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CHAPTER 6

THERMAL CHARACTERIZATION OF COMPOSITE

FILAMENT MATERIAL (PLA-G-CF)

6.1 INTRODUCTION

Thermal characterization of composite filament material (PLA-G-CF)

involves studying its thermal properties such as thermal conductivity, specific heat
capacity, thermal expansion coefficient, and melting temperature. Thermal
conductivity is the ability of a material to conduct heat, in the case of PLA-G-CF, the
thermal conductivity is determined by the thermal conductivity of the PLA matrix
and the conductive properties of the carbon fibers. Higher thermal conductivity
indicates better heat dissipation, which is important in applications that involve high
temperatures. Specific heat capacity is the amount of heat energy required to raise the
temperature of a unit mass of a material by one degree Celsius. The specific heat
capacity of PLA-G-CF is a function of the specific heat capacity of PLA and the
carbon fibers. High specific heat capacity helps to absorb heat energy, which is
important in applications that involve thermal cycling. The thermal expansion
coefficient of PLA-G-CF is a function of the thermal expansion coefficients of PLA
and the carbon fibers. Low thermal expansion coefficient is desirable in applications
where dimensional stability is critical. The melting temperature of PLA-G-CF is a
function of the melting temperature of PLA and the carbon fibers. High melting
temperature is desirable in applications where high-temperature resistance is critical.

To determine the thermal properties of PLA-G-CF, various testing

methods can be used, such as Differential Scanning Calorimetry (DSC), Thermo
Gravimetric Analysis (TGA), Thermal Conductivity Testing, and Dilatometry. These
tests can provide valuable insights into the thermal behavior of PLA-G-CF and help
to optimize its use in various applications.
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6.2 DIFFERENTIAL SCANNING CALORIMETRY (DSC) STUDIES OF

THE COMPOSITE FILAMENTS
Differential scanning calorimetry is one of the thermal analysis
methods, used to determine the difference in thermal flow between the sample and
the reference material when the sample is exposed to a regulated temperature and
environment. DSC thermographs are used to determine the thermal characteristics of
pure PLA, PLA Flexible, PLA Hard, and PLA-G-CF. During the controlled heating
and cooling of the sample, this study can monitor solid-state transitions, phase shifts,
and calculate thermodynamic parameters. Glass transition temperature, melting
temperature, crystallisation temperature, and other properties of the samples were
determined using a DSC testing equipment after they are placed in an aluminium
bowl, sealed with a press, and then placed in a DSC testing system. Glass transition
temperature, crystallization temperature, melting temperature, polymer crystallinity
%, specific heat capacity, transformation enthalpy, and many other characteristics
may be measured via DSC analysis. The findings of the DSC experiments are shown
in Figure 6.1 for all the generated filaments. According to the data, the glass
transition temperature (Tg) of Pure-PLA granules and PLA-CF-G is about 170.5 °C
and 116 °C, respectively.

Figure 6.1 DSC Analysis of PLA-G-CF Composite Filaments with PLA Variants.
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Figure 6.1 shows the DSC analysis of pure PLA, PLA Flexible, PLA Hard,
and PLA-G-CF. The graph below summarizes the change in glass transition
temperature, cold crystallization temperature, and melting temperature. The DSC
thermograph of pure PLA typically exhibits a single endothermic peak, which
corresponds to its melting point. The melting point of PLA is around 120-150°C,
depending on the grade of the polymer. The DSC thermograph of PLA Flexible may
exhibit changes in the melting point or the appearance of additional peaks, depending
on the degree of modification. The addition of plasticizers can lower the glass
transition temperature and broaden the melting peak. The DSC thermograph of PLA
Hard may also exhibit changes in the melting point or the appearance of additional
peaks, the addition of fillers can increase the melting point and sharpen the melting
peak.

The DSC thermograph of PLA-G-CF can reveal information about the

interaction between the PLA matrix and the carbon fibers. The addition of carbon
fibers can affect the melting behavior of the PLA matrix, leading to changes in the
shape or position of the melting peak. The presence of carbon fibers can also increase
the thermal conductivity of the material, which can affect its thermal behavior. The
initial transition of PLA-CF-G occurs at 116 °C, which is the glass transition
temperature. The next transition occurs between 0 and 70 °C, and it represents PLA-
CF-G melting. Melting reaches its endothermic peak at 65.6 °C. Cold crystallization
of PLA in the range of 110 °C to 364.9 °C is the third transition. At 300 °C, cold
crystallization reaches its exothermic climax. This finding shows that adding
Graphene and Carbon fiber to the PLA mixture has no effect on the polymer's
mobility inside the polymer network. All tested samples had visible variations in the
cold crystallization temperature and enthalpy of crystallization. After adding a larger
fiber concentration, the values are moved to lower locations, which is common in
composite materials.

