applied

sciences
Article
Characterization of Different Chemical Blowing
Agents and Their Applicability to Produce
Poly(Lactic Acid) Foams by Extrusion
Ákos Kmetty 1,2, * , Katalin Litauszki 1 and Dániel Réti 1
1 Department of Polymer Engineering, Faculty of Mechanical Engineering, Budapest University of
Technology and Economics, Műegyetem rkp. 3., H-1111 Budapest, Hungary; litauszkik@pt.bme.hu (K.L.);
reti.daniel92@gmail.com (D.R.)
2 MTA–BME Research Group for Composite Science and Technology, Műegyetem rkp. 3.,
H-1111 Budapest, Hungary
* Correspondence: kmetty@pt.bme.hu; Tel.: +36-1-463-2004




Received: 25 September 2018; Accepted: 11 October 2018; Published: 17 October 2018


Abstract: This study presents the applicability of different types (exothermic and endothermic) of
chemical blowing agents (CBAs) in the case of poly(lactic acid) (PLA). The amount of foaming agent
is a fixed 2 wt%. We used a twin-screw extruder and added the individual components in the
form of dry mixture through the hopper of the extruder. We characterized the PLA matrix and the
chemical blowing agents with different testing methods. In case of the produced foams we carried out
morphological and mechanical tests and used scanning electron microscopy to examine cell structure.
We showed that PLA can be successfully foamed with the use of chemical blowing agents. The best
results were achieved with an exothermic CBA and with PLA type 8052D. The cell population density
of PLA foams produced this way was 4.82 × 105 cells/cm3 , their expansion was 2.36, their density
0.53 g/cm3 and their void fraction was 57.61%.

Keywords: chemical blowing agent; poly(lactic acid) foam; foam extrusion

1. Introduction
Nowadays the number and amount of polymers produced from renewable resources are
increasing considerably. These polymers are also readily available [1]. Global market forecasts
predict a fourfold increase until 2019 (7.8 million ton/year) [2]. Polymer foams nowadays are mostly
produced from petroleum-based materials. Foamed products, made by physical [3], chemical [4] and
bead foaming techniques [5], in addition there are innovative examples of metallic foams as well [6].
Although physical foaming technique produce a lower foam density (density reduction up to 80%),
chemical foaming agents can be used without modifying the extruder [7]. Foaming can be divided into
four sections. In the initial phase, the gas enters the polymer matrix and the two phases mix. In the
next section, the matrix material is saturated with the foaming gas at an elevated temperature and
pressure. In the third section, the homogeneous system expands as the pressure decreases. In the final
section, the structure stabilizes [8]. An important foaming method is chemical foaming, when the
foaming agent requires certain conditions to decompose and in the process a gas phase is generated as
a result of a chemical change. It is important to choose the decomposition temperature range of the
foaming agent to match the processing temperature of the matrix polymer. Chemical blowing agents
can be used in different temperature ranges. Their decomposition products are various gases. The most
important is the gas that is produced in the largest quantity [9]. Foaming agents can be endothermic
and exothermic. The most often used exothermic foaming agent is azodicarbonamide (ADCA),
even though ADCA decomposes at a relatively high temperature, at 230 ◦ C. When 5% 4,40 -oxybis

Appl. Sci. 2018, 8, 1960; doi:10.3390/app8101960 www.mdpi.com/journal/applsci

Appl. Sci. 2018, 8, 1960 2 of 17

(benzenesulfonylhydrazide) (OBSH) is added, it reduces the initial temperature of decomposition

to 205 ◦ C. However, this temperature is still higher than the processing temperature of some very
common polymers (e.g., P-PVC, U-PVC, EVA and PLA). With the use of activators (zinc stearate,
zinc oxide, naphthenate, urea or benozate), the decomposition temperature range can be reduced to as
low as 40 ◦ C. The decomposition process typically yields 220 cm3 /g gas. Its decomposition products
are nitrogen (N2 ) 65%, carbon monoxide (CO) 24%, carbon dioxide (CO2 ) 5% and ammonia (NH3 )
5% [10,11]. It can produce larger cells, greatly reduce density from 1.24 g/cm3 to 0.599 g/cm3 (in
case of neat, extruded PLA) but the yellowish colour of the foaming agent affects the colour of the
product [12]. The most often used endothermic foaming agent is a mixture of sodium bicarbonate and
citric acid. It is typically whitish, can produce finer cells and less reduction in density from 1.24 g/cm3
to 0.645 g/cm3 in case of neat, extruded PLA [12–16]. Sodium bicarbonate starts to decompose at
around 160 ◦ C, while citric acid only starts decomposing at around 210 ◦ C. About 120 cm3 /g of gas is
produced. Foaming agents working in different temperature ranges can be produced by mixing the
two components at different ratios [17,18]. Such CBAs typically have water among their decomposition
products. If the polymer matrix is sensitive to moisture (e.g., polycarbonates or polyesters), a CBA
should be chosen which does not have water among its decomposition products (or only a very small
amount) because the water can hydrolyse the polymer [9].
A great disadvantage of petroleum-based polymeric materials and products made from them is
that they are difficult and costly to recycle, cannot be decomposed biologically and are a considerable
load on the environment after they lose their function. Renewable resource-based and biodegradable
polymers offer an environmentally friendly alternative. Of all biopolymers, poly(lactic acid) (PLA)
receives the most attention nowadays [19]. PLA can be foamed in many ways (extrusion foaming,
foam injection moulding, bead foaming) but currently the application of supercritical fluid state carbon
dioxide receives the most attention [20,21].
Foaming this biopolymer with chemical blowing agents is not fully researched yet. Commercially
available CBAs are mostly designed for the foaming of petroleum-based polymers and their
applicability with biodegradable polymers needs more research [22]. Our goal was to analyse a
wide range of commercially widely available conventional exothermic and endothermic foaming
agents so we selected two endothermic, one exothermic CBAs recommended for polyesters and a new
endothermic CBA specially designed for the foaming of PLA. Such a CBA, especially recommended
for PLA, has never been examined in the literature. We characterized these CBAs and investigated
their applicability for PLA in detail, using continuous extrusion as manufacturing technology.

2. Materials and Methods

2.1. Material
We used poly(lactic acid) type 2003D (4.3 mol% D-lactide content) and 8052D (4.5 mol% D-lactide
content), (Ingeo™ Biopolymer, NatureWorks© LLC, Minnetonka, MN, USA). The PLAs have a melting
temperature of 150.9 ◦ C and of 153.3 ◦ C (determined by DSC from the first melting curve, 5 ◦ C/min),
a Melt Flow Index of 2 g/10 min and 7 g/10 min (CEAST 7027.000, 2.16 kg, 190 ◦ C), respectively,
as measured by the authors. The number average molecular weight was 100,422 Da, the weight average
molecular weight was 180,477 Da, the polydispersity index was 1.79, the number average molecular
weight was 85,562 Da, the weight average molecular weight 153,235 Da and the polydispersity index
was 1.79 (Figure 1, determined by gel permeation chromatography (GPC) measurements).
Appl. Sci. 2018, 8, 1960 3 of 17
Appl. Sci. 2018, 8, x FOR PEER REVIEW 3 of 17

1.4
2003D
1.2 8052D

1.0

dw/dlogM
0.8

0.6

0.4

0.2

0.0
1 100 10000 1000000

Molecular weight [Da]

Figure The
1. 1.
Figure molecular
The weight
molecular distribution
weight of different
distribution poly(lactic
of different acid)acid)
poly(lactic (PLA) granules
(PLA) basedbased
granules on a gel
on a
permeation chromatography (GPC) test.
gel permeation chromatography (GPC) test.

