Thermal Analysis

Associate Professor Dr.

Yupaporn Ruksakulpiwat
Thermal Analysis
ความหมาย หลักการ และ วิธีการ
กระบวนการวิเคราะห์ ทางความร้ อนโดย
Differential Thermal Analysis, DTA
กระบวนการวิเคราะห์ ทางความร้ อนโดย
Thermogravimetry, TGA
 Thermal Analysis
physical
and/or chemical properties
are measured as functions of
temperature and time
 Specimens are subject to a defined temperature
program in special ovens at a defined gas
atmosphere (e.g., air, inert gases) whereby
corresponding heating or cooling curves are
recorded.
Thermal analysis
 Structural changes (glass transition,
melting/crystallization, crosslinking,volatilization,
phase transitions in the solid and liquid state),
 Mechanical properties (elastic behavior,
damping),
 Thermal properties (expansion/shrinkage, specific
heat capacity, melting/crystallization temperature,
coefficient of expansion
 Chemical reactions (decomposition and thermal
stability in different gaseous environments,
chemical reactions in solutions or liquid phase,
reactions with the purge gas, dehydration).
 Thermal Analysis Techniques

Differential Thermal Analysis (DTA)

 การวัดการเปลีย่ นแปลงอุณหภูมิของสารตัวอย่ างเทียบกับสารอ้ างอิง
Differential Scanning Calorimetry (DSC)
 การวัดการเปลีย่ นแปลงความจุความร้ อนของสารตัวอย่ างเทียบกับสารอ้ างอิง
Thermogravimetric Analysis (TGA)
 การวัดการเปลีย่ นแปลงมวลเมื่ออุณหภูมิหรื อเวลาเปลีย่ นไป
Thermomechanical Analysis (TMA)
 การวัดการเปลีย่ นแปลงขนาด เช่ น ความยาว หรื อ สมบัติหยุ่นหนืด
(viscoelastic change)
Thermal Analysis Techniques

Dynamic Mechanical Analysis (DMA)

 การวัดการเปลีย่ นแปลงความเค้ น ความเครียด รีแลกเซชั่ น
(relaxation spectra)
DSC – Differential Scanning Calorimetry
DSC – Differential Scanning Calorimetry
 forobtaining characteristic temperatures,
such as melting temperature Tm and glass
transition temperature Tg
 caloric quantities,
such as specific heat capacity cp
 morphology quantities, such as crystallinity
 Proof of annealing and curing.
 Heat flow dQ/dt to a specimen compared to
a reference is measured.
 Blend compatibility
Thermogravimetric Analysis (TGA)
Dynamic Mechanical Analysis (DMA)
Thermomechanical Analysis (TMA)
Applications
 Thermogravimetric Analysis (TGA)
- Degradation or thermal stability
- Plasticizer or solvent loss

 Thermomechanical Analysis (TMA)

- dimensional changes, glass transition temperature
Tg and linear coefficient of thermal expansion

 Dynamic Mechanical Analysis (DMA)

- a form of dynamic-mechanical analysis for
determining dynamic moduli and loss factor tanδ as
functions of test temperature and for establishing
transition temperatures
TOA – Thermooptical Analysis

 fordetermining changes in crystalline

supermolecular structure
 mostly using a hot-stage and a
microscope.
Differential Thermal
Analysis ( DTA)
and
Differential Scanning
Calorimetry (DSC)
 DSC devices
 DSC
devices are designed according to two basic
measuring principles:

- heat-flux calorimetry

- power compensation calorimetry.

Heat-flux calorimetry
 sample and reference lie in a cylindrical oven.
 Given thermal symmetry of the arrangement,
no temperature difference occurs between
pans when the oven is heated.
 However, if the specific heat capacity of the
sample changes with elevated temperature,
a temperature difference arises, which
theoretically is proportional to the specific
heat capacity.
Principle of Differential Thermal Analysis ( DTA)
power compensation calorimetry
 Sample and reference are completely separated.
 Sample and reference trays have their own heaters
and temperature sensors.
 Sample and references are heated up at the same
rate with the aid of a control unit in such a way that
no temperature difference arises between them.
 When the specific heat capacity of the sample
changes, more (in endothermic processes) or less (in
exothermic processes) heating power is transferred
to the sample to avoid a temperature difference.
Differential Scanning Calorimetry (DSC)
 S R DTA = TS –TR
SDTA: TR is not measured but
TF calculated from the furnace
temperature

TR
TS
If you run a sample and a blank:

Sample run: TS

Blank run: no sample, TR

DTA and DSC
Change in enthalpy and specific
heat capacity
DSC Applications
DSC CURVE OF HDPE
DSC CURVE OF LLDPE
DSC CURVE OF PP
DSC CURVE OF PET
 How to run DSC experiments

• Sampling

• Choosing a crucible

• The main goals of sample preparation

• Tips on DSC sample preparation

• Requirements for the crucibles

• Summary
Sampling
• Is the sample representative for the material which has to
be analyzed (i.e. an average or typical sample)?
 Standards ASTM E 105, E 122, DIN 83 803, company
internal instructions or procedures
• When taking a sample: do not modify the material (e.g.
through mechanical or thermal treatment).
• Is the sample clean?
• Are the tools used to take the sample clean?
• Storage of the sample
Selection of pan and atmosphere

Why do we need pans and “atmosphere control” ?

