Received: 12 October 2020 Revised: 23 December 2020 Accepted: 23 December 2020

DOI: 10.1002/app.50442

ARTICLE

Low-weight fractions of graphene and hydroxyapatite

enhance mechanics in photocured methacrylate adhesives

Zinah N. Alabdali1,2 | Emanuel Irizarry3 | Mary P. Reiter4 | Ali Ashraf5 |

Jennifer K. Lynch-Branzoi5 | Adrian B. Mann1,4

1
Department of Materials Science and
Engineering, Rutgers The State University
Abstract
of New Jersey, Piscataway, New Jersey, USA In many applications, it is desirable for photocured adhesives to have high-
2
Materials Engineering Department, mechanical strength in the cured state, but relatively low viscosity when liq-
University of Technology, Baghdad, Iraq
uid. This was achieved by adding less than 0.5 wt% hydroxyapatite and
3
Department of Chemistry, University of
graphene to methyl methacrylate with diurethane dimethacrylate (UDMA-
Puerto Rico, Mayaguez, Puerto Rico, USA
4
Department of Biomedical Engineering, MMA). Nanoindentation shows hardness increasing by 30–40% and indenta-
Rutgers The State University of New tion modulus by >30% compared to UDMA-MMA on its own. Rheometry
Jersey, Piscataway, New Jersey, USA shows only a small increase in uncured viscosity for the liquid state. The addi-
5
Department of Mechanical and
tives affect the optical properties, mobility of free radicals, photocuring, and
Aerospace Engineering, Rutgers The State
University of New Jersey, Piscataway, degree of conversion, the effects of which are seen in Fourier transform infra-
New Jersey, USA red and micro-Raman spectra. Thermographic images taken during curing
show that the additives impact the photocuring process. In addition, changes
Correspondence
Adrian B. Mann, Rutgers The State in intermolecular bonding are seen in the vibrational spectra when the
University of New Jersey, Materials additives are present. The enhanced mechanical properties are attributed to
Science and Engineering, 607 Taylor
Road, Piscataway, NJ 08904, USA.
the observed changes in photocuring and bonding.
Email: abmann@rutgers.edu
KEYWORDS
Funding information adhesives, composites, fullerenes, graphene, mechanical properties, nanotubes, spectroscopy
Iraqi government-Ministry of Higher
Education and Scientific Research
(MOHESR); NSF REU, Grant/Award
Number: 1659099

1 | INTRODUCTION popular way to improve the properties and functionality

Photocured adhesive systems have a wide range of uses
in engineering and health applications. Methyl methacry-
late (MMA) and diurethane dimethacrylate (UDMA) are
used commonly as matrix monomers in many photo-
cured adhesive systems. UDMA is a high-molecular
weight monomer with high-flexural strength, elastic
modulus, and hardness,1,2 while MMA is a low-molecular
weight monomer with low toxicity and high-cure speed.
MMA is a good solvent to blend with high-molecular
weight monomers such as UDMA.3
Reinforcement of adhesives with different types of
additives creating a composite structure has become a
of the adhesives.4,5 The additives have a direct influence
on the mechanical properties and viscosity of the
adhesive,6–9 with the effect being dependent on the size,
morphology, and weight fraction of the additive.10 Inor-
ganic additives incorporated in adhesives to improve
mechanical properties include silicon dioxide (SiO2), tita-
nium dioxide (TiO2), aluminum oxide (Al2O3), cerium
oxide (CeO2), and niobium pentoxide (Nb2O5).11–14 Here
we focus on two different additives, graphene (G) and
hydroxyapatite (HA), which are of interest because of
their functionality. The G has a hexagonal, planar struc-
ture with unique optical, mechanical (Young's modulus),
thermal, and electrical properties making it of potential

1 of 11 © 2021 Wiley Periodicals LLC. wileyonlinelibrary.com/journal/app J Appl Polym Sci. 2021;138:e50442.

