Next Article in Journal
Maleic Acid as a Co-Former for Pharmaceutically Active GABA Derivatives: Mechanochemistry or Solvent Crystallization?
Previous Article in Journal
A Combined Raman Spectroscopy and Atomic Force Microscopy System for In Situ and Real-Time Measures in Electrochemical Cells
Previous Article in Special Issue
Selected Properties of Single and Multi-Layered Particleboards with the Structure Modified by Fibers Implication
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Materials
Volume 16
Issue 6
10.3390/ma16062241
materials-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Thermal, Morphological and Mechanical Properties of a BioPE Matrix Composite: Case of Shell, Pulp, and Argan Cake as Biofillers

by
Jihane Zeghlouli
1,2,
Nicola Schiavone
3,
Haroutioun Askanian
3,
Amine Guendouz
1,
Cherkaoui El Modafar
1,
Philippe Michaud
2 and
Cédric Delattre
2,4,*
1
Centre d’Agrobiotechnologie et Bioingénierie, Unité de Recherche Labellisée CNRST (Centre AgroBiotech, URL-CNRST 05), Faculté des Sciences et Techniques Marrakech, Université Cadi Ayyad, Marrakech 40000, Morocco
2
Clermont Auvergne INP, CNRS, Institut Pascal, Université Clermont Auvergne, F-63000 Clermont-Ferrand, France
3
Institut de Chimie de Clermont Ferrand (ICCF), UMR 6296 Université Clermont Auvergne, CNRS, SIGMA Clermont, F-63000 Clermont-Ferrand, France
4
Institut Universitaire de France (IUF), 1 Rue Descartes, 75005 Paris, France
*
Author to whom correspondence should be addressed.
Materials 2023, 16(6), 2241; https://doi.org/10.3390/ma16062241
Submission received: 27 November 2022 / Revised: 13 February 2023 / Accepted: 25 February 2023 / Published: 10 March 2023
(This article belongs to the Special Issue Novel Lightweight Construction Composites from Agro-Materials and Wastes)
Browse Figures
Versions Notes

Abstract

:
Extrusion and hot compressing molding processes were used to create bio-polyethylene (BioPE) composites reinforced with argan byproducts (shell, pulp, and argan cake) as bio-fillers. The thermal stability of the composites wass analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Dynamical mechanical analysis and rheological testing were used to investigate their mechanical properties. The morphological results showed a good adhesion between the argan and BioPE matrix. More efficient mechanical properties have been distinguished in the case of argan byproduct-based composite. A higher Young’s modulus was noted for all the biocomposites compared to pure BioPE. Thermal analysis revealed that the addition of bio-filler to polymer reduced decomposition temperatures. This study provides an ecological alternative for upgrading the valorization of abundant and underutilized Moroccan biomass. Furthermore, the possibility of using argan byproducts in composite manufacturing will help open up new markets for what is currently considered waste.

1. Introduction

Petro-plastics are among the main materials used in the preparation of products with a short lifespan, particularly in the packaging industry [1,2]. This generates a large amount of plastic waste, which has been causing global environmental problems for decades [3,4,5,6,7]. A massive amount of plastic waste has been released into the environment all over the world, contributing to the current problem of white pollution [8]. As a result, the negative effects of plastics on society have prompted the scientific community, governments, and businesses to seek solutions to these problems.
Recycling, incineration, and landfilling are the current methods for managing plastic waste [1]. However, these steps are often limited by some issues related to the high cost of the process, the low cost of recycled plastics, the low cost of raw materials limiting plastic recycling, and the production of greenhouse gases and other irritant gases [3,4]. Also, the efficient of these methods remains very limited and only validated under certain conditions, because the scale of plastic production far outnumbers the reduction achieved by these treatment methods, and more work needs to be done on awareness of responsible waste handling methods [5].
In this respect, nature-based, renewable, and biodegradable composite represent a viable alternative to petro-plastics and present a topic of great interest [6]. Additionally, to address the issues caused by industrial waste, alternative products are being developed in collaboration with the recycling sector and renewable resources, particularly biosourced composites, which are critical in creating an environmentally friendly, economical, and sustainable raw material source [7,8,9,10,11,12,13].
Biocomposites can be created by combining biowastes, additives, polymers, and fillers with varying properties and putting them through a variety of processes. These composites can be given the desired properties based on their intended use, or new products can be improved [14]. Furthermore, numerous biopolymers such as, PLA, PHAs, protein, and starch-based plastics are being researched as potential alternatives to petro-plastics in combating the ongoing plastics problem [15,16].
Biocomposites made from biomass-based renewable resources are expected to become an indispensable alternative in the future [17]. The advantages of plant-derived composites include their biodegradability in nature and waste recycling by the environment. However, polymer composites reinforced with natural fillers from renewable natural resources, known as “Green biocomposites”, present a topic of great interest. They provide numerous benefits, such as renewability, non-toxicity, biodegradability, low density, improved thermal and acoustic insulating properties, low energy consumption during processing, low cost, etc. [18,19,20,21,22].
Many studies have been conducted to evaluate bio-fillers in order to develop composites with improved performance [23,24]. The incorporation of lignocellulosic fiber as reinforcement phases into post-consumer polymers (as matrices) improves their properties and thus broadens their applications. As a result, this method minimizes the environmental impact of waste materials [25,26,27]. Different lignocellulosic fiber can be acquired from forestry and agricultural resources (e.g., jute, sisal, hemp, kenaf, wood, cotton, flax, bagasse, etc.) [28,29], from agricultural wastes or byproducts (e.g., rice husks, coir, wheat bran, okra, pineapple, and artichoke) [30,31,32,33], and also from particles such as almond shells, almond kernels, and pistachio and peanut shells [34,35,36,37]. However, agricultural wastes are more interesting as fillers due to their ease of processing and low cost to produce as alternative, cheap, sustainable, and environmentally safe materials for several sectors. For these reasons, there is always an interest in finding new natural fibers as reinforcement of composites from agricultural waste.
The argan byproducts could have a promising future as a new bio-filler. The argan tree (Argania spinosa (L.) Skeels) exclusively grows endemically in Morocco, which represents its second forest, with about 871,210 hectares, 20 million trees, and a production of 500 kg of fruit per ha per year [38]. For centuries, it played a crucial role in the ecology and the socio-economy of the country, taking into account that 3.5 million local lives depend on the argan ecosystem [39]. This illustrious species is designated as a UNESCO biosphere reserve and is universally known for its nutritional, therapeutic, and cosmetic oil [39]. However, the production process of argan oil generated a large quantity of byproducts representing about 97% of the argan fruit weight (43% of pulp, 52.6% of shells, and 2% of argan cake generated after the extraction of oil from argan kernels) (Figure 1) which should be better exploited. So far, the main use of argan shell is for heating, while the pulp and argan cake are used as cattle feed [40].
Recently, some studies on the use of argan shell as a bio filler in different matrices were reported [41,42,43,44]. However, up to now, and to the best of our knowledge, there is no study that has evaluated the valorization of all argan byproducts (shell, pulp, and cakes) as bio filler, which could have the privilege of boosting the valorization of the local byproducts of the argan tree, with the goal of establishing an argan biorefinery and to contribute to the economic development of the argan region.
In this work, our main goal was to produce and analyze a new bio polyethylene (BioPE) based composite with argan byproducts as filler. We chose this type of polyethylene because it has the same chemical structure as petro-based polyethylene and is widely accessible on an industrial scale [45].
We investigated the impact of adding each argan byproduct (30 wt.%) to BioPE grades on the composite films. The thermal, rheological, morphological, and mechanical properties were assessed.

