Darie-Niță RN, Munteanu BS, Tudorachi N et al.

Bioinspired, Biomimetic and Nanobiomaterials

(2016) Complex poly(lactic acid)-based Volume 5 Issue BBN4
biomaterial for urinary catheters: I. Influence of Research Article
Received 18/08/2015 Accepted 17/05/2016
AgNP on properties. Bioinspired, Biomimetic and
Published online 18/05/2016
Nanobiomaterials 5(4): 132–151, Keywords: morphology/nanocomposites/thermal properties
http://dx.doi.org/10.1680/jbibn.15.00011

ice | science ICE Publishing: All rights reserved

Complex poly(lactic acid)-based

biomaterial for urinary
catheters: I. Influence of AgNP
on properties
Raluca N. Darie-Niţă PhD Elena Stoleru PhD
Researcher, ‘Petru Poni’ Institute of Macromolecular Chemistry, Iași, Researcher, ‘Petru Poni’ Institute of Macromolecular Chemistry, Iași,
Romania Romania
Bogdan S. Munteanu PhD Iuliana Spiridon PhD
Lecturer, Faculty of Physics, ‘Al. I. Cuza’ University, Iași, Romania Senior Researcher, ‘Petru Poni’ Institute of Macromolecular Chemistry, Iași,
Niţă Tudorachi PhD Romania
Senior Researcher, ‘Petru Poni’ Institute of Macromolecular Chemistry, Iași, Cornelia Vasile PhD*
Romania Head of Research Group, ‘Petru Poni’ Institute of Macromolecular
Rodica Lipşa PhD Chemistry, Iași, Romania
Researcher, ‘Petru Poni’ Institute of Macromolecular Chemistry, Iași,
Romania

The present study focused on the development of biocompatible antimicrobial/antioxidant biodegradable

bionanocomposite renewable resources based on poly(lactic acid) (PLA) plasticised with epoxidised soybean oil. To
the main PLA matrix hydrolysed collagen (HC) (to enhance biocompatibility), vitamin E (as antioxidant agent) and
silver (Ag) nanoparticles (NPs) (for imparting antimicrobial properties for medical applications and also for active
packaging) were incorporated. The blends were produced by using the classical technological flow of melt processing.
The presence of the additives in the PLA matrix improved the processability and flexibility and slightly decreased the
thermal properties. The specific interactions of silver NPs with the other components of nanocomposites, mainly with
HC protein and vitamin E (by ionic and other types of secondary bonds), led to a better HC and vitamin E dispersion
in the samples with a higher silver content (1·5%), which further caused the enhancement of the mechanical
properties for high silver NP concentration. Therefore, the silver NPs were successfully embedded into the polymer
matrix. The aim of this research was to improve the flexibility, biocompatibility and functionality of PLA and to
obtain bionanocomposites destined for medical applications such as catheters. This first part of research deals with
mechanical and thermal characterisation correlated with morphological features.

Notation TQfin torque at end of melt processing

d2 dimension coefficient according with Avrami–Erofeev TQmax maximum torque value on the torque–time curve
model W mass loss for each thermogravimetric stage
E1,E2 activation energies for each step Wr,500°C residual mass loss
n dimensional nucleation Avrami–Erofeev reaction DCp specific heat capacity
model DHcc cold crystallization enthalpy
n1,n2 reaction orders DHm melting enthalpy
R correlation coefficient
s thermal process in one step 1. Introduction
T10 temperature corresponding to 10 wt% mass loss Bionanocomposites are hybrid materials that combine the
T50 temperature corresponding to 50 wt% mass loss properties of biopolymers (biocompatibility, biodegradability,
Tcc cold crystallization temperature barrier properties) with those of synthetic polymers (easy
Tg glass transition temperature processing and possibility to be transformed into items with
Tm melting temperature complicated geometries, reproducibility of properties etc.).
Tonset onset temperature of each thermogravimetric step Usually these features are improved by embedded nanoparticles
TQ1min torque after 1 min of melt processing (NPs) and therefore are interesting in various applications. Besides
TQ5min torque after 5 min of melt processing the aforementioned advantages, there are also drawbacks, such as