We used exothermic and endothermic CBAs in 2 wt% for the extrusion foaming of PLA. Table 1
We used exothermic and endothermic CBAs in 2 wt% for the extrusion foaming of PLA. Table 1
contains the exact types and their specifications as found on their datasheets.
contains the exact types and their specifications as found on their datasheets.
Table 1. Chemical blowing agents (CBAs) used and their properties.
Table 1. Chemical blowing agents (CBAs) used and their properties.
Effective
CBATrade
CBA Trade Name TypeTypeofof CBA Blowing Agent * Effective Other Information
Other * Abbreviation
Gases *
Blowing Agent * Abbreviation
Name CBA Gases
N2 , CO,
* Information *
Tracel IM 3170 MS exothermic azodicarbonamide - Tracel3170
Tracel IM N22, CO,
CO , NH 3
exothermic azodicarbonamide -
water is formed, Tracel3170
3170
TracelMS
IMC 4200 endothermic
citric acid and CO,2H
CO , NH 3
2 2O it contains a Tracel4200
baking soda
water is formed,
nucleating agent
Tracel IMC citric acid and recommended for
endothermic
Hydrocerol CT 3168 endothermic n.d. CO 2, H2O
n.d. it contains
PLA
a Tracel4200
Hyd_3168
4200 baking soda
Luvobatch PE BA 9537 endothermic n.d. n.d. nucleating
carrier PE agent Luv_9537
recommended
Hydrocerol *—Information from Technical Datasheet, n.d.—no data from the manufacturer.
endothermic n.d. n.d. Hyd_3168
CT 3168 for PLA
2.2. Luvobatch
Testing Methods
endothermic n.d. n.d. carrier PE Luv_9537
PE BA 9537
2.2.1. Gel Permeation Chromatography (GPC)
*—Information from Technical Datasheet, n.d.—no data from the manufacturer.
The tests were performed on an Agilent PL-GPC 50 System (Santa Clara, CA, USA) GPC/SEC
2.2.
device.Testing Methodswere first dissolved in chloroform (ca. 30 mg/mL), then filtered through a PTFE
The samples
filter. Four Agilent PL-Gel columns (3 × PL-Gel Mixed C (5 µm) and 1 × PL-Gel Mixed E (3 µm)
2.2.1. Gel
columns) Permeation
were Chromatography
used in series, (GPC)chloroform (amylene-stabilised) as the eluent, at a flow
with HPLC grade
rate of The
1 mLtests − 1
minwere ◦
at performed
30 C, on a on
Waters Alliance system 50
equipped
an Agilent PL-GPC System with anClara,
(Santa Alliance
CA,2695 Separation
USA) GPC/SEC
Module. The polymer number-average molecular weight (M
device. The samples were first dissolved in chloroform (ca. 30 ) and polydispersity index (Mwa/M
n mg/mL), then filtered through n;
PTFE
PDI) were
filter. calibrated
Four Agilent against
PL-Gel low dispersity
columns polystyrene
(3 × PL-Gel Mixedstandards
C (5 μm)with
and a1 3rd order polynomial
× PL-Gel Mixed E (3 μm)fit,
linear across molar mass ranges.
columns) were used in series, with HPLC grade chloroform (amylene-stabilised) as the eluent, at a
flow rate of 1 mL min−1 at 30 °C, on a Waters Alliance system equipped with an Alliance 2695
2.2.2. Differential Scanning Calorimetry (DSC) for Chemical Blowing Agents
Separation Module. The polymer number-average molecular weight (Mn) and polydispersity index
(MwDifferential
/Mn; PDI) werescanning calorimetry
calibrated against(DSC) measurements
low dispersity of chemical
polystyrene blowing
standards withagents
a 3rdwere
order
performed
polynomialwith
fit,alinear
Setaram DSCmolar
across 92 (Caluire, France) device. The measurement temperature range was
mass ranges.
25–250 ◦ C, the heating rate was 10 ◦ C/min, the mass of the samples was between 3 mg and 6 mg
Appl. Sci. 2018, 8, 1960 4 of 17

and the tests were performed in nitrogen protective gas (20 mL/min) and with a nitrogen measuring
atmosphere (20 mL/min).

2.2.3. Differential Scanning Calorimetry (DSC) for Biopolymer Foams

Differential scanning calorimetry (DSC) measurements of biopolymer foams were carried out
with a TA Instruments Q2000 (New Castle, DE, USA) automatic sampling device. The measurement
temperature range was 0–200 ◦ C, the heating rate was 5 ◦ C/min, the mass of the samples was between
3 mg and 6 mg and the tests were performed in nitrogen protective gas (20 mL/min) and with a
nitrogen measuring atmosphere (20 mL/min). The degree of crystallinity (χc ) was calculated according
to Equation 1, where ∆Hm is the crystallization enthalpies. The degree of crystallinity (χcf ) created
via foam processing was calculated according to Equation (2), where ∆Hm is the melt and ∆Hc is the
crystallization enthalpy. PLA100% is the theoretical melting enthalpy of 100% crystalline PLA, which is
93 J/g [23].
∆Hm
χc = x 100 [%], (1)
PLA100%
∆Hm − |∆Hc |
χcf = x 100 [%], (2)
PLA100%

2.2.4. Thermogravimetric Analysis-Fourier-Transform Infrared Spectrometry (TGA-FTIR)

In the TGA-FTIR test, the two devices were connected so that the gas phases released in the TGA
test travel through the sensors of the FTIR device. The gases went through a silicon tube; flow was
maintained with nitrogen background gas. The FTIR test can determine the chemical composition of
the gas from the TGA test. With this method, the composition of the gas can be determined across
the whole temperature range. The TGA-FTIR measurements were performed with a TA Instruments
Q5000 (New Castle, DE, USA) automatic sampling device. The measurement temperature range was
40–800 ◦ C, the heating rate was 10 ◦ C/min, the mass of the samples was between 1 mg and 4 mg
and the tests were performed in nitrogen protective gas (25 mL/min) and with nitrogen measuring
atmosphere (50 mL/min). The TGA device was connected to a Bruker Tensor 37 FTIR (Billerica,
MA, USA) device. Gas was released at different temperatures in the case of the different CBAs and
the spectrum was evaluated at the maximum of effective gas generation in each case (in the case
of Tracel3170 it was 190 ◦ C, in the case of Tracel4200 it was 175 ◦ C, in the case of Luv_9537 it was
157 ◦ C, while in the case of Hyd_3168 it was 232 ◦ C). We took into account the effective gases which
are generated below manufacturing temperature.

2.2.5. Thermogravimetric Analysis Performed in Isothermal Conditions

TGA measurements were performed with a TA Instruments Q500 (New Castle, DE, USA)
automatic sampling device. The measurement temperature was 190 ◦ C, the heating rate was
100 ◦ C/min, the mass of the samples was between 1 mg and 4 mg and the tests were performed
in nitrogen protective gas (40 mL/min) and with industrial air measuring atmosphere (60 mL/min).
These conditions are closer to those in an extruder. The isothermal temperature was chosen to be
190 ◦ C because this is a usual processing temperature during the extrusion of PLA. The background
gas was chosen to be air, because the CBA may get into contact with air during the manufacturing
process. The samples reached the isothermal 190 ◦ C in 3 min and they were kept at this temperature
for another 330 s.

2.2.6. Scanning Electron Microscopy (SEM)

Scanning electron micrographs were taken from fracture surfaces with a Jeol JSM-6380LA (Tokyo,
Japan) SEM with an acceleration voltage of 10 kV. Prior to the test, the samples were sputter-coated
with a gold/palladium alloy.
Appl. Sci. 2018, 8, 1960 5 of 17

2.2.7. Foam Characterisation

The volume of foam structures was measured with a 10 mL glass cylinder (accuracy 0.1 cm3 );
the measuring medium was distilled water. Mass was measured with a Sartorius BP121S type balance
(Göttingen, Germany). Its range is 120 g, its measuring accuracy is 0.1 mg and its resolution is 0.1 mg.
Density was calculated according to Equation (3).
mfoam
ρfoam = , (3)
Vfoam

Void fraction was calculated according to Equation (4) [24].

