sample dish and
thermocouple, contact between quartz suspension wire
and purge gas feed pipe, and contact between weight
pan and arid glass cap.
 Vibration and shock may also cause noise.
 When the sample pan or suspension wire is
contaminated with deposit of decomposition product
or the like, the TGA curve shows a slight decreasing
curve.

34
Calibration- Calibration of mass changes
 Since the TGA is usually measured by the rate of the
weight change to the sample weight, calibration of
absolute value of weight is hardly necessary.
 A weight of 20 mg is read to a precision of 10 microgms
by a precision balance, and the mean (So) is determined.
 The furnace is put on, and when the TGA signal is
stabilized, the instrument balance control is adjusted to set
the automatic zero.

35
Calibration- Calibration of mass changes
 Then the furnace is put into place and the furnace is set again,
and the TGA signal value is read. This value is S1.
 Repeating the same operation several times, the mean of S1 is
obtained as S.
 In this operation it is known that a signal corresponding to S1
mg is delivered with the weight of So mg is placed on the
balance.
 The measuring precision of TGA is within ±1 % of the range.
 When calibrating the apparatus, the calibration function is
utilized.

36
Calibration-Calibration of temperature
 The temperature of the TGA may be calibrated in two
manners:
 The method of making use of the melting point of a pure
metal, and the method of utilizing the Curie point
temperature.
 In the former method, one of the metals processed in a
ribbon shape, and it is suspended on the TGA suspension
wire, and a weight of about 100mg is attached at its tip.
 When the pure metal is fused by heating, the weight drops,
and a weight drop appears on the TGA curve.

37
Calibration-Calibration of temperature
 In the latter method, the standard substance verified by
International Congress on Thermal Analysis, ICTA, is
measured. The standard substances are Ferromagnets, and
have different Curie temperatures.
 It is intended to calibrate by measuring the apparent
weight change appearing in steps at Curie temperatures by
making use of a permanent magnet.

38
Calibration-Calibration of temperature
 Based on the TGA data, thermal stability of materials
and their compositions can be predicted depending on
the weight changes caused by evaporation,
dehydration, oxidation and decomposition, up to
temperatures as high as 1000°C.

 A typical example is the TGA of calcium oxalate

hydrate, heated to 1000°C which shows three steps in
its decomposition curve.

 The weight loss data is recorded every half second

throughout the run time.

39
Applications of TGA
There is a wide range of applications of TGA, e.g,
 Composition of multi-component system
 Thermal stability of materials
 Oxidative stability of materials
 Estimated lifetime of a product
 Decomposition Kinetics of materials
 The effect of reactive or corrosive atmosphere on
materials
 Moisture and volatiles contents on materials.

40
Applications of TGA

 Evaporation of free (unbound) water begins at room

temperature due to dry gas flowing over the sample.

 Dehydration/Desolvation of bound water almost always
begins at temperatures above room temperature and
typically 125°C.

 Decomposition can have multiple stages (weight losses)

but the presence of multiple weight loss steps can also
indicate the presence of multiple components in the
sample.

41
Applications of TGA
 Determination of the bound and unbound water in the
suspension of Milk of Magnesia (MoM), used as a laxative.
 Comparison of the generic and a brand MoM.
 In an overview of thermal analysis testing it is always
preferable to do a TGA experiment on unknown samples before
doing a DSC experiment (especially for ceuticals).
 Decomposition of ceuticals renders products which are
insoluble and generally sticky on the inside of a DSC cell.
 These products will lower the life use of a DSC cell.
 Therefore, know the decomposition temperatures of all drugs
and heat in a DSC evaluation to 50°C below those
temperatures.
42
Thermogravimetry thermal analysis
(TGA) testing

 Thermogravimetric (TGA) analysis provides

determination of endotherms, exotherms, weight loss
on heating, cooling, and more.

 Materials analyzed by TGA include polymers,

plastics, composites, laminates, adhesives, food,
coatings, ceuticals, organic materials, rubber,
petroleum, chemicals, explosives and biological
samples.

43
TGA materials analysis

 Thermogravimetric analysis uses heat to force

reactions and physical changes in materials.

 TGA provides quantitative measurement of mass

change in materials associated with transition and
thermal degradation.

 TGA records change in mass from dehydration,

decomposition, and oxidation of a sample with time
and temperature.
44
TGA materials analysis

 Characteristic thermogravimetric curves are given for

specific materials and chemical compounds due to unique
sequence from physicochemical reactions occurring over
specific temperature ranges and heating rates.

 These unique characteristics are related to the molecular

structure of the sample.

 When TGA is used in combination with FTIR, TGA/FTIR

is capable of detailed FTIR analysis of evolved gases
produced from the TGA.

