Chapter 1.

THERMAL ANALYSIS 110

2
100

Heat Flow (V)

90 0

TG (%)
80 TG -2
Heat Flow
70
-4

Dr. Nguyen Tuan Loi 60

0 200 400 600 o 800 1000
Temperature ( C)
Email: nguyentuanloi@duytan.edu.vn 1
DTA DSC TGA

Heat flow

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  Basic Principle
 Sample is heated at a constant heating rate

 Sample’s property measured

• Weight TGA

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  TGA

TGA is a technique measuring the variation in mass of a sample

when it undergoes temperature scanning in a controlled
atmosphere.
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  Types of TGA
1. Isothermal/static TG: in this technique the sample weight is
recorded as a function of time at constant temperature.

2. Quasistatic TG: in this technique the sample is heated to constant

weight at each of the series of increasing temperature.

3. Dynamic TG: in this technique a sample is heated in an

environment whose temperature is changing in temperature manner
generally at linear rate. 6
  Principle of TGA
 The sample is heated in given environment (air, N2, CO2, He, Ar,
…) at controlled rate. The change in the weight of the substance is
recorded as a function of temperature or time.
 The temperature is increased at a constant rate for a known
initial weight of the substance and the changes in weights are
recorded as a function of temperature at different time interval.
 This plot of weight change against temperature is called TG curve
or thermo-gram. 7
  Instrumentation

 Recording balance
 Sample holder
 Furnace
 Furnace temperature programmer/controller
 Recorder 8
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 Deflection balances
 Beam type: the conversion of deflected beam take place into
weight change

 Helical type: elongation or contraction of spring occurs with

change in weight which is recorded by help of transducer

 Cantilevered beam: one end of beam is fixed and on the other

end sample is placed

 Torsion wire: the beam is attached to hard torsion wire which

act as fulcrum
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 Null point balances
It consists of sensor which detects the deviation from
the null point and restores the balance to its null point
by means of restoring force

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 Sample holder

 Should be inert to the sample in the

temperature range used
 Should not exhibit any physical
transitions in the temperature range used
 The melting point should be sufficiently
high
  Factors affecting TGA

1. Instrumental factors 2. Sample characteristics

 Furnace heating rate  Weight of the sample

 Furnace atmosphere  Sample particle size

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 1. Instrumental factors

Furnace heating rate

 The temperature at which the compound decompose
depends upon the heating rate is high, the
decomposition temperature is also high.

 A heating rate of 3.50C/min is usually recommended

for reliable and reproducible TGA.

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 Furnace atmosphere

 The atmosphere inside the furnace surrounding the

sample has a profound effect on the decomposition
temperature of the sample.

 A pure nitrogen gas from a cylinder passed through

the furnace which provides an inert atmosphere.
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 2. Sample characteristics
Weight of the sample
A small weight of sample is recommended using a small
weight eliminates the existence of temperature gradient
throughout the sample.

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 Sample particle size
 The particle size of sample should be small and
uniform.

 The use of large particle may result in apparent very

rapid weight loss.
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 Other factors affecting TGA curve

 Sample holder
 Heat of reaction
 Compactness of the sample
 Previous history of the sample
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  Types of transition
 Physical transition  Chemical transition
 Adsorption  Oxidation
 Desorption  Reduction
 Sublimation  Chemisorption
 Evaporation  Loss on drying
 Vaporization  Degradation
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  Advantages of TGA
 Accurate and precise method of macro quantitative analysis
 Low detection limit (up to 10-7)
 Reliable data
 Easy to use
 Minimal sample preparation
 Capable of conducting isothermal experiment and cool
experiment 20
  Disadvantages of TGA
 Destructive
 Limited range of samples
 Required meticulous time consuming
 Usually not qualitative
 Mis-step in the procedure can lead to error for the
analysis 21
  Limitations of TGA
 The chemical or physical changes which are not accompanied
by the change in mass on heating are not indicated in TGA.

 During TGA, pure fusion reaction, crystalline transition,

glass transition, crystallization and solid state reaction with
no volatile product would not be indicated because they
provide no change in mass of the specimen.
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 Application of TGA

 Physical transition
 Chemical transition
 Sample purity
 Loss of drying
 Stability of analyte 23
  Experiment difficulty
 Some curves might not be smooth and sharp
 The error of commercialized instrument is about 5%
 The higher temperature, the more problems
 High sample vapor pressure
 High sample diffusivity
 Short life time 24
 Crucible should not react with sample

BN is Boron Nitride 
 Example 1: Heating a sample of CuSO4.5H2O

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 Example 2: Heating a sample of Calcium oxalate

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 Example 3: Heating a sample of Fe(OH)3

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 Summary

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TGA-DSC
 Bài tập chương 1

1. Trình bày ngắn gọn nguyên lý đo phổ DSC?

2. Từ phổ DSC, chúng ta có thể thu được những thông tin gì?
3. Những pick thu nhiệt/tỏa nhiệt thu được trên phổ DSC có
thể là do những quá trình nào?
4. Trình bày ngắn gọn nguyên lý đo phổ TGA?
5. Từ phổ TGA, chúng ta có thể thu được những thông tin gì?
6. Những vùng tăng/giảm khối lượng thu được trên phổ TGA có
thể là do những quá trình nào gây nên?
7. Những lưu ý gì cần quan tâm để giảm sai số hay nâng độ chính
xác của phép đo TGA?
Deadline: 26/09/2021
 Vẻ phổ và phân tích TGA-DSC

 Thầy gửi data thô để các bạn vẽ lại hình và giải thích các kết quả thu
được trên hình.
 Phần mềm cần thiết cho xử lý số liệu: Origin hoặc excel.
Deadline: 26/09/2021