Key Engineering Materials Submitted: 2019-02-23

ISSN: 1662-9795, Vol. 824, pp 87-93 Revised: 2019-06-23

doi:10.4028/www.scientific.net/KEM.824.87 Accepted: 2019-06-24
© 2019 Trans Tech Publications Ltd, Switzerland Online: 2019-10-10

The Physical and Mechanical Properties of Biocomposite Films

Composed of Poly(Lactic Acid) with Spent Coffee Grounds
Nattawut Suaduanga, Sukunya Rossb, Gareth M. Rossc,
Supatra Pratumshatd and Sararat Mahasaranone *
Department of Chemistry, Faculty of Science, Naresuan University, Thailand 65000
a
nattawuts59@email.nu.ac.th, bsukunyaj@nu.ac.th, cgareth@nu.ac.th, dsupatraw@nu.ac.th,
e
sararatm@nu.ac.th

Keywords: Biocomposite film, Poly(lactic acid), Spent coffee grounds

Abstract. The aim of this research was to prepare and characterize biocomposite films from
poly(lactic acid) (PLA) with spent coffee grounds (SCG). PLA can be derived from renewable
resources. The SCG component consists of cellulose, hemicellulose and coffee oil 10.98%. SCG can
simultaneously act as plasticizer and filler in the composites that can enhance the mixing process.
The PLA/SCG biocomposite films were processed by a twin-screw extruder and blow film extruder.
They were prepared by using various SCG concentrations (0%, 5%, 7.5% and 10% of SCG). The
Scanning Electron Microscopy (SEM) results showed that the PLA matrix with SCG was miscible
and had the SCG was well good distributed. Elongation at break was increased, when the amount of
SCG was increased, with the results of PLA and PLA/SCG 10% being 5.07% and 6.63% respectively,
while hardness, brittleness and tensile strength decreased. UV-vis spectrophotometric measurement
of PLA/SCG biocomposite films showed a considerable reduction in transmission of all UV
wavelengths (UV-A, -B and -C) and visible light with increasing SCG content. Hence, in this
research, SCG can be used as filler in PLA films in order to produce biodegradable films and
developed as agricultural film products. The PLA/SCG biocomposite films have shown good
properties and are environmentally friendly.

Introduction
Recently, the use of plastic films has come to the attention of the public and governments alike.
Plastic films are widely used in numerous applications such as food packaging films, plastic and
agriculture bags. All of these applications have very short life cycles and are generally single use
products. This produces a huge amount of plastic waste, which can be difficult to disposed of, often
causing substantial pollution [1]. Therefore, to overcome these problems many researchers have
concentrated on using renewable and biodegradable resources to produce alternative materials
including poly(butylene succinate) (PBS) and poly(lactic acid) (PLA) [2-3]. These biodegradable
materials are already widely used in various applications such as 3D printing materials, food
packaging and degradable plastic bags [4-6]. Biodegradable material processing however, still needs
to use fillers either in form of inorganic fillers (titanium dioxide (TiO2) and zinc oxide (ZnO)) [7-8],
organic fillers (hemicellulose and lignin) or natural fillers (wood fiber, starch and others) [9-11]. This
research was focused on improving the properties of PLA based materials by mixed with natural
additives, in this case spent coffee ground (SCG). SCG components have the potential to improve the
processing of PLA, these components include cellulose, hemicellulose, lignin and coffee oil [12-13].
This allows SCG to act as a plasticizer and filler of composites that enhance the mixing process [14-
15]. This work concentrates on improving biocomposite films for use as packaging films and
agriculture bags which are environmentally friendly and non-toxic.

