Effects of Cooling Rate on Glass Transition

Temperature

April 24, 2024

Name Roll No.

Tilak Maheshwari 22110273
Abhishek Kumar 22110012
Shriyansh Kumar 22110247

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 Abstract
This report investigates the influence of cooling rate and system
size on the glass transition temperature (Tg) and coordination number
in a molecular dynamics simulation. We study the trends observed and
provide explanations for the observed phenomena.

1 Introduction

The glass transition temperature (Tg) is a critical point where a material

transforms from a viscous liquid to a rigid amorphous solid. Below Tg, the
material’s molecules are locked into fixed positions, and the material behaves
like a solid. Above Tg, the molecules are more mobile, and the material
behaves like a liquid.

2 Theoretical Background

The Kob-Anderson model, introduced by Wendelin Kob and William An-

derson, is a binary Lennard-Jones model that captures the glass transition
phenomenon. It involves two types of atoms with different sizes and at-
traction strengths. The model is also known as the Kob-Anderson binary
Lennard-Jones model.
The model is based on molecular dynamics simulations, where an initial
crystalline system is heated to a high temperature, equilibrated, quenched,
and then equilibrated again at a low temperature to form a metastable glass.
The glass transition temperature (Tg) can be determined by monitoring

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changes in volume or enthalpy as a function of temperature. The Kob-
Anderson model is a simplistic yet powerful framework for understanding
glass formation and has been used to study the effects of cooling rate and
system size on Tg.

3 Effect of Cooling Rate on Tg

In materials science, the glass transition temperature (Tg) serves as a crucial

indicator of a material’s transition from a rigid, glassy state to a more flexible,
viscous state. This transition is heavily influenced by the cooling rate applied
during the material’s processing.
Rapid cooling of a material results in a phenomenon known as kinetic
arrest. When molecules are cooled rapidly, they lack sufficient time to reach
equilibrium configurations. Consequently, their molecular motion becomes
restricted, effectively halting their ability to settle into lower-energy states.
This phenomenon, referred to as kinetic arrest, leads to the material be-
ing effectively ”frozen” in a higher-energy state. As a consequence, the
glass transition temperature increases with faster cooling rates, reflecting
the preservation of higher-energy molecular configurations.
Conversely, when a material is cooled slowly, molecules are afforded more
time to undergo structural relaxation. During this process, molecules can
rearrange themselves into lower-energy configurations, which promotes a de-
crease in the glass transition temperature. Slower cooling rates facilitate the

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attainment of equilibrium conditions, enabling the material to reach a more
stable state with reduced energy.
Moreover, the glass transition temperature is intimately linked to the
molecular mobility within the material. Below Tg, molecules exhibit rela-
tively limited mobility and behave akin to a solid. In contrast, above Tg,
the material undergoes a transition to a viscoelastic state, characterized by
increased molecular mobility. In this state, molecules can flow and rearrange
more easily, leading to the material exhibiting liquid-like behavior.

(a) 20L (b) 14L (c) 12L

(d) 10L (e) 8L (f) 6L

(g) 4L

Figure 1: Graph of volume vs temperature for varying run time

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4 Effect of System Size on Tg

(a) 4x4x4 (b) 6x6x6 (c) 8x8x8

(d) 10x10x10 (e) 12x12x12 (f) 14x14x14

Figure 2: graph of volume vs temperature for varying system size

The effect of system size on the glass transition temperature (Tg) appears
to be negligible. While variations in system size can introduce factors such
as confinement effects, surface effects, and finite size effects, these factors do
not seem to exert a significant influence on Tg. Computational simulations
and experimental observations suggest that changes in system size do not
lead to substantial alterations in Tg.
Consequently, it appears that Tg remains relatively stable across different
system sizes within the range studied. This finding suggests that factors
such as molecular mobility, molecular packing, and energy landscape, which

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are typically associated with changes in Tg, are not strongly influenced by
variations in system size.
Overall, the negligible effect of system size on Tg implies that other fac-
tors, such as cooling rate, molecular composition, and external conditions,
may play more prominent roles in determining the glass transition behav-
ior of materials.

5 Radial Distribution Function Analysis

The Radial Distribution Function (RDF) is a fundamental concept in mate-

rials science, particularly in the study of condensed matter systems such as
liquids, solids, and glasses. It serves as a powerful tool for understanding the
spatial arrangement of particles within a material and is closely linked to the
coordination number, which quantifies the number of neighboring particles
around a central particle.
In the context of glassy materials, the RDF and coordination number
play crucial roles in elucidating the structural properties and response to
temperature changes, particularly in relation to the glass transition temper-
ature (Tg). As a glassy material is heated towards Tg, there is typically a
reduction in structural order accompanied by an increase in molecular mo-
bility.
The RDF and coordination number provide valuable insights into the
structural rearrangements and dynamics occurring near Tg. For instance,

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near Tg, an augmentation in particle mobility may lead to a decrease in the
coordination number as particles become less densely packed. Additionally,
alterations in the RDF can signify the onset of structural relaxation, marking
the transition from a rigid, glassy state to a more fluid-like state.

