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Setyaningsih 2024 Mater. Res. Express 11 015304
Setyaningsih 2024 Mater. Res. Express 11 015304
- Characterization of mono-diacylglycerols,
diacylglycerols and cellulose nanocrystals cellulose nanocrystals, polypropylene, and
supporting materials as raw materials for
synthesis of antistatic bionanocomposites
To cite this article: Dwi Setyaningsih et al 2024 Mater. Res. Express 11 015304 Muhammad Syukur Sarfat, Dwi
Setyaningsih, Farah Fahma et al.
PAPER
Keywords: antistatic bio-nano composites, bio-polymers synthesis, cellulose nanocrystals, electrical resistivity, mono-diacylglycerols,
Original content from this polypropylene, thermal properties
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the terms of the Creative
Commons Attribution 4.0
licence.
Abstract
Any further distribution of
this work must maintain Polypropylene (PP) is known as a polymer without antistatic properties that is susceptible to the use of
attribution to the
author(s) and the title of high temperatures. Therefore, to improve the thermal and antistatic properties of PP, it is necessary to
the work, journal citation
and DOI.
modify PP to antistatic bio-nanocomposites with mono-diacylglycerols (M-DAG) as an antistatic
agent and cellulose nanocrystals (CNC) as a reinforcement. This research aimed to characterize the
electrical resistivity and thermal properties of PP-based antistatic bio-nanocomposites reinforced with
M-DAG and CNC at different concentrations of CNC (0%–5%), and 2% of M- DAG, compared to
pure PP. The results showed that the addition of 2% CNC (AS-BNC-2) gave the melting temperature
of 125.0 °C, which was higher than pure PP of 118.3 °C. The thermal stability of the antistatic bio-
nano composites with 3% CNC (AS-BNC-3) was 457.10 °C, which was higher than pure PP of
441.56 °C. The electrical resistivity of the antistatic bio-nano composites from all treatments was still
in the range of the antistatic category of 1010–1012 Ω/sq. The melting temperature and thermal
stability of bio-nano composites were higher than those of pure PP and they have antistatic properties.
This indicates the potential application of these materials in the electronics devices and packaging
industries.
1. Introduction
Polypropylene (PP) is one of the most widely used thermoplastic polymers in various industries. However, PP is
known as a polymer that is susceptible to the use of high temperatures and does not have antistatic properties.
Besides that, PP is harmful to the environment due to its non-degradable nature [1, 2], but PP is recyclable [3]. In
this work, Antistatic bio-nano composites (AS-BNC) reinforced by mono-diacylglycerols (M-DAG) as an
antistatic agent [4] and cellulose nanocrystals (CNC) as a reinforcement [4–9], where PP serves as the matrix.
These biomaterials have been investigated in systems and materials aspects for exploring and choosing new
suitable materials for future applications.
M-DAG is a mix of mono-acyl glycerol (MAG) and di-acyl glycerol (DAG) [10] which has one or two free
hydroxyl groups at glycerol which is unesterified with fatty acid. The presence of free hydroxyl groups makes it a
biocompatible and biodegradable surfactant or emulsifier, and it is widely used in foods, cosmetics, and
pharmaceuticals [4]. M-DAG can be produced from palm fatty acid distillate (PFAD), a by-product of crude
palm oil refining [11–13].
CNC is a cellulose-based nanomaterial that has better mechanical characteristics such as tensile strength
(7.5 GPa) [14], tensile modulus (100–140 GPa) [14], and thermal stability (283.5 °C) with a surface area of
569 m2 g−1 [15] compared to other cellulose-based nanomaterials such as cellulose nanofiber (CNF) which has
0.38 GPa of tensile strength [16] and 23.9 GPa of modulus tensile [16] with a surface area of 430 m2 g−1 [17].
However, CNC has a low stability (>280 °C) which causes it very susceptible to high heat treatment when used
Figure 1. Physical of the potential raw materials for the synthesis of antistatic bio-nano composites.
Table 1. Characteristics, function, and suppliers of the potential raw materials for the synthesis of antistatic bio-nano composites.