Experimental Procedure
Materials. Matrix: Poly(lactic acid) (PLA), Ingeo™ Biopolymer 4043D, film grade was purchased
from NatureWorks LLC. PLA (4043D) properties are density 1.24 g/cm3, glass transition temperature

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88 Green Convergence on Materials Frontiers II

(Tg) 55-60 °C, melting point (Tm) 145-160 ºC and melt flow rate (MFR) of 6 g/10 min at
210°C/2.16 kg, as reported by the material supplier.
Filler: Spent coffee grounds (SCG) are a by-product obtained from the residue from the coffee
beans roasting process of Café Amazon, Thailand. Before use SCG were washed with clean water
and then dried in an oven at a temperature of 60 ºC for 24 h. After drying, the physical properties of
the SCG were characterized. This resulted in a moisture content of 3.24% and coffee oil content of
10.98% when using a hexane extraction [16-17]. After that, SCG were processed with a ball mill and
then sieved through a 90 μm mesh screen (obtaining particles sized between 10-85 μm). This product
(SCG) was prepared as a brown powder and stored at room temperature until further use.
Processing of biocomposite film. Biocomposite films were prepared by using a two-step process:
the materials were compounded by a twin-screw extruder (model LTE16-40, Labtech Engineering
Co., Ltd.,) followed by a blow film extruder (model LF-250 (blow film) and model LE20-30/C (single
screw extruder), Labtech Engineering Co., Ltd.,) process.
Preparation of the PLA/SCG compound by twin screw extruder. The compound of PLA
matrix with SCG filler was mixed by using a screw extruder to obtain PLA/SCG biocomposite films.
The SCG filler was added at different concentrations at 0, 5, 7.5 and 10% of SCG, respectively with
a screw speed of 100 rpm and the temperature profile was increased from
120 ºC at the feeding zone to 180 ºC at the die. After mixing, the compound was cut into standard
sample dimensions for further characterization and developed into biocomposite films.
Preparation of the biocomposite film by blow film extruder. Biocomposite films were
manufactured using a blow film extruder. The polymer melt process used a single screw extruder,
with a screw speed set to 65 rpm and temperature range from 150 ºC to 180 ºC. The polymer melt
was then blown into a film using the standard blow film method. The control film thickness was
between 50-90 μm with a film width of 16-17 cm. These biocomposite films were then cut into
standard sample dimensions for evaluation of the physical and mechanical properties.
Characterization.
Melt Flow Index (MFI). In order to measure the melt flow index (MFI) samples were obtained
from the twin-screw extruder and measured on a melt flow indexer (Instron®'s CEAST MF20)
operating at 190 ºC with 2.16 kg load. The units of measurement are grams of material/10 minutes
(g/10 min) and the ASTM D1238 protocol was followed.
Scanning electron microscope (SEM). The morphology of the biocomposite samples was
investigated by SEM (Model Leo 1455 VP and acceleration voltage 20 kV) at different
magnifications. The samples were prepared using two different types of sample; extruded samples
that were submerged in liquid nitrogen and fractured to expose the internal structure and blow film
samples that were cut into small sizes. All samples were placed on a stub with carbon black tape. The
specimen was then coated with gold before running the SEM.
Color parameter. PLA/SCG biocomposite films color parameter was measured with a
colorimeter reader (Konica Minolta’s new Color Reader series CR-20). The samples were prepared
at a size of width and length 15.00 x 15.00 cm. Each sample was measured at 7 positions per sample.
The results show the color parameters in terms of L* (lightness), a* (redness), b* (yellowness) in
accordance with ASTM E 313-96. Then, the color difference of the sample can be analyzed by
calculating ΔE using the formula as follows.
∆E = �(L∗1 − L∗2 )2 + (a∗1 − a∗2 )2 + (b1∗ − b∗2 )2
UV-vis spectrophotometry analysis. Transparency measurement of the biocomposite films was
observed using the UV-Vis spectrophotometer (specord 210 plus). The samples were prepared at a
length and width of 5.00 x 3.00 cm. Wavelengths of 200 to 800 nm was used for analysis with a scan
rate of 50 nm/min.
Tensile Testing. Tensile properties of samples were performed by a universal testing machine
(model 5965 INSTRON® CALIBRATION LAB). The stability of the biocomposite film samples
were tested by storing at room temperature (28-30 ºC) and 55-60% of relative humidity for 0, 3, 6
and 9 months before tensile testing. The samples were prepared in the form of plastic dumbbell
 Key Engineering Materials Vol. 824 89

(5 pieces) and tested in transverse direction (TD) and machine direction (MD). The conditions used
for testing was as follows; Load Cell 1 kN and crosshead speed 20 mm/min. The mechanical analysis
was carried out following ASTM D638 standard. The tensile properties were characterized and the
reported results consisted of tensile strength at break, modulus at break and elongation at break.