https://doi.org/10.1002/app.50442
ALABDALI ET AL.
utility in many applications15 and as an additive in com-
posite materials.16–18 HA, is a calcium phosphate found
in mineralized biological tissues that has biomedical
applications19 because of its biocompatibility, high poros-
ity, high-surface area, and ability to form chemical bonds
with surrounding material. The properties of both G and
HA make them good candidate materials as additives to
improve the performance of photocured adhesive sys-
tems, with HA in particular receiving a lot of attention
for its possible dental applications.20–22
The current work examines new photocured adhesive
systems based on UDMA-MMA blends with small frac-
tions of G and HA. These are added to enhance mechani-
cal properties while still retaining low-liquid viscosity.
Mechanical testing was performed using nanoindentation
to measure hardness and indentation modulus. The effect
of the additives on the viscosity of the liquid phase was
measured by rheometry. Vibrational spectroscopy, Fou-
rier transform infrared (FTIR) and micro-Raman, were
used to examine changes in chemistry during the curing
process, including calculation of degree of conversion for
double bonds into single bonds. The additives were
expected to change the absorption and scattering of pho-
tons, and hence, the photocuring process. This is partially
seen in the vibrational spectra, but thermographic imag-
ing was also used to examine how the additives affect the
temperature and uniformity during photocuring.
2 | EXPERIMENTAL
2.1 | Materials
UDMA (≥97% pure, 470.56 g/mol Mw), a base monomer,
was used along with a diluent monomer of MMA
(≥98.5% pure, 100.12 g/mol Mw). Camphorquinone, CQ
(≥96.5% pure, 166.22 g/mol Mw), was added as a
photoinitiator and ethanol (≥99.5% pure, 46.07 g/mol
Mw) as a solvent. CQ is often used with an amine
coinitiator, but that was avoided in this study so the effect
of the additives could be identified with minimal impact
from changes caused by the coinitiator. All chemicals, as
well as the HA, were purchased from Sigma Aldrich,
(St. Louis, MO) and used without further purification.
The HA had an average particle size ≤200 nm (≥97%
pure, 502.31 g/mol Mw) and G had an average dimension
≤150 μm. Graphite was purchased from Asbury Carbons
(Asbury, NJ) and converted to G by thermal expansion
using a microwave treatment (1100w, 1 min), followed by
ultrasonication for 1 h, and then drying at 80
C over-
night. The dry material was ball milled for 96 h with a
zirconia medium, then washed with a 1:1 ratio solution
of deionized water: methanol before drying overnight at
2 of 11
80
C, and finally sieving with different meshes down to
320 mesh (63 micron).
2.2 | Adhesive preparation
The adhesive systems were prepared by mixing 40 wt%
MMA with 1 wt% CQ and 9 wt% ethanol. The remaining
weight was 0.0–0.5 wt% additive (G or HA), with the bal-
ance being UDMA, as given by Table 1. The weights of
each component were measured using a Mettler Toledo
weight scale with an accuracy of ±0.002 g and an experi-
mental accuracy of ±0.001 g. The HA enhanced, photo-
cured adhesive systems were prepared by mixing MMA,
CQ, ethanol, and HA using a magnetic stirrer (Corning)
at a speed of 1000 rpm for 1 h. UDMA was then added to
the mixture before using a shaking table overnight to
homogenize the mix. The G enhanced, photocured adhe-
sive was prepared by mixing MMA, CQ, ethanol, and G
in a container surrounded by a water bath (to maintain
temperature during mixing), inserting a rotating mixing
rod into the container, and shearing (stirring) for 1 min.
This shearing technique is commonly used for dispersion
and exfoliation, which decreases particle size, while
also giving good particle distribution and avoiding
agglomeration.23–25 UDMA was then added to the mix-
ture and further stirred using a magnetic stirrer for 1 h at
1000 rpm. All the different compositions of the photo-
cured adhesive systems were mixed in a dark room at
room temperature in amber glass.
Each of the compositions in liquid form was placed in
a silicone mold of 5 mm diameter and 2 mm depth. They
were then photocured for 10 min using a blue light
source with an optimal wavelength (420–480 nm) for
absorption by the CQ photoinitiater.26 The tip of the light
source was positioned 1 cm from the sample surface, thus
ensuring good light coverage of the silicone mold. To
allow for post-exposure curing the specimens were stored
for 2 weeks at room temperature in a dark room. Three
TABLE 1 Composition in weight percentage of blends tested
Additives
(G or HA) UDMA MMA CQ Ethanol
0 50 40 1 9
0.1 49.9 40 1 9
0.2 49.8 40 1 9
0.3 49.7 40 1 9
0.4 49.6 40 1 9
0.5 49.5 40 1 9
Abbreviations: CQ, Camphorquinone; G, graphene; HA, hydroxyapatite;
MMA, methyl methacrylate; UDMA, diurethane dimethacrylate.
3 of 11
samples of each composition were prepared for each
characterization test. Thermographic imaging was used
to assess overall uniformity of the polymerization process
during curing for the two additives.
2.3 | Characterization
2.3.1 | Nanoindentation
A Hysitron TriboIndenter with a three-sided pyramidal
shape Berkovich diamond tip (≈20 nm tip radius) was
used to measure hardness, H (GPa), and indentation Mod-
ulus, sometimes called reduced elastic modulus, Er (GPa).
The values were obtained using the standard unloading
curve analysis.25,27 The tip-area function was calibrated
using a fused quartz standard material, while tip-optic cal-
ibration was performed using a soft aluminum sample.
Three specimens per composition were tested using load-
control nanoindentation to peak loads of 20000 μN in a
6 x 6-grid pattern (10 μm spacing). The nanoindent cycle
was 20 s load, 5 s hold at peak, and 20 s unload. The statis-
tical average and standard deviation for H and Er were
calculated for each concentration of additive.
2.3.2 | Vibrational spectroscopy
The different compositions were characterized using a
Perkin Elmer FTIR over the wavenumber range
400–1800 cm−1, with a resolution of 1 cm−1, and accumu-
lations over 32 scans. The spectra were obtained for drops
of the uncured liquid state and for the cured circular
specimens previously mentioned. Three samples (n = 3)
for each composition were tested. The degree of conver-
sion (DC %) for the carbon–carbon double bonds (C C)
to carbon–carbon single bonds (C C) was measured by
comparing the area under the FTIR peak of aliphatic
C C (AC C) at ≈ 1637 cm−1 to that under two internal
standard peaks for N H (AN H) at ≈ 1528–1531 cm−1
and C O (AC O) at ≈ 1710 cm−1. The area of the peaks
for the relevant bonds were determined using OriginPro
2018b and entered in Equation (1)28,29 to find the DC %.
!
ðAC = C =AN − H Þsolid
DC% = 1 − × 100: ð1Þ
ðAC = C =AN − H Þliquid
Note that the FTIR spectra are also impacted by
hydrogen bonding between the N H group and the car-
bonyl (C O) group. The vinyl group (C C), its neighbor-
ing groups and their arrangement (cis or trans) can also
affect the vibrational spectra.
ALABDALI ET AL.
The different compositions in both the liquid and solid
phases were examined using a Renishaw inVia™ Raman
confocal microscope (West Dundee, IL 60118) equipped
with a laser of wavelength 785 nm and a 5x magnification
lens. The Raman spectra were obtained over a
wavenumber range of 250–1800 cm−1 with the laser set at
50% power (300 mW). A silicon sample was used as a stan-
dard for calibration of the wavenumber prior to sample
testing. For each composition three samples (n = 3) in the
form of uncured liquid drops placed on a silicon substrate
and for cured samples three samples (n = 3) as solid circu-
lar specimens, previously described, were tested. The
degree of conversion of the double bonds in going from
liquid to solid phase was calculated using the areas under
peaks via the same method as detailed for the FTIR
testing. However, the N H peak is not active in Raman
so only the C C (≈ 1630 cm−1) peak and C O
(≈ 1715 cm−1) internal standard peak were used.
2.3.3 | Viscosity
The viscosity of the liquid phase was measured with a
Malvern Kinexus Rotational Rheometer (Grovewood Road,
Malvern, Worcestershire, WR14, UK) using a 20 mm diam-
eter parallel plate setup with a gap of 0.5 mm, at a tempera-
ture of 25
C, and three shear rates (dγ/dt) of 2.155, 4.624,
and 10 s−1. Three samples were tested for each composition
and the average results, SD, and SE calculated.
2.3.4 | Thermographic imagery
Thermography was performed using a Fluke RSE600 ther-
mal camera equipped with a close-up lens (Macro Infrared
Lens RSE, 0.5x) to enable a sample area of 100 mm2 to be
observed. For all the microscale thermography experi-
ments video of thermal events were recorded, and image
frames were later separated out for different time intervals
to allow for data analysis. The method measures tempera-
ture values over 640 x 480 pixels covering a 100 mm2 area
for each frame. Each pixel represents one microscale point
(≈20 μm size). As the sample droplets under observation
were around 4 mm in diameter there are about 38,000
pixels or micro-sized points examined for each sample
over the entire duration of the test. During the tests each
sample was exposed to light at the UV end of the spectrum
for 20 s followed by a 20 s break in exposure. This was
repeated for a total duration of 200 s. The purpose of the
20 s breaks in exposure time was to observe the real state
of the sample while curing without simultaneous exposure
to the light. This is important as the thermal image is
affected by the additional radiation and heating caused by
ALABDALI ET AL.
the lamp. Fluke Smartview, MATLAB, Excel, and Origin
software packages were utilized to perform data analysis.
2.3.5 | Statistical analysis
All the results are expressed in terms of mean ± SE. The
results were analyzed with one-way ANOVA and then by
Tukey HSD post hoc test at a significance level of p < 0.05,
where “p” is the probability value. The errors in values and
the error bars on graphs are the standard error in
the mean.
3 | R ES U L T S A N D D I S C U S S I O N
3.1 | Nanoindentation
The data of Figure 1 shows the nanoindentation curves
and mechanical properties for the different compositions.
Notably, even small amounts of G or HA caused substan-
tial increases in hardness when compared to the
unenhanced UDMA-MMA blend (Figure 1(c),(d)). Addi-
tives such as HA are known to increase the mechanical
properties of polymers30 so this result was expected in the
F I G U R E 1 Nanoindentation results for UDMA-MMA blends with G and HA additives: (a and b) example load–displacement curves for
each composition. (c and d) Hardness, H; (e and f) indentation modulus, Er. The statistical significances are: * indicating p < 0.05; **
indicating p < 0.01. G, graphene; HA, hydroxyapatite; MMA, methyl methacrylate; UDMA, diurethane dimethacrylate [Color figure can be
viewed at wileyonlinelibrary.com]
4 of 11
UDMA-MMA blends, which on their own had a hardness
of 0.154 ± 0.001 GPa. However, the increase in hardness
with HA-added to the UDMA-MMA was surprisingly high
ranging from 0.209 ± 0.001 to 0.226 ± 0.001 GPa. When G
was added it gave a similarly remarkable increase in hard-
ness ranging from 0.181 ± 0.001 to 0.223 ± 0.001 GPa.
Analysis of the data showed these increases in hardness
with additives were statistically significant.
The indentation modulus as with hardness showed
substantial increases with the addition of HA and G, as
shown in Figure 1(e),(f). The UDMA-MMA blend had
an indentation modulus of 2.873 ± 0.011GPa which
increased with the addition of HA to the range of
3.644 ± 0.003GPa to 3.960 ± 0.002 GPa. With G added it
was in the range of 3.585 ± 0.008 GPa to
3.942 ± 0.003 GPa. In all cases the HA- and G-enhanced
UDMA-MMA showed a statistically significant increase
in indentation modulus.
3.2 | Vibrational spectroscopy
FTIR spectra for the G and HA-enhanced composites are
shown in Figure 2. Detailed spectra of specific peaks are
shown in Figure 3. Analysis of relative areas under the
5 of 11 ALABDALI ET AL.

