Ghulam Ishaq Khan Institute of Engineering Sciences and Technology Nanomaterials and Nanotechnology-II MM392Thermal analysis = Thermal analysis is a branch of materials science where the properties (mainly physical-type) of materials are studied as they change with temperature. = Several methods are commonly used — these are distinguished from one another by the property which is measured. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and Technology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 contro! data collection and processing temperature _ ee control (furnace) sensors & ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyThermal analysis = Thermogravimetric analysis (TGA): mass = Differential scanning calorimetry (DSC): heat difference = Dielectric thermal analysis (DEA): dielectric permittivity and loss factor = Differential thermal analysis (DTA): temperature difference = Dilatometry (DIL): volume = Dynamic mechanical analysis (DMA) : mechanical stiffness and damping = Evolved gas analysis (EGA) : gaseous decomposition products = Laser flash analysis (LFA): thermal diffusivity and thermal conductivity = Thermomechanical analysis (TMA): dimension = Thermo-optical analysis (TOA): optical properties ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and Technology‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyThermal analysis TOA curve DTG curve ° ‘000 15007000 2500" 3000 3500 Time [ms] easing 8G Displacement Expansion Loading: None uo 4 Oo m8 Temperature (C) ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyThermal analysis =< Differential thermal DIA Temperature analysis difference Differential scanning een psc Enthalpy Thermogravimetric ‘anal TGA Mass Sesorarachestesl ace: DMA Deformation analysis Dielectric thermal DEA Datcrmeation analysis Gaseous Evolved gas analysis EGA ae mio Thermo optical snakoa TOA Optical properties Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyThermal analysis = Thermal analysis is defined as “series of techniques for measuring the temperature dependency of a physical property of a certain substance while varying the temperature of the substance according to a specific program.” = The substance referred to here includes reaction products. = Physical properties include mass, temperature, enthalpy, dimension, dynamic characteristics, and others, and depending on the physical properties to be measured, the techniques of thermal analysis. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyBasic Principles of Thermal Analysis = Thermal Gravimetric Analysis (TGA) — Measure change in weight during heating or cooling = Differential Scanning Calorimetry (DSC) — Measure heat absorbed or liberated during heating or cooling = Thermomechanical Analysis (TMA) — Measure change in dimensions during heating or cooling = Differential Thermal Analysis (DTA) — They are use for thermal investigation where thermal change can be observed and characterized ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyThermal Gravimetric 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. R(s)4>P(s)+Gas R(s) + Gas®> P(s) = ATGA consists of four major parts * Furnace + Microgram balance + Auto sampler * Thermocouple (chromel/Pt-Rh Alloy etc.) ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyThermal Gravimetric Analysis (TGA Programmer ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyThermal Gravimetric Analysis (TGA The furnace can raise the temperature as high as 1500°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 always be taken that the thermocouple is not in touch with the sample which is in a platinum pan. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyThermal Gravimetric Analysis (TGA ~ A technique measuring the ee balance variation in mass of a sample | undergoing temperature : scanning in a controlled sample atmosphere / Thermobalance allows for monitoring sample weight as a function of temperature The sample hangs from the \ balance inside the furnace and \ the balance is thermally cnpeaee furnace isolated from the furnace ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and Technology@ (i) p Saeanaeeennnne eee ai mass (w) Temperature> Interpretation of TGA Curves 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 TGA 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 ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineeting Sciences and TechnologySerre Can ‘ ae ae (vil) temperature —» vi. Interpretation of TGA Curves vii. 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, Gain in mass due to reaction with atmosphere, e.g., oxidation of metals, Oxidation product decompose again at higher temperature; this is not often encountered. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyMass Loss (%) TiO, Nanoparticles in PVDF polymer 100 200 300 400 ‘Temperature (°C) 600Interpretation of TGA Curves [js CT © 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 temperature [°C] ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and Technology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, 10-20mg 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 +0.025mg which is 0.25% of a 10mg sample. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyExperimental Conditions = Heating Rate = Purge gas ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and Technology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. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyExperimental Conditions-Purge Gas = Nitrogen is the most common gas used to purge samples in TGA due to its inert nature. = 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. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyLimitation and Solution There are generally two limitations of TGA for analyzing materials: 1. In a multiple component system, sample can decompose in a narrow temperature range. This can be overcome by — varying the type of purge gas and/or - using a high resolution technique 2. TGA is quantitative but cannot identify the decomposition products. Hence TGA coupled with Mass Spectrometer or FTIR can be used also for quantitative Ee use fo some extent. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyCalibration = Blank test = Calibration of mass changes = Calibration of temperature ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyApplications © 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. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyPoints to Remember = 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. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineering Sciences and TechnologyPoints to Remember 295 z a cs z 4200 440460 ‘Temperature (C) 0 200 400 600 800 Temperature (°C) ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyDemonstration © https://www.youtube.com/watch?v=NOLO1uj00g4 ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyDifferential Scanning Calorimetry (DSC) = DSC measures differences in the amount of heat required to increase the temperature of a sample and a reference as a function of temperature = A calorimeter measures the heat into or out of a sample. = A differential calorimeter measures the heat of a sample relative to a reference. = A differential scanning calorimeter does all of the above and heats the sample with a linear temperature ramp. = Endothermic heat flows into the sample. = Exothermic heat flows out of the sample. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyConventional DSC Reference Temperature Temperature \ Temperature 2 Difference = Heat Flow ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyDifferential Scanning Calorimetry (DSC) Principle: = Principle DSC is a thermo-analytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. The differences in heat flow occur with the occurrence of two major events: = The heat capacity of the sample which increases with temperature (baseline) = Transitions that occur in the sample (events superimposed on the heat capacity baseline) ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyDifferential Scanning Calorimetry (DSC) Heat Flow Rate is expressed in a variety of units which can also be normalized for the weight of sample used: 1) mW (milli Watts) where W = J/sec 2) Wg 3) mCal/sec cal/sec/g 4) BTU/hr (British Thermal Units/Hour) ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyDifferential Scanning Calorimetry (DSC) Temperature, Temperature difference Ca ne ATL 2 Reference material | ~-\. —/ section temperature, > eo ie ete Sample section = temperature Melting peak Time ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyDifferential Scanning Calorimetry (DSC) 4 Power <— ENDO EXO —+ Endothermic peak - absorbes heat ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyDifferential Scanning Calorimetry (DSC) © dH/dt = Cp * dT/dt + f(T,t) Where dH/dt > heat flow measured by DSC C, is the heat capacity dT/dt is heating rate AT,t) Time dependent or kinetic component ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyThermo-Mechanical Analysis Measurement of Dimensional Change Coefficient of Linear Thermal Expansion Determination of Material Anisotropy Softening Temperatures and Glass Transition Linear Thermal Expansion ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and TechnologyThermo-Mechanical Analysis (TMA) = TMA is a thermal analysis technique used to measure changes in the physical dimensions (length or volume) of a sample as a function of temperature and time under a non oscillatory load. = This technique is widely applicable to variety of materials such as nanofilms, nanocomposites etc. = Variables considered while performing the thermal mechanical analysis are applied load, gas environment, temperature range and heating rate as well as TMA probe type. ‘Dr. Mohsin Ali | Department of Materials Science and Engineering | GIK Institute of Engineesing Sciences and Technology