Results and Discussion

PLA/SCG compounded by twin screw extruder. The melt flow rate (MFR) results of PLA/SCG
biocomposites (compound samples from twin screw extruder) are shown in table 1. As the
concentration of SCG was increased, the MFR also increased, with SCG contents of 0, 5, 7.5 and
10 wt.% giving MFR’s of 15.09, 17.48, 18.27 and 19.71 g/10min respectively. This indicates that the
SCG acts as a plasticizer (coffee oil content of SCG is 10.98 wt.%) and a filler in the composites
which help to enhance the mixing process and increased MFR as the SCG content increases (as seen
in table 1). This is due to the SCG filler decreasing the molecular interaction force between the PLA
chains. The miscibility of PLA/SCG compound demonstrates that the SCG is adequately distributed
in the matrix phase as shown in fig. 1. A good distribution of the SCG particles can clearly be seen
in the PLA matrix in the SEM images of the fracture surfaces obtained from PLA/SCG 7.5 and
10 wt.% samples. The SEM images also do not show any presence of agglomeration, even at high
SCG loadings of 7.5 and 10 wt.%.
Table 1 The melt flow index of PLA/SCG compound.

Compositions MFR (g/10min)

PLA 15.09 ± 0.01
PLA/SCG 5 wt.% 17.48 ± 0.30
PLA/SCG 7.5 wt.% 18.27 ± 1.63
PLA/SCG 10 wt.% 19.71 ± 0.50

A B C D

20 µm 20 µm 20 µm 20 µm

Fig. 1 SEM images of the fracture surfaces of biocomposites (compound samples from twin screw
extruder): (A) PLA, (B) PLA/SCG 5%, (C) PLA/SCG 7.5%, and (D) PLA/SCG 10% at 500X
magnification.

Biocomposite film by blow film extruder.

Morphology. The SEM images of the surface area of PLA/SCG biocomposite films are shown in
fig. 2A-2D. The PLA film was found to have a smooth surface morphology as shown in the fig. 2A.
As the amount of SCG was increased, the surface roughness increased from Fig. 2B to 2D. The results
also reveal that samples containing SCG particles are similarly distributed inside the PLA matrixes.
A B C D

40 µm 40 µm 40 µm 40 µm

Fig. 2 SEM images of the surface area of biocomposites film: (A) PLA, (B) PLA/SCG 5%,
(C) PLA/SCG 7.5%, and (D) PLA/SCG 10% at 200X magnification.
90 Green Convergence on Materials Frontiers II

Table 2 Color values of the biocomposite film.

Compositions Film color L* a* b* ∆E*

PLA 90.23 ± 0.10 -0.90 ± 0.00 -4.19 ± 0.07 Ref.