2. Materials and Methods

2.1. Raw Materials

Argan byproducts (shell, pulp, and two types of argan cakes) utilized in this study were supplied by Nectarome (https://www.nectarome.com/ accessed on 10 December 2019), located 35 km from Marrakech (Morocco). It represents one of the leading companies in Morocco for the production of oil and cosmetic products based on argan. We mentioned that the two types of argan cakes studied, roasted and unroasted, represent the first and second extractions from the production of edible and cosmetic oils, respectively. The company had already dried and ground the samples of argan byproducts into a fine powder. Following that, the biomass was stored until the day of use.
The content of main chemical constituents of the three argan byproducts is shown in Table 1. Argan byproduct analysis was performed using the methods highlighted in our previous study [46]. Braskem (So Paulo, Brazil) supplied the matrix, which was bio-based bimodal high-density polyethylene (HDPE) SGE 7252 with a density of 0.952 g/cm3 and a melt flow index (190 °C/2.16 kg) of 2 g/10 min.

2.2. Laser Granulometry Measurement

The samples grain size, size–volume distribution %, and the specific surface area, were measured through Laser granulometry technique based on light diffraction with a Mastersizer Laser Diffraction granulometry analyzer from Malvern Analytical (Mastersizer 3000, Malvern Instruments Co. Ltd., Malvern, UK). The samples were individually measured in a liquid bulk container, and the mixing process was conducted in water with sonification to eliminate the probability of agglomeration of the particles. Mastersizer software was used to analyze the results.

2.3. Composite Film and Filament Preparation for 3D Printing

A Thermo Fisher Scientific Pharma twin screw extruder was used to prepare composite films with argan byproduct powder (30 wt.%) (Waltham, MA, USA). Before starting the extrusion step, the bio-PE pellets and argan byproducts were dried in a vacuum oven for 24 h at 60 °C. Each single byproduct shell, pulp, or argan cake was mixed with 70% weight mass of BioPE. The extrusion conditions were 150 °C, 100 rpm, and 0.6 Kg/h for temperature, screw rate, and mass flow, respectively.
The wire was then pressed for 2 min (150 °C, 3 MPa) using hot press (Weber Pressen Hy-draulic Press, WEBER-HYDRAULI K, Güglingen, Germany). Compression molding of BioPE pellets (control) and BioPE-argan byproducts composite between Teflon®-lined mild steel plates produced a thin film approximately 0.1 mm thick. These processes produced thin films measuring 5 cm × 4 cm. Those films (Figure 2) were used for thermal, morphological, and mechanical characterization.

2.4. Rheological Testing

Shear dynamic measurements were done with an ARES rheometer (Rheometric Scientific) made by TA Instruments (New Castle, DE, USA) using a frequency sweep method and parallel plate geometry with an 8 mm diameter. The temperature of the test was 150 °C, the gap was placed to 1 mm, 5% of strain was performed, and a sweep frequency of 0.1100 rad/s was set. The calculation of the loss viscosity (η′) and the storage viscosity (η″) was made from the frequencies and the zero-shear viscosity η0, as described in a previous study [47].

2.5. Thermal Characterization

A thermogravimetric analysis was performed on all samples to verify the impact of the load of argan byproducts on the thermal properties of the polymer and to determine which of the byproducts, shell, pulp, or argan cakes, is the most thermally stable.

2.5.1. Thermogravimetric Analyses (TGA)

TGA was carried out on a PerkinElmer TGA 4000 (Waltham, MA, USA) with a heating rate of 10 °C/min. In an aluminum pan, 8 mg of the sample was heated from room temperature to 700 °C under a nitrogen atmosphere.

2.5.2. Differential Scanning Calorimetry (DSC) Analysis

Under a nitrogen atmosphere, the crystallinity and thermal behavior of the analyzed samples were assessed using differential scanning calorimetry (METTLER TOLEDO DSC 3+, Columbus, OH, USA). An 8–10 mg mass of material was tested for each sample using the heat–cool–heat cycle method described by Schiavone et al., 2021 [48].
The crystallization degree Xc was determined using the following equation:
Xu = (ΔHm − ΔHc)/(ΔHm0 − (w/w) p) × 100
with ΔHm, ΔHm0, and ΔHc as the melting enthalpy; the melting enthalpy of pure, fully crystalline polymers; and the crystallization enthalpy, respectively; (w/w) p as the polymer mass fraction in the matrix; and ΔHm0 = 287.7 J/g for PE.