ρfoam
Vf = 1 − , (4)
ρpolymer

where Vf [-] is void fraction, ρfoam is the density of the foamed polymer and ρpolymer is the density of
unfoamed polymer.
Cell population density was calculated based on the SEM images, according to Equation (5),
where n is the number of cells counted in the recorded image, A [cm2 ] is the cross section area of the
sample, M [-] is the magnification factor and ER [-] is the expansion ratio [24].
!3
n ∗ M2
2
1
Nc = x , (5)
A 1 − Vf

The expansion ratio was calculated with Equation (6), where ER is the rate of expansion, ρfoam is
the density of the foamed polymer, ρpolymer is the density of unfoamed polymer and Vf is the void
fraction [16].
ρpolymer 1
ER = = , (6)
ρfoam 1 − Vf

2.2.8. Measuring Foam Strength

Foam compressive strength tests were performed with a Zwick Z005 (Ulm, Germany) universal
testing machine (in compression mode). A Mess & Regeltechnik KAP-TC (Dresden, Germany) type
load cell was used (measuring range 0–5000 N, preload 1 N). The measurement speed applied was
2 mm/min. The specimens were cylindrical, with a diameter of 3 mm and a height of 10 mm (Figure 2).
The test was continued until a deformation of 10% was reached. Five samples were tested and the
average of the results was taken. Foam compressive strength was calculated in accordance with
Equation (7).
F
σ10% = 10% , (7)
Afoam
where compressive strength [MPa] is the compression strength at 10% deformation, F10% [N] is the
force at 10% deformation and Afoam [mm2 ] is the cross-sectional area of the foam specimen.
Extrusion foaming was carried out with a Teach-line ZK25T (Collin GmbH, Ebersberg, Germany)
twin-screw extruder (screw diameter: 25 mm, L/D = 24). The temperature profiles of the five
zones starting from the hopper were 155 ◦ C, 160 ◦ C, 175 ◦ C, 190 ◦ C and 190 ◦ C. Screw speed was
10 revolutions per minute, the residence time of the polymer was 330 s, pressure drop [MPa] was
calculated according to Equation (8), where pmelt [MPa] is the pressure that we measured during
extrusion in the die, patm [MPa] is the standard atmospheric pressure, 0,1 MPa. The extrusion die was
a rod type with a circular cross section and with a nominal diameter of 3 mm. All foaming agents
were added to the PLA granules during extrusion in an amount of 2 wt%, by dry mixing. Prior to
manufacturing, the PLA granules were dried at 80 ◦ C for 6 h in a WGL-45B type drying oven.

Pressure drop = pmelt − patm (8)

Appl. Sci. 2018, 8, 1960 6 of 17
Appl. Sci. 2018, 8, x FOR PEER REVIEW 6 of 17

Figure 2. Measurement layout of measuring foam strength.

Figure 2. Measurement layout of measuring foam strength.
3. Results of the Investigation of the Foaming Agents
Extrusion foaming was carried out with a Teach-line ZK25T (Collin GmbH, Ebersberg,
3.1. The
Germany) Thermal and Morphological
twin-screw Properties
extruder (screw of CBAs,25TGA,
diameter: mm,TGA-FTIR,
L/D = 24). DSCThe temperature profiles of the
fiveFirst,
zoneswe starting from the hopper were 155 °C, 160 °C, 175
examined the decomposition temperature ranges of chemical °C, 190 °C andfoaming
190 °C. Screw
agentsspeed was
by TGA.
10 revolutions per minute, the residence time of the polymer was 330 s, pressure
The test showed the mass fraction of the CBAs, the fraction of the gas producer useful from the aspect drop [MPa] was
ofcalculated
foaming andaccording
what istotheEquation
proportion(8), of
where
carrierp polymer
[MPa]andis the
otherpressure
residualthat we measured
materials. during
The samples
extrusion in the die, p [MPa] is the standard atmospheric pressure, 0,1
were measured with two background gases, so it was possible to compare the processes occurring MPa. The extrusion die
inwas
theadifferent
rod type media.
with a circular
We usedcross section and
a nitrogen (N2with a nominaltodiameter
) atmosphere of 3 mm. All
get measurement foaming
results agents
from an
inert atmosphere, while air was used because that is what is present during extrusion; therefore,to
were added to the PLA granules during extrusion in an amount of 2 wt%, by dry mixing. Prior
manufacturing,
the measurementthe PLA granules
approximates were extrusion
real-life dried at 80better.
°C forFigure
6 h in a3 WGL-45B
shows thattypethe drying oven. of
decomposition
CBAs occurred in several steps. In thePressure case of Luv_9537, ◦
drop = p mass − preduction starts at 136 C, this CBA(8) is
followed by Tracel4200, then Tracel3170. While in the case of the exothermic Tracel3170, mass reduction
occurs in one step up to 200 ◦ C, the endothermic Tracel4200 and Luv_9537 exhibit mass reduction
3. Results of the Investigation of the Foaming Agents
in two steps. Between 150–250 ◦ C during the thermal decomposition of CBAs probably effective
gases, taking an active part in foaming are released, above this temperature it is likely that the carrier
3.1. The Thermal and Morphological Properties of CBAs, TGA, TGA-FTIR, DSC
materials decompose. In the case of Hyd_3168 and Luv_9537, a great reduction of mass can be observed
◦ C and
at 300 First, we444 ◦ C, while
examined the in
decomposition temperature
the case of Tracel3170 andranges
4200, ofanchemical
extendedfoaming
gradualagents
decreaseby TGA.
can
beThe test showed
observed at low theintensity.
mass fraction of the CBAs,
Comparing the samethe fraction of the gas
measurements inproducer
N2 and air,useful
we from the aspect
can conclude
of foaming
that and what
gas formation occursis the
in proportion of carrier polymer
the same temperature range. In and other
air, residual
the curve materials. Thesloping,
is continuously samples
while in nitrogen the decomposition ranges separate; the degradation of the carrier polymer and thein
were measured with two background gases, so it was possible to compare the processes occurring
the different media.
accompanying We usedonly
mass reduction a nitrogen
starts at(N
around 400 ◦ C. Table
2) atmosphere to get2 measurement results from results:
contains the measurement an inert
atmosphere, while air was used because that is what is present during
the decomposition temperature ranges based on dTG and the percentage ratio of mass reduction at extrusion; therefore, the
190 ◦
measurement
C. The dataapproximates
indicate thatreal-life extrusion
in the case of the better. Figure CBAs,
investigated 3 shows inthat the decomposition
nitrogen of CBAs
and air atmosphere,
190 ◦ C, mass
atoccurred in several steps.was
reduction In the casethe
nearly of same.
Luv_9537, Theremass
is a reduction starts at only
greater difference 136 °C, thiscase
in the CBAofis
followed by Tracel4200, then Tracel3170. While in the case of the exothermic
Tracel3170; in nitrogen mass reduction was 7.5%, while in air it was only 2.8%. The greatest mass Tracel3170, mass
reduction
reduction inoccurs
nitrogenin was
one observed
step up to in200
the °C,
casethe endothermic
of Tracel3170 Tracel4200
(7.5%), and Luv_9537
it is followed exhibit
by Tracel4200 mass
(6.9%),
reduction in two steps. Between 150–250 °C during the thermal decomposition
Luv_9537 (4.8%) and Hyd_3168 (0.1%). The data indicate that Hyd_3168 probably cannot produce a of CBAs probably
effective
foam ◦ C, the
at 190gases, taking an active processing
characteristic part in foaming are released,
temperature of PLA. above this temperature
All four foaming agents it isproduced
likely that
the carrier
residual massmaterials
at 800 C,◦ decompose. In the case
which is probably of Hyd_3168
a nucleating agent. and Luv_9537, a great reduction of mass
can be observed at 300 °C and 444 °C, while in the case of Tracel3170 and 4200, an extended gradual
decrease can be observed at low intensity. Comparing the same measurements in N2 and air, we can
conclude that gas formation occurs in the same temperature range. In air, the curve is continuously
sloping, while in nitrogen the decomposition ranges separate; the degradation of the carrier polymer
and the accompanying mass reduction only starts at around 400 °C. Table 2 contains the
measurement results: the decomposition temperature ranges based on dTG and the percentage ratio
of mass reduction at 190 °C. The data indicate that in the case of the investigated CBAs, in nitrogen
and air atmosphere, at 190 °C, mass reduction was nearly the same. There is a greater difference only
in the case of Tracel3170; in nitrogen mass reduction was 7.5%, while in air it was only 2.8%. The
greatest mass reduction in nitrogen was observed in the case of Tracel3170 (7.5%), it is followed by
Tracel4200 (6.9%), Luv_9537 (4.8%) and Hyd_3168 (0.1%). The data indicate that Hyd_3168 probably
Appl. Sci. 2018, 8, x FOR PEER REVIEW 7 of 17

cannot produce a foam at 190 °C, the characteristic processing temperature of PLA. All four foaming
Appl. Sci. 2018, 8, 1960 7 of 17
agents produced residual mass at 800 °C, which is probably a nucleating agent.

(a) (b)
Figure
Figure 3. Thermogravimetric
Thermogravimetric analysis
analysis (TGA)
(TGA) results
results ofof foaming
foaming agents
agents in
in nitrogen
nitrogen and
and air
air (a)
(a) mass
mass
reduction
reduction asas aa function
function of
of temperature
temperature (50–800 ◦ C), (b)
(50–800 °C), (b) the
the rate
rate of
of mass
mass reduction
reduction as
as aa function
function of
of
temperature (50–800 ◦°C).
temperature (50–800 Thebroken
C). The brokenline
lineindicates
indicates
thethe nitrogen
nitrogen atmosphere,
atmosphere, while
while the the continuous
continuous line
line indicates
indicates air. air.

Table 2. The decomposition range of CBAs (dTG ranges relevant from the aspect of PLA extrusion
Table 2. The decomposition range of CBAs (dTG ranges relevant from the aspect of PLA extrusion
processing) and mass reduction at 190 ◦ C.
processing) and mass reduction at 190 °C.
dTG Range
dTG Range Mass Reduction
Mass Reduction at 190 °C dTG Range
dTG Range MassReduction
Mass Reductionatat190 °C
Sample
Sample N2 at 190 ◦ C N2 Air 190 ◦ C Air
N2 N2 Air Air
[-] ◦ [◦ C]
[-] [°C] [ C] [%][%] [°C] [%][%]
Tracel3170 145–239145–239
Tracel3170 7.5 7.5 147–212
147–212 2.82.8
145–188,145–188, 147–187,
147–187,
Tracel4200
Tracel4200 6.9 6.9 6.56.5
204–245204–245 196–232
196–232
Hyd_3168
Hyd_3168 186–237186–237 0.1 0.1 193–237
193–237 0.10.1
136–168,136–168, 137–165,
137–165,
Luv_9537
Luv_9537 4.8 4.8 3.93.9
168–225168–225 174–214
174–214

We evaluated the gases released at the maximum intensity of decomposition with a TGA-FTIR
We evaluated the gases released at the maximum intensity of decomposition with a TGA-FTIR
measurement. The results can be seen in Figure 4. We determined the type of gases generated under
measurement. The results can be seen in Figure 4. We determined the type of gases generated under the
the processing temperature (Table 3). The maximum intensity of gas generation in the case of the
processing temperature (Table 3). The maximum intensity of gas generation in the case of the different
different CBAs: Tracel3170—183 °C, Tracel4200—168 °C, Luv_9537—147 °C, while in the case of
CBAs: Tracel3170—183 ◦ C, Tracel4200—168 ◦ C, Luv_9537—147 ◦ C, while in the case of Hyd_3168 there
Hyd_3168 there was no observable gas generation intensity maximum under 200 °C, the maximum
was no observable gas generation intensity maximum under 200 ◦ C, the maximum occurred at 225 ◦ C.
occurred at 225 °C. Based on the spectrum measured by FTIR, in the case of Tracel3170, peaks
Based on the spectrum measured by FTIR, in the case of Tracel3170, peaks indicating carbon dioxide
indicating carbon dioxide have the highest intensity but carbon monoxide is also present with lower
have the highest intensity but carbon monoxide is also present with lower absorption. Also, a C=N
absorption. Also, a C=N bond appears as well, which indicates isocyanate (~2200–2350 cm−1), which
bond appears as well, which indicates isocyanate (~2200–2350 cm−1 ), which is a typical decomposition
is a typical decomposition product of azodicarbonamide. In the case of Tracel4200, a strong
product of azodicarbonamide. In the case of Tracel4200, a strong absorption carbon dioxide peak can
absorption carbon dioxide peak can be observed but no carbon monoxide. In the case of Luv_9537,
be observed but no carbon monoxide. In the case of Luv_9537, the absorption wavelength of carbon
the absorption wavelength of carbon dioxide can be observed. In the case of Hyd_3168, carbon
dioxide can be observed. In the case of Hyd_3168, carbon dioxide appears as an effective gas but with
dioxide appears as an effective gas but with a small intensity peak. It is important to note that the
a small intensity peak. It is important to note that the type of effective gas also has an effect on the
type of effective gas also has an effect on the final foam structure. CO2 has higher solubility (20 wt%)
final foam structure. CO2 has higher solubility (20 wt%) in the PLA matrix compared to N2 (2 wt%).
in the PLA matrix compared to N2 (2 wt%). As a result, CO2 effectively lowers melt pressure during
As a result, CO2 effectively lowers melt pressure during extrusion and increases the percentage of
extrusion and increases the percentage of crystalline fraction [25]. The reaction range of CBAs was
crystalline fraction [25]. The reaction range of CBAs was also analysed with a DSC test. Figure 5 below
also analysed with a DSC test. Figure 5 below contains the measurement results.
contains the measurement results.
Appl. Sci. 2018, 8, 1960 8 of 17
Appl. Sci. 2018, 8, x FOR PEER REVIEW 8 of 17

Tracel4200
Luv_ 9537
Tracel3170
Hyd_3168

Absorbance

3800 3400 3000 2600 2200 1800 1400 1000 600

Wavenumber [cm-1 ]

Figure 4. The
Figure Fourier
4. The transform
Fourier infrared
transform (FTIR)
infrared spectrum
(FTIR) of foaming
spectrum agentsagents
of foaming (in the(in
600–4000 cm−1 range).
the 600–4000 cm−1
range).
Table 3. The results of the TGA-FTIR measurement (10 ◦ C/min, nitrogen measuring atmosphere).

We compared the absorbanceAbsorbance

spectrum of generated
Maximums [-]effective gases with the intensity peaks of
Foaming Agent Type of Gas Generated
the spectra of materials in Wave
the IRNumber
database of
−
[cm ]the
1 National Institute of
Temperature Standards and Technology [26].
[◦ C]
600–750, 2250–2350, 3600–3750 183 CO2
Table 3. The results of the TGA-FTIR
Tracel3170 2050–2250measurement (10 °C/min,
183 nitrogen measuring atmosphere).
CO
750-1250, 1450–1800, 3200–3500 183 NH3
Absorbance Maximums [-]
Foaming Agent 600–750, Type of CO
Gas Generated
Tracel4200 Wave2250–2350,
Number [cm3600–3750
−1] 168
Temperature [°C] 2
1600–1700, 3500–3700 168 H2 O
600–750, 2250–2350, 3600–3750 183 CO2
2050–2250 147 CO
Tracel3170
Luv_9537 2050–2250 183 CO
600–750, 2250–2350, 3600–3750 147 CO2
750-1250, 1450–1800, 3200–3500 183 NH3
2050–2250 225 CO
Hyd_3168 600–750, 2250–2350, 3600–3750 168 CO2
Tracel4200
Appl. Sci. 600–750,
2018, 8, x FOR PEER REVIEW2250–2350, 3600–3750 225 CO2 9 of 17
1600–1700, 3500–3700 168 H2O
2050–2250 147 CO
Luv_9537 Tracel31703600–3750
600–750, 2250–2350, 147 CO2
Tracel4200
2050–2250 225 CO
Hyd_3168 Hyd_3168
600–750, 2250–2350, 3600–3750 225 CO2
Luv_9537
Endo

Figure 5 shows that Tracel3170 has an exothermic conversion peak, while in the case of
Tracel4200, Luv_9537 and Hyd_3168, more endothermic reaction occurred. The conversion
Heat flow [W/g]

temperatures measured by DSC can be compared to the temperature ranges measured by TGA and
this provides more accurate information concerning the temperature range of the decomposition
process. Table 4 contains these data. The initial chemical change temperature of DSC is nearly the
same as the beginning of the decomposition range measured by TGA but the end of the
decomposition range (according to dTG) falls a little after the end of the changing temperature range
registered by DSC. This is because the DSC data describe the changing process of the foaming agent
2 W/g

and only the beginning part of this process is the same as TGA. TGA, on the other hand, does not
show the energy change before and after the start of decomposition; it only registers the mass
50 75
reduction effect of the decomposition100 125 released
product 150 175in the 200 225 which
gas phase, 250 continues after the
reaction, as well. Temperature [°C]

Figure 5. Differential scanning calorimetry (DSC) results of foaming agents (50–250 ◦ C,

(50–250°C, first heating,
◦
10 °C/min).
C/min).

Table 4. Comparison of decomposition processes registered with DSC and TGA tests.

Decomposition Range Decomposition Range

State Change **
Sample According to dTG * According to dTG *
N2
Appl. Sci. 2018, 8, 1960 9 of 17

We compared the absorbance spectrum of generated effective gases with the intensity peaks of
the spectra of materials in the IR database of the National Institute of Standards and Technology [26].
Figure 5 shows that Tracel3170 has an exothermic conversion peak, while in the case of Tracel4200,
Luv_9537 and Hyd_3168, more endothermic reaction occurred. The conversion temperatures measured
by DSC can be compared to the temperature ranges measured by TGA and this provides more accurate
information concerning the temperature range of the decomposition process. Table 4 contains these
data. The initial chemical change temperature of DSC is nearly the same as the beginning of the
decomposition range measured by TGA but the end of the decomposition range (according to dTG)
falls a little after the end of the changing temperature range registered by DSC. This is because the DSC
data describe the changing process of the foaming agent and only the beginning part of this process is
the same as TGA. TGA, on the other hand, does not show the energy change before and after the start
of decomposition; it only registers the mass reduction effect of the decomposition product released in
the gas phase, which continues after the reaction, as well.

Table 4. Comparison of decomposition processes registered with DSC and TGA tests.

Decomposition Range Decomposition Range

State Change **
Sample According to dTG * According to dTG *
N2
N2 Air
[-] [◦ C] [◦ C] [◦ C]
Tracel3170 145–239 147–212 165–200
145–188, 147–187, 150–180,
Tracel4200
204–245 196–232 210–225
153–169,
Hyd_3168 186–237 193–237
208–229
136–168, 137–165, 136–160,
Luv_9537
168–225 174–214 175–200
* TGA measurement, ** DSC measurement.

3.2. Isothermal Thermogravimetric Analysis

Foaming agents have to produce effective gas at the processing temperature of PLA. In the
previous tests, a constant heating rate was used (10 ◦ C/min) but thermal conditions are different
during actual manufacturing. Therefore, as a next step, we investigated decomposition by TGA at
a constant temperature, 190 ◦ C. Figure 6a,b show the results of the isothermal TGA test. Figure 5
shows that as a result of constant temperature, decomposition also occurs. For evaluation, however,
the results must be compared to the previous results so that any possible differences could be seen.
Table 5 contains the numerical data. Comparing the TGA and isothermal TGA measurement data,
we can draw conclusions about the behaviour of foaming agents. There is no big difference between the
results of the two types of measurement but mass reduction was greater in the case of the isothermal
process. The biggest difference was observed in the case of Tracel3170, where isothermal mass reduction
was 4.9%, which is 2.1% greater than in the case of a constant heating rate. There is a difference in the
case of the other three foaming agents too but it is smaller.
Appl. Sci. 2018, 8, 1960 10 of 17
Appl. Sci. 2018, 8, x FOR PEER REVIEW 10 of 17

(a) (b)
Figure 6.
Figure 6. TGA
TGA decomposition
decomposition of foaming
foaming agents
agents at 190 ◦°C
at 190 in isothermal
C in isothermal conditions
conditions in
in aa measuring
measuring
atmosphere
atmosphere ofof air
air (a)
(a) mass
mass reduction
reduction as
as aa function
function of
of time,
time, (b)
(b) dTG
dTG asas aa function
function of
of time
time (the
(the blue
blue line
line
shows
shows the
the moment
moment of of reaching 190 ◦°C).
reaching 190 C).

Table 5. The decomposition range of CBAs at an isothermal temperature.

Table 5. The decomposition range of CBAs at an isothermal temperature.
Mass Reduction Mass Reduction
Sample Mass Reduction Mass Reduction
(10 ◦ C/min, 190 ◦ C) Air (Isothermal, 190 ◦ C, 330 s) Air
Sample (10 °C/min, 190 °C) (Isothermal, 190 °C, 330 s)
[-] [%] [%]
Air Air
Tracel3170
[-] 2.8 [%] 4.9 [%]
Tracel4200 6.5 6.8
Tracel3170
Luv_9537 3.9
2.8 5.4
4.9
Tracel4200
Hyd_3168 0.1 6.5 0.9 6.8
Luv_9537 3.9 5.4
Hyd_3168
4. Chemical Foaming of Poly(Lactic Acid) 0.1 0.9

4. Chemical
Foaming, Foaming of Poly(Lactic Acid)
Processing
The temperature
Foaming, Processing parameters of extrusion foaming were selected based on the typical processing
temperature of PLA; technical datasheets recommend processing at 190–200 ◦ C. Table 6 contains the
The temperature
designations parameters ofspecimens
of the manufactured extrusion foaming
and Table were selectedthe
7 contains based on the typicalparameters.
manufacturing processing
temperature
We experienced of PLA; technical
during datasheets
manufacturing recommend
that in the caseprocessing
of 8052_4200at 190–200 °C. Table melt
and 2003_4200, 6 contains
pressurethe
designations of the manufactured specimens and Table 7 contains the manufacturing
decreased drastically from the initial 74 to 43 bar and the viscosity of the melt changed considerably parameters. We
experienced
when it exitedduring
the diemanufacturing
and in the case ofthat in the case ofand
8052_Hyd_3168 8052_4200 and 2003_4200,
2003_Hyd_3168, we did not meltseepressure
signs of
decreased drastically from the initial 74 to 43 bar and the viscosity of the melt changed
successful cell formation in the material flow exiting the die – the sample continued to be transparent, considerably
whenitsitcolour
only exitedbecame
the die and in the
whiter. Thecase of 8052_Hyd_3168
extruded reference rod and 2003_Hyd_3168,
is basically smooth and wetransparent.
did not see Figure
signs of 7
successful
shows that cell formation
in the in the material
case of 8052_4200, flow exiting
2003_4200 the die –2003_3170,
and 8052_3170, the samplefoaming
continued to be transparent,
produced a different
only its on
surface colour
the became
specimens. whiter. The extruded
Tracel4200 producedreference rod is
a surface basically
similar smooth
to PLA but and
withtransparent. Figure
a little whitening
7 shows that in the case of 8052_4200, 2003_4200 and 8052_3170, 2003_3170, foaming
and the cells are visible. Tracel3170 produced a coarser surface and the cells can be felt on the surface. produced a
different surface
Although Tracel3170on the specimens.
is an AZO typeTracel4200 produced
foaming agent, a surface
8052_3170, similar to
2003_3170 PLAonly
show butawith
veryasmall
little
whitening and the cells are visible. Tracel3170 produced a coarser surface ◦and
yellowish tint. Foaming agents that can produce effective gases at 190 C reduced melt viscosity the cells can be felt on
the surface.
during Although Tracel3170 is an AZO type foaming agent, 8052_3170, 2003_3170 show only a
extrusion.
very small yellowish tint. Foaming agents that can produce effective gases at 190 °C reduced melt
viscosity during extrusion.
Appl. Sci. 2018, 8, 1960 11 of 17

Table 6. The designation of the samples and their recipes.

Sample Code PLA Used CBA Used CBA Dosing Note

[-] [Type] [Type] [wt%] [-]
2003_ref 2003D - 0 extruded once
8052_ref 8052D - 0 extruded once
2003_3170 2003D Tracel3170 2 -
8052_3170 8052D Tracel3170 2 -
2003_4200 2003D Tracel4200 2 -
8052_4200 8052D Tracel4200 2 -
2003_Luv_9537 2003D Luv_9537 2 -
8052_Luv_9537 8052D Luv_9537 2 -
2003_Hyd_3168 2003D Hyd_3168 2 -
Appl. Sci. 2018, 8, x FOR PEER REVIEW
8052_Hyd_3168 8052D Hyd_3168 2 - 11 of 17

Table 6. The designation of the samples and their recipes.

Table 7. Manufacturing parameters.
Sample Code PLA Used CBA Used CBA Dosing Note
Sample Code Tmelt pmelt Pressure Drop
[-] [Type] [Type] [wt%] [-]
- ◦C bar
2003_ref 2003D - 0MPa extruded once
8052_ref 2003_ref
8052D 196- 74 0 7.3 extruded once
2003_3170 8052_ref
2003D 196
Tracel3170 43 2 4.2 -
8052_3170 2003_3170
8052D 196
Tracel3170 32 2 3.2 -
8052_3170 195 21 2.0
2003_4200 2003D Tracel4200 2 -
2003_4200 196 14 1.3
8052_4200 8052D
8052_4200 Tracel4200
196 13 2 1.2 -
2003_Luv_9537 2003D
2003_Luv_9537 Luv_9537
196 18 2 1.7 -
8052_Luv_9537 8052D
8052_Luv_9537 Luv_9537
196 34 2 3.3 -
2003_Hyd_3168 2003_Hyd_3168
2003D 197
Hyd_3168 56 2 5.5 -
8052_Hyd_3168 8052_Hyd_3168
8052D 196
Hyd_3168 46 2 4.5 -

Figure7.7.The
Figure The surface
surface of 2003_3170,
of 2003_3170, 2003_4200
2003_4200 and 8052_3170,
and 8052_3170, 8052_4200
8052_4200 foam manufactured
foam structures structures
◦
manufactured
at 190 C. at 190 °C.

5. Results of the Foamed Poly(Lactic

TableAcid)
7. Manufacturing parameters.

Sample Code
5.1. Scanning Electron Microscopy Tmelt p Pressure Drop
- °C bar MPa
We evaluated the cell structure
2003_ref of the manufactured
196 74 foam samples
7.3 based on scanning electron
microscope (SEM) images.8052_ref Figure 8 shows 196 characteristic
43 SEM 4.2images of the foam structure.
They indicate that foaming2003_3170
took place in the case
196 of both
32 polymer 3.2matrices and all three foaming
agents (Tracel3170, Tracel4200 and Luv_9537). ◦
8052_3170 195 Hyd_316821 applied2.0at 190 C could not form a cell
structure in the case of either PLA
2003_4200matrix. This
196 corresponds
14 to the1.3
TGA results, which showed that
Hyd_3168 could not form effective ◦
gas at 190 196
C in 330 13
s (the modelled
8052_4200 1.2 extrusion time) and therefore a
cell structure could not form.
2003_Luv_9537 196 18 1.7
8052_Luv_9537 196 34 3.3
2003_Hyd_3168 197 56 5.5
8052_Hyd_3168 196 46 4.5

5. Results of the Foamed Poly(Lactic Acid)

5.1. Scanning Electron Microscopy

We evaluated the cell structure of the manufactured foam samples based on scanning electron
microscope (SEM) images. Figure 8 shows characteristic SEM images of the foam structure. They
indicate that foaming took place in the case of both polymer matrices and all three foaming agents
Appl. Sci. 2018, 8, 1960 12 of 17
Appl. Sci. 2018, 8, x FOR PEER REVIEW 12 of 17

8052_3170 2003_3170

Background

(a) (b)
8052_4200 2003_4200

(c) (d)
8052_Luv_9537 2003_Luv_9537

(e) (f)
8052_Hyd_3168 2003_Hyd_3168

(g) (h)
Figure
Figure 8. Scanning
Scanning electron
electron microscopy
microscopy (SEM)
(SEM) images
images ofof samples
samples foamed
foamed with
with different
different foaming
foaming
agents
agents (manufactured
(manufactured atat190 ◦ C)(a)
190°C) (a)8052_3170,
8052_3170,(b)(b)
a 2003_3170,
a 2003_3170,(c) (c)
8052_4200, (d) (d)
8052_4200, 2003_4200, (e)
2003_4200,
8052_Luv_9537, (f) a(f)2003_Luv_9537,
(e) 8052_Luv_9537, a 2003_Luv_9537,(g) (g)
8052_Hyd_3168,
8052_Hyd_3168,(h) (h)
2003_Hyd_3168
2003_Hyd_316820×20
magnification.
× magnification.

5.2. The
5.2. The Morphology
Morphology of
of Foam
Foam Structures
Structures
We graded
We gradedfoam
foamstructures
structuresbyby cell
cell population
population density,
density, expansion,
expansion, voidvoid fraction
fraction and density.
and density. The
The results can be found in Figures 9 and 10. The exothermic Tracel3170 produced more
results can be found in Figure 9 and 10. The exothermic Tracel3170 produced more cells in unit cells in unit
5 3 than in
volume in
volume in the
the case
case of
of the
the 8052_3170
8052_3170recipe
reciperecommended
recommendedfor forfoaming (4.82××10
foaming(4.82 105 cells/cm
cells/cm3)) than in
the case of 2003_3170 (4.17 × 105 cells/cm3). The 8052D polymer not only produces a higher number of
cells but the expansion of the cells is also higher, 2.36, as opposed 2.18 in the case the 2003_3170. As
2003D polymer was 1.22 and in the case of the 8052_Luv_9537 recipe, it was 1.23, which is quite little
in both cases. The SEM images show that the size and shape of the cells in the case of the
8052_Luv_9537 are not homogeneous. The densities of PLA foams made with the Luv_9537 foaming
agent are about 1 g/cm3 in both cases. In the case of 2003_Luv_9537, density is 1.02 g/cm3, while in the
Appl. Sci.
case 2018, 8, 1960
of 8052_Luv_9537, it is 1.01 g/cm3. 13 of 17
We did not characterize the 2003_Hyd_3168 and 8052_Hyd_3168 recipes with the methods used
for the characterization of foam structures, since no foam structure was formed during
the case of 2003_3170 (4.17 × 105 cells/cm3 ). The 8052D polymer not only produces a higher number
manufacturing. Only the PLA matrix formed a blend with the carrier of the CBA without the effective
of cells but the expansion of the cells is also higher, 2.36, as opposed 2.18 in the case the 2003_3170.
gases being able to form a gas phase and nucleate cells.
As a result, density with 8052_3170 was lower, 0.53 g/cm3 , while in the case of 2003_3170, it was
In the case of exothermic foaming, PLA foamed to a much greater degree than in the case of
0.57 g/cm3 . This means that a void fraction of 57.61% was achieved in the case of the 8052_3170 recipe
endothermic foaming and so densities were lower. This is due to the type of the endothermic reaction
(considering that the density of PLA is 1.24 g/cm3 . The good results can be attributed to the nucleating
products on the one hand and to the effective gas formation temperature ranges unfavourable for
agent Tracel3170 contained based on the manufacturer’s data and the TGA results (residual material
PLA and the foaming agent fraction of the CBA granules.
content of 40.96% at 800 ◦ C).

2.6 1.4
2.4 2003 1.3 2003
2.2 1.2 8052
8052
2.0 1.1
1.8 1.0
0.9

Density [g/cm3]
Expansion ratio [-]

1.6
0.8
1.4
0.7
1.2
0.6
1.0
0.5
0.8 0.4
0.6 0.3
0.4 0.2
0.2 0.1
0.0 0.0
Tracel3170 Tracel4200 Luv_ 9537 PLA Tracel3170 Tracel4200 Luv_9537 PLA

Type of CBA Type of CBA

(a) (b)
Appl. Sci. 2018, 9.
Figure 8, xFoamed
FOR PEER REVIEW
sample (a) expansion values (b) density values (manufacturing temperature 190 ◦14
C).of 17
Figure 9. Foamed sample (a) expansion values (b) density values (manufacturing temperature 190 °C).

100
2003D
90
80 8052D

70
Void fraction [%]

60
50
40
30
20
10
0
Tracel3170 Tracel4200 Luv_ 9537 PLA

Type of CBA

(a) (b)
Figure
Figure10.
10.(a)
(a)Cell
Cellpopulation
populationdensity
densityandand(b)
(b)porosity
porosityin
inthe
thecase
caseofofthe
thedifferent
differentfoaming
foamingagent
agenttypes
types
(manufacturing
(manufacturingtemperature
temperature190 ◦ C).
190 °C).

The endothermic
5.3. Differential ScanningTracel4200
Calorimetryproduced fewer cells per unit volume in the case of the 8052_4200
recipe recommended for foaming (5.58 × 104 cells/cm3 ) than in the case of the 2003_4200 recipe
We examined the morphology that formed after foaming process, using differential scanning
(1.91 × 105 cells/cm3 ). In the case of the 2003D the expansion of the cells is also better, 1.53, as opposed
calorimetry, the results of which can be seen in Figure 11 and Table 8. Figure 11 shows the DSC curves
to 1.24 in the case of the 8052_4200. This is because the decomposition products of Tracel4200 include
of the single-processed reference poly(lactic acid) (extruded granules, processed similarly to foamed
water, which probably hydrolysed the PLA, causing its melt pressure, viscosity and melt strength to
samples 2003_ref and 8052_ref) and the foamed samples in the case of the first heating curve. In the
decrease during the foaming process. Since the Mw of 8052D is lower (153,235 Da) than that of 2003D
case of foams manufactured with the same processing conditions, the glass transition temperature of
(180,477 Da), it resisted degradation by hydrolysis and produced better cell population density and
the polymer (Tg), which is the first registered endothermic change in the DSC curve, was not different
expansion than the 8052D type PLA. The density of foam structures manufactured with Tracel4200
from the reference value in the case of the Tracel4200 foaming agent and the 8052_3170 recipe. On
the other hand, in the case of the other foaming agents Tg decreased by 2–4 °C (Table 8). A change in
the second registered heat flow is the exothermic phenomenon of cold crystallization, which, in the
case of foam structures, shifts considerably to lower temperatures. The foaming agent causes cold
crystallization to happen at a much lower temperature than in the case of neat PLA. The second,
bigger endothermic peak is the crystalline fraction melting range. It can be observed that the extruded
foam samples are capable of cold crystallization during the DSC test, which is an exothermic reaction.
Appl. Sci. 2018, 8, 1960 14 of 17

was 1.00 g/cm3 in the case of the 8052_4200, while 0.81 g/cm3 in the case of the 2003_4200, which is
less than the density reduction achieved with Tracel3170.
The endothermic Luv_9537 foaming agent produced more cells per unit volume in the case of
the 8052_Luv_9537 recipe recommended for foaming (1.67 × 105 cells/cm3 ) than in the case of the
2003_Luv_9537 recipe (5.51 × 104 cells/cm3 ). Although the cells expanded, expansion in the case
of the 2003D polymer was 1.22 and in the case of the 8052_Luv_9537 recipe, it was 1.23, which is
quite little in both cases. The SEM images show that the size and shape of the cells in the case of the
8052_Luv_9537 are not homogeneous. The densities of PLA foams made with the Luv_9537 foaming
agent are about 1 g/cm3 in both cases. In the case of 2003_Luv_9537, density is 1.02 g/cm3 , while in
the case of 8052_Luv_9537, it is 1.01 g/cm3 .
We did not characterize the 2003_Hyd_3168 and 8052_Hyd_3168 recipes with the methods used
for the characterization of foam structures, since no foam structure was formed during manufacturing.
Only the PLA matrix formed a blend with the carrier of the CBA without the effective gases being able
to form a gas phase and nucleate cells.
In the case of exothermic foaming, PLA foamed to a much greater degree than in the case of
endothermic foaming and so densities were lower. This is due to the type of the endothermic reaction
products on the one hand and to the effective gas formation temperature ranges unfavourable for PLA
and the foaming agent fraction of the CBA granules.

5.3. Differential Scanning Calorimetry

We examined the morphology that formed after foaming process, using differential scanning
calorimetry, the results of which can be seen in Figure 11 and Table 8. Figure 11 shows the DSC curves
of the single-processed reference poly(lactic acid) (extruded granules, processed similarly to foamed
samples 2003_ref and 8052_ref) and the foamed samples in the case of the first heating curve. In the
case of foams manufactured with the same processing conditions, the glass transition temperature of
the polymer (Tg ), which is the first registered endothermic change in the DSC curve, was not different
from the reference value in the case of the Tracel4200 foaming agent and the 8052_3170 recipe. On the
other hand, in the case of the other foaming agents Tg decreased by 2–4 ◦ C (Table 8). A change in
the second registered heat flow is the exothermic phenomenon of cold crystallization, which, in the
case of foam structures, shifts considerably to lower temperatures. The foaming agent causes cold
crystallization to happen at a much lower temperature than in the case of neat PLA. The second,
bigger endothermic peak is the crystalline fraction melting range. It can be observed that the extruded
foam samples are capable of cold crystallization during the DSC test, which is an exothermic reaction.
This is because after processing, due to fast cooling, the crystalline fraction cannot fully form, since
the molecular chains do not have time to get ordered. During the DSC test, due to the relatively slow
temperature rise (5 ◦ C/min), the molecular chains can become more ordered, which is accompanied
by the release of heat. These crystalline fractions melt later, at a higher temperature and the polymer
melts. In the case of 8052D, two crystalline melting peaks can be observed. Frackowiak et al. [27]
provided the explanation that crystals with lower melting temperatures are smaller and formed during
cold crystallization, while, crystal types with a higher melting temperature formed during the primary
crystallization process, therefore, in our case, they are created by the technology. Therefore, foaming
agents influence the crystalline structure that forms in the polymer. The crystalline melting range
has two peaks and is composed of two different crystalline types: the α and α’ types. The α’ type
has a lower melting temperature, while the α type has a higher melting temperature and is also
thermodynamically more stable. The range between the melting of the two phases is called α0 –α phase
transition [27]. The crystalline fraction forming during manufacturing is typically low, due to the
cooling of the polymer in open air (<5%). The foam structure with the highest population density and
highest expansion has the highest crystalline fraction from manufacturing (4.3%). Crystalline fraction
was typically higher than that of reference PLA; the nucleating agents in the CBAs probably had a
beneficial effect on the forming of crystalline nuclei. Thus, the foaming agent affected the crystalline
Appl. Sci. 2018, 8, 1960 15 of 17

state and structure of the samples and also their thermal properties. In the presence of the foaming
agent, transition temperatures typically shifted to lower temperatures compared to the reference
Appl. Sci. 2018,
poly(lactic 8, x FOR PEER REVIEW
acid). 15 of 17

Figure 11. The DSC curves of reference PLA and foamed samples (1st heat-up, 5 ◦ C/min).
Figure 11. The DSC curves of reference PLA and foamed samples (1st heat-up, 5 °C/min).
Table 8. DSC results of foamed samples and unfoamed, extruded PLA (1st heat-up, 5 ◦ C/min).
Table 8. DSC results of foamed samples and unfoamed, extruded PLA (1st heat-up, 5 °C/min).
Type of Sample Tg Tc1 ∆Hc Tm1 Tm2 ∆Hm χc χcf
Type of Sample◦ Tg ◦ Tc1 𝐇 Tm1 Tm2 𝐇  𝐜𝐟
[-] [ C] [ C] [J/g] 𝐜 [◦ C] [◦ C] [J/g]𝐦 𝐜
[%] [%]
[-] [°C] [°C] [J/g] [°C] [°C] [J/g] [%] [%]
2003_ref 59.6 116.7 23.8 151.1 - 26.4 28.4 6.9
2003_ref
8052_ref 59.2 59.6115.9
116.7 25.2
23.8 151.1
150.3 -- 26.4
28.8 28.4
31 6.93.1
8052_ref 57.5 59.2108.4
2003_3170 115.9 26.5
25.2 150.3
147.3 -
153.8 28.8
28.1 31
30.2 3.11.7
2003_3170 59.6 57.5107.5
8052_3170 108.4 27.4
26.5 147.3
147.6 153.8
154.8 28.1
31.4 30.2
33.8 1.74.3
2003_4200
8052_3170 59.3 59.6114.5
107.5 29.5
27.4 147.2
147.6 154.2
154.8 32.2
31.4 34.6
33.8 4.32.9
8052_4200 59.6 107.9 29.3 143.7 154.9 30.5 32.8 1.3
2003_4200 59.3 114.5 29.5 147.2 154.2 32.2 34.6 2.9
2003_Luv_9537 57.2 105.6 28.8 146.4 154.4 30.1 32.4 1.4
8052_4200 55.4 59.6105.4
8052_Luv_9537 107.9 33.7
29.3 143.7
147.1 154.9
154.8 30.5
34.5 32.8
37.1 1.30.9
2003_Luv_953756.2 57.2112.3
2003_Hyd_3168 105.6 29.6
28.8 146.4
148.5 154.4
155.2 30.1
31 32.4
33.3 1.41.5
8052_Hyd_3168
8052_Luv_953757.5 55.4108.3
105.4 27.4
33.7 148.5
147.1 155.5
154.8 28.3
34.5 30.4
37.1 0.91.0
2003_Hyd_3168 56.2 112.3 29.6 148.5 155.2 31 33.3 1.5
8052_Hyd_3168 57.5 108.3 27.4
5.4. Foam Strength 148.5 155.5 28.3 30.4 1.0
Foam samples were finally tested mechanically. A widely used test of foamed products is the
5.4. Foam Strength
foam strength test. We only performed the test on samples deemed acceptable (void fraction >40%),
Foam
that is samples were
on 2003_3170 finally tested
and 8052_3170 mechanically.
samples. Figure 12 A shows
widelythe used test of foamed
measurement products
curves selectedis the
as
foam strength
typical. The shapetest. of
We only
the performed
curves the test on samples
is characteristically the same deemed
as thatacceptable (void fraction
of other known >40%),
foam strength
that is coincides.
curves on 2003_3170 and 8052_3170
At initial loading, insamples.
the linearFigure 12 shows
section, the measurement
deformation curves
is elastic, then selected
a peak follows,as
typical. The shape of the curves is characteristically the same as that of other known
which corresponds to “yield strength.” In elastic deformation, the cells take up the load, then they foam strength
curves
are coincides.
restored At original
to their initial loading, in the
state when linear section,
loading stops. At deformation
the inflexion is elastic, then a peak
part, however, follows,
the cells are
which corresponds
deformed and damaged.to “yield
Thestrength.” In elastic
straight section (thedeformation,
section after the cells take point)
inflexion up theappeared
load, theninthey
the
are restored
curve of everytospecimen
their original
withinstate
the when loading stops.
10% deformation Atthat
limit, the is,
inflexion part, however,
each specimen sufferedthe cells are
permanent
deformed andIn
deformation. damaged.
the case The straight section
of 2003_3170, (the ±
it is 22.8 section afterwhile
0.6 MPa, the inflexion point)
in the case of appeared
8052_3170,initthe is
curve
22.4 ±of0.7every
MPa.specimen
There was within the 10% deformation
no significant limit, that
difference between the is, each specimen
compression suffered
strength valuespermanent
of foams
deformation.
produced withInTracel3170
the case of 2003_3170,
and it is 22.8types
the two different ± 0.6 of
MPa,
PLA;while in the case ofstrengths
the compression 8052_3170, anditstandard
is 22.4 ±
0.7 MPa. There
deviations was no
are nearly thesignificant
same. Thedifference
aim was to between the compression
create biodegradable strength
hard foams values
with theof use
foamsof
produced with Tracel3170 and the two different types of PLA; the compression
commercially available CBAs. Compressive strength is higher, compared physically foamed PLA strengths and
standard deviations are nearly the same. The aim was to create biodegradable hard foams with the
use of commercially available CBAs. Compressive strength is higher, compared physically foamed
PLA in the literature [21]. The results should be considered a reference value when later modified
foam structures are developed later.
Appl. Sci. 2018, 8, 1960 16 of 17

in the literature [21]. The results should be considered a reference value when later modified foam
Appl. Sci. 2018,
structures are8, developed
x FOR PEER REVIEW
later. Appl. Sci. 2018, 8, x FOR PEER REVIEW 16 of 17

30 30

25 25

Compressive strenght [MPa]

Compressive strenght [MPa]

20 20

15 15

10 10

5 5
2003_3170 2003_3170
8052_3170 8052_3170
0 0
0 2 4 6 8 0 10 2 4 6 8 10
Deformation [%] Deformation [%]

Figure 12.
Figure 12. Compression strength deformation
Figurediagram in the casestrength
12. Compression of 2003_3170 and 8052_3170
deformation diagramrecipes.
in the case of 2003_3170 and 805

6. Conclusions
6. Conclusions 6. Conclusions
We comprehensively examined chemical blowing agents and determined their properties.
We comprehensively examined chemical blowing agents and
We comprehensively examineddetermined
chemicaltheir properties.
blowing agents Then
and determined thei
Then we foamed poly(lactic acid) with endothermic and exothermic foaming agents recommended
we foamed poly(lactic acid) with endothermic and exothermic
we foamed poly(lactic foaming
acid) with agents recommended
endothermic and exothermic for foaming agents
for polyester and an endothermic foaming agent specially recommended for poly(lactic acid).
polyester and an endothermic foaming agent
polyester andspecially recommended
an endothermic foaming for agent
poly(lactic acid).
specially We
recommended for pol
We examined the cell population density, cell expansion, void fraction, density, morphology
examined the cell population density, cell expansion,
examined void fraction,
the cell population density,
density, morphology
cell expansion, andfraction, density,
void
and mechanical properties of the manufactured foams. Our results indicate that the exothermic
mechanical properties of the manufacturedmechanical foams.
properties Ourofresults indicate that foams.
the manufactured the exothermic
Our results indicate tha
azodicarbonamide foaming agent (Tracel IM 3170 MS) added to 8052D PLA in 2 wt% is a very
azodicarbonamide foaming agent (Tracel IM 3170 MS)
azodicarbonamide added agent
foaming to 8052D PLAIM
(Tracel in 3170
2 wt%MS)is added
a very to 8052D PLA in
promising foaming agent at the processing temperature of 190 ◦ C. The cell population density of such
promising foaming agent at the processing temperature
promising foaming agentof 190at°C.
theThe cell population
processing density
temperature ofof
190such
°C. The cell populati
foams is 4.82 × 1055 cells/cm3 3 , their expansion is 2.36, their density is 0.53 g/cm33 , their void fraction is
foams is 4.82 × 10 cells/cm , their expansion is 2.36,
foams is 4.82 × 10their density
5 cells/cm is 0.53
3, their g/cm , their
expansion void
is 2.36, fraction
their is is 0.53 g/cm3, the
density
57.61% and their compression strength is 22.4 ± 0.7 MPa.
57.61% and their compression strength is 22.4 ± 0.7 MPa.
57.61% and their compression strength is 22.4 ± 0.7 MPa.
Author Contributions: Conceptualization, Á.K.; methodology, Á.K. and K.L.; formal analysis, Á.K. and K.L.;
Author Contributions: Conceptualization, Á.K.;
Author methodology,Conceptualization,
Contributions: Á.K. and K.L.; formal analysis,
Á.K.; Á.K. and
methodology, K.L.;
Á.K. and K.L.; formal anal
investigation, D.R. and K.L.; writing—original draft preparation, Á.K. and K.L.; writing—review and editing, Á.K.
investigation, D.R. and K.L.; writing—original draft preparation,
investigation, Á.K.
D.R. and K.L.; and K.L.; writing—review
writing—original and editing,
draft preparation, Á.K. and K.L.; writing—
Funding:
Á.K. Á.K.

Funding: Supported by theFunding:

ÚNKP-17-4-III New Supported
National Excellence Program of the
by the ÚNKP-17-4-III NewMinistry
NationalofExcellence Program
Human Capacities. This research was also supported
Human by The
Capacities. National
This Research,
research was alsoDevelopment
supported byand
TheInnovation
National Research, Developm
Supported by the ÚNKP-17-4-III New National Excellence Program of the Ministry of Human Capacities.
Office (NVKP_16-1-2016-0012). Office (NVKP_16-1-2016-0012).
This research was also supported by The National Research, Development and Innovation Office
(NVKP_16-1-2016-0012).
Acknowledgments: The author would like to thank Tim Stoesser,
Acknowledgments: Department
The author would of Chemistry,
like Oxford
to thank Tim University,
Stoesser, Department of Chemistry
Oxford, UK for his help with the GPC
Acknowledgments: The author would like measurements.
Oxford, UK for
to thank Timhis help with
Stoesser, the GPC measurements.
Department of Chemistry, Oxford University,
Oxford, UK for his help with the GPC measurements.
Conflicts of Interest: The authors declare no conflict
Conflicts of interest.
of Interest: The The funders
authors hadno
declare noconflict
role in of
theinterest.
design of
Thethe
funders had no role
Conflicts of Interest:
study; in the The
collection, authorsordeclare
analyses, no conflict
interpretation
study; of interest.
of collection,
in the data; The funders
in theanalyses,
writing of
or the had no roleofin
manuscript,
interpretation the
ordata; design
in the of the
in decision to of the manuscript,
the writing
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results. publish the results.
publish the results.

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