• to contain the sample

• to remove the sample
• to prevent contamination
• to control gas exchange, vaporization, reaction
• to define the heat path
• to obtain a desired catalytic effect (e.g. with copper
pans and insulation materials)
• to prevent oxidation (inert gas)
• for specific oxidation (OIT)
 How much sample do you need ?

Most important: what do you want to measure ?

• Glass transition: typical mass 10 mg

• Melting/crystallisation: low samples masses are sufficient (1 mg)
• Specific heat: heat flow should be about 4 mW  30 mg
• Comparison good/bad: same sample mass
• Additives: depends on its concentration, usually rather
large sample masses (low contents)
• Decomposition: usually huge effect  small sample mass
 Choice of crucible
 Examples :
• Normal case:
 40 µl aluminum standard pan with pierced lid
• Peak separation:
 light 20 µl aluminum crucible with helium as purge gas
• Sample possibly reacts with Al:
 medium pressure crucible
 high pressure gold-plated crucible (standard for safety
investigations)
 glass crucible (up to 500 °C, max. 5 MPa; furnace expander)
 gold crucible
How to prepare samples

Most important: good heat transfer

 Good thermal
contact between
sample and
crucible to
minimize
temperature
gradients within
the sample.
 How to prepare samples
• Solid samples: flat, if possible uniform thickness
• Powder: press gently into the crucible with a Teflon rod. Make
sure the bottom of the crucible remains flat.
• Hard, coarse samples: grind in a mortar. Be careful with
polymorphous samples. Grinding can cause a transition.
• Pastes, waxes: transfer to the crucible using a spatula, and
then gently press with a Teflon rod.
• Liquids: use a syringe, spatula or needle (depending on the
viscosity); deposit the sample in the middle or on the inside
edge of the crucible
• Fibers: if possible cut into small pieces, which fit into the
crucible; possibly pack in aluminum foil and press together
gently before the sample is put in the crucible; if the fiber
cannot be cut, wind it round the end of a pair of tweezers and
then pack it into aluminum foil.
 How to prepare sample (continued)

• With strongly exothermic samples (e.g.

explosives): dilute the sample in an inert
substance (e.g. aluminum oxide).
• With sequential measurements or comparison
measurements: always use the same amount of
sample, the same pretreatment, the same batch
of sample and identical storage conditions.
• With samples that contract or roll up: use a 20 l
crucible, or in the 40 l crucible use the lid of a 20
l aluminum crucible.
Temperature program

General types:

• Dynamic heating/cooling
• Isothermal

Parameters:
• Start- and end-temperature
• Heating rate (dynamic)
• Time (isothermal)
• Period, amplitude
 Temperature program (continued)
Heating rate

high heating rate  large DSC signal, poor resolution

larger temperature gradients within the sample

low heating rate  small DSC signal, good resolution

Start temperature: if possible at least 3 min before the first event

End temperature: if possible at least 3 min after the event

Example: heating rate 10 K/min, first event at 50°

 start temperature < 20°C

crystallizationAmyl
Amyl
alcohol
alcohol 1=crystallization
2=melting 3=boiling
boiling
melting
Tc
Tg Td PET
Tm
Iron soild-solid
- -
transition fusio
-
n
Slow heating=various reorganization process and fusion of
perfect crystal

One type of small metastable crystal

Fast heating=super heating=very broad melting peak
Reference

 Polymer Characterization - Laboratory

Techniques and Analysis
By: Cheremisinoff, N.P. © 1996; William
Andrew Publishing/Noyes
 Rapra Collection of DSC Thermograms of
Semi-Crystalline Thermoplastic Materials
By: Price, C.D. © 1997; Rapra
Thermogravimetric
Analysis, TGA
TGA application
ตัวอย่างการใช้ก๊าซไนโตรเจนและก๊าซออกซิ เจน
ตัวอย่างการใช้ก๊าซไนโตรเจนและก๊าซออกซิ เจน
ตัวอย่างการใช้ก๊าซไนโตรเจนและก๊าซออกซิ เจน
ถ้ วยใส่ สารทดสอบ ( Crucible)
มีรูปร่ าง ขนาดต่ างๆกัน
ต้ องไม่ ทาปฏิกริ ิยากับสารทดสอบ
ทาจากวัสดุได้ หลายชนิด
ชนิดของถ้ วยใส่ สารทดสอบ
Alumina - 70 l, 150 l, 900 l, reusable
- inert against most samples
- melting point >1700 °C
Platinum - 30 l, 70 l, 150 l, reusable
- use a sapphire disk between crucible and
sample if you go above 1000 °C (otherwise
crucible and sample holder glue together)
- good SDTA-signals (heat transfer)
- may act as a catalyst
- melting point 1770 °C
Aluminum - 40 l, 100 l
- melting point 660 °C
- good SDTA-signals
Sapphire - 70 l, reusable
- inert against most samples
- melting point >1700 °C

