CER122/Glass Lab #3 (1) DTA/Crystallization

WS04 February 17, 2003

Ceramic Engineering 122

DTA and Glass Crystallization

OBJECTIVE The objectives of this lab are to teach the students how to use
differential thermal analysis (DTA) to analyze the thermal
properties of glass, to relate DTA data to glass crystallization and
to introduce the student to x-ray diffraction analyses.

ELEMENTS: • Sample preparation (crushed glass and glass bars)

• Studying glass transition and crystallization temperature by
DTA
• Using DTA plots to determine Tg and Tx.
• Using a furnace to heat a glass to a temperature where
crystallization should occur.
• Making observations about the heat treated sample.
• Preparing a powder sample for x-ray diffraction and
identifying the crystallized phases.

PRINCIPLES
DEMONSTRATED • Techniques for determining thermal properties of glass.
• Techniques for characterizing crystallized glasses.

MATERIALS
AND EQUIPMENT • Glasses prepared from lab #1
• DTA cups
• Furnaces
• Refractory setter
• Mortar and pestle
• Sieves

SUGGESTED
READING • James E. Shelby, Introduction to Glass Science and
Technology, ARC Paperbacks, U.K. (1997); pages 20-24; 224-
225.

• Arun K. Varshneya, Fundamentals of Inorganic Glasses,

Academic Press, New York (1994); pages 43-59; 280-282

Introduction
The goal of this lab is to determine the glass transition temperature (Tg) and
crystallization temperature (Tx) of glass samples by differential thermal analysis (DTA),
to use that information to crystallize a piece of glass, then to use x-ray diffraction (XRD)
to characterize the crystallized sample.
CER122/Glass Lab #3 (2) DTA/Crystallization
WS04 February 17, 2003

Background

Tg and Tx
The glass transformation region represents a range of temperatures over which the
glass undergoes both thermal and physical changes. Upon heating, the sample transforms
from a solid to a viscoelastic solid. A single temperature, Tg, is often used to indicate the
glass transformation region. However, Tg is dependent upon the measurement method
(dilatometry or differential thermal analysis (DTA)), thermal history (fictive temperature
effects) and experimental heating rate, and so it is important to indicate the experimental
details when reporting Tg. When a glass goes through Tg, there is a structural relaxation
that is detected by a dilatometer and there is a change in heat capacity, which is detected
by a DTA.

The crystallization temperature, Tx, of a glass represents the temperature at which a

thermodynamically stable phase crystallizes from the melt. (Note that Tx is greater than
Tg for all but very unusual systems.) Crystallization is an exothermic process than can be
detected with a DTA. More than one phase can crystallize, and as such multiple
crystallization exotherms can be detected for some samples.

The difference between Tx and Tg is often a useful measure of glass stability.

Greater differences between Tx and Tg often indicate increased glass stability, because
there is a larger temperature range for processing the glass.

DTA
Differential Thermal Analysis: Measure the temperature difference between a
sample (S) and an inert reference material (R) as both are heated. The sample will
undergo endothermic (glass transition) and exothermic (crystallization) processes that
change its temperature relative to the reference.

Differential Thermal Analysis is Used to Characterize

Glassforming Ability and Thermal Stability

Tx

Tg

‘S’ is sample
‘R’ is inert reference
•measure the temperature •Large (Tx-Tg): Better
difference between the two glassforming ability, better
thermal stability
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WS04 February 17, 2003

Differential thermal analysis is a technique for measuring differences in heat flow in

a sample. A constant heating rate is used and a standard material (typically alumina) that
undergoes no phase transitions in the temperature range of interest is used as the
reference. The heat flow to the sample relative to the reference is recorded. When the
sample goes through the glass transition temperature there is a change in heat capacity
and there is an endothermic relaxation of the glass structure. As a result, the sample
consumes more heat than the standard in this temperature range.

When the sample crystallizes, the atomic re-arrangement is an exothermic process,

and the sample releases more heat than the standard. Glasses that do not crystallize
during a DTA experiment might phase separate or simply form a homogeneous liquid
when heated to T>Tg. Subtle inflections in the DTA plot may indicate the presence of a
diffuse exothermic peak associated with phase separation.

XRD
X-ray diffraction (XRD) can be used to detect crystallinity in previously amorphous
samples. In order for a sample to diffract x-rays, several criteria must be met. First, the
sample must have a regular and repeating arrangement of atoms, and second the spacing
between those atoms must be approximately the same length as the radiation used to
probe the sample. When the x-rays used to probe the sample hit the surface, they are
either scattered or they pass through to the next atomic layer. When the x-rays are
scattered from planes at a regular spacing, they interact constructively. This constructive
scattering only occurs at specific angles for a given inter-planar distance. W.L. Bragg
developed a criterion for determining the inter-planar distances (d) based upon the
incident x-ray angle (θ). This criteria is known as the Bragg Condition:
nλ = 2d sin θ
where λ is the wavelength of the radiation, and n is an integer [1].

