Composites Part A 107 (2018) 326–333

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Composites Part A
journal homepage: www.elsevier.com/locate/compositesa

Impact modified PLA-hydroxyapatite composites – Thermo-mechanical T

properties
⁎
John O. Akindoyoa,b,c, Mohammad D.H. Bega,b, , Suriati Ghazalia, Hans P. Heimc,
Maik Feldmannc
a
Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, Gambang 26300, Kuantan, Malaysia
b
Center of Excellence for Advanced Research in Fluid Flow, Universiti Malaysia Pahang, Lebuhraya Tun Razak, Gambang 26300, Kuantan, Pahang, Malaysia
c
Institute of Materials Engineering, Mönchebergstr. – 3, 34125 Kassel, University of Kassel, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Synergistic composites from poly(lactic acid) (PLA) and hydroxyapatite (HA) hold great potential for load
A. Polymer-matrix composites (PMCs) bearing applications. In this study, PLA-HA composites were produced through extrusion, and test specimens
B. Impact behaviour were subsequently prepared through injection molding. Impact properties of the composite was improved by
Thermomechanical incorporating different amount (0 to 15 wt%) of Biomax® Strong 120 (BS) impact modifier. The mechanical,
E. Injection moulding
thermal, morphological and dynamic mechanical properties of the resulting composite were investigated.
Likewise, chemical interactions during blending were investigated through Fourier transforms infrared spec-
troscopy. Incorporation of BS decreased the crystallization activities at the PLA-HA interface, but with a right
shift in crystallization temperature as the BS content increases. Also with increasing BS content, mechanical
properties of the PLA-HA composite were reduced. However there is an obvious increment in impact strength
(78%) and elongation at break (206%). The composite containing 5 wt% BS content presents the best com-
promise among the investigated properties.

1. Introduction packaging industry [7]. Interestingly, there is much interest in PLA for
bone replacement applications. In fact PLA based medical devices are
Recently, calcium orthophosphate based biomaterials have received recently becoming commercially recognized [8], based on its peculiar
much attention. They are being investigated for different medical ap- properties: PLA is biodegradable, biocompatible and bioresorbable [9].
plication such as bone replacements and other fixations. Specifically, In addition, PLA is characterized by considerable level of stiffness [7],
for bone replacement applications, interest in these materials is based acceptable physicomechanical properties such as rigidity, high tensile
on their salient properties such as biocompatibility, chemical stability, and flexural strength [10], and the ease of processability on conven-
low density, and the close chemical resemblance to natural bones mi- tional laboratory equipment such as extrusion and injection molding
nerals [1,2]. Hydroxyapatite (HA) is of particular interest because HA is [11]. These properties make PLA suitable for different applications and
the main calcium phosphate phase present in bone. Literature revealed specifically, based on their versatility, PLA based materials are often
that HA possesses the main properties desirable for effective bone re- considered as a standard for most regenerative applications [12].
placement applications. These include noninflammatory, bioactive, Therefore, by taking advantage of the individual properties of PLA and
nonimunogenic, biocompatible, nontoxic, osteointegration, and osteo- HA, synergistic PLA-HA composites can be produced with suitable
conductive properties [3–5]. However, HA is inherently hard, fragile bioactive, biocompatible, bioresorbable, osteoconductive and biode-
and brittle which makes it difficult to be processed into the required gradable properties. One major benefit of this approach is property
form and shape. Also, the strength of HA is low which restricts its use to tunability for different application, and it can also help to overcome the
non-load bearing applications. Currently, HA is being investigated as several surgical procedures associated with non-degradable biomater-
filler for different polymeric matrices to produce biomaterials with ials [13].
potential loadbearing replacement application [6]. However, one major issue that need to be addressed when produ-
One of the most important and suitable polymer matrix is poly cing PLA-HA composite is the poor adhesion between the hydrophilic
(lactic acid) (PLA), which at the moment is majorly used in the HA and hydrophobic PLA. Another main challenge is the high rate of