(a) 4L (b) 6L (c) 8L

(d) 10L (e) 12L (f) 14L

(g) 20L

Figure 3: RDF plot for varying run time

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6 Results

Table 1: Effect of Cooling Rate on Glass Transition Temperature

Cooling Rate Glass Transition Temperature

At 20L runsteps 0.441955343
At 14L runsteps 0.447315617
At 12L runsteps 0.449640537
At 10L runsteps 0.45101524
At 8L runsteps 0.47609257
At 6L runsteps 0.491246571
At 4L runsteps 0.501017037

(a) Tg vs cooling rate

The area under the curve till the end of the first peak of the RDF is
0.65617.

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 Table 2: Effect of System Size on Glass Transition Temperature

System Size Glass Transition Temperature

4×4×4 0.47455753
6×6×6 0.480940553
8×8×8 0.487268232
10×10×10 0.471197459
12×12×12 0.47603732
14×14×14 0.472913861

7 Discussion and Observation

• Faster cooling rates result in a higher Tg due to kinetic arrest, where

molecular motion is restricted, and the freezing-in of molecular configu-
rations before reaching equilibrium. Computational simulations consis-
tently demonstrate that Tg rises with increasing cooling rate. On the
other hand, when a material is cooled slowly, the molecules have more
time to undergo structural relaxation. They can rearrange into lower-
energy configurations, which leads to a decrease in the glass transition
temperature.

• As we varied the system size, there was negligible differences in the

values of Tg. So, it means that Tg is independent of the variation
in system size. Computational simulations and experimental observa-
tions suggest that changes in system size do not lead to substantial
alterations in Tg.

• The curve was very much scattered for both cooling rate and system
size. So to smoothen our curve, we applied the Savitzky-Golay filter.

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 We varied the value of window size and poly order in order to get a
smooth curve. After trying so many iterations, we got the desired
curve.

• The average coordination number came out to be same with changing

cooling rates. In summary, the observation of a constant average coor-
dination number with changing cooling rates suggests that the system
reaches a stable structural arrangement relatively quickly during the
cooling process, and further changes in cooling rate do not significantly
alter this arrangement. This could be due to factors such as robust
packing arrangements, consistent equilibration times, and limited ki-
netic pathways for structural rearrangement.

8 Conclusion

1. The glass transition temperature (Tg ) is significantly influenced by the

cooling rate applied during material processing. Rapid cooling rates
induce kinetic arrest, restricting molecular motion and leading to an
increase in Tg . Conversely, slower cooling rates facilitate structural
relaxation, allowing molecules to rearrange into lower-energy configu-
rations, thereby decreasing Tg .

2. The effect of system size on Tg appears to be negligible. Despite vari-

ations in system size introducing factors such as confinement effects

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 and surface effects, changes in Tg were not significant. This suggests
that factors such as cooling rate and molecular composition may play
more prominent roles in determining the glass transition behavior of
materials compared to system size.

3. The Radial Distribution Function (RDF) and coordination number

analysis provide valuable insights into the structural properties of glassy
materials near Tg . Alterations in the RDF and coordination number
near Tg indicate the onset of structural relaxation and the transition
from a rigid, glassy state to a more fluid-like state. These findings
contribute to a deeper understanding of the glass transition process
and have implications for material processing and property tailoring in
materials science.

References

1. W. Kob and H. C. Andersen, ”Scaling behavior in the beta-relaxation

regime of a supercooled Lennard-Jones mixture,” Physical Review E.

2. R. Yamamoto and A. Onuki, ”Glass transition of a two-dimensional

Lennard-Jones system: Equilibrium and nonequilibrium molecular dy-
namics simulations,” Physical Review E.

3. G. Biroli and J. P. Bouchaud, ”Jamming and glass transitions: A mi-

croscopic view,” in Perspective and Problems in Statistical Physics and

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 Complex Systems, edited by G. Rapisarda and C. Tsallis, Springer.

4. D. Coslovich and G. Pastore, ”Effect of cooling rate on the glass tran-

sition temperature of model systems,” Journal of Chemical Physics.

5. Kob-Anderson, W., & Andersen, H. C. (1995). Scaling behavior in the

beta-relaxation regime of a supercooled Lennard-Jones mixture. Phys-
ical Review E, 51 (5), 4626-4641. Retrieved from Kob Anderson 1.pdf

6. Yamamoto, R., & Onuki, A. (1998). Glass transition of a two-dimensional

Lennard-Jones system: Equilibrium and nonequilibrium molecular dy-
namics simulations. Physical Review E, 58 (3), 3515-3525. Retrieved
from Kob Anderson 2.pdf

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