*Corresponding author e-mail address: cvasile@icmpp.ro

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the high hydrophobicity, low biocompatibility and degradability of
synthetic polymers, while polymers from natural resources show
inferior mechanical properties, and all their characteristics are
dependent on their provenance and method of obtaining.
Modern polymeric matrices for bionanocomposites may contain
environmentally degradable polymers such as poly(lactic
acid) (PLA), polyglycolic acid, poly(e-caprolactone) (PCL),
poly(hydroxybutyrate) and so on, and naturally renewable
polymers such as polysaccharides (cellulose, starch, alginate,
chitosan or chitin and their derivatives etc.), proteins (soybean,
collagen, silk, fibrinogen) and less frequently lignin.1 In most
cases the problems related with the compatibility of components
must be solved.
PLA became a polymer of large interest not only in biomedical
and pharmaceutical applications but also in the commodity area –
that is, mainly packaging applications – owing to its advantages
such as biodegradability, annually renewable availability and
processability by traditional melt processes such as injection
moulding, film blowing or melt spinning.2
PLA is an aliphatic thermoplastic, semicrystalline or amorphous
(depending on optical configuration of monomer used) poly(a-
hydroxyacid).3 A polymer obtained from a levo-monomer is
considered a good solution to replace conventional polymers such
as polyethylene, polypropylene, polyethylene terephthalate (PET)
or polystyrene, being generally recognised as safe, non-toxic and
useful in the medical field and as an additive in the food industry,
while the dextro-isomer of lactic acid, D-lactic acid, is toxic to the
human body, leading to bone decalcification and producing
acidosis. PLA does not significantly modify the greenhouse effect
because the quantity of carbon dioxide produced during its
biodegradation is equivalent to that consumed by plants during
growth (which is used for lactic acid production).4
PLA is a hydrophobic polyester that is unstable in humid
conditions, degraded in the human body into non-toxic products
such as lactic acid, carbon dioxide and water, and eliminated by
the Krebs cycle and through urine. This is why it is recognised as
safe by the US Food and Drug Administration. The hydrolytic
degradation of PLA produces oligomers that are metabolised by
cells and enzymes.5 The biocompatibility and the use of PLA in
medical applications are well documented.6 It is recommended for
urological stents due to the minimal tissular reactions7 in
comparison with those of the steel one, offering also the advantage
of degradability after less than a year, while that from poly(L-lactic
acid-co-D-lactic acid) copolymer degrades up to 6 months.8
Infections of the urinary tract are the most frequent nosocomial
infections and constitute approximately 40% of infections from
hospitals, and 80% of these are associated with urinary catheter
use. Besides infections, the use of metallic catheters is associated
with harm to the urethra at repeated introduction and removals,
deposition of mineral salts, blood clot formation, catheter
Complex poly(lactic acid)-based
biomaterial for urinary catheters: I.
Influence of AgNP on properties
Darie-Niță, Munteanu, Tudorachi et al.
obturation, bacterial colonisation, and so on.9–11 This cascade of
events is particularly determined to be caused by the excessive
adsorption of proteins that play an essential role in bacterial
colony growth and infections and can be diminished or avoided
by using biocompatible/biodegradable polymer materials
containing antimicrobial agents.
Hydrolysed collagen (HC) is used to improve the biological
characteristics required by materials in prolonged contact with
blood and tissues. Numerous researches have been carried out
related to the use of collagen for enhancing biocompatibility in
biomedical applications12–16 because it shows low toxicity and
controllable biodegradability.17
Blending of two or more immiscible polymers is an attractive
route to generate new materials. PLA was modified by using
collagen through a grafting method to improve its biocompatibility
and degradability.18 Hybrid biocompatible porous PLA/collagen
scaffolds for tissue engineering have been prepared by using
various methods such as mechanically reinforced collagen with
surface-activated PLA fibres19 by combining freeze-dried natural
components and synthetic PLA mesh. The three-dimensional PLA
mesh gives mechanical strength and the natural polymers, collagen
and/or chitosan, mimic the natural cartilage tissue environment of
chondrocytes20 by assembling nanohydroxyapatite into a collagen/
PLA composite in order to obtain a bioactive biomimetic bone
scaffold21 as a multilayer scaffold obtained from electrospun PLA/
PCL/collagen nanofibres22 and so on.
NPs of noble metals (silver (Ag), gold (Au), platinum (Pt)) have
physical, chemical and biological properties, particularly optical,
electrochemical and electronic ones, distinct from those of
matrices and which are also dependent on their shape and
dimensions.23 Silver (colloidal or ionic) is an antimicrobial
agent with a unique capacity to attack and kill a series of
microorganisms involved in infections;24 moreover, no pathogens
exist that are resistant to its actions, as it happens in the case of
antibiotics such as penicillin.25 It was used in the past few years
in medical devices for tissue regeneration and in urinary
catheters.26,27 Its antibacterial activity depends on the silver
cation, which bonds with electron donor groups of biological
molecules, mainly those containing sulfur, oxygen (O) or nitrogen
(N), sometimes replacing other metal ions as calcium and zinc
(Zn).28 It has been established that urinary catheters coated with
silver reduce the biofilm formation and colonisation of bacteria by
silver ion release in the urinary tract.29 However, the use of silver
alloy in urinary catheters needs supplementary studies to prove its
efficiency and also because of its very high cost.30
Blending of polymers with different chemical structures typically
results in a coarse morphology with poor properties. Hence the
need to generate and stabilise a fine morphology is obvious and
block copolymers are typically used as compatibilisers. Recently
it has been suggested that the use of NPs could be an alternative
to ‘compatibilising’ immiscible polymer pairs31 because they
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affect phase separation behaviour.32 It was supposed that the
silver NPs will have a double role as an antimicrobial agent and
they will improve the compatibility of PLA with plasticisers and
biological polymers (HC).
Several processing technologies can be applied to biodegradable
polyesters to formulate coatings, implants, microparticles and NPs
or micro- and nano-capsules. Melt processing is utilised in the
production of sutures and preformed implants.
In a previous paper by the authors, the antibacterial property of
silver NPs and the antioxidant activity of vitamin E were
combined by incorporation of these two active components within
PLA nanofibres by electrospinning.33 The present study focused
on the development of biocompatible antimicrobial/antioxidant
biodegradable bionanocomposite renewable resources based on
plasticised PLA with epoxidised soybean oil (USE), HC to
enhance biocompatibility, vitamin E as antioxidant agent and
silver NPs to impart antimicrobial properties for medical
applications and also for active packaging by using the classical
technological flow of melt processing. The aim of this research is
to improve the flexibility, biocompatibility and functionality of
PLA and to obtain bionanocomposites that are destined for
medical applications such as catheters. This first part of this
research dealt with mechanical and thermal characterisation
correlated with morphological features.
2. Experimental
2.1 Materials
PLA obtained from renewable resources, transparent (trade name:
PLA 2002D) from NatureWorks LLC, UK, with a melt flow
index of 5–7 g/10 min (conditions 210°C/2·16 kg) and with a
content of 96% L-lactide and 4% isomer D, was used. The
average molecular weight determined by gel permeation
chromatography was 4475 kDa. However, the main medical
applications of PLA are limited owing to its high cost and
brittleness, which interferes with controlled degradation, reducing
compatibility with soft tissues.34 One approach to overcoming the
brittleness of PLA is to modify its properties by plasticisation.
Many plasticisers are known for improving the ductility of PLA,
such as poly(ethylene glycol),35 tributyl citrate, tributyl acetyl
citrate, triacetin or glycerol triacetate and triethyl acetyl
Property Value
Total nitrogen: g/100 g 14·14
Total proteins: g/100 g 84·36
Hydroxyproline: g/100 g 8·98
Collagen: g/100 g 81·00
Neutral saccharides: g/100 g 2·50
Hexozamines: g/100 g 12·50
Average molecular weight: Da 301 000
Table 1. Characteristics of HC
134
Complex poly(lactic acid)-based
biomaterial for urinary catheters: I.
Influence of AgNP on properties
Darie-Niță, Munteanu, Tudorachi et al.
citrate.36–40 In this study USE was selected because it
significantly improved elongation at the point of break in
comparison with those of other plasticisers had been recorded.41
Soybean oil contains 10 wt% palmitic acid, 25 wt% oleic acid,
51 wt% linoleic acid and 7 wt% linolenic acid. Unsaturated
groups can be used for functionalisation. They were epoxidised
with hydrogen peroxide in the presence of a mixture of glacial
acetic acid/toluene.42,43 The obtained USE has an epoxy
equivalent of 270 g/equivalent, an average molecular weight of
1000 and a density of 0·991 g/cm3. It can act as either a
plasticiser or a stabiliser.
HC was obtained by enzymatic extraction from bovine tendon
and has the characteristics shown in Table 1.
Vitamin E as synthetic (±)-a-tocoferol with a molecular mass of
430·71 g/mol, a density of 0·95 g/ml at 20°C and purity of >96%
(determined by high-performance liquid chromatography) was
purchased from Sigma-Aldrich, Steinheim, Germany.
2.1.1 Silver NP preparation
Silver NPs were obtained from silver nitrate (AgNO3) by a redox
reaction with N,N-dimethylformamide (DMF).44
Silver nitrate was homogenised 5 min in DMF and added to
15% (m/v) PLA solution in dichloromethane (DCM). The DMF/
DCM ratio was 3/7 (v/v), and the silver nitrate concentration was
adjusted to a final silver NP concentration of 0·1, 0·3 or 1·5 wt%
with respect to the polymer. The process of reduction of silver
ions to atomic silver takes place rapidly at room temperature, and
it is evidenced by colour change (due to the plasmonic resonance
phenomenon) from yellow to brown.33,45 Through the solvent
casting method, a PLA/silver NP masterbatch was obtained,
which was extensively dried in a vacuum oven to remove residual
solvents and was then used for PLA-based bionanocomposite
preparation. Pluronic F127 (PL) (Mw = 1·26 × 104 g/mol)
purchased from BASF was used as a compatibiliser. The reactants
silver nitrate, DCM and DMF (99%) were purchased from Sigma-
Aldrich. Double-distilled ultrapure water (Milli-Q) was used.
2.1.2 Bionanocomposite preparation
Several bionanocomposites with PLA matrix were obtained
by melt processing in a Brabender plastograph with mixer
counterrotating rotors at 60 revolutions/min for 10 min, the
processing temperature being 175°C. Since PLA can degrade by
hydrolysis of the ester bond, drying of PLA pellets is commonly
performed before processing. Thus, before mixing, the PLA was
dried for 24 h at a temperature of 60°C, while the HC was dried
for 4 h at 30°C in a vacuum oven. The quantity of HC in the PLA
matrix was 15 wt%, while that of vitamin E was 5 wt%.
After mixing, the samples were pressed by using a 4394 Carver
press at 175°C (3 min pre-melting and 3 min pressing at 200 bar)
to obtain sheets with a thickness of 1 ± 0·05 mm for tensile tests
Bioinspired, Biomimetic and Nanobiomaterials Complex poly(lactic acid)-based
Volume 5 Issue BBN4 biomaterial for urinary catheters: I.
Influence of AgNP on properties
Darie-Niță, Munteanu, Tudorachi et al.