⁎
Corresponding author at: Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, Gambang 26300, Kuantan, Malaysia.
E-mail addresses: [email protected], [email protected] (M.D.H. Beg).

https://doi.org/10.1016/j.compositesa.2018.01.017
Received 31 October 2017; Received in revised form 15 January 2018; Accepted 17 January 2018
1359-835X/ © 2018 Elsevier Ltd. All rights reserved.
J.O. Akindoyo et al. Composites Part A 107 (2018) 326–333

HA agglomeration in the PLA matrix which sometimes lead to un- Table 1

desirable failure at the interface and a subsequent decrease in me- Code names and composition of the composite categories.
chanical properties. Efforts had been concerted towards modifying the
Code Sample composition (wt%)
HA surface in order to increase its compatibility with hydrophobic
polymers [14,15]. In a recent study, a phosphate based modifier was PLA HA BS
used to enhance the dispersion of HA in PLA, enhance the interfacial
PLA 100 – –
adhesion, and to improve the composite properties [16]. However, the
PLA + HA 90 10 –
inherent brittleness of the PLA-HA composites demands further delib- PLA + HA + 5% BS 85 10 5
erate attention. Although the impact strength of the modified HA PLA + HA + 10% BS 80 10 10
composites was improved compared with unmodified HA composite, PLA + HA + 15% BS 75 10 15
the improved impact strength is still lower than for neat PLA [16].
Toughening of PLA to overcome the inherent brittleness of its compo-
sites and increase the impact properties have been well reported in content < 0.1%), using TR–Dry–Jet EASY 15 (TORO-systems) air
literature [10,11,17,18]. Different plasticizers and impact modifiers drier. Likewise, the HA was dried (moisture content < 1%), in a con-
have been investigated for PLA toughening [17–19], but report showed vectional laboratory oven. HA was fed through the side of the com-
that there is high tendency for low molecular weight plasticizers to pounder carrying the pre-melted PLA and BS, followed by mixing and
migrate out as a result of their high mobility within the PLA [18]. homogenization [23]. The extruded composite strand was cooled down
Therefore, high molecular weight plasticizers with low mobility within on a discharge conveyer and then cut to a length of about 3 mm by a
PLA such as poly(propylene glycol) (PPG), and poly(ethylene glycol) Scheer SGS 25-E strand pelletizer. The pellets were then dried (moisture
(PEG) are more preferable [18]. However, high molecular weight content < 0.1%) and test specimen were prepared in an injection
plasticizers often present undesirable decreases in mechanical and molding machine (Arburg allrounder 320C golden edition). The re-
thermal properties of the composite [20,21]. levant parameters for extrusion and injection molding processes are
An alternative approach for improving the impact properties of PLA reported in previous article [16].
based materials is the use of impact modifiers. This can help to reduce
the inherent brittleness without adversely sacrificing the mechanical 2.2.2. Fourier transform infrared (FTIR) spectroscopy
and thermal properties [20]. Among the available impact modifiers, A Shimadzu FTIR spectrometer (Model-IR affinity-1S) was used for
Biomax strong (BS) from Dupont have been reported to offer good the FTIR analysis. To obtain viable information about possible reactions
impact and toughness enhancement to PLA, as the material was pro- within the composite, FTIR spectra of the individual components as
duced with special chemistry suitable for PLA toughening [10]. Indeed well as the composites were all taken. The IR spectra were obtained