2.6. Mechanical Characterization

The tensile properties were determined utilizing a Universal Testing Machine (Hounsfield, Model H50 Ks 0404, UK) with a cross-head speed of 50 mm/min. The specimens (Figure 3) measured 75 ± 0.2 mm in length, 5 ± 0.1 mm in width, and 0.2 ± 0.05 mm in thickness. The tests were carried out at a temperature of 25 °C. Data reported were the means of five replicates.

3. Results and Discussion

3.1. Granulometry Distribution

The granulometry of argan byproduct granules was determined using a laser granulometry technique (Figure 4, Table 2). The sizes at 10 (D10), 50 (D50), 90y (D90), and D [4;3] (volume mean diameter) of cumulative volume were calculated. The low granulometry was obtained in the case of roasted cakes; the obtained values were 5.6 μm, 29.2 μm, 95.0 μm, and 43.3 μm for D10, D50, D90 and D [4;3], respectively. However, the pulp predefined the sample with the largest particle size with 19.3 μm, 101.0 μm, 301.0 μm, and 135.0 μm for D10, D50, D90, and D [4;3], respectively. Additionally, the specific surface area was 559.1 cm2/g and 139.0 cm2/g for roasted argan cake and pulp, respectively. The distribution lacked dispersibility, and the size of the narrow distribution (span) for roasted argan cake and pulp, respectively, was 3.1 and 2.8, calculated by dividing the difference in diameter at 90% and 10% of the cumulative volume by the diameter at 50% of the cumulative volume [49].

3.2. Composite Thermal and Rheological Properties

3.2.1. Analysis of Differential Scanning Calorimetry (DSC)

Differential scanning calorimetry was used to investigate the impact of argan byproduct on the thermal characteristics of BioPE composites. The second heating and cooling DSC thermograms of pure BioPE and BioPE/argan byproduct composites are shown in Figure 5a,b. The curves depicted do not show significant distinctions in terms of melting and cooling transitions; we obtained the same trend curve, approximatively. The thermal parameters, including melting enthalpy (ΔHm), melting temperature (Tm), crystallization temperature (Tc), crystallization enthalpy (ΔHc), and crystallinity degree (Xc) are stated in Table 3. The adding of argan byproducts had no effect on the glass transition and melting temperatures of the biocomposites studied. However, we noticed a reduction in melting enthalpy (ΔHm) and crystallization enthalpy (ΔHc) values in the presence of argan by product composite compared to pure BioPE.
The melting temperature of neat Bio-HDPE is 133 °C, the melting enthalpy is 111 j/g, and the crystallinity XC is 39.6%. Schiavone et al. [48] reported comparable results. Melting enthalpy decreases slightly after the addition of argan particles to the Bio-PE, falling to 73 j/g, 56 j/g, 32 j/g, and 31 j/g for shell, pulp, roasted argan cake, and unroasted argan cake composite, respectively. We suggest that the reduction of melting enthalpy can be an advantage for ease of extrusion during 3D printing of the composite, which represents the last stage of valuation of a composite. Less thermal energy allows a rapid phase transition of the polymer filament compared to the residence of the material in the extruder [50,51]. On the other hand, crystallinity drops dramatically to 23.1%, 25.9%, 27.6%, and 30.5% for shell, pulp, roasted argan cake, and unroasted argan cake composite, respectively. This was related to the decrease in polymer chain mobility. In addition, while argan particles can stimulate heterogeneous nucleation during the polymer’s crystallization process, increased argan byproduct concentrations (over 10%) can make concessions to the nucleation due to particle–particle contact. As a result, there is a limitation in space for crystal formation and growth [52,53]. Essabir et al. [41] also noticed this phenomenon.

3.2.2. Thermogravimetric Analysis (TGA)

Thermogravimetric analysis (TGA) has been investigated. Figure 6 depicts TGA curves for all composites in the presence of various argan byproducts. As can be seen, the maximum degradation rate temperature in the case of pure BioPE was 480 °C. For pure Bio-PE, Montanes et al. [54] discovered a comparable thermal profile.
However, the presence of fillers significantly influenced the decomposition kinetics. In other words, using argan byproducts as fillers appears to have reduced the initial degradation temperature. We discovered that the decomposition of argan byproduct-based composites begins around 220 °C. This is primarily due to the presence of argan byproducts in the polymer structure, which reduces thermal stability in some ways. Essabir et. al. [36] investigated a similar study on the properties of polypropylene and almond shell flour blends. Jorda-Reolid et al. [53] recently reported on the properties of plastic composites based on argan shell as a filler and high-density polyethylene in the presence of different compatibilizers. Contrary to the pure PE, the biocomposites based on argan byproducts curves show several stages of degradation. This can be explained by the degradation of the three major components of argan byproducts, namely, hemicellulose, cellulose, and lignin, as shown in Table 1 [36,55,56].

3.2.3. Rheology

Melt viscoelasticity experiments in oscillatory shear mode with a rotational controlled stress rheometer were used to investigate the effect of argan byproduct as a filler content on the viscoelastic properties of the composites. Figure 7 depicts the Cole–Cole plots for all samples. The Cole–Cole distribution reveals a significant increase in zero-shear viscosity by adding argan byproduct as a filler, especially in the case of argan shell, as shown in the results. The increased effect of viscosity after the addition of the filler is normally due to the restricted mobility of chain segments, which alters the normal polymer flow [57,58]. In addition, the good distribution and good affinity of rigid bio-filler into the polymer increases its resistance to flow and subsequently results in an increase in viscosity [59,60]. Therefore, the presence of argan byproducts enhances viscoelastic properties and demonstrates good interfacial interaction between the argan byproduct fillers and the BioPE matrix. Moreover, the dynamic rheological properties of treated argan shell bio-filler reinforced high density polyethylene matrix were assessed in order to determine the dispersion state of the bio-filler within the polymer [61]. The results showed a raise in complex viscosity with the incorporation of bio-filler, and the composite containing the highest load of bio filler (25%) led to the highest complex values of viscosity. Moreover, the formulations of composites produced with pozzolan as a filler and bio-based polyethylene have been reported [48]. There was a proportional increase in viscosity with increasing pozzolan loading.

