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Maulana Azad National Institute of Technology , Bhopal

(Material Science & Metallurgical Engineering Department)

Differential Scanning Calorimeter


Faculty in-charge Mr. Sunil Kumar Professor MSME Department MANIT Bhopal

Presented By Avinaw Pansari Babu Lal Meena Sintu Jain Chetan Ghadle Ram Bihari Soni

PHASE - I
Introduction Type Working

Avinaw Pansari

Definition
According to International Confederation for Thermal Analysis and Calorimetry

DSC (Differential Scanning Calorimetry) is a technique in which the heat flow rate (or thermal power) to the sample is monitored against time or temperature while the temperature of the sample in a specified atmosphere is programmed

DSC
DSC is one of the thermal analysis technique.

Earlier versions of the DSC were known as

Differential Thermal Analyzers (DTA).

Why we require DSC


Solid-liquid phase transition Ex- Melting of ice Visible from naked eyes

Why we require DSC


A solid-solid phase transition
There are however several different phase changes within water in a solid state. Ex- Ice at colder and colder temperatures can have several different crystal structures and undergo many solid-solid phase transitions, each of these phases, the ice has different properties ranging from brittleness to conductivity Not visible from naked eyes totally. Thermal analysis, it is possible to understand what is happening in a material, even if there is no visual evidence that a change has occurred

Principle of DSC

Whenever a material is subjected to a heating or cooling conditions ,there are some physical or chemical changes take place in material. This changes are associated with either a gain of energy or loss of energy ,

Working of DSC is based on measurement of this gain or loss of energy .

What Does a DSC Measure?


Differential Scanning Calorimetry (DSC) measures the temperatures and heat flows associated with transitions in materials as a function of time and temperature in a controlled atmosphere. These measurements provide quantitative and qualitative information about physical and chemical changes that involve endothermic or exothermic processes, or changes in heat capacity

Type of Reactions
Endothermic Heat Flow - Endothermic: heat flows into the sample as a
result of either heat capacity (heating) or some endothermic process (glass transition, melting, evaporation, etc.) Exothermic Heat Flow -Exothermic: heat flows out of the sample as a result of either heat capacity (cooling) or some exothermic process (crystallization, cure, oxidation, etc.)

Various Types of Processes


Process / Transition Solid state Transition Crystallisation Melting Vaporisation Sublimation Adsorption Desorption Drying (solvent Rmoval) Decomposition
Y Y Y Y Y

Exothermal
Y Y

Endothermal
Y

Y Y Y

Solid State Reaction


Solid Liquid Reaction Solid Gas Reaction Polymerisation Crystal reaction

Y
Y Y Y Y

Y
Y Y

DSC Apparatus
A DSC apparatus is built around : a differential detector a signal amplifier a furnace a temperature controller a gas control device a data acquisition device

Gas control

Furnace

Sample

Reference

Detectors

Furnace controller

four

Microvolt amplifier

Data acquisition

DSC Apparatus

Types of DSC

Q10

Q100

Q1000

DSC2010

DSC2910

DSC2920

Classification of DSC

Power Compensation DSC or Heat Flow DSC DSC

Heat Flux DSC

Power Compensation DSC


Developed in 1960 by Mike O Neil of Perkin Elmer to measure heat flow, the movement of heat in and out of sample directly. The specimen (TS) and reference (TR) temperatures are controlled independently using separate (identical) ovens.

Power Compensation DSC


The temperature difference between the sample and reference is maintained to zero by varying the power input to the two furnaces. This power difference is then a measure of the enthalpy or heat capacity changes in the test specimen S (relative to the reference R). The computer keeps track of the sample & reference temperature, their power input and records the difference in power input between the reference pan and the sample pan , and plots it against temperature as shown in

Heat Flux DSC


In this DSC, there are two pans isolated from the ambient environment in a same chamber. One pan contains the sample to be analyzed, and the other pan is empty or may contain Alumina sometime and is used as a reference pan

Heat Flux DSC


Both pans have heaters underneath them that are used to raise or lower the temperature Each pan also has a sensor that indicates what the temperatures of the pans are at any given moment. Using computer controlled sensors and logic, the heaters are set to heat the pans at a constant rate.

Although the pans heat at a constant rate, but the heat flow (the rate at which thermal energy is supplied to the pans) does differ, due to the fact that there is material in one of the pans, and nothing in the other pan.
Computer will have to supply a higher heat flow to the pan containing material as compare to reference empty pan in order to force the pans to heat at the same rate.

Heat Flux DSC

The computer keeps track of the starting temperature, heating rate, and heat flow, and records the difference in heat flow between the reference pan and the sample pan , which is the heat flow for the sample, and plots it against temperature as shown in

Why two types of DSC is required?


For the vast majority of simple applications, the data from both types of instruments are comparable and both instruments can give good data. However, both designs have strengths and weaknesses, and if we are doing more than just looking at simple glass transitions and melts, we may need one or the other.
Process Heat Flow Double Furnace DSC Yes High High Very easy Moderate Excellent Yes Heat Flux Single furnace DSC No Moderate Moderate Moderate Easy Affected by Temperature Yes

Fast Heating (250C/min plus) Accuracy of Cp Values Delta H Accuracy Ease of Cleaning OIT Testing Isothermal Performance Modulated Techniques

Comparing Curves of both type of DSC


In a heat flow DSC, the endothermic peaks those events which require energy point up because the instrument must supply more power to the sample to keep the sample and reference furnaces at the same temperature. In a heat flux DSC, these same events cause the sample to absorb heat and be cooler than the furnace, so they point down.

Solid Line Heat flow DSC Dotted Line Heat Flux DSC

PHASE - II
Application DSC Thermogarm Analysis

Babu Lal Meena

What can DSC measure?


Glass Transitions Temperature (Tg) Melting Point (Tm)and Boiling Points (Tb) Crystallization time and Temperature (Tc) Percent crystallinity Heats of Fusion and Reactions Specific Heat Capacity Oxidative/Thermal Stability Rate and Degree of Cure Reaction Kinetics Purity

Heat Capacity
Heat capacity is the amount of heat required to raise or lower the temperature of a material by a given amount. In a DSC experiment, heat capacity is measured as the absolute value of the heat flow, divided by the heating rate , and multiplied by a calibration constant. dH/dt = Cp (dT/dt)
or

Cp = [(dH/dt)/(dT/dt)] x K
K = calibration constant dH/dt heat flow rate dT/dt Heating Rate (constant)

Specific Heat Capacity

Specific heat capacity refers is defined as the heat capacity per unit mass of a material.

In DSC Specific heat is measured by the help of the following equation.

Cp = E x H x 60 Hr x M
Cp = Specific Heat Capacity (J/g/C) E = Calibration Constant (dimensionless) H = Heat Flow rate (mW) 60 = conversion constant (min sec) Hr = Heating Rate (C/min) M = Sample Mass (mg)

What Affects the Specific Heat Capacity?

Amorphous Content Aging Side Chains Polymer Backbone Copolymer Composition

Anything that effects the mobility of the molecules, affects the Heat Capacity.

Enthalphy Change
Enthalpy change is the name given to the amount of heat evolved or absorbed in a reaction carried out at constant pressure. The integral under the DSC peak, above or below the baseline, gives the total enthalpy change for the process .

Glass Transition Transition Temperature Glass


The glass-liquid transition (or glass transition for short) is the reversible transition in amorphus materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle state into a molten or rubber-like state.

The temperature at which this transition takes place is called Glass Transition Temperature (Tg)
The glass transition has been called the melting of amorphous material Glass transitions can only take place in an amorphous material. A glass transition has no latent heat associated with it and such transitions are referred to as second order transitions. It is an Endothermic Process

How to measure Tg From DSC ?


Tg is assigned to the mid point temperature of the range of temperature during the transition.

A simple example of a glass transition - When a plastic or rubber material is placed in a freezer, it becomes very brittle and can easily be shattered, the plastic or rubber is then in a glass state. When it is warmed the plastic or rigid rubber becomes very pliable, or goes into a rubbery state.

Some Properties Affected at Tg

Physical property Specific volume


Modulus Coefficient of thermal expansion Specific heat

Response on Heating Through Tg Increases


Decreases Increases Increases

Enthalphy
Entrophy

Increases
Increases

What Effects Tg in DSC

Heating Rate Crystalline Content Heating & Cooling Copolymers Aging Side Chains Molecular Weight Polymer Backbone Plasticizer Hydrogen Bonding
Microstructure of polymer, as determined by cryo-SEM its during freezing

Crystallization
It is defined as the process in which the material gain enough

energy so that its atoms/molecules could re-arrange into a more stable and ordered state.
When a material is crystallized, it becomes ordered. Crystallization is a first order transition, and thus a latent heat is associated with the transition. It is an Exothermic Process.

The temperatute at which material crystallise is called Crystallisation Temperature (Tc ) of material.
Crystallisation of water

Observation of Tc in DSC
The crystallization temperature (Tc) is the peak of the graph.

Since crystallization is a two step process Nucleation & Growth , so crystallization of material takes place over a range of temperature. Temperature at onset of crystallization is Tn. The area of the peak can be obtained and using the heating rate and the mass of the sample and the latent heat of crystallization can be calculated.

