Low-weight fractions of graphene (G)

and hydroxyapatite (HA)

enhance mechanics in photocured
methacrylate adhesives (UDMA-MMA)
Ehsanul Azim
Bangladesh University of Engineering and Technology
Aim
To develop adhesives that have:
• High hardness and mechanical properties in cured state
• Low viscosity in uncured state
Methodology
• Graphene (G) and Hydroxyapatite (HA) (Ca₁₀(PO₄)₆(OH)₂ crystal
unit cell formula) were added to UDMA-MMA (diurethane
dimethacrylate- methyl methacrylate ) to ehance mechanical
properties while still retaining low viscosity
• Different samples of 0.1-0.5% wt of either G or HA were added to the
UDMA-MMA control
• Properties of these modified samples were tested usind experimental
procedures
Experimental Procedures used
1. Nano-indentation (measure hardness and indentation modulus)
2. Vibrational Spectroscopy (FTIR and Raman Spectroscopy for
chemical bonds)
3. Rheology (testing for viscosity)
4. Thermography (show the change in temperature during curing with
UV)
Results
Nanoindentation
• All samples with additions of G and HA significantly enhanced
mechanical properties (Hardness, H and Indentation modulus) when
compared to unenhanced UDMA-MMA
• For HA addition, the hardness increased by an average of 42% and the
indentation modulus increased by an average of 32%
• For G addition, the hardness increased by an average of 31% and
indentation modulus increased by an average of 30%
• Rule-of-mixtures approach cannot explain this remarkable increase of
hardness due to such small additions of HA or G
• For HA, based on the Rule-of-mixtures approach a much lower
increase in hardness (≤12%) and indentation modulus (≤10%) would
be expected even for the highest weight fraction of HA used
• For G, the Rule-of-mixtures approach is inappropriate since it cannot
be applied to a 2D structure like Graphene
Vibrational Spectroscopy
• %DC (Degree of Conversion), is a measure of the conversion of monomeric carbon-carbon single
bonds to polymeric carbon-carbon double bonds during the curing process
• Both FTIR and Ramen Spectroscopy data indicate that the degree of conversion, %DC, decreases
with addition of G or HA

• FTIR result showing %DC decreases for additions of G and HA in different concetrations
• (c and d) are taken using peak area of N-H, whereas (e and f) are taken using peak area of C=O
Raman Spectroscopy result for %DC for different concentrations of G
and HA
For Raman Spectroscopy,
addition of G shows no
statistically significant change in
%DC, however, addition of HA
shows decreasing trend of %DC
with increasing concentration of
HA

• The results for both FTIR and Raman indicate that the %DC decreases
with then amount of additives of G and HA being added.
• This means, longer curing time, and higher curing temperature for
more concentration of G and HA additives in the UDMA-MMA
adhesive
• Results are also supported by the Thermography result
The changes of peak in FTIR and Raman spectroscopy due to G and HA
additives are indicative of the changes in bonding in the mixture
• Increased bonding between polymer and matrix due to additions of
these additives could be the reason for change in spectral peaks and
enhanced mechanical properties
• For G, the changes in peaks indicate the changes of hybridization at
defects where the carbon based G can bind to the polymer matrix
• For HA, the hydroxyl group in HA forms hydrogen bonds with N-H,
and C=O in UDMA-MMA
Thermography
• Thermography shows the change in temperature of droplets of the
samples during the curing process
After the 50sec mark, the sample with no additives
show a wrinkled orange surface, indicating the
formation of a solidifying cure skin layer resulting
from high degree of conversion
However, the samples with additives 0.1%wt G or
0.1%wt HA show no such wrinkles within the same
time and have more uniform colors, indicating no
solidified cure-skin within that time.
This means samples with more additives of G and HA
have longer curing time
Shows the change of temperature w/r time of curing
for additions of G and HA to UDMA-MMA
Shows that samples with 0.1%wt G or 0.1%wt HA
experience greater change in temperature than just
UDMA-MMA alone
This also explains the higher temperature observed by
IR camera during curing of the droplets in the last
figure
The reason can be attributed to photon scatter or
blocking phenomena of HA and G
More additives of HA and G mean that photons are
absorbed and remitted in shorter wavelengths to less
cured parts of the sample.
Hence the reason for uniform curing and no wrinkled
skin as seen from the figure of previous page
G has higher emissivity in the infrared region and can
high absorption of UV, hence the temperature change
with the G additive is much more
Rheology (Viscosity testing)
• Rheology results show that viscosity of uncured state increases with
the increasing concentrations of additives G or HA (T = 25 degC)
For the same %wt of additives, the viscosity is higher
for HA than for G
This change in viscosity is expected in case of
polymers (ref-13, 45, 46)
Although the test wanted to have low viscosity in
uncured state, however, this increase in viscosity is not
too costly and are appropriate for adhesive
applications
Change in viscosity w/r shear rate is shown
Here, we see that increase in shear rate leads to
decrease in viscosity,
non-Newtonian Fluid
Conclusion
• Aim was to of UDMA-MMA adhesive due to additions of G and HA while
still having low viscosity in uncured state
• Additions of G and HA have increased hardness and indentation modulus
beyond what would have been expected from composites as using the
Rule-of-mixtures approach
• Although the viscosity on uncured state increases somewhat due to
addition of G and HA, these increases are still reasonable for this
composite to be used as an adhesive
• Further investigation of Vibrational Spectroscopy and Thermography
results indicate that the enhanced mechanical properties are a result of
additional bonding between additives and matrix (changes in hybridization
at defects due to G, and increase of hydrogen bond due to hydroxyl group
of HA)
Future Plan
• HA (hydroxyapatite) is a biocompatible material that naturally occurs
within human bones
• HA is widely used in biomedical hard tissue applications, like 3D
printing of human bone supports
• Research on HA might lead to breakthroughs for:
• Biomineralization – the process of forming bone-like hard tissues in
living organisms through gradual mineralization
• artificial bone-implants, 3D printing of hard tissues etc.
Non-destructive Investigation of
Dispersion, Bonding, and
Thermal Properties of Emerging
Polymer Nano-composites using
Infrared Thermography
Ehsanul Azim
Bangladesh University of Engineering and Technology
Aims
• To do Thermography investigation of nano-composites in micro-scale
using Close-up IR Camera
• To detect the following properties of nano-composites:
• Thermal Diffusivity
• Dispersion of Nano-particles
• Detection of voids, cracks, contamination within the matrix of nano-
composite
Methodology
• Experimental techniques were used
• Fluke RSE600 thermal camera (with close-up lens, Macro Infrared
Lens RSE, 0.5x) was used to detect IR radiation
• ASTM E1461 method was used to measure Thermal Diffusivity
• ASTM D4496 method was used to measure Electrical conductivity
• Sample area of 5x5 mm^2 (resolution 20 micron) was analyzed
• Morphology was examined using Zeiss Field emission scanning
electron microscope (FESEM) of the cooled fractures surfaces
Experimental setup
• Xenon flash lamp was used to heat up the sample
• Thermal Imager, Fluke RSE600 was used to get image of
IR emission from the heated sample

• The 5x5mm^2 sample area analyzed contained 150,000

pixels (each of 20micron).
All these pixels were analyzed
• Thermal Diffusivity was found by the following relation:
• Thermal Diffusivity is inversely proportional to time of Half-rise
Hence, the ratio of Maximum to Minimum
Thermal Diffusivity is equal to the ratio of
Minimum Half-rise time to Maximum Half-
rise time of the pixels of a sample
Out of the 150,000 micro-samples in each
Image, the minimum Half-rise time and
maximum Half-rise time of pixels were
found
Samples
The Graphene nano-composites that were investigated are as follows
• GPET – (polyethene terephthalate with 35 % wt. Graphene nano-
flakes)
• GPSU – (polysulphone with 20, 30, 40% wt. of Graphene nano-flakes)
• Graphite-Silicone (Ecoflex 00-30) composites with 30% loading of
Graphite
Result
Dispersion of Nano-particles along direction
of injection molded GPET sample
• GPET parts were taken from different parts of injection molded
product, along the direction of runner

• Point C is the end point, furthest from the runner, and point A is the
point closes to the runner of injection mold
• Thermography using the Fluke RSE600 Thermal imager was able to
detect differences in dispersion in parts A and C,
• However, these differences could not be inferred from the results
from Raman Spectroscopy and FESEM electron microscope
• Thermography using the Fluke RSE600 Thermal imager was able to detect differences in dispersion in parts
A and C,
• GPET C showed 12% higher thermal diffusivity than GPET A
• GPET C also showed higher conductivity than GPET A
• However, these differences could not be inferred from the results from Raman Spectroscopy and FESEM
electron microscope
• Thermal Imaging results for Dispersion of nano-
flakes of Graphene and its relation to higher
thermal diffusivity (calculated from Half-rise
time) for parts B and C of the GPET injection
molding sample
• GPET C has better dispersion than GPET B
• Better dispersion of nano-flakes could be the
reason for better thermal and electrical
conductivity at part C (end point of injection
molding products)
• Thermal Imaging succeeded in detecting
dispersion o graphene nano-flakes, whereas
spectroscopy and electron microscopy failed
Variation of Thermal Diffusivity with the variation
of nano-filler loading in GPSU composites
• With the increase of
nano-filler loading
(from 20, 30 to
40%wt) in GPSU
composites, the
Thermal Diffusivity
increases linearly
Void, Crack, Dispersion of Graphite Flakes in
Ecoflex elastomer composite
• At steady state, (figure 6a) the graphite flakes appear as the bright
spots, the matrix is the purple region and voids and cracks appear as
dark spots acting as black-body, absorbing more heat from
surroundings
• During Heating (figure6b) with heatgun, the polymer matrix of Ecoflex
becomes hotter than the graphene fillers
Hence, more layers near the surface are visible
Hence, we can get idea of filler depression from this
• It is expected that graphite flakes should heat faster, however,
figure6b shows graphite flakes heat slowly
• To further investigate this property, loose graphite flakes are used as
sample for figure6e&d
• At steady state the graphite flakes are bright indicative of high
thermal conductivity, (figure 6d)
• But at heated state, (figure 6e), only the edges of the graphite flakes
are bright
• This indicates, that during heating, high thermal conductivity along
the plane of the graphite flakes transfers the heat to the polymer
matrix, so the edges so the edges behave as black bodies and radiate
energy
Conclusion
• Thermography using the Fluke RSE600 Thermal Imager and Close-Up lens
in the experimental setup was able to successfully determine Thermal
Diffusivity under conditions where Raman Spectroscopy and electron
microscopy failed
• The Technique was a success in showing the variation of Thermal
Diffusivity at different parts of injection molded GPET sample and linking
that variation to the different levels dispersion of Graphene flakes in the
different parts along the runner line
• Variation of Thermal Diffusivity in GPSU composites with different amounts
of Graphene nano-fillers (20, 30, 40 % wt) could be easily decipherd from
this flash thermography method
• Void, cracks, contamination, and dispersion of nano-flakes are also easily
observable through this thermography technique
Future Plan
• To boost the accuracy of gap, crack, and filler dispersion
determination in nano-composites, mathematical methods such as
topological derivatives or the modal method may be used to minimize
noise and clearly distinguish features of interest.
• Better close-up lens, and InSb detector could be used to reach
resolution of upto 4 microns