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Number Sample composition Symbol

1 PLA PLA
2 PLA mixed with 15% USE PLA/USE
3 PLA mixed with 15% USE and 5% vitamin E PLA/USE/VE
4 PLA mixed with 15% USE, 5% vitamin E and 15% HC PLA/USE/VE/HC
5 PLA mixed with 15% USE, 15% HC and 5% PL PLA/USE/HC/PL
6 PLA mixed with 15% USE, 5% vitamin E, 15% HC and 5% PL PLA/USE/VE/HC/PL
7a PLA mixed with 15% USE, 5% vitamin E, 15% HC, 5% PL and 0·1% silver NP PLA/USE/VE/HC/PL/0·1AgNP
7b PLA mixed with 15% USE, 5% vitamin E, 15% HC, 5% PL and 0·3% silver NP PLA/USE/VE/HC/PL/0·3AgNP
7c PLA mixed with 15% USE, 5% vitamin E, 15% HC, 5% PL and 1·5% silver NP PLA/USE/VE/HC/PL/1·5AgNP

Table 2. PLA-based samples obtained by melt mixing

and of 4 ± 0·05 mm for impact tests. After pressing, the material
was inspected to note the particle dispersion and was then
prepared for mechanical tests.
The processing conditions assured a good dispersion of the
components and that all active components maintained their
activity. The prepared and studied samples are given in Table 2.
find the suitable strain value. The determined value of 10% was
further used in all frequency sweep modes, so that all samples
were tested in the linear viscoelastic region (LVE). Oscillatory
frequency sweeps ranging from 0·01 to 1000 s−1 with a fixed
strain of 10% were performed at 175°C, when the temperature
had stabilised after loading the sample between the rheometer’s
plates. Each sample was recorded three times.

2.2 Characterisation methods 2.2.5 Scanning electron microscopy

2.2.1 Processing behaviour The fractured surfaces were analysed by using a FEI Quanta 200E
The processing behaviour was evaluated by analysis of processing scanning electron microscopy (SEM) device (Hillsboro, OR,
characteristics following the torque–time curves registered during USA). Air-dried samples were fixed onto aluminium (Al) stubs
blending on a Brabender mixer. through carbon (C) adhesive disks, and their surface was observed
with a low-vacuum secondary electron detector by using an
2.2.2 Stress–strain measurements accelerating voltage of 25·0 kV. The samples were analysed at
Stress–strain measurements were performed at room temperature room temperature at an internal pressure of 0·50 torr.
on dumbbell-shaped samples (1 mm thickness), on an Instron
Single Column Systems tensile testing machine (Instron 3345, 2.2.6 Thermal methods
Instron Corp., Norwood, MA, USA) equipped with as 5-kN load Differential scanning calorimetry (DSC) was performed on a
cell and activated grips, which prevented slippage of the sample Netzsch DSC 200F3 instrument (Netzsch, Germany). A sample
before breaking. The cross-head speed used was 10 mm/min, and
gauge length was 40·0 mm. Young’s modulus, tensile strength at TQmax: TQ1min: TQ5min: TQfin:
the point of break and strain at the point of break were evaluated Sample
Nm Nm Nm Nm
according to SR EN ISO 527-2/1996.46 Before measurement, the
samples were maintained at 23°C and 50% relative humidity (RH). PLA 66·4 17·2 13·3 12·6
Each reported value is the average of at least five determinations. PLA/USE 20·9 7·2 4·9 4·6
PLA/USE/VE 26·6 6·6 2·8 2·8
2.2.3 Impact tests PLA/USE/VE/HC 13·5 1·8 1·4 1·3
Impact tests were performed according to SR EN ISO 179/2001,47 PLA/USE/HC/PL 6·3 1·5 1·7 1·7
on a Ceast impactor (Ceast SpA, Pianezza, Italy), equipped with PLA/USE/VE/HC/PL 6·2 1·7 1·6 1·7
a Charpy-type hammer with 50 J energy. All samples were PLA/USE/VE/HC/PL/ 9·8 1·9 0·9 0·7
conditioned before testing at 23°C and 50% RH. Similarly, with 0·1AgNP
tensile tests, all unnotched samples were measured five times and PLA/USE/VE/HC/PL/ 7·2 0·8 0·8 0·8
the average was calculated. 0·3AgNP
PLA/USE/VE/HC/PL/ 9·9 1·1 0·9 1·0
2.2.4 Dynamic rheological measurements 1·5AgNP
The rheological properties were measured by means of a stress- Table 3. Melt processing characteristics of PLA and its composites.
controlled rheometer (Anton Paar MCR301, Austria) with a TQ1min, torque after 1 min of melt processing; TQ5min, torque after
CTD450 device using parallel plate-plate geometry (upper 5 min of melt processing; TQfin, torque at end of melt processing;
diameter of 25 mm), with a fixed gap of 1 mm. Rheological TQmax, maximum torque
measurements started with the strain sweep mode, performed to

135
Bioinspired, Biomimetic and Nanobiomaterials Complex poly(lactic acid)-based
Volume 5 Issue BBN4 biomaterial for urinary catheters: I.
Influence of AgNP on properties
Darie-Niță, Munteanu, Tudorachi et al.

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3000

2500
Young’s modulus: MPa

2000

1500

1000

500

0
PLA A/USE SE/VE VE/HC /HC/PL /HC/PL ·1AgNP ·3AgNP ·5AgNP
PL PLA/U /USE/ /USE E/VE PL/0 PL/0 PL/1
PLA PLA PLA/US VE/HC/ VE/HC/ VE/HC/
S E / S E / S E /
/U LA/U /U
PLA P PLA
(a)
60
Tensile strength at point of break: MPa

50

40

30

20

10

0
PLA /USE E/VE /HC C/PL C/PL AgN
P
AgN
P
AgN
P
PLA PLA/US /USE/VE /USE/H SE/VE/H /PL/0·1 /PL/0·3 /PL/1·5
PLA PLA PLA/U E/HC E/HC E/HC
/ U SE/V /USE/V /USE/V
PLA PLA PLA
(b)
45
Elongation at point of break: mm

40
35
30
25
20
15
10
5
0
PLA /USE E/VE /HC C/PL C/PL AgN
P
AgN
P
AgN
P
PLA PLA/US /USE/VE /USE/H SE/VE/H /PL/0·1 /PL/0·3 /PL/1·5
PLA A
PL PLA/ U HC VE/HC VE/HC
/VE/ / /
L A /USE LA/USE LA/USE
P P P
(c)

Figure 1. Tensile strength of PLA and its blends and biocomposites: (a)
Young’s modulus; (b) tensile strength at point of break; (c) elongation
at point of break

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Volume 5 Issue BBN4 biomaterial for urinary catheters: I.
Influence of AgNP on properties
Darie-Niță, Munteanu, Tudorachi et al.

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with a mass of 3·5 mg and without previous drying was sealed in
a closed aluminium pan and heated at a heating rate of 10°C/min
in the temperature range of 20–200°C in a nitrogen atmosphere at
a flow rate of 50 ml/min. Temperature calibration was made with
five different metals. Indium (Tm = 156·6°C; DHm = 28·45 J/g)
was used for calibration. The glass transition temperature (Tg),
cold crystallisation temperature (Tcc), melting temperature (Tm),
specific heat capacity (DCp), cold crystallisation enthalpy (DHcc)
and melting enthalpy (DHm) were determined from cooling,
and the second heating was run at 10°C/min. Melting and
crystallisation temperatures were measured as the peak temperature
of the endothermal (Tm) or exothermal (Tcc) process respectively.
2.2.7 Thermogravimetry
Thermal degradation behaviour was performed on an STA 449
F1 Jupiter system (Netzsch, Germany). By using a 7–10 mg sample
heated from 25 to 700°C at a heating rate of 10°C/min under
nitrogen (purity 99·999%, 50 and 20 ml/min for microbalance
protection) in an open aluminium pan, aluminium oxide (Al2O3)
was used as the reference material. The temperature and sensitivity
of the instrument were calibrated in the 0°C to 660°C range with
respect to the melting temperatures of standard metals (mercury
(Hg), gallium (Ga), tin (Sn), zinc, aluminium), and data processing
was done with the software Proteus.
3. Results and discussion
3.1 Processing behaviour
From the torque–time curves (not shown) registered during
mixing, data on processing behaviour were extracted (Table 3).
The PLA matrix showed a high melting viscosity, which was
maintained during the entire processing period (Table 3, first row).
USE and vitamin E incorporation led to a significant decrease in
the torque moment over the entire processing process, the melt
flow and processability being improved. Further addition of HC