Melting is a transition from a solid to a liquid state, and it occurs at

temperatures higher than the glass transition temperature, which is the temperature at
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which a material transitions from a glassy or rigid state to a more flexible or rubbery
state. In the case of PLA-CF-G, melting occurs between 0 and 70 °C, which is above
the glass transition temperature of 116 °C. It is also noted that melting is an
endothermic process, meaning that it requires energy input to occur. The
endothermic peak at 65.6 °C in PLA-CF-G's melting curve suggests that this is the
temperature at which the most energy is required to melt the material, and that
beyond this temperature, the amount of energy required to melt the material
decreases.

The exothermic climax mentioned at 300 °C is likely due to a different

transition called the melting peak, which is a characteristic feature of many
crystalline materials. The cold crystallization transition of PLA-CF-G occurs in the
temperature range of 110 °C to 364.9 °C, which is higher than the glass transition
temperature but lower than the melting temperature. During cold crystallization, the
material undergoes a rearrangement of its molecular structure as it transits from an
amorphous or disordered state to a crystalline state, but this occurs without the input
of heat, so the process is referred to as "cold" crystallization. After the cold
crystallization transition, if PLA-CF-G is heated further, it eventually reaches its
melting temperature, which is the temperature range where the material undergoes a
transition from a solid to a liquid state. The melting peak of PLA-CF-G occurs at
65.6 °C, as mentioned earlier. Beyond the melting temperature range, the material
undergoes further changes in its structure and properties, such as degradation or
decomposition.

6.3 THERMOGRAVIMETRIC ANALYSIS (TGA)

Thermogravimetric Analysis (TGA) is a thermal analysis technique

used to determine the changes in the weight of a sample as it is subjected to a
controlled temperature program. The sample is typically heated in a furnace under a
controlled atmosphere, while its weight is continuously monitored. As the
temperature increases, the sample undergoes thermal degradation, which is
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characterized by weight loss. TGA can provide information about the thermal
stability, composition, and behavior of a wide range of materials, including
polymers, composites, and inorganic materials. TGA can also be used to determine
the moisture content of materials, as weight loss due to water evaporation, which is
often distinguishable from other forms of weight loss. TGA thermograph typically
shows a plot of weight percent versus temperature or time. TGA thermograph reveals
important information about the sample, such as the onset temperature and rate of
weight loss, the temperature at which maximum weight loss occurs, and the extent of
weight loss. From these measurements, TGA is used to determine the composition of
the sample, the degradation kinetics, and the thermal stability of the material.

Thermogravimetric Analysis (TGA) of pure PLA, PLA Flexible, PLA

Hard, and PLA-G-CF provides information about their thermal stability and
degradation behavior. The TGA thermograph of pure PLA and PLA Hard typically
exhibits a single stepwise weight loss, which corresponds to its thermal degradation.
PLA begins to degrade around 200°C and undergoes significant weight loss above
300°C. The TGA thermograph of PLA Flexible exhibits changes in the thermal
degradation behavior, depending on the degree of modification. The addition of
plasticizers can lower the temperature at which degradation begins and increase the
rate of weight loss. The TGA thermograph of PLA-G-CF can reveal information
about the interaction between the PLA matrix and the carbon fibers. The presence of
carbon fibers can increase the thermal conductivity and thermal stability of the
material, which can affect its thermal degradation behavior. The TGA thermograph
of PLA-G-CF exhibits changes in the weight loss rate or the temperature at which
degradation begins.

PLA is a commonly used biodegradable polymer that has good thermal

stability up to a certain temperature range. TGA analysis of pure PLA typically
shows a single stepwise weight loss, which corresponds to its thermal degradation.
PLA begins to degrade around 200°C and undergoes significant weight loss above
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300°C. PLA-G-F, on the other hand, is a composite material that contains both PLA
and glass fibers. The addition of glass fibers can increase the thermal conductivity
and thermal stability of the material, which can affect its TGA values. The TGA
thermograph of PLA-G-F may exhibit changes in the weight loss rate or the
temperature at which degradation begins compared to pure PLA.

Figure 6.2 TGA Analysis of Composite Material

6.4 PERCENTAGE OF CRYSTALLINITY

Thermogravymetric Analysis (TGA) Method: Temperature program from 30 ºC to

700 ºC at a heating rate of 20 ºC min-1 and nitrogen gas atmosphere (66 mL min-1).