F I G U R E 2 (a and b) FTIR spectra normalized to the C O peak for uncured and cured samples of 0.5 wt% G in UDMA-MMA and
0.5 wt% HA in UDMA-MMA; (c and d) the degree of conversion versus wt% G and HA using internal standard peak area AN H; (e and f) the
degree of conversion versus wt% G and HA using internal standard peak area AC O. statistical significance of differences is given by *
indicating p < 0.05 and ** indicating p < 0.01. FTIR, Fourier transform infrared; G, graphene; HA, hydroxyapatite; MMA, methyl
methacrylate; UDMA, diurethane dimethacrylate [Color figure can be viewed at wileyonlinelibrary.com]

F I G U R E 3 FTIR spectra
showing: (a and b) low
wavenumber range for the
composites with G and HA
added, respectively. The peaks
associated with the polymer are
seen in both and in (b) peaks at
567 and 603 cm−1 are due to the
ν4 bending mode of PO4 in HA;
(c and d) higher wavenumber
ranges showing peaks in
(c) associated with G and
graphene oxide (GO) and in
(d) a shoulder at 962 cm−1 due
to the ν1 stretching mode and a
peak at 1090 due to the ν3
stretching mode of PO4 in
HA. FTIR, Fourier transform
infrared; G, graphene; HA,
hydroxyapatite [Color figure can
be viewed at
wileyonlinelibrary.com]
ALABDALI ET AL. 6 of 11