45
TGA thermogravimetric capabilities
 Compositional analysis of materials
 Decomposition temperatures
 Rate of degradation
 Product lifetimes
 Oxidative stability
 Evaluation of polymer flammabilities
 Thermal stabilities
 Determination of rancidity of edible oils

46
TGA thermogravimetric capabilities
 Fingerprinting unknown polymers
 Moisture Content
 Volatiles content, VOC analysis
 Analysis of evolved gases using TGA/FTIR
 Competitive product evaluation
 Measurement of oil extender content in elastomers
 Effects of reactive atmospheres on materials
 Determination of inert filler or ash contents
 ASTM D6375 Noack Method

47
Summary of ceutically Relevant information
Derivation from TGA Analysis

48
DIFFERENTIAL THERMAL ANALYSIS
(DTA)
DIFFERENTIAL THERMAL ANALYSIS

 Digunakan untuk menyelidiki interaksi reaksi pada

 Banyak dilakukan dalam dunia Industri dan farmasi .
 Bisa digunakan untuk melihat pola dari masing masing
komponen.
 jika interaksi terjadi, hal itu ditunjukkan dalam
termogram dengan munculnya satu / lebih puncak
yang sesuai dengan komponen tersebut

50
 ROLE OF THERMAL ANALYSIS IN
PREFORMULAION
 Merupakan metoda yang unik diguanakn untuk berbagai
material misalnya analisa pada polimer maupun solid state
analysis
- Beberapa aplikasi pada DTA
a) Study of complexation
b) Detection of impurity
c) Study of polymorphism

51 Goa College of Pharmacy, Goa. 02 January 2013

Instrumentation
 Differential Thermal Analysis (DTA)

 DTA measures temperature difference between a sample and

an inert reference (usually Al2O3, MgO and SiC)while heat flow
to the reference and the sample remains the same
Crucibles
Operasional
• Beberapa mg sampel (S) dan zat inert R terkandung dalam
cruseibel dari Alumina atau lainnya aluminium kecil yang
terletak di atas sampel dan termokopel referensi dalam
tungku yang dipanaskan dengan listrik.
• Bahan standard adalah bahan inert seperti alumina, silikon
karbida atau manik-manik kaca.
• Potensial keluaran Vs dari termokopel sampel masuk ke
komputer di mana ia dibuat untuk mengontrol masukan arus
ke tungku sedemikian rupa sehingga suhu sampel meningkat
secara linier dan pada laju yang telah ditentukan.
• Sinyal termokopel sampel juga diubah menjadi suhu Ts dan
kemudian dicatat sebagai absis dari termogram diferensial.
Kriteria
• Potensial keluaran yang ada pada sampel dan termokopel
dengan referensi E merupakan kriteria dari perubahan
perbedaan suhu T = (Tr-Ts) yang berfungsi sebagai ordinat
termogram.
• Sirkulasi gas inert seperti N2 atau gas reaktif seperti O2 dalam
sampel dan referensi sbagai apakah diperlukan atau tidak
bergantung pada suasana yang dikehendaki.
• Ada perbedaan suhu konstan T antara s dan r karena terjadi
kelebihan, akibat dari kapasitas panas yang berbeda sebelum
dan sesudah proses.
• Tetapi ketika sampel mengalami perubahan Exsotermik atau
indutermik pada nilai T menjadi berbeda yang ditunjukkan
dalam termogram.
• Perbedaan termogram tersebut ditunjukkan dengan grafik
seperti pada penjelasan berikut di bawah
DTA Comparative Traces

57
DTA Combined with TGA

* The area under a DTA peak is

the enthalpy change

Lowering heating rate;

Reducing sample weight

sharper peaks with improved

resolution
DTA + DTG
Example
 General principles

• Penurunan awal T disebabkan

oleh transisi kaca/glas transisi.
• Temperatur transisi gelas Tg adalah
temperatur karakteristik dimana
polimer amorf seperti kaca menjadi
fleksibel.
• Setelah dipanaskan sampai suhu
tertentu Tg polimer berubah dari
gelas menjadi karet.
• Transisi seperti itu tidak melibatkan
penyerapan atau evolusi panas
(tidak ada perubahan entalpi H= 0)
 General principles

• Namun kapasitas panas karet berbeda

dengan kaca (pada nilai baseline yang lebih
rendah).
• Tidak ada hasil puncak selama transisi ini
(karena tidak ada perubahan entalpi H = 0).
• Puncak Kedua tersebut adalah hasil dari
proses eksotermik di mana panas berevolusi
dari sampel (terjadi kenaikan temperature T).
• Pada puncak ketiga terjadi
peleburan(melting) berupa nilai minimum
adalah konsekuensi dari proses endotermik
dimana terjadi absorbs panas
• Kristalisasi polimer amorf merupakan proses
eksotermik (puncak eksotermik pertama).
• Selanjutnya terjadi proses dekomposisi
analisis termal dengan DTA dihasilkan dari perubahan
fisik dan reaksi kimia yang disebabkan oleh perubahan
T dalam sampel.

Proses fisika:
• Proses Endotermik: meliputi fusi, penguapan, sublimasi,
absorpsi dan desorpsi.
• Proses Eksotermik: Adsorpsi dan kristalisasi (terjadi
umumnya tetapi beberapa beristiwa harus dijelaskan lebih
detail).
Reaksi kimia:
• Proses Endotermik: termasuk dehidrasi,
pengurangan atmosfer gas, dan dekomposisi.
• Proses Eksotermik: oksidasi di udara atau oksigen,
polimerisasi dan reaksi katalitik.
Area puncak di DTA Untuk menghitung nilai H
bergantung pada:
1. Massa sampel (m)
2. Entalpi H dari proses kimia atau fisika.
3. Faktor geometri dan konduktivitas.