there are several reports on PLA toughening using BS, most of which are over a wavelength range of 400–4000 cm−1 using the standard KBr
recent [10,18,21]. However, there is no report on incorporation of BS to technique.
modify the impact properties of PLA-HA composites. Although BS has
not been medically approved, its well proven suitable chemistry for PLA 2.2.3. Scanning electron microscopy
modification makes it a good candidate to investigate the effect of Morphology of the composite fractured surfaces after impact test
impact modifiers on PLA-HA composites. Therefore, the aim of the was investigated with the help of a Camscan Electron Optics Scanning
study is to investigate the effect of impact modifier on mechanical, Electron Microscope (SEM) (Model-MV2300). Before SEM observation,
thermal and dynamic properties of PLA-HA composites containing dif- the samples were dried to make them moisture free after which they
ferent wt% impact modifier content. were coated with thin layer of gold through sputtering so as to make
them conductive.
2. Materials and methods
2.2.4. Tensile test
2.1. Materials Tensile testing was conducted on specimens prepared according to
EN ISO 527, using a Zwick/Roell Z010 testing machine. The dry spe-
The matrix used for this research is NatureWorks Poly(lactic acid) cimens were conditioned at 23 °C and 50% relative humidity before
(PLA), 3052D Biopolymer. The PLA is an injection molding grade testing at speed of 5 mm min−1. Average result of seven specimens was
(Mw = 139,000 g/mol), with 1.25 g/cm3 density, melt flow index of recorded for tensile strength (TS) and tensile modulus (TM). In addi-
30–40 g/10 min (190 °C/2.16 kg), and melting temperature of tion, elongation at break of the composites under stress was obtained as
160–170 °C. The HA used was produced in our laboratory and its sur- part of the tensile results.
face was modified as described in previous articles [16,22]. The impact
modifier Biomax® Strong 120, referred to as BS in this paper was kindly 2.2.5. Flexural test
supplied by Dupont. Other chemicals used such as ethyl acetate and Specimen for flexural test was prepared according to EN ISO 178.
ethanol are of analytical grade and were procured from Roth, Germany. Testing was conducted on a Zwick/Roell Z010 universal testing ma-
These reagents were used without additional purification. Fabulase® chine at a speed of 10 mm min−1. Prior to testing, the specimens were
361 used as surface modifier for HA was obtained from Chemische conditioned at 23 °C and 50% relative humidity. Flexural strength (FS)
Fabrik Budenheim KG, Germany. and flexural modulus (FM) were obtained as average result of seven
specimens.
2.2. Methods
2.2.6. Charpy impact test
2.2.1. Production of composites Charpy impact test was conducted using a Zwick charpy impact
Composites were produced from PLA and surface modified HA [22] machine according to EN ISO 179-1, on samples without notch. The test
with different wt% (0–15 wt%) BS. The amount of HA in the composite speed was 2.93 m/s, and a hammer weighing 1 J was allowed to fall
was fixed at 10 wt% based on previous research [16]. The different freely to break the positioned impact specimens. Impact strength (IS)
categories of composites produced and their code names are listed in was recorded as average result of seven specimens.
Table 1. Components of the composites were mixed and compounded
using a twin screw extruder (Leistritz ZSE 18 HPE, D = 18 mm, L/ 2.2.7. Thermogravimetric analysis
D = 40) [23]. Before the extrusion process, PLA was dried (moisture Thermogravimetric analysis (TGA) and differential thermal

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gravimetry (DTG) analysis were performed using a TA analyzer (TGA

Q500 V6.4, Germany). Samples were placed in a platinum crucible and
analysis was conducted in a nitrogen atmosphere (gas flow rate:
40 mL min−1) at 10 °C/min from room temperature to 800 °C.

2.2.8. Differential scanning calorimetric analysis

Calorimetry analysis (DSC) was conducted using a TA instrument
(DSC Q1000). Samples were heated from 20 to 250 °C at a scanning rate
of 10 °C min−1. From the DSC thermogram, glass transition tempera-
ture (Tg), crystallization temperature (Tc) and melting temperature (Tm)
were determined. In addition, crystallinity index (XDSC%) of PLA in the
composite was calculated using Eq. (2) [24].
HOCl→H+ + OCl−
Low pH High pH (1)

ΔH
%crystallinity (XDSC ) = × 100%
ΔHm W (2)
where, ΔH is the heat of fusion of the samples, ΔHm is the heat of fusion
of 100% crystalline PLA, and W is the mass fraction of the matrix. The
PLA crystallinity in the composites was calculated by taking the heat of
fusion (ΔHm) of 100% crystalline PLA to be 93.6 J/g [25].

2.2.9. Dynamic mechanical analysis

Dynamic mechanical analysis (DMA) was performed using a
Dynamic Mechanical Analyzer (DMA Q800). A single cantilever mode
(deformation amplitude: 20 µm) was used, from room temperature to
130 °C, at a constant frequency (1 Hz) and heating rate of 3 °C min−1.
The cantilever has a clamp length of 35 mm, and 10 mm x 4 mm spe-
cimens were analyzed.

3. Results and discussion

3.1. Mechanical properties

The tensile and flexural properties of PLA and its composites with
Fig. 1. (a) Tensile strength (TS) and tensile modulus (TM), and (b) flexural strength (FS)
HA and BS are illustrated in Fig. 1. As can be seen, the tensile and
and flexural modulus (FM) of PLA and the composites.
flexural properties of the PLA-HA-BS composites are influenced by the
impact modifier content. From Fig. 1a, the tensile strength (TS) and
tensile modulus (TM) of the impact modified composites can be seen to
reduce as the BS content increases. Similar trend is observed for flexural
strength (FS) and flexural modulus (FM) as illustrated in Fig. 1b. The
mechanical properties of PLA compared with the composites revealed
that the largest reduction in tensile and flexural properties was ob-
served for composite with the highest BS content (15 wt%). It is not out
of place to observe a reduction in tensile and flexural properties of
polymeric materials after the inclusion of softer materials. Generally, in
semicrystalline materials such as PLA, it is expected that the inherent
bulk crystallinity would enhance the tensile and flexural properties of
its composites [26]. Therefore, the reduction in tensile and flexural
properties of the impact modified composites can be accrued to possible
suppression of PLA crystallinity in the PLA-HA-BS blend [26]. In an-
other vein, these decreases can probably be as a result of weaker in-
terface between the BS and other components of the composite espe-
cially HA. It can also be as a result of reduced load bearing capacity of
the impact modified composites due to reduction in the actual volume
of the stiffer and more stronger load bearing phase (PLA) within the
composite [27]. However, tensile and flexural properties alone are not
sufficient for overall assessment of materials suitability for specific load
bearing applications. Specifically, a very high capacity to absorb energy Fig. 2. Impact strength (IS) of PLA and the composites.
is well desirable [17]. In fact, literature reveals that one necessary
feature of fixation materials is the need for good energy absorption when impact modifiers are incorporated into semi crystalline polymers
capacity during fracture [28]. such as PLA, the impact modifiers would act as lubricants to lubricate
The impact properties of PLA and its composites with HA and BS is the PLA molecules, thereby reducing its inherent brittleness and en-
illustrated in Fig. 2. Obviously, the incorporation of BS strongly hance its flexibility. As can be seen from Fig. 2, IS of the PLA-HA
modifies the impact strength (IS) of the PLA-HA composites. In general,