N H, C C, and C O peaks, as previously described,

was used to give a measure of degree of conversion per-
centage, DC %, for double bonds. The DC % decreased
with the addition of both G and HA. The composites con-
taining G had lower DC % (7.2 ± 5.8% to 20.6 ± 2.0%)
compared to the composites containing HA (DC %
15.8 ± 6.8% to 43.9 ± 3.8%), as shown in Figure 2(c)–(f).
In general, the measured value of DC % decreases with
increasing additive concentration in UDMA-MMA. The
vibrational spectra and the DC % are changed by the
additives due to several different effects. These include
increased scattering of photons, decreased mobility of
free radicals, and the reduced concentration of carbon–
carbon double bonds available in the monomers.31
When G is included in the composite the FTIR spectra
shows some effects due to the many vibrational modes seen
in carbon-based materials. In particular there is evidence of
different hybridized carbon states as well as oxygen in the
spectra over the range 1000–1200 cm−1 (see Figure 3(c)).
The double peaks at 1440/1450 cm−1 are present in the
polymer spectra,32 but these do change shape and shift with
the addition of G which is expected for G and related mate-
rials like graphene oxide.33 The polymers have a peak at
around 1635 cm−132 which does not change when the G is
added; this would have been expected if there was a signifi-
cant amount of graphite present.33 Peaks are expected at
1130 and 1344 cm−1 for diamond,33 but these are not pre-
sent. FTIR is helpful when looking at the polymers and G,
though it is generally accepted that micro-Raman spectros-
copy is better for identifying carbon and its polytypes as
detailed in the following micro-Raman results section.
The FTIR spectra of HA has several peaks associated
with stretching and bending vibrational modes of the
phosphate group, PO4. These are seen in the detailed
spectra of Figure 3(b),(d), which show the ν1 and ν3
stretch modes and the ν4 bending mode.34,35 However,
the main peaks associated with the polymer are mostly F I G U R E 4 (a and b) Micro-Raman spectra normalized for
unchanged with the exception of very small shifts in the uncured and cured samples of 0.5 wt% G in UDMA-MMA and
N H peak ≈ 1528 cm−1 and the C O double over- 0.5 wt% HA in UDMA-MMA; (c and d) the degree of conversion
lapping peaks ≈ 1701 and ≈ 1710 cm−1. These are both versus wt% G and HA using internal standard peak area AC O.
statistically significant differences are given by * indicating p < 0.05
affected by hydrogen bonding36–38 and are slightly modi-
and ** indicating p < 0.01. FTIR, Fourier transform infrared; G,
fied by the hydroxyl group of the HA.
graphene; HA, hydroxyapatite; MMA, methyl methacrylate;
Micro-Raman spectra for the composites are shown in UDMA, diurethane dimethacrylate [Color figure can be viewed at
Figure 4(a),(b) and DC % based on the C C and C O wileyonlinelibrary.com]
Raman peaks are given in Figure 4(c),(d). Intriguingly, when
G is added to the UDMA-MMA the value obtained for DC %
shows no statistically significant difference between any of associated with the phosphate group in HA and carbon
the concentrations, which contrasts with the FTIR spectra. polytypes are commonly characterized and identified
As expected HA reduced the DC % compared to the UDMA- using micro-Raman.39 Details of specific regions in the
MMA blend, and only the lowest concentration of 0.1 wt% spectra of the composites with G and HA are shown in
HA did not have a significant impact on DC %. Figure 5. When G is added, there are several regions of
The micro-Raman spectra for the composites are par- interest in the Raman spectra (see Figure 5(a),(e)), most
ticularly significant since there are strong Raman peaks notably the characteristic G-peak at ≈1570 cm−1 which is
7 of 11 ALABDALI ET AL.

F I G U R E 5 (a and b) Detailed low-wavenumber micro-Raman spectra for UDMA-MMA with G and HA showing in (b) the shoulder
around 280 cm−1 due to, the shoulder at 430 due to ν2 symmetric bending and the peak at 525 due to ν4 antisymmertic bending; (c and d)
show changes in the double peaks at 960 and 980 due to ν1 symmetric stretch in PO4 and the a shoulder at 1090 cm−1 due to ν3
antisymmetric stretch in HA; (e and f) detailed high-wavenumber range showing a number of carbon related peaks in (e) and in (f) the
dependence of double-bond conversion (C C intensity) on HA content. The spectra of (e) shows evidence of multiple carbon peaks
including D4 (≈1280 cm−1), D1 (1390 cm−1), G (≈1565 cm−1), and D2 (≈1630 cm−1). G, graphene; HA, hydroxyapatite; MMA, methyl
methacrylate; UDMA, diurethane dimethacrylate [Color figure can be viewed at wileyonlinelibrary.com]

expected when G is present.40 Two other parts of
the spectra show features associated with defective G
and the edges of graphite sheets. These give rise to a
D0 -peak at 1630 cm−1 and a D-peak in the range
≈1270–1400 cm−1.39,41 With HA, the micro-Raman spec-
tra of Figure 5(b),(d),(f) show the presence of all the
expected PO4 vibrational modes: ν1, ν2, ν3, and ν4.34,35,42
Comparing the spectra for the G and HA additives shows
significant differences in three regions: the low
wavenumber shoulder around 275 cm−1 in Figure 5(a),
(b); the double peaks at 960 and 980 cm−1 in Figure 5(c),
(d); the carbon peaks (D, D0 , and G) in Figure 5(e),(f). All
of these are attributable to the different vibrational
modes of the phosphate group and carbon polytypes of,
respectively, HA and G .
enhanced with either G or HA, indicating thixotropic or
non-Newtonian behavior.43,44 Viscosity increases with
increasing G or HA concentration, which is expected in
additive containing polymers.13,45,46 The viscosity at a
shear rate of 10 s−1 for the composites containing G ranges
from 0.024 ± 0.001 to 0.043 ± 0.001 Pas, while the viscos-
ity for composites containing HA ranges from
0.024 ± 0.001 to 0.074 ± 0.001 Pas. Interestingly, for the
same wt% of additive the viscosity is higher for HA than
for G. Statistical analysis confirmed the significance of the
viscosity increases when G or HA are added compared to
UDMA-MMA without any additives.
3.4 | Thermography results