1·6

1·2
Impact energy: J

0·8

0·4

0
PLA A/USE SE/VE VE/HC /HC/PL /HC/PL ·1AgNP ·3AgNP ·5AgNP
PL PLA/U /USE/ /USE E/VE PL/0 PL/0 PL/1
PLA PLA PLA/US VE/HC/ VE/HC/ VE/HC/
/ / /
/USE LA/USE LA/USE
PLA P P
(a)
40
Impact strength: kJ/m2

30

20

10

0
PLA A/USE SE/VE VE/HC /HC/PL /HC/PL ·1AgNP ·3AgNP ·5AgNP
PL PLA/U /USE/ /USE E/VE PL/0 PL/0 PL/1
PLA PLA PLA/US VE/HC/ VE/HC/ VE/HC/
E / E / E /
/US LA/US LA/US
PLA P P
(b)

Figure 2. (a) Impact energy and (b) impact strength of PLA and its
blends and biocomposites

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decreased the torque moment by four times with respect to that of
PLA after 1 min of mixing, and with a longer mixing time, the
values were very small. The decrease is very significant when the
plasticiser (USE) and the compatibiliser (PL) were incorporated,
proving the improvement of the processing characteristics with
respect to that of PLA. The thermal stability during processing
was determined by comparing the temperatures at different
processing intervals. It was observed that additive incorporation
reduced the processing temperature by ~5–8°C at the beginning
of processing (1 min). After 5 min and at the end of processing,
the processing temperature of PLA increased from an initial
set-up of 175–183°C because of the high friction shear forces
developed by its high viscosity. The processing temperature of
all complex formulations of biocomposites reached after 5 min
172–175°C, which was kept for the entire process. The change in
silver NP content does not affect the processing behaviour of the
complex materials.
3.2 Mechanical behaviour
The tensile and impact properties of the studied samples are
presented in the Figures 1(a)–1(c), 2(a) and 2(b). For each column
bar, the confidence intervals (calculated as the range of values
around the middle estimated point, within which the true value
can be expected to fall with a 95% probability) are presented. The
results were considered statistically significant if the upper and
lower limits of the confidence interval for the compared samples
do not overlap.48
mechanical strength is required.37 Flexibility is very important for
the medical application of materials, mainly when they are used
as urinary catheters. To reach a certain level of elasticity,
plasticisation is required. When comparing various plasticisers for
PLA, USE was selected because it significantly increased this
property.41 Although elongation at the point of break significantly
increased with USE addition and decreased when the other
components are incorporated, particularly HC, it is still higher for
all studied systems in comparison with the value of PLA (Figure
1(c)). The compatibiliser PL and vitamin E improve this property,
but it decreased again with silver NP incorporation. Silver NPs do
not affect Young’s modulus values, but the increase in silver NP
concentration improves both tensile strength and elongation at the
point of break.
Impact strength and energy take high values for blends and
composites with respect to PLA, particularly for blends containing
USE and VE, mainly due to the plasticising effect of USE and
the good compatibility of the components as mentioned earlier
(Figures 2(a) and 2(b)). For the composites containing silver NPs,
the impact properties increase with silver NP content. The higher
the silver NP concentration, the better the impact properties

Tensile properties significantly vary by incorporation of each

component of biocomposites (Figure 1). Both Young’s modulus
and tensile strength decreased with respect to the values 20 mm 100 mm
corresponding to neat PLA, and values remained in close limits (a) (b)
for all the studied blends/composites, namely 2000–2400 and
20–30 MPa, respectively (Figures 1(a) and 1(b)), although in the
case of the PLA/USE blend, an increase in Young’s modulus to
2730 MPa with respect to that of PLA (2588 MPa) is evident.
This increase was explained in the authors’ previous paper on the
basis of the interactions of polar components (oxirane epoxy in
USE) and carbonyl and carboxylic ester functionality, which
100 mm 200 mm
assure a good compatibility of components.41 Blends and
(c) (d)
composites show a 50% decrease in tensile strength. The decrease
in the mechanical properties of PLA composites with respect to
those of neat PLA was reported by other authors,49,50 being
explained as a result of phase separation. Shumigin et al.51
showed that the incorporation of cellulose into the PLA matrix
lead to stiffer but slightly more brittle and weaker materials, since
Young’s modulus increases and tensile strength and elongation at
point of break slightly decrease. The phase separation appears as 200 mm 200 mm
microdomains with bigger dimensions with increasing material (e) (f)
composition complexity – see Figures 3 and 4.
Figure 3. SEM micrographs of PLA and some blends and composites:
However, despite PLA’s numerous advantages, such as good (a) PLA; (b) PLA/USE; (c) PLA/USE/VE/HC/PL; (d) PLA/USE/VE/HC/PL/
optical, physical and mechanical properties (high flexural and 0·1AgNP; (e) PLA/USE/VE/HC/PL/0·3AgNP; (f) PLA/USE/VE/HC/PL/
tensile moduli and strengths), the inherent brittleness impedes 1·5AgNP. The scale is shown in the figure
significantly its applications in many fields where a high level of

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lowered the glass transition temperature of PLA but only at low

USE content (£20%), which indicates52 its plasticiser role, but
with a partial compatibility with PLA.

3.3 Dynamic rheological measurements: oscillatory

melt rheology tests
Variation in the storage (G0 ) and loss (G″) moduli and the
50 mm 20 mm
complex viscosity of the melts with angular frequency were
(a) (b) recorded in the LVE region indicates the dependence of
rheological behaviour on composition, mainly in the angular
frequency in the 1–100 s−1 region (Figure 5), where elastic
properties are dominant.

The processing temperature of PLA is related to melt viscosity,

which depends on the average molecular weight, the amount of
20 mm 200 mm plasticiser, the shear rate and the type of melting process.53 PLA,
like many thermoplastics, is a pseudoplastic, non-Newtonian fluid.
(c) (d)
For all studied samples, G″ > G0 ; therefore, they behave as
viscous liquids, the elastic characteristic being dominant at high
frequencies (i.e. G0 > G″). The curves of the variation in moduli
with frequency show that neat PLA presents a sudden descent of
the dynamic moduli with decreasing frequency. Low-frequency
points take a long time (>10 min) to acquire, so that a decrease in
molecular weight is a significant possible effect during this
100 mm 100 mm testing, leading to the decrease in G0 and G″ values. One can
(e) (f) observe that the incorporation of plasticiser changes the melt
behaviour of the plasticised PLA within the tested frequency
sweep range (Figure 5). Sears and Darby54 mentioned that
plasticisation on the molecular level is the weakening or rupturing
of selective bonds between molecules, increasing intermolecular
space (free volume), while leaving others strong, thus allowing
the shaping, flexing or moulding of the material.
20 mm 100 mm
Rheological properties are improved through the addition of a
(g) (h)
plasticiser as also observed from the decrease in complex
viscosity plotted in Figure 5(c). USE can penetrate into PLA
chains, increasing fluidity and decreasing melt strength. Moreover,
vitamin E addition improves this supplementary characteristic.
Nanocomposites displayed a pseudoplastic behaviour, with a
viscosity decreasing with the shear rate until ~10 s−1 and then
increasing at a high shear rate.
100 mm
(i) The lack of an apparent rubber plateau in the melt phase of PLA
was observed also for many polyesters – for example
Figure 4. SEM micrographs of (a–e) PLA/USE/VE/HC/PL/0·1AgNP and poly(caprolactone) (PCL) and PET due to the lower-molecular
(f–i) PLA/USE/VE/HC/PL/0·3AgNP with (a, d, g, h, i) irregular or (b, c, e, weight materials crystallising below their melting point.55 The
f) polygonal morphological units. The scale is shown in the figure dependence of dynamic moduli on angular frequency plotted
in Figure 5 for PLA/USE show that the incorporation of the
plasticiser led to appearance of a plateau region or ‘rubbery’ zone
obtained. This increase could be due to a good dispersion of in the 10–100 s−1 frequency region, more obvious for PLA/USE
components and the strengthening of the interface, which is able and PLA/USE/VE blend, where G0 and G″ are constant,
to respond to impact forces – see SEM results in the following independent of frequency.
section. The partial miscibility of USE with PLA was also
reported in the literature. Empty microvoids were evidenced by Both G0 and G″ moduli increase with angular frequency
SEM in the fractured surfaces, while DSC revealed that the USE (Figure 5(a)) because at low frequencies, the entanglement of