FFA: free fatty acid, MFI: melt flow index, ρ: density, CI: crystal index, d: diameter, Tinf: thermal degradation.
as reinforcing material in polymer matrices. Therefore, a stabilizer is needed that can protect CNC from thermal
degradation during the process. M-DAG can act as a stabilizer and lubricant so that the processing time is shorter
and reduces thermal degradation.
The addition of M-DAG as an antistatic agent [4] and CNC as a reinforcement [4–9] to the PP as a
thermoplastic matrix [4–9] had a positive impact on the characteristics of the resulting PP-based antistatic bio-
nano composites and PP-based bio-nano composites [4–9]. The combination of the added M-DAG and CNC is
expected to produce a synergistic effect to improve the quality of the antistatic bio-nano composites. Adriana
et al [18] reported the addition of CNC and glycerol monostearate (GMS) as an antistatic agent on a polystyrene
(PS) matrix and showed a positive effect on PS-based antistatic bio-nano composites. However, there are no
reports regarding the use of these two materials simultaneously in PP matrix. In addition, the use of M-DAG
synthesized from palm fatty acid distillates (PFAD), a byproduct from palm oil refinery, is of particular interest,
because it increases the added value of this material.
Presumably, the addition of M-DAG and CNC will improve the electrical resistivity and thermal properties
of PP-based antistatic bio-nano composites. Therefore, this study aimed to identify the electrical resistivity and
thermal properties of composites at different concentrations of CNC compared to that of pure PP.
2. Experimental
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Mater. Res. Express 11 (2024) 015304 D Setyaningsih et al
Table 2. Characteristics of supporting materials for the synthesis of antistatic bio-nano composites.
1 SCONA TPPP 9012 FA MFI = 50–110 g/10 min Coupling agent (MAPP) BYK Chemie GmbH
MAH > 0.90%
2 Irganox® 1010 Tm = 1105 °C–125 °C AO 1010 BASF Schweiz AG Switzerland
TB = 297 °C
ρ = 1.12 g ml−1
Irgafos® 168 n = 1.18 g mol−1 BASF Schweiz AG Switzerland
Tm = 1835 °C–186 °C AO 168
ρ = 1.03 g ml−1
n = 646.90 g mol−1
3 Forane® 1233zd ρ = 1.27 g cm−3 Blowing agent (MO) Arkema France
TB = 18.60 °C
FFA: free fatty acid, MFI: melt flow index, ρ: density, CI: crystallinity index, Tm: melting temperature, MAH: maleic anhydride, TB:
boiling point, n: molarity.
this research was conducted. MAPP, AO, and MAU were used for synthesis with the purposes listed in the
table 2.
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Treatment (%)
The antistatic bio-nano composites sheets cooled to room temperature of 25 °C, with a pressure of 3 MPa
for ±24 h at 50% humidity before finally characterizing the antistatic bio-nano composites. Table 3 shows the
symbols of each treatment. The formulation of each treatment was based on the ratio of molarity concentration
of CNC with maleic anhydride (MA) in MAPP, which was 1:1. It is expected that the availability of 1 mole of MA
can bind to 1 mole of CNC in the form of a single ester bond during the extruding process.
In this study, the range of CNC concentration referred to the results of previous studies conducted by
Adriana et al [18], while the determination of 2.00% M-DAG concentration referred to Salsabila et al [4]. For
supporting materials, the concentration was based on the usage dosage listed on the technical data sheet of each
supporting material.
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Figure 3. DSC analysis of antistatic bio-nano composites. AS-BNC: antistatic bio-nano composites.
Figure 4. Thermal degradation of antistatic bio-nano composites: AS-BNC: antistatic bio-nano composites.
Treatment
AS-BNC: antistatic bio-nano composites, number 0–5 indicated CNC concentration (%).
was a decrease in melting temperature with the addition of 3.00% CNC. According to Yousefian and Rodrigue
[22], the distribution of CNC particles in the polymer matrix greatly influences the thermal properties of the
resulting bio-nano composites.
The use of M-DAG and CNC simultaneously on the PP matrix, of course, will form a unique pattern of
interaction or reaction which can certainly have an impact on the thermal properties of antistatic bio-nano
composites. A similar case was found by Adriana et al [18]. This causes the highest melting temperature of
antistatic bio-nano composites AS-BNC-2 treatment (addition of 2.00% CNC and 2.00% M-DAG).
