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.
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 ,
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.)
Exothermal
Y Y
Endothermal
Y
Y Y Y
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
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.
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
Fast Heating (250C/min plus) Accuracy of Cp Values Delta H Accuracy Ease of Cleaning OIT Testing Isothermal Performance Modulated Techniques
Solid Line Heat flow DSC Dotted Line Heat Flux DSC
PHASE - II
Application DSC Thermogarm Analysis
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 refers is defined as the heat capacity per unit mass of a material.
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)
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 .
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
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.
Enthalphy
Entrophy
Increases
Increases
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.
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
Melting Points Ranges DSC Melting Point and & Ranges inin DSC
To is the onset to melting
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
Area under the curve may be used to find the latent heat of fusion.
PHASE - III
Calibration
Sintu Jain
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 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)
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
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
206.85C 1.025J/g/C
1.0
56.85C 0.8380J/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
Temperature (C)
PHASE - IV
Sample Preparation for DSC
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
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*
*instrument should be calibrated with the same purge gas as used to run a sample
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.
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)
SDT 2960
SDT 2960 Simultaneous DSC-TGA: measures heat flow and weight changes simultaneously
PHASE - VI
DSC Experiment (Video)
Avinaw Pansari
Thank You