Thermal Analysis

By: Andrew Paul, Martin Antensteiner, Maddie Boyer, Ahmad Alraddadi, Dave Walkling

Introduction

Dilatometry: CTE (coefficient of thermal expansion) of titanium. TGA (Thermogravimetric analysis) the amount of water in zirconyl nitrate hydrate. DSC (Differential scanning calorimetry) : percent crystallinity of PET (polyethylene terephthalate)

Procedure: Dilatometry of Ti

Theta Industries Dilatronic

o
o

Initial Temperature 0oC 6oC/min to 1100oC

Ambient Nitrogen Gas

o

0.5SCFH

Initial Length 25.42mm

Procedure: Dilatometry of Ti

Polycrystalline Ti (assumed to be isotropic) Assume sample is homogenous Calibrated Equipment Rod composed of alumina
o

To limit the oxidation of Ti to TiO2

Dilatometry of Ti Results

CTE = 10.614 ppm/K

Dilatometry of Ti Results

860oC used as the cutoff between cool and hot CTEs.

Dilatometry of Ti Results

CTEcool = 10.594 ppm/K ppm/K

CTEhot = 11.692

Dilatometry of Ti Discussion

The distinct change of CTE was due to a phase change in Ti Phase Change at 882oC which is similar to the 860oC used in

the data

Dilatometry of Ti Discussion

CTEcool = 10.594 ppm/K CTEhot = 11.692 ppm/K Accepted values based on MatWeb
o 8.9 ppm/K at temperatures from 20oC to 100oC o 10.1 ppm/K at temperatures above 1000oC

CTE of TiO2 minerals

o Rutile - 7.14 ppm/K o Anatase - 10.2 ppm/K o Brookite - 11.0 ppm/K

Dilatometry of Ti Discussion

CTE data predicts that there was some oxidation of the titanium sample with higher CTEs

Procedure: TGA of zirconyl nitrate hydrate

SDT Q600 from TA Instruments Inc. Initial mass of zirconyl nitrate hydrate
o = 10.905mg

Gas used; Nitrogen at 100.0mL/min Calibrated with Al2O3 sample for reference
o Identical mass to test sample o DTA and TGA run simultaneously

Increase of 5 C/min to 500.00C

TGA Results

Water

Nitrogen

Oxygen

Mass of zirconium dioxide = 4.154mg

Determination of water content in zirconyl nitrate hydrate

Balanced Stoichiometric Equation => ZrO(NO3)2*xH2O ZrO2+2NO2+1/2O2+xH2O Finding "x"

Ratio of end to starting mass o Ratio of ending to starting molecular weight (MW) o Set ratios equal to each other o Solve for "x"
o

Determination of water content in zirconyl nitrate hydrate

Finding "x"
o
o o

Ratio of end to starting mass = 0.381 Ratio of end to starting MW in g/mol ZrO2/(ZrO(NO3)2 + xH2O)

123.218/(231.233 +x*18.001) = 0.381

o

x = 5.333 ~ 5 total water molecules

ZrO(NO3)2*5H2O ZrO2+2NO2+1/2O2+5H2O

TGA Discussion

Effects of testing conditions

o

Heating Rate 5C/min standard Faster rates lead to poor resolution o Result of increased reaction rates at higher temperature

TGA Discussion

Effect of Testing Conditions

o

Sample Size Smaller grain size reduces temperature gradient across sample
Results in more gradual mass reduction during testing

Atmosphere Altering the atmosphere can give rise to the origin of the thermal reaction
Different gasses can dictate at what temperature a compound decomposes

Alters precision of the test

Procedure: DSC of PET

DSC Q100 from TA Instruments Inc.

o heat-flux type DSC

Inert Gas used; Nitrogen 20 ml/min Calibrated with air sample for reference 7.1 mg of sample used

Figure: Schematic of the Q100 DSC by TA Instruments.

Procedure: DSC of PET

2nd heating

1st heating

DSC of PET Results

1st Melting

2nd Melting

Cooling

DSC of PET Results

DSC of PET Results cont.

Estimated Hf= 27.4J/g Delta Hm of pure PET: 140.1 J/g

%Percent Crystalization: 27.4/140.1*100 =19.5

DSC of PET Discussion

Explanation of Calculations Differences in heating cycle

o o
First heating cycle Second heating cycle

Conclusion

Dilatometry: different CTEs - different phases of Ti. TGA: heated the sample to produce Zirconia, find water amount. DSC: enthalpy of formation relates to % crystallinity.