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Treatment
Specific Gravity (%
Symbols of treatments MFI (g/10 min) w/v)
Based on the results of thermal degradation (figure 4 and table 5), the thermal stability of the antistatic bio-
nano composites treated with AS-BNC-0, AS-BNC-2, AS-BNC-3, and AS-BNC-5 were 456.75 °C, 456.50 °C,
457.10 °C, and 452.50 °C higher than that of pure PP with an increase of 3.33%, 3.27%, 3.40%, and 2.36%
respectively. However, when compared with AS-BNC-1, it had lower thermal stability than pure PP with a
decrease of 6.32%. Therefore, the addition of 3.00% CNC and 2% M-DAG to the PP matrix can increase the
thermal degradation of the resulting antistatic bio-nano composites. According to Al-Haik et al [17], the thermal
stability of bio-nano composites with the addition of 1.00%, 2.00%, and 3.00% CNC on the PP matrix showed a
greater value when compared to pure PP and the addition of 4.00% and 5.00% CNC, with the highest thermal
stability on the addition of 3.00% CNC. CNC particles are thought to increase the thermal resistance of antistatic
bio-nano composites by inhibiting the diffusion of volatile decomposition products or by forming a charred
CNC surface that dissipates heat by absorbing it in the inorganic phase [23, 24]. In addition, the presence of
M-DAG can inhibit the thermal degradation of the antistatic bio-nano composites. The reduced thermal
resistance in the antistatic bio-nano composites with the treatment of 2.00% M-DAG, and 1.00% CNC may
have been due to the non-uniform dispersion of the CNC particles [23].
This also happens to the melting temperature of antistatic bio-nano composites, where the addition of
3.00% CNC and 2.00% M-DAG to the PP matrix can increase the thermal degradation of the resulting antistatic
bio-nano composites. The use of M-DAG and CNC simultaneously on the PP matrix, of course, will form a
unique pattern of interaction or reaction which can certainly have an impact on the thermal properties of
antistatic bio-nano composites.
Based on the results of MFI analysis (table 6), the MFI of AS-BNC-0 antistatic bio-nano composites was
lower than pure PP with a reduction of 10.70%. While the antistatic bio-nano composites with the treatment of
AS-BNC-1, AS-BNC-2, AS-BNC-3, and AS-BNC-5 had higher MFI values than pure PP with an increase of
21.75, 39.85, 24.62, and 40.39%, respectively. M-DAG has a lower melting temperature value than pure PP, so
the addition of M-DAG to the PP matrix can reduce the MFI value of the produced antistatic bio-nano
composites. On the other side, CNC has a higher melting temperature than pure PP, so the addition of CNC to
the PP matrix can increase the MFI value of the antistatic bio-nano composites. The specific gravity is also
influenced by CNC concentration, the higher CNC concentration, the lower the specific gravity of antistatic bio-
nano composites. This showed that the density of antistatic bio-nano composites was getting smaller possibly
because the CNC molecules can form a three-dimensional structure among the PP molecules.
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Figure 5. Electrical resistivity of antistatic bio-nano composites. AS-BNC: antistatic bio-nano composites.
composites, the values were in the range of the antistatic category of 1010–1012 Ω/sq. In addition, the surface
resistivity value of antistatic bio-nano composites was the static dissipative value range of 106–1012 Ω/sq which
has the potential used for electrostatic discharge prevention or the presence of a sudden electric current caused
by an electric short circuit, a dielectric fault, or the contact between two electrically charged objects [25]. In
general, the polymer matrix is highly insulated. Therefore, the presence of electrically conductive nanomaterials
with a large aspect ratio dispersed in small quantities can drastically increase the electrical conductivity to a level
that can support use for electrostatic discharge protection [26]. Adriana et al [18] reported that the electrical
resistivity of PS nanocomposite decreased sharply with the addition of glycerol mono stearate (GMS) up to
3.00%, and was almost stable until the addition of 5% GMS. Meanwhile, at the same concentration of GMS
(3.00%), the electrical resistivity of PS nanocomposite decreased with the addition of a not-so-much variation of
the CNC concentration.