% of Crystallinity from DSC


Sample must be pure material, not copolymer or filled We Must know enthalpy of melting for 100% crystalline material (Hlit ) H(lit) can be use for calculating relative crystallinity DSC: Calculation of % Crystallinity For standard samples: % crystallinity = 100* Hm / H(lit)

Melting Melting
Melting, or fusion, is a physical process that results in the phase transition of a substance from a solid to a liquid and the temperature at which this transition takes place is called Melting point of that material.
Melting always occurs with an increase in disorder. There is always a change in volume (positive or negative)during melting. there is always a change in heat capacity. A material cannot melt unless it is a crystal. Therefore, any material that melts must first crystallize .Similar to when the material gave off heat/energy as it became a crystal, at the melting point (Tm) it must now absorb energy to go to higher energy state. Therefore Melting is a endothermic process

Why should we use Tm for DSC?


Melting is often measured using a simple melting point apparatus adequately. However, the number is often imprecise and difficult to reproduce. Using a DSC for this task helps to get the melting temperature from a calibrated and highly precise system .
We can also get the onset of melting, the Tm, and also the peak temperature which corresponds to complete melting in organics. Enthalpy of melting can also be calculated which can further be used to estimate both purity and degree of crystallinity for materials by using the leading edge method.

Melting Points Ranges DSC Melting Point and & Ranges inin DSC
To is the onset to melting

Tp is the melting peak temperature Te is the end of melting


Pure, low molecular weight materials (mw<500 g/mol) To - Melting temperature(Tm) for the material, Between To and Tp - the sample is melting Between Tp and Te - the molten sample is returning to the DSC temperature .

Area under the curve may be used to find the latent heat of fusion

Melting Points Ranges DSC Melting Point and & Ranges inin DSC
To is the onset to melting

Tp is the melting peak temperature Te is the end of melting Polymers


Tp - Melting temperature(Tm) for the polymer, Between To and Tp - Crystal perfection is occurring (both melting and crystallization occurs simultaneously) Between Tp and Te - the sample is finishing melting and returning to the DSC temperature .

Area under the curve may be used to find the latent heat of fusion.

DSC Thermogram DSC Thermogram

Amorphous material Glass transition ( Cp is increases, but no latent heat is present).

Crystallize (Solid Solid Transition ,release energy).


Melting Additional phase changes in the liquid phase. (may or may not be)
Inherently crystalline materials thus may only undergo solid to solid transitions and then melt.

PHASE - III

Calibration

Sintu Jain

How do I get obtain good data? How to good data in DSC


Good data requires at a minimum a valid calibration with suitable standards, a smooth baseline, and reasonable separation of the sample peak from any noise in the baseline. It should be both repeatable and reproducible. By calibration, it means the instrument has to be set up against known standards and checked so it gives reasonable values.

DSC Calibration DSC Calibration


baseline evaluation of the thermal resistance of the sample and reference sensors measurements over the temperature range of interest 2-step process the temperature difference of two empty crucibles is measured the thermal response is then acquired for a standard material, usually sapphire, on both the sample and reference platforms amplified DSC signal is automatically varied with temperature to maintain a constant calorimetric sensitivity with temperature

DSC Calibration
temperature goal is to match the melting onset temperatures indicated by the furnace thermocouple readouts to the known melting points of standards analyzed by DSC should be calibrated as close to the desired temperature range as possible heat flow use of calibration standards of known heat capacity, such as sapphire, slow accurate heating rates (0.52.0 C/min), and similar sample and reference pan weights
calibrants high purity accurately known enthalpies thermally stable light stable (hn) nonhygroscopic unreactive (pan, atmosphere) metals In 156.6 C; 28.45 J/g Sn 231.9 C Al 660.4 C inorganics KNO3 128.7 C KClO4 299.4 C organics polystyrene 105 C benzoic acid 122.3 C; 147.3 J/g anthracene 216 C; 161.9 J/g

Heat Flow Calibration (Cell Constant)

Heat Flow Calibration of Differential Scanning Calorimeters ASTM E-968 Enthalpy Calibration Performed using Calibration Wizard One Run
Indium metal
Sample Weight 1-5mg Pre-melt sample the first time you run it Heating rate of 10C/min Dependent upon purge gas

Cell Constant

The cell constant is calculated as the ratio of the theoretical heat of fusion of a standard material, to the measured heat of fusion
Cell Constant Hf
(Theoretic al)

/ Hf (Measured)

Cell Constant should be 0.95-1.20 in N2

Temperature Calibration

Temperature Calibration of Differential Scanning Calorimeters ASTM E-967 Performed using Calibration Wizard Indium Cell constant run also performs temperature calibration Can do up to 5 standards
Pure metals typically used - In, Sn, Zn, Pb Weve found that on the Q series DSCs one temperature calibration point is all that is usually needed

Direct Cp Calibration (Q1000 Only)

Required to measure the absolute value of Heat Capacity (Cp) with a single run Reset previous calibration value to 1.0 Run standard material (sapphire) in standard mode, @ 10-20C/min

Set to 1.0

The heat capacity calibration constant, K, is calculated as the ratio of the theoretical heat capacity of a standard material, to the measured heat capacity of the material

Cp K Meas. Cp

Theo.