Critical points: - reaction with the sample

- melting point
การวางภาชนะสาหรับใส่ สารทดสอบ
ตัวอย่ างเครื่ อง TGA
ตัวอย่ างเครื่ อง TGA
 The TGA/SDTA851e
Gases
Reactive
Protective

Purgee

Gas
outlet

Water cooling
ปัจจัยทีอ่ าจมีผลต่ อผลการทดสอบ
อัตราการให้ ความร้ อน
สารทดสอบ (มวล รู ปร่ าง และ การเตรียม)
ถ้ วยใส่ สารทดสอบ ( วัสดุ มวล ลักษณะรู ปร่ าง)
อากาศในเตาเผาและอัตราการไหลเวียนของก๊ าซ
 อิทธิพลของอัตราการให้ ความร้ อน

 Thehigher the heating rate the lower the

temperature resolution, i.e. the separation
of overlapping effects becomes worse.

 The lower the heating rate the longer the

measuring time and the lower the weight
loss per unit time.

 Typical heating rate: 10 K/min to 30 K/min

อิทธิพลของอัตราการให้ ความร้ อน
อิทธิพลของมวลสารทดสอบ
อิทธิพลของภาชนะใส่ สาร (Pan)
การชั่งนา้ หนักสาร (Weighing in samples)
 Weighing in on an external balance
 Weighing in on the TGA-balance
 Automatic weighing in (pan and sample)

Note: if the mass of the pan and an initial sample

mass are indicated, the TGA curve starts at the
total current mass (pan+sample) minus the mass of
the pan. In this case, the TGA-curve does not
necessarily begin at 100 %.

To prevent e.g. loss (or uptake) of moisture during

the time before the experiment is started you
should seal your pan (only for aluminum pans) and
let the sample robot pierce the lid before the
experiment begins.
What is essential
• a well thermostatted instrument (otherwise you will observe drifts !)
• good contact of the sample to the pan (SDTA)

• blank curve
• constant protective gas flow through the instrument

Tips and tricks

• use a pierced lid to shift e.g. evaporation reactions
• use an inerst sample as reference for the blank
• use whenever possible aluminum pans (SDTA)
• use not more sample than necessary; heat clean from time to time
the furnace (thermocouples).
How to proceed
• Warm-up“ of the instrument
• Calibration check (weekly or if any changes at the instrument have
been
made)
• Check delivers a negative result: check the check
• Instrument needs to be adjusted
- Manual adjustment (use the results of the calibration)
- predefined adjustment procedures:
 Single temperature
 Single Sample holder ‚calibration‘
 Total ‚calibration‘
• Check the new calibration
• The thermocouples may be poisoned by e.g. carbon  heat cleaning
• Blank curves to judge the performance of the balance (noise)
What are the smallest weight losses that
can be measured with the
thermobalance?

• Noise: typically about 0.5 – 1 g (RMS)

• Blank: reproducibility  5 g @ 500 °C and 10 K/min
• Drift: typically 5 g/h

To identify a weight step, the weight change should be at least twice as large as
the peak-to-peak noise. The peak-to-peak noise is about 2 g. For unambiguous
identification, the weight change should therefore be at least
4 g.
Determination of residues (ash)

In this case, the reproducibility of the blank curve and the amount
of sample are critical.

Task
An ash content of approx. 1% should be determined with a
relative accuracy of 1%, i.e.  0.01% ?

What sample weight is needed?

Answer

• Assumption: reproducibility of the blank curve  10 g

• 1% accuracy  residue must be 1 mg
• the sample must therefore weigh 100 mg.
Applications of TGA
Moisture content
ตัวอย่าง TGA curve ของ พอลิเมอร์ชนิดต่างๆ
ตัวอย่าง TGA curve ของ พอลิเมอร์ชนิดต่างๆ
ตัวอย่างการใช้ TGA ในการหาสภาวะทางความร้อนที่
เหมาะสมในการสังเคราะห์สารบริ สุทธ์

ช่วงที่น้ าหนักคงที่ คือ ช่วงที่

สารประกอบแคลเซี ยมจะเสถียร
ตัวอย่าง TGA curve