3.3. Mechanical Characteristics

Table 4 displays the mechanical properties of pure BioPE and BioPE/argan byproduct composites, including Young’s modulus (E), maximum tensile strength (max), ultimate strain (max), and elongation at break (b).
These findings are important for assessing the efficacy of various argan byproducts in terms of Bio-PE resistance improvement and compatibility with argan byproduct particles.
The films obtained by hot press showed an increase in stiffness by adding argan byproduct (30 wt.%) in the polymer matrix, characterized by an increase in Young’s modulus and a slight decrease in ultimate strength and ultimate strain.
Incorporation of shell, pulp, roasted argan cake, and unroasted argan cake (30 wt.%) into the BioPE matrix increased the Young modulus up to 498 MPa, 349 MPa, 324 MPa, and 330 MPa, respectively. This can be explained by the distribution of argan byproduct particles in the polymer matrix, which results in good filler–polymer adhesion and a more rigid material [62]. The higher Young’s modulus in the case of argan shell (498 MPa) could be explained by the complex composition of this material compared to the pulp and cakes shown by a high percentage of cellulose, hemicellulose, and lignin (Table 1).
However, there is a significant reduction in elongation at break, which can be attributed to the use of an excess of argan byproduct, which increases the stiffness of the material [63]. Furthermore, the presence of a filler causes phase heterogeneity and discontinuity in the polymer matrix. In general, this discontinuity reduces ductility [64,65].
Moreover, Essabir et al. [61] noted the same behavior using HDPE with argan particles, in that Young’s modulus increased with MAS concentration, but tensile strength began to decrease as argan shell particle load increased. In 2021, Schiavone et al. [53] also obtained improved stiffness from BioPE and pozzolane-based composites. The modulus of elasticity of the composites was three times that of pure BioPE, and the ability to print BioPE with filler mass ratios of up to 60% without any chemical treatment on the filler has been validated.
Finally, this work studied the development of a 100% bio-sourced agrocomposite from all argan byproducts (shell, pulp, and argan cake) without any chemical treatment and BioPE as a matrix. It can be deduced that all the byproducts studied can be used as a bio-filler of the biocomposites due to their mechanical performance. Indeed, in the majority of cases, only the argan shell was studied as a filler and it was always chemically treated, thus the maximum mass ratio added was about 25% [36,43,61].

4. Conclusions

The adding of Moroccan argan byproducts as fillers in the polymer matrix represents promising new and eco-friendly products, with high performance and low cost for such industrial application as packaging. The present study deals with the thermal, structural, and mechanical properties of argan byproducts (shell, pulp, and cake) as a new bio-filler. The high-performance mechanical properties of the used bio-fillers (Young’s modulus and tensile strength) yielded an improvement in the mechanical properties of the final composite compared to those of the pure BioPE. Overall, the use of shell, pulp and argan cake particles shows potential for applications in the plastics industry due to their ability to yield improved mechanical properties in a cost-effective manner. Argan byproducts used as bio-filler appear to be a good alternative for obtaining environmentally friendly products.

Author Contributions

Conceptualization, J.Z., C.D., A.G., P.M. and C.E.M.; methodology, J.Z., C.D., A.G., N.S. and H.A.; supervision C.D., N.S., H.A., A.G. and P.M.; writing original draft, J.Z., C.D., N.S., H.A., A.G. and P.M.; writing—review and editing, J.Z., C.D., A.G., P.M. and C.E.M. All authors have read and agreed to the published version of the manuscript.