Direct Cp Calibration

1.2

Theoretical Values 106.85C 0.9168J/g/C 156.85C 0.9775J/g/C

206.85C 1.025J/g/C

1.0

56.85C 0.8380J/g/C

Heat Capacity (J/g/C)

0.8

0.6

56.85C 0.7932J/g/C

106.85C 0.8567J/g/C

156.85C 0.9054J/g/C

206.85C 0.9467J/g/C

Measured Values

0.4

0.2

0.0 0 50 100 150 200 250

Temperature (C)

PHASE - IV
Sample Preparation for DSC

Ram Bihari Soni

Sample Preparation
Sample Weight 1. Selection of the optimum weight is dependent on a number of factors. The sample to be analyzed must be representative of the total sample 2.The change in heat flow due to the transition of interest should be in the range of 0.1 - 10mW - metal or chemical melting: <5mg - polymer Tg or melting: 10mg - composites or blends: >10mg 3.The accuracy of the analytical balance - sample weight should be accurate to +1%

Sample Preparation
Sample Shape 1. Keep sample as thin as possible and cover as much of the pan bottom as possible 2. Samples should be cut rather than crushed to obtain a thin sample 3. Lids should be used with sample pans in order to keep the sample in contact with the bottom of the pan Sample Pans 1. Use lightest, flattest pan possible 2. Use hermetic pans to prevent evaporation if it occurs in the same temperature range as the transition of interest

Experimental Conditions
Reference Pan 1. Always use a reference pan of the same type used to prepare the sample 2. Never use a material in the reference pan that has a transition in the temperature range of interest 3. Because DSC measures the difference in heat flow between a sample and reference, the baseline stabilizes faster if the difference in heat capacity between the sample and reference is kept small by adding weight (same material as pan) to the reference pan so that it is similar in total weight to the sample pan.

Experimental Conditions

1.Heating/Cooling Rates
High rates increase sensitivity

Low rates increase resolution by providing more time at any temperature

2.Purge Gas nitrogen increases sensitivity because it is a relatively poor thermal conductor helium increases resolution because it is a good conductor of heat to or from the sample

Experimental Conditions
General Summary Condition To increase sensitivity
increase increase increase nitrogen*

To increase resolution
decrease decrease no effect helium*

Sample size heat rate ref pan weight purge gas

*instrument should be calibrated with the same purge gas as used to run a sample

Effect of Heating Rate on Nylon 66 Melting Behavior

Effect of Cooling Rate on Crystallization of HDPE

Effect of Polymer Structure

PHASE - V
Limitations DSC Related Instruments

Chetan Ghadle

Limitations of DSC

1. It is not possible to optimize both sensitivity and resolution in a single DSC experiment.
2. Baseline curvature and drift limit the sensitivity of DSC for detecting weak transitions 3. Transitions are often difficult to interpret because DSC can only measure the Sum of Heat Flow within the Calorimeter

4. The DSC measurement of polymer crystallinity is often wrong because it fails to detect the formation of crystalline structure as the sample is heated 5. DSC cannot measure Heat Capacity under isothermal conditions.

DSC: Related Instrumentation

Modulated DSC (MDSC) : sinusoidal oscillation superimposed on linear temperature ramp Differential Thermal Analysis (DTA) Pressure DSC (PDSC) Differential Photo calorimetry (DPC) Dual Sample DSC SDT 2960 Simultaneous DSC-TGA

DTA
Differential Thermal Analysis (DTA) measures the temperatures and temperature differences (between sample and reference) associated with transitions in materials as a function of time and temperature in a controlled atmosphere.

PDSC
Pressure DSC (PDSC) is capability of operating at elevated pressure or at a vacuum (TAI PDSC: 1 Pa 7 Mpa)

DPC & Dual Sample DSC


Differential Photo calorimetry sample is exposed to UV/Vis radiation Dual Sample DSC: Allows two samples to be ran simultaneously

SDT 2960
SDT 2960 Simultaneous DSC-TGA: measures heat flow and weight changes simultaneously

PHASE - VI
DSC Experiment (Video)

Avinaw Pansari

Thank You

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