In an XRD experiment, the incident x-rays are scanned at various angles (typically
2θ = 10 to 80o), and the angles at which the Bragg Condition are met are recorded. A
comparison of those angles to known compounds will aid the identification of the
crystalline phases.

X-ray diffraction can be used to determine if a crystalline phase was formed and then
to identify that phase. A glass that turns white during heat treatment may not be
crystalline, since phase separated glasses can scatter light and appear “milky white”, but
not meet the Bragg Condition.

References
1. Douglas A. Skoog, F.James Holler, Timothy A. Nieman, Principles of Instrumental
Analysis, Fifth Edition, Harcourt Brace College Publishers, Philadelphia, 1998.
CER122/Glass Lab #3 (4) DTA/Crystallization
WS04 February 17, 2003

Experimental Procedure
DTA Analysis:

1) Approximately 1 gram of each glass should be crushed into a fine powder using the
steel glass crusher and sieved to 450-500 µm particles. Each glass powder should be
placed in a small vial that is labeled with the appropriate glass composition.

2) Give the samples to the GTA for analysis. You must sign up for a time to have your
samples run. Note: Your entire group must be present for the initial DTA run and
your entire group should analyze the final results.

3) Use the computer software to obtain Tg and Tx using the linear intercept method.
Repeat steps 1 through 3 for each of your three samples.

Crystallization:

1) Select one of your glass samples for which the DTA plot shows a distinct Tg and Tx.
Groups that do not have glasses that show distinct Tx in the DTA plot should select a
sample for which the DTA plots imply phase separation.
2) Place a chunk of the glass on a piece of refractory setter (from Kristy), and insert
both into one of the annealing furnaces. Be sure to position the glass sample close to
the thermocouple.
3) Heat your sample at an appropriate rate (20 K/min) to temperature (Tg+50°C) and
hold for 30 minutes. Examine your sample and record any changes in shape and
color. Return to furnace, increase temperature another 50ºC, hold for another 30
minutes and again examine your sample. Continue these heat treatments in 50ºC
increments until your sample begins to turn white or until the glass has flowed to
cover your setter. Hold the sample for at least two hours at the final heat-treatment
temperature. NOTE: Wear refractory gloves and safety glasses and use tongs
when removing your sample from the furnace.

4) After the final heat-treatment, shut off the furnace and allow it to cool. Once cooled,
remove the sample and make observations regarding the appearance of the sample.

5) Each group should make at least one crystallized or phase separated sample. If your
first sample did not form a translucent or white material, try again using another
sample.

6) Measure the density of your heat treated piece.

CER122/Glass Lab #3 (5) DTA/Crystallization
WS04 February 17, 2003

X-RAY Diffraction:

1) Crush and grind some of the “white” region from your heat-treated sample; this will
be analyzed by X-ray diffraction (XRD).

2) Make arrangements with one of the GTA's to schedule a time for your group to
collect and analyze an XRD pattern from your heat-treated sample. NOTE: Your
entire group must be present for this demonstration.

3) Sharp diffraction peaks will be present in the XRD spectrum if the “white” portion
of the your sample is crystalline. Broad peaks (>5 degrees at FWHM) will be
present if the “white” portion of the rod is phase separated. Again, notes should be
taken regarding the appearance of the XRD plot.

4) Record the crystalline phases (if any) formed in your heat-treated sample.

Report
The reports for the first four ‘glass melting’ segments will be brief (several pages)
reviews of the procedures and results from each segment. Each student will write an
individual report, but should collaborate on the collection and interpretation of the results.
Each report will include the following:

Introduction and Purpose Statement:

• Explain the purpose of the laboratory exercise and review pertinent background
information (if any) gleaned from textbooks or course notes.

Experimental Procedures
• Provide experimental details- how an experiment was run (experimental
parameters), how a property was measured (e.g., the temperature range used in
your CTE calculation), etc.
• Discuss uncertainties associated with your measurements; include statistical
information if possible.

Results and Discussion

• Present your experimental results in tables and/or graphs, including the
compositional dependence of Tg and Tx (if detected) and the sample density
before and after the heat treatment. Be sure to note the statistical significance of
your data.
• Can you explain trends in your results based on what you know of the effects of
glass composition on properties, including density changes (if any) after heat
treatment? Can you provide a citation to a textbook or course notes to support
your explanation?
• What crystalline phases were detected (if any)?
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WS04 February 17, 2003

• Did everything work out just right, or were there problems with an experiment
that might produce erroneous results?

Summary
• Summarize the most significant results of this lab segment- If you were writing
this for a boss on a job, what are the most important points you would want that
boss to understand from your work.
• Provide suggestions for improving your experiments or for other experiments that
might support the conclusions you have drawn or might provide interesting
results.

Appendices
• Add to your report copies of important results; for example, copies of your DTA
and XRD runs.
• Include answers to the following questions as an appendix to your report:
1. Describe a DTA experiment- What is measured and what can be revealed?
2. Your heat-treated sample turns white. Describe an experiment that will help you
determine if the sample crystallized or phase-separated.

This report is worth 75 points.

The individual report is due Tuesday, March 2nd in class.