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Figure 8. Visuals of PP-based antistatic bio-nano composites pellet with the addition of 15% CNC and 5% M-DAG.
the PP reinforced with CNC during the extrusion process would work 24–48 h after the extrusion process to
migrate to the surface of the PP reinforced with CNC, forming a hygroscopic film that attracts water, so that has
a conductive function, as it discharges static electricity and reduces the level of plastic charge [28].
Based on the initial indication, M-DAG acts as a barrier to thermal degradation during the production
process. This was demonstrated during the antistatic bio-nano composites synthesis process, where at the same
CNC concentration (15.00%), without the addition of M-DAG to the raw material mixture, there was no
formation of masterbatch pellet because the extruded product was crushed and charred to a dark black color.
Meanwhile, the addition of 5.00% M-DAG showed the formation of extruded pellets, although the color was
dark brown (see figure 8).
The thermal degradation inhibition by M-DAG is probably because of the presence of a free hydroxyl group
in M-DAG, and makes it function as a heat stabilizer [4] and lubricant to shorten the synthesis time of antistatic
bio-nano composites. Of course, the presence of free hydroxyl groups on M-DAG will protect the surface
materials of CNC and PP from exposure to excessive heat. However, using too high a temperature can reduce the
availability of free hydroxyl groups on M-DAG. This can have an impact on reducing the antistatic properties of
antistatic bio-nano composites.
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Based on odour analysis, the antistatic bio-nano composites have a slightly woody and fatty smell compared
to odourless pure PP. It probably comes from CNC and M-DAG. Meanwhile, based on the texture analysis, the
antistatic bio-nano composites have a coarser texture along with the high concentration of CNC used. The
slightly rough texture of antistatic bio-nano composites is possibly caused by friction between CNC and the
moulding surface because CNC has a very hard texture [14] and high surface area [15]. Therefore, it is necessary
to pay attention to the odour and texture of the bio-nanocomposite because it affects the acceptability of
products made with these materials.
Based on the characteristics of the antistatic bio-nano composites produced, indicate the reliability of
antistatic bio-nano composites for application in the industry such as electronics industries. In particular, this
material can be used as electronic device packaging with the category of electronic device packaging level 5 (outer
casing or enclosures), which protects a single electronic device, because of their superior electrical, thermal, and
mechanical properties [31]. However, to ensure its reliability as an electronic device packaging, it is necessary to
carry out further verification.
4. Conclusion
Antistatic bio-nano composites reinforced by CNC and M-DAG (AS-BNC-2) showed a melting temperature of
125.00 °C higher than pure PP of 118.30 °C with an increase of 6.42%. The melting temperatures of AS-BNC-0,
AS-BNC-1, and AS-BNC-3 were also higher than that of pure PP with an increase of 2.20%, 1.44%, and 0.59%,
respectively. However, the addition of a higher CNC concentration (5.00%) can reduce the melting point. The
thermal stability of the antistatic bio-nano composites AS-BNC-0, AS-BNC-2, AS-BNC-3, and AS-BNC-5 were
higher than that of pure PP with an increase of 3.33%, 3.27%, 3.40%, and 2.36%, respectively. The electrical
resistivity value of the antistatic bio-nano composites from the different concentrations of CNC were still in the
range of the antistatic category of 1010–1012 Ω/sq. The addition of M-DAG can reduce thermal degradation due
to its nature as a lubricant in the moulding process.
The findings in this study show that the melting temperature, thermal stability, and electrical resistivity of
antistatic bio-nano composites are better than those of pure PP. This indicates potential applications in the
electronics and packaging industries. In addition, the use of natural materials, M-DAG and CNC, is expected to
increase the biodegradability of antistatic bio-nano composites. Optimization of M-DAG and CNC
concentration should be done further, completed with morphological analysis using scanning electron
microscopy (SEM) to understand the morphology and surface topography of antistatic bio-nano composites.
Acknowledgments
Much appreciation goes to Palm Oil Plantation Fund Management Agency (POPFMA)—Ministry of Finance
Republic Indonesia for supporting this research.
All data that support the findings of this study are included within the article (and any supplementary files).
ORCID iDs
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