Funding

This project was financially supported by the Ministry of Europe and Foreign Affairs; the Ministry of Higher Education, Research, and Innovation; and the French Institute of Rabat (PHC TOUBKAL 20/94 (French-Moroccan bilateral program). Grant number: 43678RH.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The authors acknowledge Nectarome Company.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Agustin-Salazar, S.; Ricciulli, M.; Ambrogi, V.; Cerruti, P.; Scarinzi, G. Effect of thermal annealing and filler ball-milling on the properties of highly filled polylactic acid/pecan (Carya illinoinensis) nutshell biocomposites. Int. J. Biol. Macromol. 2022, 200, 350–361. [Google Scholar] [CrossRef] [PubMed]
  2. Hazrati, K.Z.; Sapuan, S.M.; Zuhri, M.Y.M.; Jumaidin, R. Preparation and characterization of starch-based biocomposite films reinforced by Dioscorea hispida fibers. J. Mater. Res. Technol. 2021, 15, 1342–1355. [Google Scholar] [CrossRef]
  3. Izwan, S.M.; Sapuan, S.M.; Zuhri, M.Y.M.; Mohamed, A.R. Effects of benzoyl treatment on NaOH treated sugar palm fiber: Tensile, thermal, and morphological properties. J. Mater. Res. Technol. 2020, 9, 5805–5814. [Google Scholar] [CrossRef]
  4. Tarique, J.; Sapuan, S.M.; Khalina, A. Effect of glycerol plasticizer loading on the physical, mechanical, thermal, and barrier properties of arrowroot (Maranta arundinacea) starch biopolymers. Sci. Rep. 2021, 11, 13900. [Google Scholar] [CrossRef] [PubMed]
  5. Shen, M.; Song, B.; Zeng, G.; Zhang, Y.; Huang, W.; Wen, X.; Tang, W. Are biodegradable plastics a promising solution to solve the global plastic pollution? Environ. Pollut. 2020, 263, 114469. [Google Scholar] [CrossRef]
  6. Yu, J.; Chen, L.X.L. The greenhouse gas emissions and fossil energy requirement of bioplastics from cradle to gate of a biomass refinery. Environ. Sci. Technol. 2008, 42, 6961–6966. [Google Scholar] [CrossRef]
  7. Khodaei, D.; Oltrogge, K.; Hamidi-Esfahani, Z. Preparation and characterization of blended edible films manufactured using gelatin, tragacanth gum and, Persian gum. LWT 2020, 117, 108617. [Google Scholar] [CrossRef]
  8. Ren, L.; Yan, X.; Zhou, J.; Tong, J.; Su, X. Influence of chitosan concentration on mechanical and barrier properties of corn starch/chitosan films. Int. J. Biol. Macromol. 2017, 105, 1636–1643. [Google Scholar] [CrossRef]
  9. Ilyas, R.A.; Sapuan, S.M.; Atikah, M.S.N.; Ibrahim, R.; Hazrol, M.D.; Sherwani, S.F.K.; Harussani, M.M.; Jamal, T.; Nazrin, A.; Syafiq, R. Natural fibre: A promising source for the production of nanocellulose. In Proceedings of the 7th Postgraduate Seminar on Natural Fibre Reinforced Polymer Composites; Institute of Tropical Forest and Forest Products (INTROP), Universiti Putra Malaysia: Serdang, Malaysia, 2020. [Google Scholar]
  10. Tarique, J.; Sapuan, S.M.; Khalina, A.; Sherwani, S.F.K.; Yusuf, J.; Ilyas, R.A. Recent developments in sustainable Arrowroot (Maranta arundinacea Linn) starch biopolymers, fibres, biopolymer composites and their potential industrial applications: A review. J. Mater. Res. Technol. 2021, 13, 1191–1219. [Google Scholar] [CrossRef]
  11. Wang, J.; Cheng, F.; Zhu, P. Structure and properties of urea-plasticized starch films with different urea contents. Carbohydr. Polym. 2014, 101, 1109–1115. [Google Scholar] [CrossRef]
  12. Perdana, M.I.; Ruamcharoen, J.; Panphon, S.; Leelakriangsak, M. Antimicrobial activity and physical properties of starch/chitosan film incorporated with lemongrass essential oil and its application. LWT 2021, 141, 110934. [Google Scholar] [CrossRef]
  13. Yusoff, N.H.; Pal, K.; Narayanan, T.; de Souza, F.G. Recent trends on bioplastics synthesis and characterizations: Polylactic acid (PLA) incorporated with tapioca starch for packaging applications. J. Mol. Struct. 2021, 1232, 129954. [Google Scholar] [CrossRef]
  14. Aydoğmuş, E.; Dağ, M.; Yalçin, Z.G.; Arslanoğlu, H. Synthesis and characterization of EPS reinforced modified castor oil-based epoxy biocomposite. J. Build. Eng. 2021, 47, 103897. [Google Scholar] [CrossRef]
  15. Chen, S.; Wu, M.; Wang, C.; Yan, S.; Lu, P.; Wang, S. Developed chitosan/oregano essential oil biocomposite packaging film enhanced by cellulose nanofibril. Polymers 2020, 12, 1780. [Google Scholar] [CrossRef]
  16. Sherwani, S.F.K.; Sapuan, S.M.; Leman, Z.; Zainuddin, E.S.; Ilyas, R.A. Application of polymer composite materials in motorcycles: A Comprehensive review. Biocompos. Synth. Compos. Automot. Appl. 2021, 401–426. [Google Scholar] [CrossRef]
  17. Aly, N.M.; ElNashar, D.E. Polyester/flax biocomposites reinforced using date palm leaves and wood flour as fillers. Int. J. Eng. Technol. 2016, 8. Available online: https://www.enggjournals.com/ijet/docs/IJET16-08-03-150.pdf (accessed on 20 November 2022).
  18. Rafeeq, S.N.; Abdulmajeed, I.M.; Saeed, A.R. Mechanical and thermal properties of Date Palm Fiber and Coconut shell particulate filler reinforced Epoxy composite. Indian J. Appl. Res. 2013, 3, 89–92. [Google Scholar] [CrossRef]
  19. Nguong, C.W.; Lee, S.N.B.; Sujan, D. A review on natural fibre reinforced polymer composites. Int. J. Mater. Metall. Eng. 2013, 7, 52–59. [Google Scholar]