Dirumuskan :
A = -kGm H
= -K’mH
Di mana
A = adalah luas puncak,
G =adalah faktor kalibrasi yang bergantung pada geometri sampel,
K = adalah konstanta yang terkait dengan konduktivitas termal sampel
 Dirumuskan :
A = -kGm H
= -K’mH
Di mana
A = adalah luas puncak,
G =adalah faktor kalibrasi yang bergantung pada geometri sampel,
K = adalah konstanta yang terkait dengan konduktivitas termal sampel

• Jika nilai K tetap konstan dengan cara variabel seperti

kecepatan pemanasan yang dikontrol
• dan ukuran partikel/sampel dan penempatan sampel
relatif terhadap termokopel sampel dikontrol,
• serta massa analitik dari sampel dapat ditentukan maka
dapat diketahui nilai enthalpinyaH
Applications of DTA digunakan secara
DTA luas Untuk:

1) Menentukan perilaku termal dan komposisi

produk alami dan produk manufaktur

Contoh:
Mempelajari dan karakterisasi polimer.
Gambar disamping menggambarkan jenis
perubahan fisik dan kimiawi pada bahan polimer.
Transisi termal terjadi untuk polimer pada jarak
yang diperpanjang karena polimer murni adalah
campuran homolog

2) Identifikasi kuantitatif dan penilaian

kemurnian bahan dilakukan dengan
membandingkan kurva DTA dari
sampel dan standard
Beberapa Kunci proses dalam
thermogram DTA
Endoterm puncak tajam ke bawah artinya pada
temperature itu terjadi peristiwa :
penataan ulang kristal, fusi, transisi keadaan padat.

Endoterm yang lebih luas proses yang terjadi adalah:

dehidrasi, pelelehan polimer, reaksi lambat

Proses Eksoterm sempit: kristalisasi

Proses Eksoterm tajam: perubahan fase
The figure is a DTA of a
physical mixture of 7
commercial polymers.
Setiap puncak mewakili sesuai
dengan titik leleh dari salah satu
komponen.

Misalkan :
PTFE memiliki puncak
T rendah dibawah 100 C
PP pada temperature kisaran 10 C
Nylon serat pada T > 200 C
Nylon type nylon 66 pada T > 250 C

DTA can identify the polymers.

DTA digunakan untuk mempelajari perilaku termal senyawa
anorganik murni atau zat anorganik: Silikat, ferit, lempung,
oksida, keramik, katalis dan gelas.

Proses dalam Desolvasi fusi, dehidrasi,

oksidasi, adsorpsi reduksi dan reaksi
solid-state
Figure di samping : spectrum DTA dari calcium
Oksalat CaC2O4.H2O
Dua puncak minimum (sampel lebih dingin dari
ref) merupakan dua reaksi proses endotermik
(endo).
Proses pada Puncak maksimum (5000 C):
 Pada daerah suasana oksigen (O2)terjadi
oksidasi kalsium oksalat menghasilkan
karbon dioksida dan kalsium karbonat
(exotermis).
 Dengan menggunakan gas inert (N2) tiga
minimum ditemukan (dekomposisi
endotermik oksalat menghasilkan karbonat
dan karbon monoksida.
DTA digunakan Untuk Studi Diagram
phasa dan transisi phasa dari Sulfur
(Belerang)

• Puncak pada 1130C sesuai

dengan bentuk perubahan fase
padat rhombohedral  monoclinic)
• Puncak pada 1240C terjadi titik
leleh/lebur dari elemen dari fasa
tersebut (pholymorphik).
• Puncak pada 1790C tampaknya
melibatkan transisi ini). (Tiga
bentuk belerang cair diketahui)
• Puncak pada 4460C sesuai
dengan titik didih sulfaur.
Penentuan titik leleh dengan akurat, titik didih dan
dekomposisi senyawa organik secara sederhana
dan akurat.

Gambar menunjukkan termogram dari

asam benzoat pada :

Tekanan atmosfer :(A)

Tekanan 200 psi (B).

• Puncak pertama adalah titik leleh

• Puncak kedua untuk titik didih asam.
DTA DAPAT MEMBEDAKAN DUA BAHAN YANG
MEMILIKI STRUKTUR SAMA
Misalkan DTA dapat membedakan antara mentega dengan
margarin.

b temp 

DTA perbedaan pola pada lemak/minyak dari minyak:

(a) Mentega dan (b) margarine
 Kelebihan dari DTA
 Instrumen dapat digunakan pada suhu yang sangat tinggi.
 Instrumen sangat sensitif.
 Karakteristik transisi atau suhu reaksi dapat ditentukan
secara akurat.

Factors factor yang mempengaruhi dan harus

diperhatikan dengan baik saat pengujian sampel
• Berat sampel
• Ukuran partikel
• Tingkat pemanasan
• Kondisi atmosfer
• Kondisi pengemasan sampel ke dalam crusibel
THANK YOU