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composite was increased at the incorporation of BS which is an in- ethylene. It is worthy of note that this band exhibit a very high intensity
dication of improved toughness. Similar observation was seen for the in the BS spectra which is attributed to the reasonably high amount of
elongation at break of the samples (Figure not shown). Compared to ethylene components in BS. The intense peak at 1750 cm−1 represents
PLA, the IS of the composite with 15 wt% BS content is about 61% C]O stretching vibration of acetyl, carboxylic and ester groups [24].
higher (Fig. 2) whereas compared with the composite without impact The peak at 1452 cm−1 and the small band around 1365 cm−1 is at-
modifier (PLA + HA), the IS increased by about 78%. Interestingly, tributed to CH3 stretching and CeH deformation respectively. The peak
after incorporation of just 5 wt% BS, the IS of the PLA + HA composite at 1083 cm−1 is a characteristic peak from CeO stretching band [31].
was increased by about 42% from 17.4 kJ/m2 to 24.7 kJ/m2. Similarly, One peculiarity of the BS spectra is the peaks at 1641 cm−1 and
the elongation at break of the unmodified composite was improved by 1555 cm−1 which corresponds to C]C stretching, attributed to the
about 144% after incorporation of 5 wt% impact modifier. These im- acrylic groups of BS.
provements after the incorporation of impact modifier suggest that the The FTIR spectra of the PLA-HA composite and the PLA-HA-BS
impact modifier might have acted as stress concentrators. This would composites are illustrated in Fig. 4b. The possible sites for bond for-
enhance the energy absorption of the impact modified composites mation between the individual components include the –OH groups of
during fracture, thereby resulting in increased impact and elongation HA [16], the epoxy groups of BS [27], and the functional –OH groups as
properties. Increase in impact strength of PLA composite at the in- well as the carboxylic groups in the PLA chain [32,33]. As illustrated in
corporation of BS impact modifier is also reported in literature [18,29]. Fig. 4b, the spectra of all the composites are similar but by comparing
Based on the results of the mechanical properties, it can be inferred that them with the spectra of the components in Fig. 4a, it can be seen that
the composite with 5 wt% BS content presents the best compromise as the BS content increased the intensity of the band around
between impact strength, elongation, tensile and flexural properties of 3050–2830 cm−1 also increases. This is attributed to the increasing wt
impact modified PLA-HA composites. Specifically, the IS and elongation % BS [10,21]. The –OH groups at the higher wavelength region around
at break were obviously improved without adversely reducing the 3400 cm−1 in the HA spectra was not detected in the PLA-HA compo-
tensile and flexural properties. site which is an indication of hydrogen bond formation between HA and
the functional groups of PLA. Likewise, the peaks at 1641 cm−1 and
3.2. Morphological analysis 1555 cm−1 in the BS spectra were not detected in the PLA-HA-BS
composites. Literature revealed that there is high possibility for che-
Dispersion of HA in PLA matrix is very important for good me- mical reaction between BS and PLA [27]. Therefore the disappearance
chanical performance of the resulting composite. Improvement of HA of the peaks is a strong indication of chemical reactions at the mole-
dispersion in PLA is reported in previous study [16]. However, due to cular level between BS, HA, and PLA. Furthermore, the peaks at
the inherent brittle nature and low impact strength of the PLA-HA 1750 cm−1 and 1083 cm−1 in the PLA-HA composite spectra can be
composites, impact modifier (BS) has been incorporated into the PLA- seen to slightly shift to a lower wavelength in the spectra of the PLA-
HA system described in previous study [16]. It is well known that aside HA-BS composites and the shift becomes further as the BS content in-
dispersion, the bond strength at the interfacial boundaries of the PLA, creases. This gives further evidence for intermolecular interaction
HA and BS is of paramount importance for desirable toughness prop- within the composite.
erties. To investigate this, SEM images of the sample fractured surfaces
were taken and presented in Fig. 3. As shown in Fig. 3a, neat PLA re- 3.4. Thermal properties
vealed smooth morphology, typical of brittle materials. Surface of the
PLA-HA composite without BS (Fig. 3b) also revealed fairly smooth The TGA and DTG thermograms of PLA and its composites with HA
morphology, attributed to little contribution of plastic deformation and BS are illustrated in Fig. 5. Thermal degradation properties of the
from the brittle PLA matrix, as reported in a similar research [21]. samples are summarized in Table 2. Comparing the degradation prop-
On the other hand, morphology of the BS containing composites erties of the composites with pure PLA, it can be seen that the de-
revealed well dispersed droplets of BS, which becomes more con- gradation onset temperature (Tonset), and degradation temperature (Td)
spicuous as the amount of BS in the system was increased (Fig. 3c–e) of the composite are all lower than for pure PLA. This can be attributed
similar to what was reported in literature [11]. It is well known that to higher destabilization of PLA structural framework within the com-
dispersion and size of BS droplets in the PLA matrix could influence the posites. Among the composites, the unmodified composite (PLA + HA)
PLA toughness [11]. Also, there is possibility for good chemical inter- revealed the highest thermal stability and among the composites con-
action between PLA and BS [26]. As stated in Section 2.2.1, HA was taining BS, composite with the lowest wt% BS (PLA + HA+5% BS)
side-fed into the compounder carrying the pre-melted PLA and BS. revealed the least thermal stability. The strength of interfacial bonding
Therefore, it is believed that as BS becomes dispersed into the PLA in within a composite is known to be one of the determinants of the
form of micro domains (Fig. 3c–e), it might modify the interfacial composite thermal stability. Electrostatic attraction between the Ca2+
boundary of PLA and HA. Interestingly, this might be responsible for ions of HA and the carboxylate group of polymers is reported to largely
the increased impact strength of the PLA-HA-BS composites (Fig. 2), influence the interfacial interaction in HA based polymer composites
most probably due to crack bridging, matrix shear yielding and energy [4]. Interference with this electrostatic interaction might be responsible
absorption as reported previously [21]. However, this might also con- for the reduced thermal stability of the composites containing BS,
tribute to the reduced tensile and flexural properties of the PLA-HA-BS compared with the unmodified composite.
systems compared with the PLA-HA composite (Fig. 1). This may be On the other hand, the lower thermal stability of the composite
attributed to disrupted interfacial adhesion between PLA and HA, due containing 5 wt% BS suggests inferior interfacial bonding compared to
to possible modification of the PLA-HA interface by BS. composites containing higher BS content. Literature revealed that there
is high possibility for molecular interaction between PLA and BS when
3.3. Fourier transforms infrared (FTIR) spectroscopy the BS content is > 1 wt% [27]. The possible reaction between PLA and
BS is illustrated in Fig. 6. Therefore, as the BS content increases, there is
The FTIR spectra of PLA, HA, and BS are illustrated in Fig. 4a. The larger possibility for interaction between PLA and BS which might have
major peaks common to all the components include the higher wave- increased the thermal stability of the impact modified composites as the
length vibrational stretching band of bonded –OH groups [30], obvious BS content increases. Increase in thermal resistance of composites fol-
around 3300–3200 cm−1 in BS spectra and 3500–3400 cm−1 in HA lowing the incorporation of impact modifiers was also reported else-
spectra. The characteristic stretching band at 3050–2830 cm−1 corre- where [17]. The residue after 700 °C is included in Table 2 and it can be
sponds to asymmetric and symmetric stretching of CeH of ethyl and seen that the composites revealed higher residue content compared to

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Fig. 3. SEM images of fractured surfaces of (a)

pure PLA, (b) PLA + HA, (c) PLA + HA + 5% BS,
(d) PLA + HA + 10% BS, and (e)
PLA + HA + 15% BS.

neat PLA which is attributed to the presence of HA in the composites. higher temperature and the right shift can be seen to increase as the BS
content increases. As explained in previous research, the lower tem-
3.5. Differential scanning calorimetry (DSC) analysis perature shift of the PLA-HA composites is an indication of increased
crystallization rate attributed to the ability of HA to induce hetero-
The DSC thermograms of PLA and its composites with HA and BS geneous nucleation into the PLA matrix [16,34]. This also contributes
are illustrated in Fig. 7, and the important transitions were analyzed. to the right shift in Tm peak of the PLA-HA composite owing to the
From Fig. 7, Tg of the unmodified PLA-HA composite can be seen to shift formation of less perfect crystals which would normally melt at higher
towards the right side whereas the Tg of the composites containing BS temperature compared with the more prefect crystals [16]. For the
was shifted to the left side compared with pure PLA. Reason for the composites containing BS, it can be seen that the exothermic crystal-
right shift of the unmodified composites is well explained in literature lization peak became broader with decreased magnitude coupled with a
[16]. It is well know that at temperature close to the Tg of polymers, the right shift as the BS content increases. It is well known that variation in
polymer chains are more flexible and can therefore move more freely. crystallization temperature of a material after incorporation of other
One of the main reasons for incorporating impact modifier into semi components would manifest in the form of either a faster or slower rate
crystalline polymers such as PLA is to lubricate the polymer chains, of crystallization [35]. For the composites containing 10 and 15 wt%
make them more flexible and increase their mobility. Therefore the left BS, the crystallization peak is not obvious which can be explained as
shift in Tg of the BS composites suggest enhanced polymer chain mo- follows: the crystallization behaviour of semi crystalline matrices such
bility. The DSC parameters of PLA and the different composite cate- as PLA in partially miscible blends is influenced by the nucleating ac-
gories are summarized in Table 3. tivities at the surface boundaries of the two components [26]. Due to
The Tc of the unmodified composite moved to a lower temperature the rubbery nature of BS, increasing the BS content could lead to
than pure PLA whereas Tc of the composites containing BS moved to creation of increased number of droplets (confirmed through SEM

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Fig. 4. FTIR spectra of (a) components of the composites, and (b) PLA-HA composites
Fig. 5. (a) TGA and (b) DTG thermograms of PLA and the different composite categories.
with different BS wt% content. (For interpretation of the references to colour in this figure
(For interpretation of the references to colour in this figure legend, the reader is referred
legend, the reader is referred to the web version of this article.)
to the web version of this article.)

observation), leading to reduced interfacial contact area between PLA Table 2

and HA such that the crystallization activities at the interface becomes Thermal properties of PLA and the different composite categories.
reduced. This indicates that incorporation of impact modifier can in-
fluence the crystallization behaviour of the PLA-HA composite as shown Sample code Tonset (°C) Td (°C) Residue (%) at T ≥ 700 °C
in Fig. 7 and Table 3.
PLA 330 369 0.33
The endothermic melting peak of PLA and PLA-HA composite re- PLA + HA 314 360 10.29
veals two distinct peaks. This is attributed to the different crystalline PLA + HA + 5% BS 272 324 10.17
structure of the beta- and alpha- forms of semi crystalline PLA [26]. On PLA + HA + 10% BS 276 332 10.14
PLA + HA + 15% BS 280 334 9.95
the other hand, the BS composites showed single and reduced Tm peaks
which are due to the reduced crystallization activity at the interfacial
boundaries, due to hindrance to PLA crystallization within the com-
posites. Similar observation was also reported in literature for PLA and
epoxidized natural rubber composites [26]. Crystallization of PLA in
the composites was calculated as described in Section 2.2.8 and the
result is included in Table 3. The result shows that the crystallinity of
PLA in the PLA-HA composite was reduced and the effect become in-
creased as the BS content was increased. Reduced crystallinity is an
indication of higher free volume content within the composite, and an
increase in the amorphous content [27]. Increase in amorphous nature
of the composites as the BS content increases would lead to reduction in
the composite stiffness and this might have contributed to the low
tensile and flexural properties of the BS composites as illustrated in
Fig. 1. Interestingly, controllable PLA crystallinity is a positive from Fig. 6. Possible reaction between PLA and BS during blending.
medical point of view as it can facilitate controlled degradation of the

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Fig. 8. Storage modulus, E′ curves of PLA and the different composite categories. (For
Fig. 7. DSC thermograms of PLA and the different composite categories.
interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
materials such that the active components can be made available at the
implant site at the desired time [28]. DSC result and also aligns with observation from previous research
[27].
3.6. Dynamic mechanical properties

The storage modulus (E′) curves of PLA, PLA-HA composite and 4. Conclusions
PLA-HA-BS composites are illustrated in Fig. 8. As can be seen from
Fig. 8, addition of HA led to increase in storage modulus of PLA which Composites were prepared from poly(lactic acid) (PLA) and hy-
is attributed to the higher modulus of HA compared with PLA [16]. droxyapatite (HA) for potential load bearing applications. To reduce the
Incorporation of BS into the PLA-HA composite led to decrease in the inherent brittle nature of the composites, different wt% (0–15 wt%)
storage modulus of the composite and the decrease becomes greater as biostrong impact modifier (BS) was incorporated into PLA-HA compo-
the BS content increases. For example, at 5 wt% BS content, there was sites containing 10 wt% HA content. Impact strength of the PLA-HA
less than 1% decrease in storage modulus of the PLA-HA composite composite was increased at the incorporation of BS which is an in-
whereas at 15 wt% HA content, the decrease in storage modulus is dication of improved toughness and enhanced energy absorption
about 37%. The storage modulus values of PLA and the composites are ability. Elongation at break of the unmodified PLA-HA composite was
included in Table 3. The decrease in storage modulus of the composites also enhanced by about 144% at 5 wt% BS content. The composite with
as BS content increases can be associated with the possible reduction in 5 wt% BS content presents the best compromise between impact
stiffness of the composite. This also aligns with what has been reported strength, tensile and flexural properties. On the other hand, evidence of
in literature for impact modified PLA blends [27]. Generally, the sto- intermolecular interaction between PLA and BS was confirmed through
rage modulus of all the samples gradually decreases with increasing FTIR analysis but interference with the electrostatic interaction be-
temperature but with a sharp drop around 57–63 °C. This region re- tween PLA and HA was observed to reduce the thermal stability of the
presents the glass transition region and the steep drop in storage impact modified composites. Similarly, disrupted crystallization activ-
modulus is attributed to increased chain mobility due to softening and ities at the PLA-HA interface led to reduced crystallinity of the PLA-HA-
segmental movement of the PLA molecules [27]. BS composites. Understanding of the mechanical, thermal and crystal-
Furthermore, the influence of BS on the PLA-HA composite was lization behaviour of impact modified PLA-HA composite can help to
evaluated through the damping coefficient (tan δ). One important tailor the composite performance for desirable properties. It is evident
feature of the tan δ curve is its ability to provide accurate measurement from this study that incorporation of impact modifier led to sacrifice of
of the Tg. From the tan δ curve, the Tg is determined as the temperature mechanical, thermal and dynamic mechanical properties of PLA-HA
at the maximum tan δ peak. The Tg obtained from the tan δ peak (not composites. However, at 5 wt% impact modifier content, the reduction
shown) is included in Table 3 with the corresponding maximum tan δ is minimal and it came alongside a remarkable improvement in impact
peak value. From Table 3, magnitude of the tan δ peak of the PLA-HA and elongation properties which makes it suitable for potential load-
composite can be seen to gradually reduce as the BS content increases, bearing applications.
accompanied by a reduction in Tg. This observation conforms to the

Table 3
DSC and DMA parameters of PLA and the different composite categories.

Sample code DSC DMA

Tg (°C) Tc (°C) Tm1 (°C) Tm2 (°C) Xc (%) E′ (MPa) Tg (°C) Tan δ peak

PLA 62.21 111.34 148.23 155.35 28.48 2295 65.65 2.29

PLA + HA 63.64 108.37 150.09 158.44 34.43 3064 66.78 1.93
PLA + HA + 5% BS 60.91 132.35 149.58 – 5.66 3048 65.22 1.89
PLA + HA + 10% BS 60.91 – 149.44 – 2.63 2232 65.20 1.82
PLA + HA + 15% BS 60.91 – 148.19 – 1.55 1923 64.98 1.70

332
J.O. Akindoyo et al. Composites Part A 107 (2018) 326–333

Acknowledgement 2017;103(Suppl. C):96–105.

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