Differential Scanning Calorimetry (DSC): Heating program for DSC runs was
from 30 ºC to 350 ºC at a heating rate of 10 ºC min-1.

The percentage crystallinity of PLA was calculated by means of the following

equation 6.1:
𝑿𝒄 (%) = (Δ𝑯𝒎−Δ𝑯𝒄 / 𝒘 Δ𝑯𝒎𝟎) x 100 ………(6.1)

𝑿𝒄 Percentage cristallinity value of PLA Blend

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ΔHm and ΔHc are the experimental melting enthalpy and cold crystallization
enthalpy w is the weight fraction.

From the study of Jen-Taut Yeh et al 2009, A value of ΔHm0 = 0.93(mW)(mg)-1 was
used according to a reported enthalpy of melting of 100% crystalline PLA.

Figure 6.3 DSC analysis of PLA-G-CF composite filaments to find ΔHm0

Neat Graphene had no cold crystallization peak and a value of ΔHm0 = 0.302
(mW)(mg)-1 was used according to a reported melt enthalpy of 100% crystalline
PLA-G-CF.
𝑿𝒄 (%) = (Δ𝑯𝒎−Δ𝑯𝒄 / 𝒘 Δ𝑯𝒎 𝟎) x 100
= (0.302-0 / 2 x 0.93) x 100
= 16.24 %
𝑿𝒄 Percentage crystallinity value of reinforcement to PLA = 16.24 %
The addition of graphene and carbon fibers to PLA (Polylactic Acid)
as reinforcement can have a significant effect on the percentage of crystallinity of the
resulting material. Graphene is a two-dimensional material that has excellent
mechanical, electrical, and thermal properties, which makes it an excellent candidate
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for reinforcing materials. Carbon fibers are also known for their exceptional
mechanical properties and are commonly used as a reinforcing material in composite
materials. When graphene and carbon fibers are added to PLA, they act as nucleating
agents, promoting crystallization and increasing the degree of crystallinity in the
resulting composite material. The degree of crystallinity refers to the percentage of
the material that is made up of crystalline regions, and it is an important factor that
affects the material's mechanical properties.

Studies have shown that the addition of 2% graphene and carbon fibers
to PLA can increase the percentage of crystallinity by up to 16%. The increase in
crystallinity results in improved mechanical properties such as stiffness, strength, and
toughness. However, it is important to note that the degree of crystallinity is not the
only factor that affects the mechanical properties of the material. The distribution,
orientation, and size of the graphene and carbon fibers also play a significant role in
determining the mechanical properties of the composite material.

6.5 SUMMARY

Due to its capacity to manufacture thermoplastic parts with advantages

in the design and optimization of models with complex geometries, significant
design freedom, recyclability, and reduced material waste, Fused Filament
Fabrication (FFF) is a potential Additive Manufacturing (AM) technique. Due of the
limited mechanical qualities of pure thermoplastics parts, this technology has been
widely employed to create conceptual prototypes rather than practical components.
By solution mixing and melting extrusion with a screw extruder, a new 3D printing
filament made of PLA-G-CF composite was effectively prepared. These novel
composites may be utilized as filament material in commercial FDM devices without
needing to be modified, according to the findings of the tests.
According to the test results.
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• Graphene and carbon fiber reinforced PLA composite filaments for FDM
type 3D printers were developed using a twin-screw extruder at temperatures
ranging from 190 to 220 degrees Celsius without matrix degradation.
• DSC thermographs were used to determine the thermal characteristics of pure
PLA and PLA-CF-G blends. Due to decreased Tg values, DSC testing
revealed that the developed filaments were compatible with commercial 3D
printers. However, Melt Flow Index (MFI) testing on the composite polymers
is required to determine the appropriate processing temperature.
• The solvent system improved the dispersion of graphene and carbon fibers in
the PLA matrix.
• The thermal characteristics of PLA-CF-G composite material was enhanced
by the dispersion of graphene and carbon fiber particles.
• Improved mechanical qualities confirmed that 3D printed PLA-CF-G could
be used in engineering applications. Carbon fiber and Graphene were used to
naturally improve the tensile strength and Young's modulus of PLA.
Furthermore, the elongation at break was decreasing and needs to be
improved.
• Studies have shown that the addition of 2% graphene and carbon fibers to
PLA can increase the percentage of crystallinity by up to 16%. The increase
in crystallinity results in improved mechanical properties such as stiffness,
strength, and toughness.

The research revealed one of the most active initiatives to produce

PLA-CF-G based composites directly using the FFF 3D printing technology. The
printed part quality, functions, and applications based on the printed PLA-CF-G
composite, on the other hand, required to be explored further.