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1 × 106 1 × 105
PLA PLA
PLA/USE PLA/USE
1 × 105 PLA/USE/VE
PLA/USE/VE PLA/USE/VE/HC
1 × 104
1 × 104
PLA/USE/VE/HC PLA/USE/HC/PL
PLA/USE/HC/PL PLA/USE/VE/HC/PL
PLA/USE/VE/HC/PL PLA/USE/VE/HC/PL/1·5AgNPP
1 × 103 1 × 103
PLA/USE/VE/HC/PL/1·5AgNP

G’’: Pa
G’: Pa

1 × 102
1 × 102
1 × 101

1 × 100
1 × 101
1 × 10–1

1 × 10–2 1 × 100
0·01 0·1 1 10 100 1000 0·01 0·1 1 10 100 1000
Angular frequency: s−1 Angular frequency: s−1
(a) (b)
1 × 104

1 × 103
Complex viscosity: Pa s

1 × 102
PLA
PLA/USE
PLA/USE/VE
1 × 101 PLA/USE/VE/HC
PLA/USE/HC/PL
PLA/USE/VE/HC/PL
PLA/USE/VE/HC/PL/1·5AgNP
1 × 100
0·01 0·1 1 10 100 1000
Angular frequency: s−1
(c)

Figure 5. Variations in (a) storage modulus (G0 ), (b) loss modulus (G″)
and (c) complex viscosity against angular frequency for PLA matrix and
PLA-based blends/composites melts at 175°C

chains is affected and relaxation takes place slowly. At high
angular frequencies, the chains are deformed and they have no
enough time to reorient, leading to increase in moduli. In all curves
of G0 , G″ and complex viscosity evolution with angular frequency,
a shoulder appears in the case of complex materials, which is much
evident in the case of the PLA/USE/VE system. This can be
explained by a supplementary elasticity induced by incorporation
of USE and other components. The decrease in the dynamic
viscosity of blends and composites (Figure 5(c)) indicates the
diminution of the brittleness of PLA, which is more important in
formulation containing all components.56
The slopes of G0 (w) and G″(w) for all PLA blends melts were
considerably lower than that for neat PLA melt, particularly at
high oscillation frequencies.
The enhancement observed in the values of the dynamic modulus
G0 for the obtained composites is significantly higher at low w up
to 1 s−1, where all the registered G0 curves decreased related to
that for neat PLA. The slope of the storage modulus curves
diminishes with increase in the blend components. The additional
low-frequency contributions in G0 can be due to the relaxations of
the large dispersed domains of the minor phases.51 At low
frequencies, the dispersion of components in composite materials
is usually not homogeneous. The incorporation of collagen led to
an increase in the volume fraction and the droplet size of
dispersed phase, G0 being higher at low w. At high angular
frequencies, the effect of components decreases and the matrix
contributions dominate.
The curves of G0 and G″ recorded by frequency sweep tests
showed the cross-over point G0 = G″ in the studied frequency
range (Figure 6(a) and Table 4) only for some samples, which
was found at lower values in complex materials with respect to
PLA. The cross-over frequency (w) can be used to determine the
relaxation time of a polymer, which is important in rheology and
processing because it provides a timescale for how long it takes to
relax after a deformation or stress is applied.57 The cross-over
frequency and modulus decreased for samples with complex
composition, while the relaxing time increased (Figure 6(b)).
The incorporation of HC within plasticised PLA led to obtaining of
materials with changes in viscoelasticity within the LVE region as
observed from the values of the cross-over frequencies. Increased
relaxation time is needed for the blends containing HC, as the
relaxation of the dispersed phase itself is often much longer
than the relaxation of the polymer chains of the individual
components.58

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1 × 105
G0 = G″: v: t = 1/v :
G’ Sample
1 × 104 G’’
MPa rad/s × 103 s
PLA 81·78 507·50 1·97
1 × 103
ω i = 440·8 rad/s PLA/USE/VE/HC 9·06 426·40 2·35
G’, G’’: Pa

1 × 102 PLA/USE/VE/HC/PL/1·5AgNP 7·46 440·80 2·27

1 × 101 Table 4. Rheological characteristics of PLA and its blends and

composites
1 × 100 PLA/USE/VE/PL/HC/1·5AgNP

1 × 10−1
0·01 0·1 1 10 100 1000
Angular frequency: s−1 3.4 Morphology
(a)
The SEM images (Figures 3 and 4) show two types of particles
3·0 distributed in the PLA matrix: one distribution of large (3 ÷
10 mm) spherical morphological units with aspect of microvoids,
2·5
which represents the USE phase, and another distribution of finer
particle distribution (~1 mm) with aspect of (bright) spherical
Relaxation time: s

2·0
microparticles. Bright particles evidence the existence of the
1·5 charged particles that normally appear from components having
ionisable groups (e.g. HC), which are in large numbers in the case
1·0
of the PLA/USE/VE/HC/PL/1·5AgNP sample. For all samples,
0·5
some of the larger voids have inside spherical bright
microparticles (indicated with black/white arrows in Figures 4(a)
0 and 4(f)).
PLA HC gNP
SE /VE/ /1·5
A
PLA/U HC/PL Thus, the SEM images indicate that a partial compatible blend
SE /VE/
P LA/U is formed, with PLA as the matrix and the USE and HC as
(b)
the dispersed phase. Particles of various sizes are distributed in
the matrix, and this aspect is maintained for all the studied
Figure 6. (a) Cross-over point and (b) variation in relaxation time with samples, although the addition of vitamin E, HC and PL seems
sample composition to make distribution of microdomains more homogeneous; the
silver NPs are present both in matrix and in distributed phase
(Figure 3).

The increased values of relaxation time corresponded to the Dependence of the histogram shapes on the silver NP
relaxation of the long, heavy and branched chains due to the concentration is evident from Figure 7 and Table 5. The curves
presence of epoxy (from USE) or functional groups introduced by
HC, which interact with other components, restrict the chain
60
mobility of the neat polymer and retard the overall relaxation of 60 50 ‘Small particles’

modified polymers.59 This might be also attributed to the polar

PLA/USE
40
Counts

PLA/USE/VE/HC/PL/0 AgNP
30
PLA/USE/VE/HC/PL/0·1 AgNP
interactions (i.e. hydrogen bonding) between the components and 50 20
PLA/USE/VE/HC/PL/0·3 AgNP
10
the polymer matrix, which greatly impede the polymer chain’s 0 PLA/USE/VE/HC/PL/1·5 AgNP

mobility. HC could introduce some hydrophilic groups, such as 40 0

Diameter: µm
2
Counts

–NH2, –COOH and –OH, and enhance the intermolecular ‘Empty voids’
30 PLA
interactions between the components. This is in accordance with PLA/USE/VE/HC/PL/0 AgNP

Fourier transform infrared spectroscopy (FTIR) results. 20

PLA/USE/VE/HC/PL/0·1 AgNP
PLA/USE/VE/HC/PL/0·3 AgNP
PLA/USE/VE/HC/PL/1·5 AgNP

As shown by FTIR spectra examination in Figure 1 in the second 10

part of this paper60, silver NPs interact with components of
formulation; this explains the decrease in the relaxation time. 0

0 2 4 6 8 10 12 14 16 18 20
The cumulative effects of the orientation of the molecular chains, Diameter: µm
polar interactions and crystallinity that developed during melt
processing of PLA-based blends are reflected by their mechanical Figure 7. The histograms of the studied samples
properties.

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Average dimensions of
Average dimensions of
charged/uncharged bright
Sample microphases’ charged/uncharged Total counts
particles read at
bright particles: mm
maximum of histogram: mm
PLA/USE 1·0 ± 0·2/3·0 ± 1·4 ~1·0/~2·4 72/427
PLA/USE/HC/PL 0·9 ± 0·3/4·5 ± 3·2 ~0·60/~2·5 191/178
PLA/USE/VE/HC/PL/0·1AgNP 0·7 ± 0·2/6·2 ± 3·1 ~0·65/~4·9 86/208
PLA/USE/VE/HC/PL/0·3AgNP 0·9 ± 0·3/6·9 ± 3·3 ~0·9/~4·8 83/185
PLA/USE/VE/HC/PL/1·5AgNP 1·0 ± 0·4/8·8 ± 5·4 ~0·90/~6·9 175/163

Table 5. Average dimensions of the microphases evidenced in

SEM micrographs

become much wider with increasing silver NP concentration, and

the dimensions of the particles increase.

In the SEM images of 0·1 and 0·3% silver NP nanocomposites,

present are various polymorphic/irregular morphological
units (Figures 4(b), 4(d) and 4(g)–4(i)) or, frequently, all
polygonal (Figures 4(b) and 4(c)), spherical and irregular,
some of them distributed inside the bigger microvoids
(Figure 4(e)). This indicates specific interactions of silver
NPs with the other components of nanocomposites, mainly HC
protein and vitamin E, by ionic and other types of secondary
bonds, which could explain the better HC and vitamin E
dispersion in the samples with a high silver content (1·5%).
The better dispersion also explains the enhancement of
the mechanical properties for high silver NP concentration.
Therefore, the silver NPs are successfully embedded into the
polymer matrix.

Vandebril et al.31 showed that coalescence of the dispersed phase AgL 100 mm
is slowed down or even totally suppressed when NPs are present (a)
at the interface. This effect is stronger when the particle
concentration is increased or the (aggregate) size is reduced. As a
result, NPs with a suitable surface chemistry can be used to tune
the flow-induced microstructure of immiscible polymer blends by
optimising their concentration, size and shape.

Energy-dispersive X-ray spectroscopy data confirm the

homogeneous distribution of silver NPs through the entire sample
(Figure 8).

Silver NPs are constituted from metallic silver of nanoscale size –

see part II of this paper.60

The average surface composition of two samples given in Table 6

is close to the experimental one.60 AgL 10 mm
(b)
3.5 Thermal behaviour
3.5.1 DSC results Figure 8. Silver NP distribution in (a) PLA/USE/VE/HC/PL/0·1AgNP and
PLA thermal behaviour is dependent on thermal history. The (b) PLA/USE/VE/HC/PL/1·5AgNP bionanocomposite samples
thermal transitions occurring in PLA-based samples are

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Element
Sample Carbon Nitrogen Oxygen Silver
wt% at% wt% at% wt% at% wt% at%
PLA/USE/VE/HC/PL 67·1 72·8 2·9 2·7 29·9 24·5 — —
PLA/USE/VE/HC/PL/0·1AgNP 66·5 72·5 4·8 4·5 27·7 22·7 0·12 0·015
PLA/USE/VE/HC/PL/0·3AgNP 69·5 75·7 3·5 3·3 24·8 20·2 0·4 0·05
PLA/USE/VE/HC/PL/1·5AgNP 72·2 77·8 4·1 3·81 22·6 18·3 1·09 0·13

Table 6. Average surface composition of some PLA-based

composites

Run 1 PLA/USE
Exo 2 PLA
Run 2 PLA
PLA/USE/VE
0
DTA: mW/mg

PLA/USE/VE/HC/PL/1·5AgNP −2
Heat flow: mW/mg

PLA/USE/VE/HC
PLA/USE/HC/PL
−4
PLA/USE/VE/HC
−6

PLA/USE
−8

−10
0 50 100 150 200 250 300 100 200 300 400 500 600
Temperature: ºC Temperature: ºC
(a) (b)

4 PLA/USE/VE/HC/PL

2 PLA/USE/HC/PL

0
DTA: mW/mg

−2
PLA/USE/VE/HC/PL/1·5AgNP
−4
USE
HC
−6

−8

−10
100 200 300 400 500 600
Temperature: ºC
(c)

Figure 9. (a) DSC curves for neat PLA and some systems; (b) DTA
curves for neat PLA, PLA/USE, PLA/USE/VE and PLA/USE/VE/HC; and
(c) DTA curves for USE, HC, PLA/USE/VE/HC/PL, PLA/USE/HC/PL and
PLA/USE/VE/HC/PL/1·5AgNP

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determined from DSC and differential thermal analysis (DTA) with the dry ones, excepting PLA, which, being hydrophobic,
curves (Figure 9 and Table 7). absorbs less water.

The neat PLA shows a glass transition temperature Tg = 59·6°C
and a ‘cold’ crystallisation process with a peak temperature
Tcc ~ 126°C, which is not separated from the melting process,
which shows a peak temperature Tm = 154°C. All these data are
in accordance with those found in literature, where values of
Tg = 55–59°C and melting temperature Tm = 150–160°C (or
173–178°C depending on its crystallinity) are given.53,61,62
Optical purity is an important physical characteristic that
determines the crystallisation process, but if the conditions are not
favourable, the polymer is amorphous. After the first run, samples
were quenched so that the cold crystallisation and melting peak
are smaller and they do not appear as separated processes in the
second run (Figure 9(a)).
Incorporation of HC and other additives such as USE, VE, PL and
silver NPs also affects the cold crystallisation of PLA, which
appears as a distinct process separated by melting, and Tcc
takes characteristic values for each system. Tcc decreased
by approximately 20°C for PLA/USE probably owing to the
increase in the chains’ mobility,67 and this thermal phenomenon
occurs at lower temperatures in the case of other composites
in both the dry and hydrated states, the lowest value being recorded
for bionanocomposite containing silver NPs, which has Tcc values
of 96·9°C in the dry state and 84·8°C in the hydrated state. This
behaviour can be explained both by an increased flexibility and by
the nucleating activity of incorporated additives, which promote
small organised structure formation in amorphous state.68

Investigations were performed also in the hydrated state (RH
70%) (DSC curves not shown), being known that urinary
catheters are used in biological medium. It is well known and was
also demonstrated by data presented earlier that plasticiser
incorporation improves the flexibility and processability of PLA
due to Tg reduction.63 Indeed USE lowers the Tg of the PLA/USE
blend by approximately 3·5°C in the dry state and by ~10°C in
the hydrated state. Pamfil et al.,64 Nistor et al.65 and Guan et al.66
demonstrated that water has a plasticiser effect on the glass
transition temperature. The decrease in Tg was observed not only
for all studied composites compared with PLA because they
contain USE but also for samples in the hydrated state compared
The melting temperatures (Tm) of the blends and composites
have slightly higher values, suggesting formation of crystallites
with much ordered structures. Moreover, a single melting
peak characterises neat PLA at 151·6°C, while in the DSC
melting curves of the blends and composites, observed is
either a shoulder or splitting of the melting peak, indicating
formation of crystallites with different degrees of ordering or
crystallographic structures. This observation is in accordance with
literature data.69
The thermal behaviour of collagen-based materials is
characterised by the effect of temperature on collagen itself and

Tg: °C DCp: J/g K Tcc: °C DHcc: J/g Tm: °C DHm: J/g

Sample X: %
DSC DTA DSC DTA DSC DSC DSC DTA/DDTA DSC DTA
1: PLA 59·6 65·1 0·885 1·942 125·9 19·9 154 152·4/147·2 22·3 5·8 23·8
2: PLA/USE 57·3 60·4 0·268 104·0 19·7 151·6 155·7/150·0 23·8 9·5 25·4
3: PLA/USE/VE 58·3 58·3 0·483 4·174 107·9 18·5 148·0 155·3/148·6 21·4 13·2 22·9
156·6
4: PLA/USE/VE/HC 55·1 57·6 0·505 0·430 123·5 16·9 149·1 155/148·1 22·6 12·4 24·1
156·6
5: PLA/USE/PL/HC 58·3 57·1 — 2·367 105·6 14·3 148·1 156·5/152·0 20·97 11·9 22·4
155·8
6: PLA/USE/VE/PL/HC 50·4 57·1 0·507 0·931 101·9 14·5 147·1 155·7/150·1 19·1 8·6 20·4
155·6
7a: PLA/USE/VE/HC/ — 51·9 — 0·551 — — — 154·5 — 16·8 —
PL/0·3AgNP
7b: PLA/USE/VE/HC/ — 51·5 — 0·469 — — — 154·9 — 15·8 —
PL/0·5AgNP
7c: PLA/USE/VE/HC/ 50·4 54·8 0·555 0·016 120·9; 27·9 156·2 156·1/150·5 22·7 11·8 24·2
PL/1·5AgNP 96·9 13·2
8: Collagen — 45·9 — 0·288 — — — 192/175·1 — 2·2 —

Table 7. DSC and DTA data (the first run) for PLA and its blends melting temperature; X, crystallinity index; DHcc, cold crystallisation
and biocomposites. DDTA, derivative of the DTA curve; Tcc, cold enthalpy; DHm, melting enthalpy
crystallisation temperature; Tg, glass transition temperature; Tm,

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by the presence of water molecules, which can exist in both
bonded and free states.66 An endothermal process was evident in
the −28 to 10°C temperature range in the DSC curve for samples
containing HC in the hydrated state, which can be assigned to
bonded water. The mass fraction of bonded and free water for
these samples was 29·9% and 0·8%, respectively.
3.5.2 Thermogravimetry
In the case of polyesters, many several degradation mechanisms
can happen depending on the processing conditions. The main
reactions are hydrolysis and random main-chain scission.
Hydrolysis of the ester linkage, a water-based degradation
mechanism, takes place randomly in the polymer at low
temperatures, while at temperatures above 180°C random main-
chain scission of C–O ether linkage, carbonyl C–C linkage and
carbonyl C–O linkage scission occur,70,71 accompanied by
hydrogen transfer reaction, leading to a vinyl ester and acid end
groups. The chain end groups’ contributions are more pronounced
in the temperature range of 270–360°C.71 The trans-esterification
mechanism is a dominant degradation mechanism of PLA at high
temperatures (above 200°C), where cyclic oligomers are
formed,72,73 while cis-elimination occurs at a high temperature
range (300–500°C).74 Chain ends promote the depolymerisation by
backbiting (chain end scission or intramolecular transesterification)
in the temperature range of 270–360°C.75 The control of thermal
degradation of PLA during processing is still a challenge for the
industry. This task can be achieved by using blends, chain
extenders and other additives.76,77
The main components of blends and biocomposites decompose in
a particular way (Figure 10 and Table 8). PLA (P1) decomposes
almost totally (98% mass loss) in a single step in the 321–367°C

100 −100 −120

80 PLA 80 −100
−80 PLA/USE/HC/PL
60 60
−80

DTG: %/min
DTG: %/min

PLA/USE PLA/USE/VE/HC/PL
40 −60
40
Mass: %

Mass: %

PLA/USE/VE/HC/ −60
20
PLA/USE/VE −40 20 PL/1·5AgNP
−40
0 HC
0
PLA/USE/VE/HC −20
−20 USE −20
−20
−40 0
0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature: ˚C Temperature: ˚C
(a) −80 (b)
100
PLA/USE/VE/HC/PL/AgNP
80 0·1% AgNP
−60
0·3% AgNP
60 1·5% AgNP
DTG: %/min
Mass: %

40 −40

20

0 −20

−20
0
−40
200 300 400 500
Temperature: ˚C
(c)

Figure 10. TG/DTG curves for (a) neat PLA, PLA/USE, PLA/USE/VE and
PLA/USE/VE/HC, (b) USE, HC, PLA/USE/VE/HC/PL, PLA/USE/HC/PL and
PLA/USE/VE/HC/PL/1·5AgNP and (c) PLA/USE/VE/HC/PL/0·1AgNP; PLA/
USE/VE/HC/PL/0·3AgNP and PLA/USE/VE/HC/PL/1·5AgNP

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Degradation Tonset: Tpeak: Tendset: W: Wr,500°C: T10: T50:

Sample
stage °C °C °C % % °C °C
1: PLA I 321 349 367 98·92 1·08 325 346
2: PLA/USE I 329 347 361 98·14 1·86 326 346
3: PLA/USE/VE I 311 340 372 98·67 1·33 310 340
4: PLA/USE/VE/HC I 320 338 356 98·17 1·83 324 339
5: PLA/USE/PL/HC I 313 328 341 97·28 2·72 317 329
6: PLA/USE/VE//PL/HC I 307 325 338 96·75 3·25 311 325
7a: PLA/USE/VE/PL/HC/ I 315 338 361 95·42 4·58 322/329 341
0·3AgNP
7b: PLA/USE/VE/PL/HC/ I 310 331 349 96·63 3·37 315/322 333
0·5AgNP
7c: PLA/USE/VE/PL/HC/ I 308 326 339 96·60 3·40 314 327
1·5AgNP
8: HC I 37 90 132 7·82 25·47 222 348
II 207 — 243 3·95 — — —
III 250 324 381 62·76 — — —
9: USE I 355 370 375 21·16 3·27 367 401
II 375 386 397 25·86 — — —
III 400 — 430 30·38 — — —
IV 440 — 483 19·33 — — —

Table 8. TG data for PLA and PLA-based blend and composites. temperature of each TG step; W, mass loss for each
T10, temperature corresponding to 10 wt% mass loss; T50, thermogravimetric stage; Wr,500°C, residual mass loss
temperature corresponding to 50 wt% mass loss; Tonset, onset

temperature range with a peak temperature of 349°C. The onset
decomposition temperature (Td) was higher than 320°C under
nitrogen atmosphere. TG/derivative thermogravimetric (DTG)
curves of HC (P8) show two steps of mass loss; the first one
is due to water loss (7·82 wt%), and the second one of
decomposition occurs in 250–380°C with a peak temperature of
324°C and a mass loss of 62·76 wt%. USE is thermally stable up
to 355°C and then decomposes in four steps. The decomposition
of the blends and composites follows the trend for PLA, the
differences appearing in the TG characteristics, all their
decomposition temperatures being lower than that of PLA and
mass loss being smaller with increasing residual mass loss at
500°C (Table 7).
The T10 and T50 temperatures show the same variation among the
samples; therefore, the blends and biocomposites are a little less
thermally stable than PLA. Similar results were obtained by other
authors.78 TG characteristics decrease with increasing silver NP
content probably because the metallic silver acts as a catalyst for
thermal decomposition of matrix.
heating rate of 1°C/min in a nitrogen atmosphere). The MNLR
programme was applied to determine the complex mechanisms of
the investigated processes and the kinetic parameters on the
temperature domain of 250–420°C. In Table 8 the kinetic and
statistic parameters appropriate to all the tested models and the
thermal degradation mechanisms are summarised. The best results
were obtained by running the experimental data for the extent of
conversion of 0·10 £ a £ 0·80 to each selected reaction model
and considering the following conversion functions79
1. nth-order reaction; model Fn:  f ðaÞ ¼ ð1  aÞn
where a is the extent of conversion of the thermal degradation
reaction and n is the reaction order.
n-dimensional nucleation ðAvrami​ ErofeevÞ reaction;
​
ðn1Þn
2.  model An:  f ðaÞ ¼ nð1  aÞ½lnð1  aÞ
where n is a constant parameter.

To obtain new insights on the thermal decomposition process,
kinetic parameters were evaluated.
The most probable kinetic models of the degradation processes
were obtained with the ‘multivariate non-linear regression’
(MNLR) method (applied for experimental conditions and a
The thermal degradation is a one- and two-step mechanism, with
consecutive or independent reactions of types A-1 → B, A-1 →
B-2 → C and A-1 → B, C-2 → D. The codifications are those
used in the Thermokinetics 3 program: A, B, C and D are solid
compounds; 1 and 2 denote the mechanism steps; s is a thermal
process in one step, d:f and d:i are thermal processes in two

146
 Volume 5 Issue BBN4

PLA/USE/ PLA/USE/ PLA/USE/

PLA/ PLA/USE/ PLA/USE/ PLA/USE/
PLA PLA/USE VE/PL/HC/ VE/PL/HC/ VE/PL/HC/ HC USE
USE/VE VE/HC PL/HC VE/PL/HC
P1 P2 0·3AgNP 0·5AgNP 1·5AgNP P8 P9
Bioinspired, Biomimetic and Nanobiomaterials

P3 P4 P5 P6
Parameter P7a P7b P7c
df:Fn,An df:Fn,Fn df:Fn,Fn df:Fn,An df:Fn,An df:Fn,Fn df:Fn,Fn df:Fn,Fn di:Fn,Fn df:Fn,An
s:Fn A-1 → A-1 → A-1 → A-1 → A-1 → A-1 → A-1 → A-1 → A-1 → B A-1 →
A-1 → B B-2 → C B-2 → C B-2 → C B-2 → C B-2→C B-2 → C B-2 → C B-2 → C C-2→D B-2 → C
E1: mol−1 273·5 199·6 189·7 189·7 179·8 160·8 138·1 128·3 154·5 98·2 50·2
log A1: s−1 21·2 14·9 14·6 14·4 13·7 12·1 9·8 8·9 11·6 5·9 1·4
n1 1·22 0·67 2·10 0·74 0·48 0·47 0·2 0·4 0·43 1·87 0·86
E2: mol−1 — 199·5 181·5 189·8 176·9 147·9 155·3 206·5 171·9 170·7 199·8
log A2: s−1 — 15·68 13·64 14·88 14·38 11·80 12·3 16·5 13·90 11·88 14·58
n2 — — 1·00 2·23 — — 2·99 2·99 3·00 2·99 —
d2 — 0·30 — — 0·20 0·22 0·11 0·08 — — 0·44
Indep react1 — — — — — — — — — 2·83 —
Foll react 1 — 0·36 0·38 0·11 0·09 0·12 — — 0·05 — 0·001
R 0·99995 0·999994 0·999991 0·999992 0·999948 0·999929 0·99981 0·99991 0·999903 0·999997 0·999962

Table 9. Kinetic and statistic parameters determined by non-linear regression method for Avrami–Erofeev model; E1, E2, activation energies for each step; Foll react 1, share of
the most probable mechanism of thermal degradation of the blends by applying a
Complex poly(lactic acid)-based

reaction step 1 (A → B) in the total mass loss; Indep react1, independent reaction 1; log
Influence of AgNP on properties

multiple-step kinetic model, with consecutive reactions in the 250–420°C temperature A1, log A2, pre-exponential factor for each step; n1, n2, reaction orders; R, correlation
biomaterial for urinary catheters: I.

Darie-Niță, Munteanu, Tudorachi et al.

Author copy for personal use, not for distribution

interval. Code models: type reaction. d2, dimension coefficient according with coefficient
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147
Bioinspired, Biomimetic and Nanobiomaterials
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stages where the individual steps are linked by consecutive and
independent reactions of nth order of Fn type and n-dimensional
nucleation Avrami–Erofeev reaction model.
The following mechanisms of the thermal decomposition
processes were also taken into account, the scheme coded as s:Fn;
df:Fn,An; df:Fn,Fn; and di:Fn,Fn.
It can be noticed that in all cases the thermal decomposition takes
place according to some resembling kinetic models, in multiple
stages with consecutive reactions of nth order. The accuracy
of the kinetic parameters was checked by comparing the
experimental thermograms with those simulated by the computer
program. More models were tested for the thermal decomposition
reactions of the blends according to the Thermokinetics 3
software, where various methods of kinetic analysis and of
predictions are integrated. The model-based analysis was used
because it enables to solve the system of differential equations
and make statistical comparison of used models and to select the
most suitable one.80,81
In Table 9 the data with the best-fit quality are presented. A very
good correlation of the experimental data with the theoretical ones
was observed. The values for the correlation coefficients being
close to 1 demonstrates that the kinetic and statistic parameters
have a good accuracy.
PLA kinetics follows a kinetic model with a single step, while the
kinetics of decomposition of other components, blend and
composites can be described by a kinetic model of two consecutive
reactions. Both reaction orders, pre-exponential coefficient and
average activation energies decreases with incorporation of each
supplementary components in the PLA matrix, the smallest values
are obtained for the bionanocomposite of interest, PLA/USE/VE/
PL/HC/silver NP and, of course, for HC and USE incorporation. It
is seems that reaction 2 is prevalent for samples P4–P9. However,
the decrease in all thermal characteristics is not very important, they
remain close to those of base polymer, PLA.
4. Conclusion
The aim of this research was to improve the flexibility,
biocompatibility and functionality of PLA and to obtain
bionanocomposites that are destined for medical applications
such as catheters. The present study focused on the development
of biocompatible antimicrobial/antioxidant biodegradable
bionanocomposite renewable resources based on PLA plasticised
with USE. In the PLA matrix HC (to enhance biocompatibility),
vitamin E (as antioxidant agent) and silver NPs (to impart
antimicrobial properties for medical applications and also for active
packaging) were incorporated. PL was used as compatibiliser. The
systems were obtained by using the classical technological flow of
melt processing. Young’s modulus and tensile stress at the point of
break decreased, while the elongation at the point of break and the
impact strength increased for the prepared blends in comparison
with those for the pure PLA. The specific interactions of silver NPs
148
Complex poly(lactic acid)-based
biomaterial for urinary catheters: I.
Influence of AgNP on properties
Darie-Niță, Munteanu, Tudorachi et al.
with the other components of nanocomposites, mainly with HC
protein and vitamin E (by ionic and other types of secondary
bonds), led to a better dispersion of HC and vitamin E in the
matrix, particularly for the formulation with a high silver content
(1·5%), which further caused the enhancement of the mechanical
properties. Therefore, the silver NPs were successfully embedded
into the polymer matrix. The DSC and TG studies showed that the
thermal characteristics are slightly inferior to those of PLA. The
kinetics of composites decomposition can be described by a kinetic
model with two consecutive reactions with specific kinetic
parameters. The decrease in all thermal characteristics is not very
important; they remained close to those of base polymer, PLA. The
multifunctionality and biocompatibility characteristics are evidenced
by the results given in the second part of this research work.60
Acknowledgements
The authors acknowledge that the research leading to their results
received funding from Romanian-East European Area (EEA)
Research Programme operated by Ministry of National Education
under EEA Financial Mechanism 2009–2014 project contract
number 1SEE/2014 and from Romanian Executive Agency for
Higher Education, Research, Development and Innovation
Funding through the research project Bionanomed 164/2012.
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