  20. Setswalo, K.; Molaletsa, N.; Oladijo, O.P.; Akinlabi, E.T.; Rangappa, S.M.; Siengchin, S. The Influence of Fiber Processing and Alkaline Treatment on the Properties of Natural Fiber-reinforced Composites: A Review. Appl. Sci. Eng. Prog. 2021, 14, 632–650. [Google Scholar] [CrossRef]
  21. Jawaid, M.; Khalil, H.P.S.A.; Hassan, A.; Dungani, R.; Hadiyane, A. Effect of jute fibre loading on tensile and dynamic mechanical properties of oil palm epoxy composites. Compos. Part B Eng. 2013, 45, 619–624. [Google Scholar] [CrossRef]
  22. AL-Oqla, F.M.; Alothman, O.Y.; Jawaid, M.; Sapuan, S.M.; Es-Saheb, M.H. Processing and properties of date palm fibers and its composites. In Biomass and Bioenergy; Springer: Berlin/Heidelberg, Germany, 2014; pp. 1–25. [Google Scholar]
  23. Petchwattana, N.; Covavisaruch, S. Mechanical and morphological properties of wood plastic biocomposites prepared from toughened poly (lactic acid) and rubber wood sawdust (Hevea brasiliensis). J. Bionic Eng. 2014, 11, 630–637. [Google Scholar] [CrossRef]
  24. Pérez, E.; Famá, L.; Pardo, S.G.; Abad, M.J.; Bernal, C. Tensile and fracture behaviour of PP/wood flour composites. Compos. Part B Eng. 2012, 43, 2795–2800. [Google Scholar] [CrossRef]
  25. Josefsson, G.; Berthold, F.; Gamstedt, E.K. Stiffness contribution of cellulose nanofibrils to composite materials. Int. J. Solids Struct. 2014, 51, 945–953. [Google Scholar] [CrossRef] [Green Version]
  26. Delgado-Aguilar, M.; Julián, F.; Tarrés, Q.; Méndez, J.A.; Mutjé, P.; Espinach, F.X. Bio composite from bleached pine fibers reinforced polylactic acid as a replacement of glass fiber reinforced polypropylene, macro and micro-mechanics of the Young’s modulus. Compos. Part B Eng. 2017, 125, 203–210. [Google Scholar] [CrossRef]
  27. Brodin, M.; Vallejos, M.; Opedal, M.T.; Area, M.C.; Chinga-Carrasco, G. Lignocellulosics as sustainable resources for production of bioplastics—A review. J. Clean. Prod. 2017, 162, 646–664. [Google Scholar] [CrossRef]
  28. Bari, E.; Sistani, A.; Morrell, J.J.; Pizzi, A.; Akbari, M.R.; Ribera, J. Current strategies for the production of sustainable biopolymer composites. Polymers 2021, 13, 2878. [Google Scholar] [CrossRef] [PubMed]
  29. Sreenivas, H.T.; Krishnamurthy, N.; Arpitha, G.R. A comprehensive review on light weight kenaf fiber for automobiles. Int. J. Lightweight Mater. Manuf. 2020, 3, 328–337. [Google Scholar] [CrossRef]
  30. Charlet, K. Natural fibres as composite reinforcement materials: Description and new sources. Nat. Polym. 2012, 1, 37–62. [Google Scholar]
  31. Zini, E.; Scandola, M. Green composites: An overview. Polym. Compos. 2011, 32, 1905–1915. [Google Scholar] [CrossRef]
  32. Totaro, G.; Sisti, L.; Vannini, M.; Marchese, P.; Tassoni, A.; Lenucci, M.S.; Lamborghini, M.; Kalia, S.; Celli, A. A new route of valorization of rice endosperm by-product: Production of polymeric biocomposites. Compos. Part B Eng. 2018, 139, 195–202. [Google Scholar] [CrossRef]
  33. Yap, S.Y.; Sreekantan, S.; Hassan, M.; Sudesh, K.; Ong, M.T. Characterization and Biodegradability of Rice Husk-Filled Polymer Composites. Polymers 2021, 13, 104. [Google Scholar] [CrossRef] [PubMed]
  34. Hongsriphan, N.; Kamsantia, P.; Sillapasangloed, P.; Loychuen, S. Bio-based composite from poly (butylene succinate) and peanut shell waste adding maleinized linseed oil. In IOP Conference Series: Materials Science and Engineering; IOP Publishing: Bristol, UK, 2020; Volume 773, p. 12046. [Google Scholar]
  35. Liminana, P.; Garcia-Sanoguera, D.; Quiles-Carrillo, L.; Balart, R.; Montanes, N. Optimization of maleinized linseed oil loading as a biobased compatibilizer in poly (butylene succinate) composites with almond shell flour. Materials 2019, 12, 685. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  36. Essabir, H.; Nekhlaoui, S.; Malha, M.; Bensalah, M.O.; Arrakhiz, F.Z.; Qaiss, A.; Bouhfid, R. Bio-composites based on polypropylene reinforced with Almond Shells particles: Mechanical and thermal properties. Mater. Des. 2013, 51, 225–230. [Google Scholar] [CrossRef]
  37. Rojas-Lema, S.; Arevalo, J.; Gomez-Caturla, J.; Garcia-Garcia, D.; Torres-Giner, S. Peroxide-Induced Synthesis of Maleic Anhydride-Grafted Poly (butylene succinate) and Its Compatibilizing Effect on Poly (butylene succinate)/Pistachio Shell Flour Composites. Molecules 2021, 26, 5927. [Google Scholar] [CrossRef]
  38. Heller, D.; Einfalt, D. Wildflower mixtures for bioethanol production—Pretreatment and enzymatic hydrolysis. Biomass Bioenergy 2020, 141, 105727. [Google Scholar] [CrossRef]
  39. Perry, W. Social sustainability and the argan boom as green development in Morocco. World Dev. Perspect. 2020, 20, 100238. [Google Scholar] [CrossRef]
  40. Zeghlouli, J.; Christophe, G.; Guendouz, A.; El Modafar, C.; Belkamel, A.; Michaud, P.; Delattre, C. Optimization of Bioethanol Production from Enzymatic Treatment of Argan Pulp Feedstock. Molecules 2021, 26, 2516. [Google Scholar] [CrossRef]
  41. Essabir, H.; Bensalah, M.O.; Rodrigue, D.; Bouhfid, R. Biocomposites based on Argan nut shell and a polymer matrix: Effect of filler content and coupling agent. Carbohydr. Polym. 2016, 143, 70–83. [Google Scholar] [CrossRef]
  42. El Moumen, A.; N’Guyen, F.; Kanit, T.; Imad, A. Mechanical properties of poly–propylene reinforced with Argan nut shell aggregates: Computational strategy based microstructures. Mech. Mater. 2020, 145, 103348. [Google Scholar] [CrossRef]