Figure 7 shows thermography results for UDMA in MMA

3.3 | Rheometer
Rheology results for the composites with G and HA addi-
tives are shown in Figure 6(a),(b). Viscosity decreases with
increasing shear rate for all UDMA-MMA composites
without and with the two additives. The additives give
different curing characteristics. At the 50 second mark, as
shown in Figure 7(a), the sample without additives forms
a solid skin layer with wrinkles (orange color), which is
different from the underlying bulk layer (purple color).
ALABDALI ET AL.
F I G U R E 6 Rheometer results for UDMA-MMA blends with
different concentrations of G and HA at T = 25
C: (a and b)
viscosity of UDMA-MMA blends as a function of shear rate; (c and
d) viscosity versus wt% of G and HA at shear rate of 10 s−1. The
viscosity-shear rate graphs are presented on a log–log base 10 scale
for clarity. Statistically significant differences are shown with **
indicating p < 0.01. G, graphene; HA, hydroxyapatite; MMA,
methyl methacrylate; UDMA, diurethane dimethacrylate [Color
figure can be viewed at wileyonlinelibrary.com]
On the other hand, samples with additives show a more
uniform color indicating the lack of a cured skin layer.47
The same phenomenon was observed after 110 seconds.
In addition, the droplet shapes are indicative of change
in the viscosity of the samples. The more spherical shape
for the sample with the HA additive indicates higher
8 of 11
F I G U R E 7 Thermography results for 50 wt% UDMA-MMA
without additives, with 0.1 wt% of graphene and 0.1 wt% of
hydroxyapatite: (a) thermal images showing droplet curing
conditions with respect to time. Scale bar in the image represents
1 mm. Temperature scales on the right are in Celsius; (b) change in
temperature of sample droplets versus time during curing
experiment. 20 s of light curing is followed by 20 s of break in light
exposure. G, graphene; HA, hydroxyapatite; MMA, methyl
methacrylate; UDMA, diurethane dimethacrylate [Color figure can
be viewed at wileyonlinelibrary.com]
viscosity when compared to the sample with the G addi-
tive where the droplet is more spread out (Figure 7(a)).
This is consistent with the rheology data of Figure 6.
Figure 7(b) shows the change in temperature of the sam-
ples during the same thermography tests. Radiation and
the heat supplied by the lamp initiate and speed up the
exothermic curing reaction, and hence, increase the tem-
perature of the sample. Without the additives the samples
show a change in temperature (ΔT) that remains around
≈1
C during the entire experiment except for the initial
peak. This indicates that there is only mild heating while
the curing reaction takes place, rather than a substantial
increase in temperature. In contrast, the samples with
the additives show ΔT of ≈3
C or higher indicating a
9 of 11
significant change in the curing due to photon scattering
or blocking phenomena.48,49 The photon energy in these
cases is absorbed and re-emitted at longer wavelengths
and goes toward increasing the temperature of the less
cured parts of the sample. The sample with the G additive
showed higher ΔT over time when compared to the sam-
ple with HA. Due to its high emissivity, G can emit more
electromagnetic radiation in the far-infrared region over
the curing time, this is then detected by the infrared cam-
era during the experiment, which results in ΔT of ≈7
C
at ≈180 s (Figure 7(b)).48
3.5 | Discussion
The results show that using G and HA additives in the
polymers resulted in surprisingly large increases in the
mechanical properties of the composite.50,51 When
adding HA, the hardness increases by an average of 41%
and the indentation modulus increased by an average of
32%. For comparison a rule-of-mixtures approach can be
used to estimate the expected mechanical properties of
the composite when it contains HA. Based on a polymer
density of 1.16 g/cm3, HA density of 3.16 g/cm3, HA
hardness of 10 GPa and HA indentation modulus of
150 GPa 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 applying a
rule-of-mixtures estimate is problematic because the
hardness and indentation modulus are meaningless for a
2-dimensional material. None-the-less the composites
when compared to the UDMA-MMA blend on its own
exhibit a remarkable increase in hardness, averaging
31%, and indentation modulus, averaging 30%. Similar
large increases in mechanical properties have been previ-
ously reported for nanocomposites containing small
amounts of G.52 Overall, the results are striking because
even low-weight fractions of HA and G give significantly
higher mechanical properties while still having the low-
liquid viscosity needed for adhesive applications.
Many factors affect the mechanical properties of com-
posites when measured with nanoindentation including
the size and shape of additives,53 and their distribution
within the matrix.54 For large particles (>indenter tip
radius) the measured properties will depend on whether
the contact is on a single additive particle, or on the sur-
rounding matrix, or the interface of the two. Surface
roughness can also give scattered and inconsistent
values.55 While each of these may contribute to the mea-
sured hardness and indentation modulus, it does not
explain the increases seen in this study.
The origin of the increased mechanical strength is most
likely due to a modified polymerization process and
changes in intermolecular bonding. This is suggested by the
ALABDALI ET AL.