PLA/SCG 5 wt.% 75.77 ± 0.66 3.71 ± 0.19 8.37 ± 0.45 19.70

PLA/SCG 7.5 wt.% 68.99 ± 0.76 5.87 ± 0.29 12.47 ± 0.40 27.83

PLA/SCG 10 wt.% 65.87 ± 0.35 6.70 ± 0.14 14.99 ± 0.26 31.92

Color parameters. Photographs of PLA/SCG biocomposite films, prepared by the blow film
extruder, and the results of the color parameters of PLA/SCG biocomposites films are shown in table
2. The L*, a* and b* values of the biocomposite films show that the L* value of PLA film is 90.23,
which is the highest value of lightness of all samples. As the SCG content increases (PLA/SCG film
5, 7.5 and 10 wt.%) the lightness values are 75.77, 68.99 and 65.87, respectively. The L* value
decreases because the distributed SCG particles act as a light barrier in the biocomposites films (as
seen in the SEM images (fig. 2B-2D)). The a* and b* values increase, as they are related to increasing
amounts of SCG, with the films having a light brown color. The results of ∆E values of PLA/SCG
films with different amounts of SCG at 5, 7.5 and 10 wt.% are 19.70, 27.83 and 31.92, respectively.
∆E values are influenced by the color of the film with high amounts of SCG particles in the PLA
matrix. These color parameters of the biocomposite films vary due to the brown color of SCG.
Transparency analysis. The percentages of light transmission (%T) values for PLA and
PLA/SCG biocomposite films are shown in the table 3. PLA films showed light transmission of
95.67%, 96.33%, 96.33% and 97.67% of radiation in the UV and visible light region, respectively.
The PLA film sample has a high light transparency which confirms the result of the color values in
table 2. Interestingly, the PLA/SCG biocomposite films %T values decreased with increasing SCG
contents at all UV and visible light regions. The PLA/SCG 10 wt.% sample shows a large decrease
in %T with the reduced values being 3.00%, 3.33%, 4.67% and 6.00% in the UV-C, UV-B, UV-A
and visible light regions, respectively. Therefore, adding SCG particles in the PLA matrix had a
considerable affect on adsorbing UV-A, UV-B, UV-C and visible light.
Table 3 Percentage of light transmission (%T) values for the biocomposite film.

% Transmittance (%T)
Compositions at 280 nm at 315 nm at 400 nm at 700 nm
(UV-C region) (UV-B region) (UV-A region) (Visible region)
PLA 95.67 ± 1.15 96.33 ± 0.58 96.33 ± 0.58 97.67 ± 0.58
PLA/SCG 5 wt.% 15.00 ± 1.10 16.00 ± 1.00 17.67 ± 1.53 19.67 ± 1.53
PLA/SCG 7.5 wt.% 4.67 ± 0.58 5.33 ± 0.58 6.67 ± 1.15 8.00 ± 1.00
PLA/SCG 10 wt.% 3.00 ± 0.00 3.33 ± 0.58 4.67 ± 0.58 6.00 ± 1.00

Tensile Testing. Mechanical properties are shown as tensile strength at break, % elongation at
break and modulus at break for neat PLA and the PLA/SCG biocomposite films. The samples were
tested in transverse direction (TD) and machine direction (MD) and the values are presented in table
4. The tensile strength at break of neat PLA was 75.93 MPa (TD) and 63.33 MPa (MD) and the results
decreased to 20.70 MPa (TD) and 18.53 MPa (MD) with SCG content of 10 wt.%. The reduction in
tensile strength of the PLA/SCG biocomposite films was caused by the increase in SCG content and
distribution of the SCG particles in the PLA matrix. In table 4, the elongation at break (%) values for
PLA/SCG films at 7.5 and 10 wt.% of SCG rise with SCG content as compared to the PLA film. The
modulus at break decreases to 22.97% (TD) and 21.87% (MD) when the SCG content increases to
 Key Engineering Materials Vol. 824 91

10 wt.%. Reduction in the modulus at break is because the SCG particles from the production process
of PLA/SCG biocomposite films reduce the brittleness compared to a neat PLA film. This
corresponds to a decrease in tensile strength and an increase in elongation.
The film stability of PLA/SCG biocomposite films was shown to influence the tensile properties.
Table 4 shows the tensile strength at break of the neat PLA film tested after 3, 6 and 9 months, the
results show tensile strength values of 66.17, 65.12 and 50.66 MPa (TD) and 60.21, 53.64 and
51.86 MPa (MD), respectively. This is reduced from 75.93 MPa (TD) and 63.33 MPa (MD) of neat
PLA film tested before film stability (0 months). The decreased tensile strength at break is caused by
the degradation of PLA over time in the samples. Atmospheric moisture is attracted to the PLA chains,
which break down in the polymer backbone [18]. Tensile strength at break of the PLA/SCG 10 wt.%
sample at months 3, 6 and 9 only presents slightly different results to the freshly prepared PLA/SCG
10 wt.% sample. In the same way, increased SCG content and time for stability testing showed the
trend of decreased tensile strength at break because of the SCG distribution. The results for %
elongation at break of all samples showed a reduction with increasing storage time. This is because
of the same rational as stated in the tensile analysis, i.e, the degradation of the PLA present in the
samples. The modulus at break of neat PLA after stability testing was reduced. On the other hand, the
10 wt% SCG (other SCG containing films less so) biocomposite film shows an increase in modulus
at break because the SCG exhibits reinforcing and plasticizing behavior [18-19].
The tensile properties of neat PLA and PLA/SCG at different SCG contents vary. Similarly, for
neat PLA and PLA/SCG biocomposite films, the tensile properties after testing the stability decrease
with greater storage time. That is because of PLA degradation mechanisms such as hydrolysis and
oxidative degradation [18].
Table 4 The mechanical properties show the tensile strength at break, % elongation at break and
modulus at break for neat PLA and PLA/SCG biocomposite films. The sample was tested in
transverse direction (TD) and machine direction (MD). The biocomposite film samples were tested
for film stability by storing at room temperature for 0, 3, 6 and 9 months before tensile testing.