  43. Laaziz, S.A.; Raji, M.; Hilali, E.; Essabir, H.; Rodrigue, D.; Bouhfid, R. Bio-composites based on polylactic acid and argan nut shell: Production and properties. Int. J. Biol. Macromol. 2017, 104, 30–42. [Google Scholar] [CrossRef]
  44. Akhzouz, H.; El Minor, H.; Tatane, M.; Bendarma, A. Physical characterization of bio-composite CEB stabilized with Argan nut shell and cement. Mater. Today Proc. 2021, 36, 107–114. [Google Scholar] [CrossRef]
  45. Tarrés, Q.; Melbø, J.K.; Delgado-Aguilar, M.; Espinach, F.X.; Mutjé, P.; Chinga-Carrasco, G. Bio-polyethylene reinforced with thermomechanical pulp fibers: Mechanical and micromechanical characterization and its application in 3D-printing by fused deposition modelling. Compos. Part B Eng. 2018, 153, 70–77. [Google Scholar] [CrossRef]
  46. Zeghlouli, J.; Christophe, G.; Ogura, K.; Sawamura, N.; Guendouz, A.; El Modafar, C.; Michaud, P.; Delattre, C. High-Pressure Water Jet System Treatment of Argan Nut Shell and Enzymatic Hydrolysis for Bioethanol Production. Fermentation 2022, 8, 627. [Google Scholar] [CrossRef]
  47. Marek, A.A.; Verney, V. Rheological behavior of polyolefins during UV irradiation at high temperature as a coupled degradative process. Eur. Polym. J. 2015, 72, 1–11. [Google Scholar] [CrossRef]
  48. Schiavone, N.; Verney, V.; Askanian, H. High-Density Bio-PE and Pozzolan Based Composites: Formulation and Prototype Design for Control of Low Water Flow. Polymers 2021, 13, 1908. [Google Scholar] [CrossRef]
  49. Schiavone, N.; Verney, V.; Askanian, H. Pozzolan Based 3D Printing Composites: From the Formulation Till the Final Application in the Precision Irrigation Field. Materials 2020, 14, 43. [Google Scholar] [CrossRef] [PubMed]
  50. Turner, B.N.; Strong, R.; Gold, S.A. A review of melt extrusion additive manufacturing processes: I. Process design and modeling. Rapid Prototyp. J. 2014, 20, 192–204. [Google Scholar] [CrossRef]
  51. Ravi, A.K.; Deshpande, A.; Hsu, K.H. An in-process laser localized pre-deposition heating approach to inter-layer bond strengthening in extrusion based polymer additive manufacturing. J. Manuf. Process. 2016, 24, 179–185. [Google Scholar] [CrossRef]
  52. Das Lala, S.; Deoghare, A.B.; Chatterjee, S. Effect of reinforcements on polymer matrix bio-composites—An overview. Sci. Eng. Compos. Mater. 2018, 25, 1039–1058. [Google Scholar] [CrossRef]
  53. Jorda-Reolid, M.; Gomez-Caturla, J.; Ivorra-Martinez, J.; Stefani, P.M.; Rojas-Lema, S.; Quiles-Carrillo, L. Upgrading Argan Shell Wastes in Wood Plastic Composites with Biobased Polyethylene Matrix and Different Compatibilizers. Polymers 2021, 13, 922. [Google Scholar] [CrossRef] [PubMed]
  54. Montanes, N.; Garcia-Sanoguera, D.; Segui, V.J.; Fenollar, O.; Boronat, T. Processing and characterization of environmentally friendly composites from biobased polyethylene and natural fillers from thyme herbs. J. Polym. Environ. 2018, 26, 1218–1230. [Google Scholar] [CrossRef]
  55. Ouajai, S.; Shanks, R.A. Composition, structure and thermal degradation of hemp cellulose after chemical treatments. Polym. Degrad. Stab. 2005, 89, 327–335. [Google Scholar] [CrossRef]
  56. Albano, C.; Gonzalez, J.; Ichazo, M.; Kaiser, D. Thermal stability of blends of polyolefins and sisal fiber. Polym. Degrad. Stab. 1999, 66, 179–190. [Google Scholar] [CrossRef]
  57. Kumar, A.; Commereuc, S.; Verney, V. Ageing of elastomers: A molecular approach based on rheological characterization. Polym. Degrad. Stab. 2004, 85, 751–757. [Google Scholar] [CrossRef]
  58. Dealy, J.M.; Wang, J. Melt Rheology and Its Applications in the Plastics Industry; Springer Science & Business Media: Berlin, Germany, 2013; ISBN 9400763956. [Google Scholar]
  59. Ogunsona, E.O.; Misra, M.; Mohanty, A.K. Impact of interfacial adhesion on the microstructure and property variations of biocarbons reinforced nylon 6 biocomposites. Compos. Part A Appl. Sci. Manuf. 2017, 98, 32–44. [Google Scholar] [CrossRef]
  60. Shenoy, A.V. Rheology of Filled Polymer Systems; Springer Science & Business Media: Berlin, Germany, 2013; ISBN 9401592136. [Google Scholar]
  61. Essabir, H.; El Achaby, M.; Bouhfid, R.; Qaiss, A. Morphological, structural, thermal and tensile properties of high density polyethylene composites reinforced with treated argan nut shell particles. J. Bionic Eng. 2015, 12, 129–141. [Google Scholar] [CrossRef]
  62. Zhang, D.; Yu, J.; Wu, H.; Jaworska, B.; Ellis, B.R.; Li, V.C. Discontinuous micro-fibers as intrinsic reinforcement for ductile Engineered Cementitious Composites (ECC). Compos. Part B Eng. 2020, 184, 107741. [Google Scholar] [CrossRef]
  63. Granda, L.A.; Espinach, F.X.; Méndez, J.A.; Vilaseca, F.; Delgado-Aguilar, M.; Mutjé, P. Semichemical fibres of Leucaena collinsii reinforced polypropylene composites: Flexural characterisation, impact behaviour and water uptake properties. Compos. Part B Eng. 2016, 97, 176–182. [Google Scholar] [CrossRef]
  64. Askanian, H.; Verney, V.; Commereuc, S.; Guyonnet, R.; Massardier, V. Wood polypropylene composites prepared by thermally modified fibers at two extrusion speeds: Mechanical and viscoelastic properties. Holzforschung 2015, 69, 313–319. [Google Scholar] [CrossRef]