modified degree of conversion seen in the composites. The
DC % is impacted by light intensity, wavelength, and light
tip area, as well as additive properties like concentration,56
size, shape, and composition.57 FTIR and micro-Raman
gave different values for DC % (Figures 2 and 4), which
may be due to the micro-Raman laser heating the samples,
however, both methods showed conversion was less when
G or HA were added compared to UDMA-MMA alone.
Similar results have been obtained previously for additives
to the Bis-GMA/TEGDMA matrix.58 The additives impact
the absorption and scattering of light during the cure pro-
cess. Differences in the refractive index of the additives and
monomers can also impact degree of conversion since light
transmission during the photopolymerization process is
dependent upon refractive index of the medium, especially
at the interface between the additives and matrix.59 It is also
important to note that the additives (especially graphene
oxide, and to a lesser extent G, graphite, and HA) have
strong absorption peaks and their own vibrational spec-
tra60,61 in the wavenumber ranges examined (see Figures 3
and 5), this can modify the observed peaks and impact the
ability to accurately calculate degree of conversion. Other
researchers have seen decreased mobility of free radicals
during photocuring with additives present which affects
polymerization62 and, hence, potentially degree of conver-
sion. This result is supported by the thermographic results
shown in Figure 7, where the sample without additives
shows a wrinkled, solid skin layer that results from the high
degree of curing (total light exposure time ≈80 s). The addi-
tives, especially G, have blocking properties at the UV end
of the spectrum and high emissivity. This results in a lower
degree of conversion and longer curing time, but higher
curing temperatures, with all being dependent on the total
filler content.48,49
Additional information is provided by the vibrational
spectra that suggest changes in bonding (see Figures 3
and 5) occur when the additives are present. For G, the
presence of D, D0 , and G peaks are indicative of changes
in hybridization at defects where the carbon additive can
bind to the polymer matrix. For HA, the hydroxyl group
affects the N H and C O groups in the UDMA-MMA.
This is seen in the FTIR spectra and our prior work has
shown the importance of hydrogen bonds in these poly-
mers.38 The increased bonding between the polymer
matrix and the additives is likely to be the origin of the
increase in mechanical properties for the composites
beyond the rule-of-mixtures values.
4 | CONCLUSIONS
The effect of G and HA in UDMA-MMA on the mechani-
cal properties of the photopolymerized blends was found
to be significant even at very low wt% when compared
ALABDALI ET AL.
with UDMA-MMA alone. Concentration of the additives
(G or HA) had a noticeable effect on the measured degree
of conversion of double C C bonds to single C C bonds.
Specifically, FTIR data indicated a decrease in the degree
of conversion as did micro-Raman, though to a lesser
extent. These values should be viewed as a qualitative
measure because the additives likely had many effects on
the observed spectra including modifying the heights,
widths, and positions of peaks. The refractive index, scat-
tering of light and absorption of photons by the additives
impacts the vibrational spectra obtained with FTIR and
micro-Raman, as well as the photocuring process itself.
The net effect of the addition of either G or HA to the
UDMA-MMA was to increase the hardness and indenta-
tion modulus beyond what would be expected for a sim-
ple composite structure. This indicates that the curing
and, hence, the properties of the blends is changed by the
additives. Collectively, the vibrational spectra, mechani-
cal properties, and imaging suggest the additives change
the mechanical properties by modifying the curing and
bonding in the composites. This combination of modified
curing rates and additional bonding between the matrix
and additives is likely the source of the increased
mechanical properties seen in the cured state. In the
uncured state, the liquid's viscosity is affected by the
additives, but the impact is less than when it is cured.
The results suggest the use of these additives could be a
way to improve the mechanical properties of the adhesive
system while still retaining low viscosity in the uncured
state. There is the additional benefit that both G and HA
have functional properties that may be beneficial in spe-
cific applications, for instance HA in biomedical hard tis-
sue applications where its biocompatibility may
encourage biomineralization.
A C K N O WL E D G M E N T S
Zinah N. Alabdali was sponsored by the Iraqi government-
Ministry of Higher Education and Scientific Research
(MOHESR). Emanuel Irizarry was supported by an NSF
(https://doi.org/10.13039/100000001) REU, award number
1659099. Graphene preparation procedure was performed
with the help of Justin Hendrix in the Materials Science
and Engineering Department at Rutgers University.
ORCID
Adrian B. Mann https://orcid.org/0000-0002-0948-7164
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How to cite this article: Alabdali ZN, Irizarry E,
Reiter MP, Ashraf A, Lynch-Branzoi JK, Mann AB.
Low-weight fractions of graphene and
hydroxyapatite enhance mechanics in photocured
methacrylate adhesives. J Appl Polym Sci. 2021;
138:e50442. https://doi.org/10.1002/app.50442