Tensile Strength at % Elongation at Modulus at Break

Compositions

Stability Test

Break (MPa) Break (MPa)

(Month)

TD MD TD MD TD MD

0 75.93±4.70 63.33±3.56 4.47±0.33 5.07±0.53 1706±72.83 1264±98.88

3 66.17±3.02 60.21±5.95 4.10±0.10 4.92±0.47 1616±116.20 1221±34.14
PLA

6 65.12±3.86 53.64±1.83 4.32±0.16 4.76±0.26 1510±110.13 1130±85.00

9 50.66±2.82 51.86±3.68 3.60±0.20 4.98±0.20 1421±129.69 1039±22.34
0 23.97±0.51 23.10±1.90 3.49±0.53 4.02±0.14 695±92.61 574±17.82
G 5 wt.%
PLA/SC

3 20.28±0.31 19.27±0.45 3.67±0.19 4.83±0.35 554±37.55 446±58.85

6 24.83±1.45 24.32±1.56 3.02±0.04 3.18±0.28 822±42.43 700±85.23
9 22.78±1.81 22.52±1.71 3.03±0.13 3.34±0.30 751±48.20 654±72.74
0 24.40±0.28 23.64±1.17 4.24±0.45 5.13±0.33 579±68.48 461±7.29
PLA/SCG

3 17.18±1.52 18.04±1.59 3.19±0.12 3.90±0.41 540±58.68 465±47.32

7.5 wt.%

6 18.43±1.14 15.19±1.02 2.87±0.15 2.28±0.16 645±68.06 665±15.63

9 17.31±2.49 18.12±0.83 2.62±0.18 3.06±0.47 660±87.17 599±77.25
0 20.70±0.61 18.58±1.14 5.33±0.71 6.72±0.20 392±41.57 276±11.14
PLA/SCG
10 wt.%

3 17.81±1.24 16.91±1.46 3.41±0.42 2.45±0.09 532±108.85 691±78.66

6 21.23±1.56 16.03±0.39 2.92±0.12 2.11±0.10 728±61.31 760±19.05
9 20.71±2.96 18.66±1.47 2.64±0.26 2.56±0.21 784±61.70 729±46.81
92 Green Convergence on Materials Frontiers II

Conclusion
The preparation of biocomposite films from PLA with SCG showed that SCG performed as both a
plasticizer (coffee oil) and filler in the composites. That helps to enhance the mixing process as
confirmed by the melt flow rate increasing and viscosity decreasing. The PLA/SCG biocomposite
films showed good distribution of SCG in the PLA matrix, which is evident in the morphology
analysis. The elongation at break of PLA was 5.07% and when the amount of SCG was increased the
elongation at break increased to 6.63%, while hardness, brittleness and tensile strength decreased. In
neat PLA and PLA/SCG biocomposite films the tensile properties decreased with longer storage
periods due to PLA degradation. The PLA/SCG biocomposite films showed a considerable reduction
in transmission of all UV wavelengths (UV-A, -B and -C) and visible light with increasing SCG
content. So SCG can be used as filler in PLA matrices in order to produce biodegradable films. It can
develop agricultural products, such as planting bags that in the soil have the advantages of
overcoming the lack of roots and reducing non-degradable plastic wastes.

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