  65. Kiran, M.D.; Govindaraju, H.K.; Jayaraju, T.; Kumar, N. Effect of fillers on mechanical properties of polymer matrix composites. Mater. Today Proc. 2018, 5, 22421–22424. [Google Scholar] [CrossRef]
Materials 16 02241 g001 550
Figure 1. The argan tree (Argania spinosa (L) Skeels) and its different parts: (a) tree, (b) immature fruits, (c) pulp, (d) shell, (e) kernels.
Figure 1. The argan tree (Argania spinosa (L) Skeels) and its different parts: (a) tree, (b) immature fruits, (c) pulp, (d) shell, (e) kernels.
Materials 16 02241 g001
Materials 16 02241 g002 550
Figure 2. Preparation of composite. 1: BioPE 100%; 2: BioPE-30% shell; 3: BioPE-30% pulp; 4: BioPE-30% unroasted argan cake; 5: BioPE-30% roasted argan cake.
Figure 2. Preparation of composite. 1: BioPE 100%; 2: BioPE-30% shell; 3: BioPE-30% pulp; 4: BioPE-30% unroasted argan cake; 5: BioPE-30% roasted argan cake.
Materials 16 02241 g002
Materials 16 02241 g003 550
Figure 3. Preparation of composite specimens. 1: BioPE 100%; 2: BioPE-30% shell; 3: BioPE-30% pulp; 4: BioPE-30% unroasted argan cake; 5: BioPE-30% roasted argan cake.
Figure 3. Preparation of composite specimens. 1: BioPE 100%; 2: BioPE-30% shell; 3: BioPE-30% pulp; 4: BioPE-30% unroasted argan cake; 5: BioPE-30% roasted argan cake.
Materials 16 02241 g003
Materials 16 02241 g004 550
Figure 4. Particle size distribution of argan byproduct granules.
Figure 4. Particle size distribution of argan byproduct granules.
Materials 16 02241 g004
Materials 16 02241 g005 550
Figure 5. Differential scanning calorimetry: (a) second heating thermogram, (b) second cooling thermogram.
Figure 5. Differential scanning calorimetry: (a) second heating thermogram, (b) second cooling thermogram.
Materials 16 02241 g005
Materials 16 02241 g006 550
Figure 6. Thermogravimetric analysis thermogram.
Figure 6. Thermogravimetric analysis thermogram.
Materials 16 02241 g006
Materials 16 02241 g007 550
Figure 7. Cole–Cole plot for all the composites studied.
Figure 7. Cole–Cole plot for all the composites studied.
Materials 16 02241 g007
Table
Table 1. Content of main chemical constituents of argan byproducts (pulp, cake, and shell).
Table 1. Content of main chemical constituents of argan byproducts (pulp, cake, and shell).
Composition %w/wPulpRoasted CakeUnroasted CakeShell
Dry matter5.02 ± 0.163.48 ± 0.113.42 ± 0.105.02 ± 0.13
Ash0.29 ± 0.010.20 ± 0.010.21 ± 0.013.20 ± 0.01
Fat5.46 ± 0.267.8 ± 0.227.01 ± 0.201.02 ± 0.16
Protein5.02 ± 0.1638.1 ± 0.136.7 ± 0.63.46 ± 0.12
Cellulose19.35 ± 0.1417.6 ± 0.117.1 ± 0.146.15 ± 0.12
* NDF/total fibers29.26 ± 0.1921.2 ± 0.121.1 ± 0.194.58 ± 0.15
** ADF Lignocellulose22.52 ± 0.0517.38 ± 0.0317.36 ± 0.0475.58 ± 0.10
Hemicellulose6.75 ± 0.103.82 ± 0.113.85 ± 0.1119.06 ± 0.10
Lignin3.17 ± 0.122.78 ± 0.102.75 ± 0.1229.17 ± 0.14
* NDF: Neutral-Digestible Fiber; ** ADF: Acid-Digestible Fiber.
Table
Table 2. Distribution of argan byproduct granules.
Table 2. Distribution of argan byproduct granules.
Argan ByproductsGranule Size (μm)SpanSpecific Surface Area (m²/kg)
D10D50D90D [4;3]
Shell18.062.2144.073.02.0217.9
Pulp19.3101.0301.0135.02.8139.0
Roasted Argan cake5.629.295.043.33.1559.1
Unroasted Argan cake4.726.2131.053.04.8646.7
Table
Table 3. Thermal parameters determined using differential scanning calorimetry (DSC).
Table 3. Thermal parameters determined using differential scanning calorimetry (DSC).
PolymerΔHm (J/g)Tm (°C)Tc (°C)ΔHc (J/g)Xc (%)
PE111133112114.0339.6
PE 30% Shell7313411266.5323.1
PE 30% Pulp5613211274.7825.9
PE 30% Roasted Argan cake3213211279.4827.6
PE 30% Unroasted Argan cake3113311287.7730.5
Table
Table 4. Summary of mechanical property results. Young’s modulus (E), maximum tensile strength (σmax), ultimate strain ε max (%), and elongation at break (εb).
Table 4. Summary of mechanical property results. Young’s modulus (E), maximum tensile strength (σmax), ultimate strain ε max (%), and elongation at break (εb).
PolymerPEPE 30% ShellPE 30% PulpPE 30% Roasted Argan CakePE 30% Unroasted Argan Cake
E (Mpa)206 ± 36498 ± 39349 ± 47324 ± 31330 ± 41
σmax (Mpa)10.15 ± 0.8110.18 ± 0.579.58 ± 0.939.99 ± 0.679.99 ± 0.54
εmax (%)5.83 ± 0.14.28 ± 0.25.86 ± 0.14.94 ± 0.15.13 ± 0.3
εb (%)26.75 ± 0.327.82 ± 0.1211.34 ± 0.109.01 ± 0.1019.67 ± 0.21
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Zeghlouli, J.; Schiavone, N.; Askanian, H.; Guendouz, A.; El Modafar, C.; Michaud, P.; Delattre, C. Thermal, Morphological and Mechanical Properties of a BioPE Matrix Composite: Case of Shell, Pulp, and Argan Cake as Biofillers. Materials 2023, 16, 2241. https://doi.org/10.3390/ma16062241

AMA Style

Zeghlouli J, Schiavone N, Askanian H, Guendouz A, El Modafar C, Michaud P, Delattre C. Thermal, Morphological and Mechanical Properties of a BioPE Matrix Composite: Case of Shell, Pulp, and Argan Cake as Biofillers. Materials. 2023; 16(6):2241. https://doi.org/10.3390/ma16062241

Chicago/Turabian Style

Zeghlouli, Jihane, Nicola Schiavone, Haroutioun Askanian, Amine Guendouz, Cherkaoui El Modafar, Philippe Michaud, and Cédric Delattre. 2023. "Thermal, Morphological and Mechanical Properties of a BioPE Matrix Composite: Case of Shell, Pulp, and Argan Cake as Biofillers" Materials 16, no. 6: 2241. https://doi.org/10.3390/ma16062241

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop