materials

Article
Bio-Based Polyethylene Composites with Natural
Fiber: Mechanical, Thermal, and Ageing Properties
Patrycja Bazan *, Dariusz Mierzwiński , Rafał Bogucki and Stanisław Kuciel
Faculty of Materials Engineering and Physics, Institute of Materials Engineering, Tadeusz Kosciuszko Cracow
University of Technology, Al. Jana Pawła II 37, 31-864 Cracow, Poland; dariusz.mierzwinski@pk.edu.pl (D.M.);
rbogucki@mech.pk.edu.pl (R.B.); stask@mech.pk.edu.pl (S.K.)
* Correspondence: patrycja.bazan@pk.edu.pl




Received: 21 May 2020; Accepted: 5 June 2020; Published: 6 June 2020


Abstract: The study evaluated the possibility of using natural fibers as a reinforcement of
bio-polyethylene. Flax, coconut, basalt fiber, and wood flour were used in the work. Strength
tests like static tensile test, three-point flexural test, or impact strength showed a positive effect
of reinforcing bio-polyethylene-based composites. The effect of water and thermal ageing on the
mechanical behavior of composites was assessed. In order to analyze the structure, SEM microscope
images were taken and the effect of natural fibers on the change in the nature of cracking of composites
was presented. Composites with natural fibers at a content of 12% by weight, resulting in increase of
strength and rigidity of materials. The greatest strengthening effect for natural fibers was obtained
for the composite with basalt fibers.

Keywords: bio-polyethylene; composites; basalt fiber; flax fiber; wood flour; coconut shell fibers

1. Introduction
The problems of environmental protection, depletion of fossil raw materials (mainly petroleum),
and environmental sustainability are important reasons why many producers and scientists undertook
intensive research in the field of material engineering, recycling, and technology for the production of
new, polymeric, user-friendly materials for the natural environment [1].
Examples of such materials may be bio-composites composed of natural fibers and matrices of
synthetic non-biodegradable polymers that only partially biodegrade over time, or composites
containing both biodegradable components called green composites [2]. The most popular
biodegradable materials include polylactide (PLA), poly (3-hydroxybutyrate-co-3-hydroxyvalerate)
(PHBV), and thermoplastic starch. The advantages of biodegradable plastics are their high mechanical
properties, but most importantly they are environmentally friendly materials, decomposing into
products that occur naturally in nature and they are used in the automotive, construction, and fiber
optics industries [3–7].
Polymers as carbon compounds are most often produced from petrochemical sources,
but increasingly from renewable sources. Non-biodegradable plastics from renewable resources include
the plastics where biomass is used for production of plastics without the biodegradation property. They
are mostly made from bioethanol produced from sugar fermentation, biofuel such as polyethylene
(bio-PE). Some other examples are polyvinyl chloride(bio-PVC), polyethylene terephthalate (bio-PET),
or polypropylene (bio-PP) [8].
The basic monomer of polymer polyethylene is ethylene. Ethanol, which is similar to ethylene,
can be produced by fermenting corn or sugar cane, which is why the expression “bio-polyethylene
(bio-PE).” It is chemically and physically similar to traditional polyethylene. It is not biodegradable,
but can be recycled. Bio-polyethylene is currently produced on an industrial scale from bioethanol

Materials 2020, 13, 2595; doi:10.3390/ma13112595 www.mdpi.com/journal/materials

Materials 2020, 13, 2595 2 of 18

from sugar cane. In addition, it is an environmentally friendly material and has similar technical
properties and processability of the resin from fossil sources. Therefore, processing green plastic does
not require any technical adjustments or new investment in equipment [9].
The continuous increase of requirements for materials, both for general use and construction
materials causes the increasingly widespread introduction to the market of petrochemical composite
materials with artificial fibers, bio-composites, and green composites. To meet the requirements,
especially those regarding environmental changes, natural fibers and particles that do not have a
negative impact on the environment are more often used. Natural additives are obtained from
renewable sources and also provide fairly good mechanical properties. The most well-known plant
fibers are: oil palm, wood, rice straw, sisal, ramie, hemp, doum fruit, bagasse, pineapple leaf, cotton,
flax, date palm, rice husk, wheat straw, curaua, coir, jowar, kenaf, bamboo, rapeseed waste, roselle,
mesta, banana, abaca, agave, maize, and jute [10,11].
Natural fibers (NF) can be divided into wood fiber and non-wood fiber. Wood is a natural and
complex polymer composite that essentially contains cellulose, hemicellulose, lignin, and extracts [12].
Most non-wooded plants are annual plants that develop the full potential of fibers in one growing
season. Plant fibers can be in the form of hair (cotton, kapok), hard fibers (pen, sisal), and fiber discs (flax,
hemp, jute). There are six types of plant fibers, namely bast fibers (flax, hemp, jute, kenaf, and ramie),
leaf fibers (abaca, pineapple, and sisal), seed fibers (coir, cotton, and kapok), straw fibers (corn, rice,
and wheat), grass fibers (bagasse and bamboo), and wood fibers (softwood and hardwood) [13].
Flax fibers are considered to be the most important member of the bast family used as a
reinforcement in composites because of their unique properties. The natural high strength and stiffness
of flax, low elongation to break, make them particularly interesting in composite research. Flax fibers
are not continuous compared to synthetic ones, but have a similar structure as composites and they are
hierarchically organized. Their macroscopic properties result from their micro and nano-structural
level [14,15]. Flax composites were extensively studied. They were introduced to composite materials
based on thermoplastics, thermosets, and bio-materials. Yan et al. in his review of composites with
flax fiber, presented in detail the advantages and disadvantages of flax fibers, both in the form of cut
fibers and fabrics [14]. The results showed that flax as a reinforcement causes an increase in strength
properties, however the results were strongly dependent on the fiber geometry, surface treatment,
and humidity. Assarar et al. studied the effect of water ageing on composites based on epoxy resin with
glass fiber and flax fiber. Studies proved that water ageing has a strong effect on flax fiber composites,
and greatly reduces the Young’s modulus and strain at break compared to glass fiber materials [16].
Cheour et al. investigated the effect of water ageing on flax fiber-reinforced epoxy composites and
their mechanical and damping properties. The results showed a decrease in flexural modulus and an
increase in loss coefficients. It was also confirmed that these changes are virtually reversible for loss
factors, but irreversible for flexural modules [17]. Chilali et al. also studied the effect of water on flax
fiber composites. Tensile strength tests showed a reduction of approximately 10% in the rigidity of aged
composites compared to non-aged materials and indicated a strong effect of water damage behavior [18].
Moudood et al. examined effect of humidity on flax epoxy composites. The results showed that
the production of composites with highly wet fabrics causes deformation of finished elements after
treatment, and also leads to poor microstructural quality. The moisture content of the fibers reduces
the tensile and flexural stiffness but also increases fracture toughness [19]. Dhakal et al. also presented
the susceptibility of flax fibers to water. Bending properties tend to decrease as the percentage of
moisture absorption increases. Comparison of flexural strength and flexural modulus between dry
flax bio-composites and wet flax showed that wet samples lost about 50% of strength and stiffness
compared to dry flax samples, hence researches were carried out to improve flax fibers behavior [20].
Stambolis et al. presented research on improved flax fiber, which was 30% less water-sensitive, and
composites with those fiber were characterized by maintaining strength and stiffness despite adverse
environmental effects [21].
Materials 2020, 13, 2595 3 of 18

Coconut fibers are obtained from the fibrous husk of the coconut from the coconut palm. Coconut
fibers have a high lignin content and therefore a high cellulose content, making them elastic, strong,
and very durable. The properties of composites with coconut fibers as well as with flax fibers and other
natural fibers strongly depend on the volume, diameter, and length of the fibers, as well as moisture
content [22]. Singh et al. evaluated the effect of coconut shell powder with different particle sizes
and volumes on the tensile and bending properties of composites based on the epoxy resin matrix.
Coconut improves the mechanical properties of epoxy resins but changes of properties are influenced
by the volume of fillers [23]. However, in studies provided by Reddy T. on thermoplastic coconut
fiber composites, where high density polyethylene (HDPE) was used as a matrix, the mechanical
properties were more depended on the fiber length [24]. Siva et al. studied the optimal volume content
of fibers. The study examined four volumetric parts, the results showed that with increasing fiber
content, the strength properties increase and the resistance to dynamic impact decreases. However,
because of its higher density, thickness, and more de-laminations, high fiber volume fraction may not
always be good for reinforced polyester composites [25]. Onuegbu et al. presented work on various
surface treatments of coconut fibers, studies showed that alkali treatment of coconut fibers significantly
improves their tensile properties [26].
Wood flour is obtained from wooden raw material and is characterized by a loose, very fine,
and even consistency. In the chemical composition of wood flour we find cellulose in about 50%, lignin
in about 20–25%, hemicellulose in 20–25%, and also, among others: resins, waxes, rubber, proteins,
and mineral salts. The exact concentration of individual substances depends on the species of trees,
soil, and weather conditions in the area where the trees grow. The influence of wood flour size on
mechanical properties and density of HDPE composites was investigated. The results showed that the
wood particle size had a significant effect on wood plastic composite (WPC) properties. The change in
the number of meshes has a great effect on the flexural modulus, tensile modulus, and impact strength,
however, it has little effect on flexural and tensile strength [27].
Thermoplastics commonly modified with wood flour include work on polypropylene composites
with wood flour provided by Sheshmani et al. and Ichazo et al. [28,29], high density polyethylene,
and recycled high density polyethylene presented by Hamzeh et al. and Nourbakhsh et al. [30,31].
Despite the advantages, the use of wood in thermoplastic materials has some problems; limitation of
wood thermal stability, difficulties in obtaining good dispersion of filler, and weak interphase adhesion.
This is due to the natural incompatibility between hydrophilic polar wood fibers and hydrophobic,
non-polar thermoplastics. This phase mismatch causes a poor interface between the wood filler and the
polymer matrix. In addition, the strong interaction of wood-wood resulting from hydrogen binding
and physical entanglement reduces the dispersion of fillers in the viscous matrix.
Recently, basalt fibers (BF) has appeared as a new type of NF. They are widely used in the area
of reinforced polymer materials. BF, which are similar to chemical composition of glass fibers, have
interesting properties, including high melting points (in the range from 1350 to 1700 ◦ C), high stiffness,
excellent heat resistance, and excellent vibration insulators. In addition to these promising properties,
BF are relatively cheaper than carbon reinforcement, non-toxic, and natural, which undoubtedly makes
them a good alternative to artificial reinforcement polymer materials [32–34].
The growing interest in biobased polymer forces researches and manufacturers to work on new
composites containing bio-matrix and natural fibers. Serra-Parareda et al. presented research on
polyethylene composites with barley straw as an alternative to using agricultural waste. The barley
straw content ranged from 15–40% by weight. Strength results showed the fiber has a high ability to
provide strength and rigidity for such composites [35]. Castro et al. used curaua fibers as a reinforcement
for high density bio-polyethylene. The presence of curaua fibers improved some properties such as
bending strength and storage modulus, but they also pointed to the high importance of manufacturing
methods and introduction of other modifiers to obtain high-grade composites [36]. In another work by
Castro et al. it was confirmed that the introduction of castor and canola oils as a potential compatibilizer
for bio-Pe composites with curaua fiber additionally improves the strengthening effect [37]. Kuciel
Materials 2020, 13, 2595 4 of 18

et al. introduced natural additives into bio-polyethylene (HDPE and LDPE) as an additive, such as
wood flour, kenaf fibers, cellulose power, and tuff particles. The introduction of natural particles does
not affect the results of tensile strength, however, the use of wood flour and kenaf fibers increases the
stiffness several times. The introduction of natural particles causes an increase in water absorption
that affects the surface quality of the tested materials [38]. Tarres et al. presented the bio-based
polyethylene matrix with thermomechanical pulp (TMP) fibers. In addition, the effect of melamine
anhydride on mechanical properties was investigated. Studies pointed an increase in the mechanical
properties of the tested composites, especially with the addition of a compatibilizer. Researchers
proved that thermomechanical pulp fibers facilitate 3D printing and provide products with high
strength properties [39].
This work presents new composites based on bio-polyethylene with natural fibers as the first stage
of research on hybrid connections of natural fibers. Knowledge of the mechanisms of strengthening
natural fibers such as flax fiber, coconut, wood flour, and basalt fibers posed at a further stage to use
the full potential of hybrid reinforcement for the same fibers.

2. Materials and Methods

2.1. Materials
In this work composites based on a high density bio-polyethylene (Green PE SHC7260 produced
from renewable source (sugarcane-based ethanol), Braskem, Brazil) were investigated. The standard
dog bones samples and bars were made at Cracow University of Technology using KM 40-125 Winner
Krauss Maffei. The temperatures in the subsequent zones ranged from 170 ◦ C to 200 ◦ C, injection
pressure 1300 bar and the injection speed was set to 60 mm/s. As a reinforcement basalt fiber (BF),
(KV02M chopped strand series with diameter of 13 µm, length about 3.2 mm, Kemenny Vek, Dubna,
Russia), coconut shell fibers (Coco MLD 2 mm with diameter of 100 µm and length about of 2 mm,
Procotex S.A., Moeskroen, Belgium), flax fibers (Flax MLD 2 mm with diameter of 50–70 µm and length
about of 2 mm, Procotex S.A., Moeskroen, Belgium), and wood flour (Lignocel BK 40/90 from soft
wood (spruce) with particle size 300–500 µm J. Rettenmaier & Söhne Company, Rosenberg, Germany)
were used. As a compatibilizator Scona TPPP 9112 FA was used (BYK, Altana, Germany). Composites
with a content of 6 and 12 percent by weight were prepared to analyze the reinforcement with natural
fibers as a basis for testing hybrid composite materials containing a combination of natural fibers in the
next stage of research. Manufactured materials for the experiment are described below in Table 1.

Table 1. Description of tested materials.

Index Description
PE 100 wt.% Green PE SHC7260 Braskem (Bio-PE)
PE6W 92 wt.% of Bio-PE + 6 wt.% wood flour + 2 wt.% Scona TPPP 9112 FA
PE6K 92 wt.% of Bio-PE + 6 wt.% coconut shell fibers + 2 wt.% Scona TPPP 9112 FA
PE6F 92 wt.% of Bio-PE + 6 wt.% flax fibers + 2 wt.% Scona TPPP 9112 FA
PE6B 92 wt.% of Bio-PE + 6 wt.% basalt fibers + 2 wt.% Scona TPPP 9112 FA
PE12W 86 wt.% of Bio-PE + 12 wt.% wood flour + 2 wt.% Scona TPPP 9112 FA
PE12K 86 wt.% of Bio-PE + 12 wt.% coconut shell fibers + 2 wt.% Scona TPPP 9112 FA
PE12F 86 wt.% of Bio-PE + 12 wt.% flax fibers + 2 wt.% Scona TPPP 9112 FA
PE12B 86 wt.% of Bio-PE + 12 wt.% basalt fibers + 2 wt.% Scona TPPP 9112 FA
Materials 2020, 13, 2595 5 of 18

2.2. Characterization of Natural Fibers

As described above natural fibers can be divided into wood fiber and non-wood fiber. Tables 2
and 3 present chemical composition of the used fibers: flax fibers, coconut shell fibers, wood particles,
and basalt fibers and their mechanical properties [11].

Table 2. Chemical composition of used fibers.

Wood Flour (wt.%) Coconut Shell (wt.%) Flax Fibers (wt.%) Basalt Fibers (%)
Cellulose: 40–50 Cellulose: 26.5 Cellulose: 71 SiO2 : 51.6–59.3
Hemicellulose: 15–25 Pentosans: 27.7 Hemicellulose: 18–20 AL2 O3 : 14.6–18.3
Lignin: 15–30 Lignin: 29.4 Lignin: 2.2 CaO: 5.9–9.4
Moisture: 8–16 Moisture: 8 Moisture: 10 MgO: 3.0–5.3
- Solvent extractives: 4.2 Pectin: 2.3 FeO + Fe2 O3 : 9–14
- Uronic anhydrides: 3.5 Wax: 1.7 TiO2 : 0.8–2.25
- Ash: 0.6 - Na2 O + K2 O: 0.09–0.13

Table 3. Physic–mechanical properties of used fibers [40–43].

Density Diameter Length Tensile Tensile Strain at

Fibers
(g/cm3 ) (µm) (mm) Strength (MPa) Modulus (GPa) Break (%)
Wood flour 1.3–2.2 300–500 - 44–90 6–13 2.0–3.0
Coconut shell 1.1–1.3 100 2.0 130–250 4–15 2.0–4.0
Basalt 2.7 13–22 3.2 2800–2900 70–110 2.5–3.5
Flax 1.40–1.45 50–70 1–65 400–1200 40–70 1.8–3.2

Microstructures of fibers used in this work were taken and are presented in Figure 1. Figure 1a
presents microscopic picture of wood flour. As with most natural materials, wood anatomy is complex.
Wood is porous, fibrous, and anisotropic. Wood consists mainly of hollow, spindle-shaped cells, which
are arranged parallel to each other along the trunk of the tree. These fibers are heavily cemented
together and form a structural element of wood tissue. The length of wood fibers is variable, but on
average about 250–500 µm. The fiber diameters are usually about 15–45 µm. When wood is reduced to
wood flour, the resulting particles are actually bundles of wood fibers rather than individual fibers [44].
Figure 1b shows unprocessed coconut fiber. Fiber morphology shows surface roughness. The increased
surface roughness of the coconut fiber is the result of higher amount of exposed cellulose. Figure 1c
displays basalt fiber. The surface of the fiber is smooth and plane, without visible damage to the fiber.
The structure of flax fiber is quite complex. Flax fiber is characterized by multiwalled anatomy which
can been seen in the Figure 1d.

2.3. Method of Testing

Basic physical and mechanical tests of bio-polyethylene and its composites were carried out.

2.3.1. Physic-Mechanical Characterization

Density was measured by the hydrostatic method by scale RADWAG WAS 22W (Radom, Poland).
Static tensile test (PN-EN ISO 527-1:20100) and the three-point flexural test (PN-EN ISO 178:2011) were
carried out with a MTS Criterion Model 43 universal testing machine (MTS System Corp., Eden Prairie,
MN, USA), using the MTS axial extensometer. The test speed was set to 10 mm/min. Charpy impact test
(PN-EN ISO 179-1:2010) was examined on unnotched specimens using a Zwick HIT 5.5P (Zwick Roell
Group, Ulm, Germany). In order to determine the initial mechanical hysteresis loops with forced
displacement cyclic load and unload tests were investigated using the MTS Criterion 43 universal
 - Ash: 0.6 - Na2O + K2O: 0.09–0.13

Table 3. Physic–mechanical properties of used fibers [40–43].

Density Diameter Length Tensile Tensile Strain at

Fibers
Materials 2020, 13, 2595
(g/cm3) (µm) (mm) Strength (MPa) Modulus (GPa) Break 6(%)
of 18
Wood
1.3–2.2 300–500 - 44–90 6–13 2.0–3.0
flour
testing machine with the MTS software TestSuites 1.0 to analyze the dissipation energy. The speed of
Coconut
forced 1.1–1.3
displacement specimens100 2.0
was 100 mm/min, which130–250
is translated into a4–15
low frequency2.0–4.0
of cycles
shell
andBasalt
allows to visualize
2.7 viscosity phenomena.
13–22 3.2The values were obtained from
2800–2900 an average at
70–110 least of
2.5–3.5
five specimens.
Flax 1.40–1.45 50–70 1–65 400–1200 40–70 1.8–3.2

Figure 1.
Figure 1. Scanning
Scanning electron
electronmicroscopy
microscopy(SEM)(SEM)images
imagesofofsurface ofof
surface natural fibers:
natural (a) (a)
fibers: wood flour,
wood (b)
flour,
coconut
(b) shell,
coconut (c) (c)
shell, basalt fiber,
basalt (d)(d)
fiber, flax fiber.
flax fiber.

2.3.2. Microstructures
Water Absorption of and Water
fibers usedDiffusion Coefficient
in this work were taken and are presented in Figure 1. Figure 1a
presents
Watermicroscopic
absorption picture of wood
was carried flour. Astowith
out according ASTM most natural
D570-98 materials,
standard. Thewood anatomy
specimens wereis
complex. Wood is porous, fibrous, and anisotropic. Wood consists mainly of hollow,
periodically weighed using an electronic weighing balance (RADWAG WAS 22W). Water absorption spindle-shaped
cells,calculated
was which areusing
arranged parallel to
the following each other along the trunk of the tree. These fibers are heavily
equation:
cemented together and form a structural element of wood tissue. The length of wood fibers is
variable, but on average about 250–500 W% µ m. =
TheWnfiber
− Wdiameters
0 are usually about 15–45 µ m. When
·100 (1)
W
wood is reduced to wood flour, the resulting particles are actually bundles of wood fibers rather than
0

where W 0 is the initial weight of the sample, Wn is the weight of the saturated sample, and W% is the
percentage increase in weight.

2.3.3. Thermal Aging

Physic-mechanical investigation was repeated after thermal aging. Accelerated ageing tests were
conducted in autoclave (Parr Instrument Company, Moline, IL, USA) according to the EN ISO 2440
standard. At first, samples were conditioned at a temperature of 23 ± 2 ◦ C and a humidity equal to
50 ± 5% for 24 h. After the conditioning process, samples were placed in an autoclave where the
temperature was set up to 120 ◦ C, the humidity was 100%, and the pressure was 0.3 MPa. The ageing
process lasted for 144 h.
Materials 2020, 13, 2595 7 of 18

2.3.4. Scanning Electron Microscopy (SEM)

The microstructure pictures were made on tensile-test fracture surfaces covered by gold layer
to avoid electrostatic charging during SEM analyses. The micrographic images were taken in high
vacuum mode with 10 kV accelerating voltage and 13.7 mm working distance using a scanning electron
microscope JEOL JSN5510LV (JEOL Ltd., Tokyo, Japan).

2.3.5. Short-Time Relaxation Test

Composites based on bio-polyethylene were subjected to the relaxation process, 2 mm deformation
was applied with a forced speed of 1 mm/min, and then the stretching process was stopped and changes
in forces needed to maintain the deformation at 2 mm were recorded for 3 h. The tests were carried out
on a Shimadzu AGS-X testing machine, with a measuring range up to 1 kN with Trapezium software.

3. Results and Discussion

3.1. Mechanical Investigation of Composites

Knowledge of basic strength properties is necessary for modeling and designing construction
materials. The properties of the composite depend on many factors such as: matrix properties,
fiber properties, content of reinforcement, geometry and orientation of the fibers, adhesion between
composite components, manufacturing conditions etc. Each of the above-mentioned factors is extremely
important and also depends on other factors. In order for the composite material to fulfill its task,
there must be a proper connection between components. Adhesion in qualitative terms is the connection
of one material to another by means of chemical bonds, intermolecular interactions (Van der Waals
forces), hydrogen bonds, ionic bonds, electrostatic interactions, or mechanical bonding of surfaces in
contact with each other. Factors affecting the amount of adhesion include: degree of wetting of the
fibers; chemical structure of ingredients; the amount of mechanical friction forces at the component
boundary; size and direction of shrinkage stress; occurrence and size of physical and chemical forces
(adhesion forces), defects in the form of voids, air bubbles, etc., during manufacturing [2]. Table 4
presents the results obtained through basic strength tests.

Table 4. Basic mechanical properties of tested material.

Tensile Tensile Flexural Flexural Impact

Strain at
Index Density, g/cm3 Strength, Modulus, Strength, Modulus, Strength,
Break, %
MPa MPa MPa MPa kJ/m2
PE 0.961 ± 0.002 18.1 ± 0.3 1062 ± 26 >200 19.3 ± 0.5 809 ± 21 unbroken
PE6W 0.976 ± 0.001 18.7 ± 0.5 1974 ± 21 5.6 ± 0.6 23.4 ± 0.6 995 ± 25 13.5 ± 0.1
PE6K 0.968 ± 0.004 18.5 ± 0.6 1596 ± 12 5.1 ± 0.4 24.9 ± 1.1 978 ± 54 16.6 ± 1.6
PE6F 0.969 ± 0.001 19.2 ± 0.8 1508 ± 36 7.0 ± 0.5 24.4 ± 1.5 1065 ± 14 31.7 ± 2.4
PE6B 0.988 ± 0.002 24.7 ± 1.2 2280 ± 15 4.1 ± 0.9 30.1 ± 1.2 1316 ± 16 16.6 ± 0.2
PE12W 1.001 ± 0.002 19.3 ± 0.4 1695 ± 25 5.3 ± 0.7 29.9 ± 0.9 1465 ± 26 13.5 ± 1.1
PE12K 0.988 ± 0.003 18.9 ± 1.1 1389 ± 14 5.4 ± 0.5 30.2 ± 0.7 1190 ± 24 13.0 ± 0.1
PE12F 0.991 ± 0.002 21.3 ± 0.7 2311 ± 34 2.8 ± 0.5 33.6 ± 1.8 1633 ± 15 15.9 ± 0.3
PE12B 1.011 ± 0.001 34.0 ± 1.4 2484 ± 18 4.0 ± 0.7 44.9 ± 2.3 2160 ± 31 17.1 ± 0.1

The results of basic strength tests showed the largest impact of basalt fiber on strength properties,
which of course is associated with the high mechanical properties of the fiber. From natural fibers, the
increase in tensile strength was provided by flax fiber, with an amount of fibers of only 6% by weight,
the gain was small, by about 5%, with a fairly small rise in stiffness about 40%, which is a poor result in
relation to wood flour modification (increase in the module by almost 90%); however, the results of
materials with a content of 12% by weight of flax fiber caused an increase in strength by 20% and the
Materials 2020, 13, 2595 8 of 18

module more than twice compared to neat polyethylene which is most likely related to the structure
of flax fiber. Flax is cellulose fiber, but its structure is more crystalline, owing to which, although it
is more fragile, it is much stronger, and its cross-section contains about 40 fibers [45]. In the case of
other fibers, doubled content of fillers did not bring about large changes in mechanical properties,
which is associated with very poor adhesion of natural fibers and particles to polymer matrices because
of the hydrophilicity of fibers and the hydrophobicity of polymers. This is due to the basic fiber
components such as cellulose, hemicellulose, and lignin. All these materials contain hydroxyl groups
and other oxygen-containing groups that facilitate moisture absorption through hydrogen bonding and
this is responsible for dimensional changes because of swelling and shrinkage, affecting mechanical
properties [46]. The possible solution to this problem may be surface treatment of fibers with adhesion
increasing agents (containing functional groups capable of chemical reactions with functional groups
contained in the polymer) or increasing wettability and reducing surface tension.
Microscopic images show the microstructures of composites. Figure 2a,b present composites with
basalt fiber. The polyethylene matrix had a fibrous, ductile character, and basalt fibers had a relatively
smooth2020,
Materials surface. ThePEER
13, x FOR connection
REVIEWbetween composite components was purely mechanical without major 8 of 19
chemical changes in interphase. The picture also shows holes as a result of the phenomenon of pulling
reactions
fibers outwith
of thefunctional
matrix asgroups
well ascontained in the
the surfaces polymer)
of fiber or which
cracks, increasing wettability
indicates and nature
the mixed reducingof
surface
composite tension.
damage. Random fiber orientation can also be observed.

.
Figure 2. SEM images of bio-polyethylene with basalt fibers (a) 500× and (b) 2000× magnification.
Figure 2. SEM images of bio-polyethylene with basalt fibers (a) 500× and (b) 2000× magnification.
Figure 3 shows composites with coconut fiber, wood flour, and flax fiber. The structure of the
Microscopic images show the microstructures of composites. Figure 2a,b present composites
coconut fiber composite (Figure 3a) was more brittle without plastic extensions. In the case of wood
with basalt fiber. The polyethylene matrix had a fibrous, ductile character, and basalt fibers had a
flour composite (Figure 3b), the nature of the cracking was plastic and the developed surface around
relatively smooth surface. The connection between composite components was purely mechanical
the wood particles could be observed. Nonetheless, free spaces can be observed between the fiber and
without major chemical changes in interphase. The picture also shows holes as a result of the
the matrix, indicating a lack of chemical connection between the components. The appearance of the
phenomenon of pulling fibers out of the matrix as well as the surfaces of fiber cracks, which indicates
microstructure only confirms the results obtained in mechanical tests and indicates the necessity of
the mixed nature of composite damage. Random fiber orientation can also be observed.
using coupling agents. Figure 3c presents flax fiber composites. The polygonal shape of flax fibers with
sides 5–7 can be seen. The microstructure of the fiber is extremely complex because of its heterogeneous
nature along the entire length. The fiber orientation in the compositions was random, and the matrix
exhibited a fairly plastic character. A better connection between the ingredients compared to the other
compositions is visible.
Plastics and composites as construction materials are subject to various external factors.
An important physical factor for plastics is the exploitation temperature. The behavior of composites
at temperatures is significantly influenced by the geometry and volume of fibers. Figures 4 and 5
show the results of a three-point flexural test over a wide temperature range (−24, 21, 80 ◦ C). The
results showed a proportional decrease in mechanical properties with increase in temperature, which
is associated with a higher mobility of polymer segments at elevated temperatures. The highest results
were obtained for the material with basalt fiber. Noteworthy is the fact that in the case of materials
working
Figureon3.bending conditions,
SEM images not much higher
of bio-polyethylene content
composites withof(a)flour or coconut
coconut fiber
shell fiber, (b) (12%
woodby weight)
flour, and can
(c) flax fiber.
provide similar strength parameters as the material with basalt fiber in an amount of 6% by weight.

Figure 3 shows composites with coconut fiber, wood flour, and flax fiber. The structure of the
coconut fiber composite (Figure 3a) was more brittle without plastic extensions. In the case of wood
flour composite (Figure 3b), the nature of the cracking was plastic and the developed surface around
the wood particles could be observed. Nonetheless, free spaces can be observed between the fiber
 .
Figure 2. SEM images of bio-polyethylene with basalt fibers (a) 500× and (b) 2000× magnification.

Microscopic images show the microstructures of composites. Figure 2a,b present composites
Materials 2020, 13, 2595
with basalt fiber. The polyethylene matrix had a fibrous, ductile character, and basalt fibers had a9 of 18
relatively smooth surface. The connection between composite components was purely mechanical
without major chemical changes in interphase. The picture also shows holes as a result of the
Analyzing the effect of temperature on bending properties, it was flax fiber that provided the greatest
phenomenon of pulling fibers out of the matrix as well as the surfaces of fiber cracks, which indicates
stability of measured
the mixed parameters,
nature of since the
composite damage. decrease
Random with
fiber increasecan
orientation in also
temperature conditions was the
be observed.
smallest for this material.

Materials 2020, 13, x FOR PEER REVIEW 9 of 19

were obtained for the material with basalt fiber. Noteworthy is the fact that in the case of materials
working on bending conditions, not much higher content of flour or coconut fiber (12% by weight)
can provide similar strength parameters as the material with basalt fiber in an amount of 6% by
weight. Analyzing the effect of temperature on bending properties, it was flax fiber that provided the
greatest
Figure 3. stability
SEM imagesof measured parameters,composites
of bio-polyethylene since the decrease
with (a)with increase
coconut shellin temperature
fiber, (b) wood conditions
flour, and
was the smallest
(c) flax fiber. for this material.
Figure 3. SEM images of bio-polyethylene composites with (a) coconut shell fiber, (b) wood flour, and
(c) flax fiber.

Figure 3 shows composites with coconut fiber, wood flour, and flax fiber. The structure of the
coconut fiber composite (Figure 3a) was more brittle without plastic extensions. In the case of wood
flour composite (Figure 3b), the nature of the cracking was plastic and the developed surface around
the wood particles could be observed. Nonetheless, free spaces can be observed between the fiber
and the matrix, indicating a lack of chemical connection between the components. The appearance of
the microstructure only confirms the results obtained in mechanical tests and indicates the necessity
of using coupling agents. Figure 3c presents flax fiber composites. The polygonal shape of flax fibers
with sides 5–7 can be seen. The microstructure of the fiber is extremely complex because of its
heterogeneous nature along the entire length. The fiber orientation in the compositions was random,
and the matrix exhibited a fairly plastic character. A better connection between the ingredients
compared to the other compositions is visible.
Plastics and composites as construction materials are subject to various external factors. An
important physical factor for plastics is the exploitation temperature. The behavior of composites at
temperatures is significantly influenced by the geometry and volume of fibers. Figures 4 and 5 show
the results of a three-point flexural test over a wide temperature range (−24, 21, 80 °C). The results
showed a proportional decrease in mechanical properties with increase in temperature, which is
associated with a higher mobility of polymer segments at elevated temperatures. The highest results

Figure 4. Comparison of flexural strength of tested material.

Figure 4. Comparison of flexural strength of tested material.

There are various sources of dissipation energy in fiber-reinforced composites: the viscoelastic
nature of the matrix, the phase between the fiber and the matrix, damages, viscoelastic suppression,
and thermoplastic suppression. The low dissipation energy value corresponds to the large volumetric
strain, which in turn means that the cavitation process is not the main source of dissipation energy.
The general point of view for polymers and polymers filled with particles is assumed that dissipation
energy mainly comes from matrix deformation [47].
Composites of bio-polyethylene with natural fibers were tested using load-unload process. As the
number of cycles increased, the decrease in dissipation energy could be observed at the same stain
level. Its value stabilized after the first few load cycles (Figure 6). The differences between the amounts
of dissipated energy can be excellent information to learn about the structure and interrelationships
between the matrix and the filler. It can be assumed that in the micro-areas, the adhesive bonds between
the fiber and the matrix are in more or less randomly distributed configurations because of their ability
to absorb external loads and therefore to approach critical stress states. The first load cycles reveal
this phenomenon. They eliminate local, extreme stress areas in the volume of material by successively
cracking the critical tension of adhesive joints between components. This interpretation is supported
Materials 2020, 13, 2595 10 of 18

by the fact that the value of dissipated energy gradually decreases in subsequent load cycles. The size
and nature of this phenomenon are closely related to the type of adhesion between the matrix and
reinforcement as well as toFigure
the degree of non-homogeneity
4. Comparison of flexural strengthofofthe state
tested of the stress in the composite.
material.

Materials 2020, 13, x FOR PEER REVIEW 10 of 19

Figure 5. Comparison of flexural modulus of tested material.

There are various sources of dissipation energy in fiber-reinforced composites: the viscoelastic
nature of the matrix, the phase between the fiber and the matrix, damages, viscoelastic suppression,
and thermoplastic suppression. The low dissipation energy value corresponds to the large volumetric
strain, which in turn means that the cavitation process is not the main source of dissipation energy.
The general point of view for polymers and polymers filled with particles is assumed that dissipation
energy mainly comes from matrix deformation [47].
Composites of bio-polyethylene with natural fibers were tested using load-unload process. As
the number of cycles increased, the decrease in dissipation energy could be observed at the same
stain level. Its value stabilized after the first few load cycles (Figure 6). The differences between the
amounts of dissipated energy can be excellent information to learn about the structure and
interrelationships between the matrix and the filler. It can be assumed that in the micro-areas, the
adhesive bonds between the fiber and the matrix are in more or less randomly distributed
configurations because of their ability to absorb external loads and therefore to approach critical
stress states. The first load cycles reveal this phenomenon. They eliminate local, extreme stress areas
in the volume of material by successively cracking the critical tension of adhesive joints between
components. This interpretation is supported by the fact that the value of dissipated energy gradually
decreases in subsequent load cycles. The size and nature of this phenomenon are closely related to
the type of adhesion between the matrix and reinforcement as well as to the degree of non-
homogeneity of theFigure Comparison
state of5.the ofcomposite.
stress in the flexural modulus of tested material.

Figure 6. Comparison
Figure of of
6. Comparison dissipated
dissipatedenergy
energy as a function
functionofoffollowing
following hysteresis
hysteresis loops.
loops.

Figure 7 shows
Figure the the
7 shows dissipation
dissipationenergy
energyvalue
value in
in the firstand
the first andfifth
fifthcycle
cycle
of of load-unload.
load-unload. EachEach
of of
the additives raised
the additives the the
raised dissipation energy
dissipation energyrelative
relative to
to the unreinforcedmaterial.
the unreinforced material. Doubled
Doubled content
content of of
woodwood particles
particles in compositions
in compositions did
did notchange
not changethe
the dissipation
dissipation energy.
energy.Basalt fiber
Basalt andand
fiber coconut fiber fiber
coconut
materials were characterized by the highest dissipation energy, especially in the first
materials were characterized by the highest dissipation energy, especially in the first cycle, which, cycle, which,
according
according to theory
to the the theory mentionedabove,
mentioned above,may
may suggest
suggest aalarge
largeamount
amount of of
stress inside
stress the material.
inside the material.
Related to natural fibers, it seems to be the most advantageous to use flax fibers, because increase in
Related to natural fibers, it seems to be the most advantageous to use flax fibers, because increase in
the fiber content from 6 to 12% by weight did not bring about such large changes in the dispersed
energy in relation to the other fibers, and the difference in energy dissipation between the first and
the fifth cycle was the smallest, which may suggest a lower degree of internal stress.
Materials 2020, 13, 2595 11 of 18

the fiber content from 6 to 12% by weight did not bring about such large changes in the dispersed
energy in relation to the other fibers, and the difference in energy dissipation between the first and the
fifth cycle was the smallest, which may suggest a lower degree of internal stress.
Materials 2020, 13, x FOR PEER REVIEW 11 of 19

Figure
Figure 7. 7. Relation
Relation of dispersed
of dispersed energy
energy andand Young
Young modulus
modulus obtainedin
obtained in first
first and
and fiftieth
fiftiethhysteresis
hysteresis loop.
loop.
The relaxation process consists of recording changes in force or stress in a specimen during a
The relaxation process consists of recording changes in force or stress in a specimen during a
sustained period of time. When a plastic material is suddenly deformed, high internal stresses are
sustained period of time. When a plastic material is suddenly deformed, high internal stresses are
created,created,
which gradually decrease
which gradually overover
decrease time,time,
andand thatthat
reaction is called
reaction relaxation.
is called relaxation. This
This process
process occurs
both in occurs
the glassy
both inand the highly
the glassy elasticelastic
and the highly phase. In In
phase. the
theglass phase,
glass phase, relaxation
relaxation occurs
occurs by rotating
by rotating
the chain segments (Kuhn segments). In the elastic phase the relaxation is
the chain segments (Kuhn segments). In the elastic phase the relaxation is caused by the gradualcaused by the gradual
conversion
conversion of theofpolymer
the polymer chains
chains into
into newplaces.
new places. TheThedecay
decayof of
stress is fast
stress is in theinbeginning
fast and
the beginning and
slows down later. This is due to the effect of stress on the segmental rotation time and the time needed
slows down later. This is due to the effect of stress on the segmental rotation time and the time needed
to shift to the new position of the macromolecules. time. Relaxation curves are presented in Figure 8.
to shift to the new position of the macromolecules. time. Relaxation curves are presented in Figure 8.
Materials 2020, 13, x FOR PEER REVIEW 12 of 19

Figure 8. Relaxation short-term relaxation test curves of exanimated composites.

Figure 8. Relaxation short-term relaxation test curves of exanimated composites.
3.2. Thermal Aging and Water Immersion Investigation
The visible effect of chemical changes occurs during heating of the polymers, such as: decrease
of molecular weight and emission of low molecular weight gas products. In linear polymeric
materials, as a result of degradation, the macromolecular chain is shortened and consequently, the
molar mass is reduced. In the polymers with more complicated chain structure, apart from the
processes of cracking of the main polymer chain, there are also side group breaks reactions. Thus, the
Materials 2020, 13, 2595 12 of 18

3.2. Thermal Aging and Water Immersion Investigation

The visible effect of chemical changes occurs during heating of the polymers, such as: decrease of
molecular weight and emission of low molecular weight gas products. In linear polymeric materials,
as a result of degradation, the macromolecular chain is shortened and consequently, the molar mass
is reduced. In the polymers with more complicated chain structure, apart from the processes of
cracking of the main polymer chain, there are also side group breaks reactions. Thus, the stability,
i.e., the durability of the polymers, is strongly dependent on the strength of the bonds. The type and
energy of bonds influences both the mechanism of degradation process and its rate.
Effect of immersion samples in water is presented in Figure 9. A large water absorption effect
of up to about 2 weeks can be seen. This is related to two facts, the first of which is the introduction
of fibers that act as capillary and transports water into the material. Second, natural fibers belong to
strengthening materials that absorb water, hence the increased absorption effect. After 14 days the
water absorption
Materials decreased,
2020, 13, x FOR striving to saturate the composites.
PEER REVIEW 13 of 19

Figure9.9.Water
Figure Waterabsorption
absorptionof
oftested
testedcomposites.
composites.

Mechanical properties resultedproperties

Table 5. Mechanical after water and thermal
measured ageing
after water are compared
and thermal ageing. in Table 5. The
interaction of water with polymers is characterized by several mechanisms. Examples include
Properties after Water Incubation Properties after Thermal Ageing
hydration—i.e., the binding of macromolecules to water; formation and stabilization of ordered
Index Tensile Tensile Strain at Tensile Tensile Strain at
molecular structures, formation or destruction of hydrogen bonds. The resistance of composites to
Strength, MPa Modulus, MPa Break, % Strength, MPa Modulus, MPa Break, %
water depends on the polymer, which is the matrix of the composite, the filler, and the method of
PE 21.3 ± 0.1 1210 ± 27 >100 18.7 ± 0.9 1315 ± 26 4.0 ± 0.6
connection
PE6W of 21.4
the matrix
± 0.1 with 1818
the filler.
± 106 In the composite-water
5.3 ± 0.3 15.2system,
± 0.1 both the 1644chemical
± 21 and2.3
physical
± 0.1
changes
PE6K mentioned above
21.0 ± 0.1 can occur. Further
1727 ± 203 changes
5.1 ± 0.7 under the influence
13.2 ± 0.1 of water include
1621 ± 86 swelling
1.8 ± 0.1of
thePE6F
material caused by
19.3 ± 0.1 the migration
1527 ± 19of water molecules
4.7 ± 0.1 into their
16.6 ± 0.8interior of the material.
1439 ± 23 In
3.4front
± 0.4of
thePE6B
swelling front,
27.8 ±tensile
1.2 stresses
2134arise,
± 97 which 4.0can±cause
0.2 the formation
20.6 ± 1.2 of microcracks
2745 ± 162[2]. The1.8 analysis
± 0.3
ofPE12W
mechanical20.4 properties
± 0.1 carried
2055out
± 16for materials after 30 days
3.8 ± 0.5 14.6 ±of1.0
immersion in ±water
2024 24 did not 2.0 ±show
0.3
any significant19.9
PE12K changes.
± 0.4 For materials
1504 ± 36with a filler content of11.8
4.5 ± 0.1 6%±by 0.5weight, a1391
several
± 25 percent1.9
increase
± 0.7
inPE12F
strength was 21.6noticed.
± 0.3 1935properties
Strength ±8 3.7
for±materials
0.4 16.1 ±a0.6
with 1813 ±of14filling decreased,
higher degree 2.6 ± 0.9
PE12B 35.0 ± 1.1 3231 ± 19 2.6 ± 0.1 23.1 ± 0.7 3175 ± 35 3.8 ± 0.4

Mechanical properties resulted after water and thermal ageing are compared in Table 5. The
interaction of water with polymers is characterized by several mechanisms. Examples include
hydration—i.e., the binding of macromolecules to water; formation and stabilization of ordered
molecular structures, formation or destruction of hydrogen bonds. The resistance of composites to
water depends on the polymer, which is the matrix of the composite, the filler, and the method of
Materials 2020, 13, 2595 13 of 18

which suggests that together with the increase of the filling and water content in the material increased,
the new resulting stress worsen the connection between the components.

Table 5. Mechanical properties measured after water and thermal ageing.

Properties after Water Incubation Properties after Thermal Ageing

Index
Tensile Tensile Tensile Tensile
Strain at Strain at
Strength, Modulus, Strength, Modulus,
Break, % Break, %
MPa MPa MPa MPa
PE 21.3 ± 0.1 1210 ± 27 >100 18.7 ± 0.9 1315 ± 26 4.0 ± 0.6
PE6W 21.4 ± 0.1 1818 ± 106 5.3 ± 0.3 15.2 ± 0.1 1644 ± 21 2.3 ± 0.1
PE6K 21.0 ± 0.1 1727 ± 203 5.1 ± 0.7 13.2 ± 0.1 1621 ± 86 1.8 ± 0.1
PE6F 19.3 ± 0.1 1527 ± 19 4.7 ± 0.1 16.6 ± 0.8 1439 ± 23 3.4 ± 0.4
PE6B 27.8 ± 1.2 2134 ± 97 4.0 ± 0.2 20.6 ± 1.2 2745 ± 162 1.8 ± 0.3
PE12W 20.4 ± 0.1 2055 ± 16 3.8 ± 0.5 14.6 ± 1.0 2024 ± 24 2.0 ± 0.3
PE12K 19.9 ± 0.4 1504 ± 36 4.5 ± 0.1 11.8 ± 0.5 1391 ± 25 1.9 ± 0.7
PE12F 21.6 ± 0.3 1935 ± 8 3.7 ± 0.4 16.1 ± 0.6 1813 ± 14 2.6 ± 0.9
PE12B 35.0 ± 1.1 3231 ± 19 2.6 ± 0.1 23.1 ± 0.7 3175 ± 35 3.8 ± 0.4

Apart from the chemical or physical action of the same factor, the durability of the material used in
the environment is significantly influenced by additional physical or mechanical factors. Temperature
is a factor that not only affects the acceleration of possible chemical reactions between the environment
and plastic, but also accelerates the diffusion of liquids or gases. Both of these phenomena reduce the
mechanical strength of the material and increase its susceptibility to other physical and chemical factors.
In addition, by increasing the temperature, regardless of the presence of aggressive factors, it reduces
the immediate strength of thermoplastics. The variability of working conditions is a factor significantly
reducing the durability of a material. For example, temperature changes due to the high thermal
expansion of plastics cause deformations and lead to fatigue damage. Therefore, cyclical changes in
environmental temperature are very harmful than the continuous impact of elevated temperature.
Moreover, constant contact with the liquid is less harmful than repeated wetting and drying of the
material, which alternately causes swelling and shrinkage, which leads to faster destruction as during
changes in temperature [48].
These phenomena were observed during accelerated ageing, where the materials were exposed
to elevated temperature and high humidity. First, ageing effect in neat bio-polyethylene caused an
increase in strength as well as modulus by about 10% and substantial reduction in strain from over 100
to 4% probably as an effect of developing oxidation process in bio-polyethylene [49]. Bio-polyethylene
belongs to semi-crystalline materials which do not absorb water, but higher temperature can lead to
build up the degree of crystallinity, affecting the increase in strength properties, which was confirmed
in the research. In the case of polyethylene-based composites, accelerated ageing significantly reduced
the strength and plastic properties.
Research of water absorption led to making theoretical calculation of diffusion coefficient and
its kinetics. Diffusion coefficient, parameters k and n are presented in Table 6. The Fick’s diffusion
coefficient (D) was estimated by Equation (2) in the range where the values of percent weight gain
were less than 60% of the equilibrium value (Mm):

k·h 2
D = π·( ) (2)
4Mm
Materials 2020, 13, 2595 14 of 18

where Mm is the maximum moisture content, h is the thickness of the sample, and k is the initial slope
of a curve of M(t) versus t1/2 , as it can be seen in Equation (3):

M2 − M1
k= √ √ (3)
t2 − t1

Table 6. Estimated parameters for diffusion coefficient and its kinetics.

Samples ID D (m2 /s) Parameter k Parameter n

PE 4.0 × 10−12 0.00003 1.0000
PE6W 3.2 × 10−12 0.0004 0.4792
PE6K 2.5 × 10−12 0.0004 0.4342
PE6F 3.2 × 10−12 0.0004 0.5633
PE6B 7.8 × 10−13 0.00004 0.3001
PE12W 3.5 × 10−12 0.0005 0.5155
PE12K 3.2 × 10−12 0.0007 0.5606
PE12F 3.1 × 10−12 0.0005 0.4854
PE12B 5.8 × 10−12 0.0003 0.7102

Figure 10 shows water absorption for composites as a function of square root of immersion time.
Each point corresponds to the average of five samples. Each of the composites has a similar pattern of
water absorption. The initial linear and rapid increase in absorbency is followed by a plateau effect
without gain in water absorption representing a Fick’s mode of diffusion.
Materials 2020, 13, x FOR PEER REVIEW 15 of 19

Figure
Figure 10.
10. Water
Water absorption
absorption curves
curves of
of different
different composites
composites as
as function
function of
of square
square root
root of immersion
of immersion
time
time in
in seconds.
seconds.

In general, diffusion behavior can be classified according to the relative mobility of penetrant
and polymer segments. There are three types.
Type I or Fick’s diffusion (Equation (2)), in which the diffusion rate is much lower than the
mobility of the polymer segment. The balance inside the material is quickly reached and maintained
regardless of time.
Materials 2020, 13, 2595 15 of 18

In general, diffusion behavior can be classified according to the relative mobility of penetrant and
polymer segments. There are three types.
Type I or Fick’s diffusion (Equation (2)), in which the diffusion rate is much lower than the mobility
of the polymer segment. The balance inside the material is quickly reached and maintained regardless
of time.
Type II, in which penetration mobility is much higher than in other relaxation processes. This
diffusion is characterized by the development of the border between the swollen outer and inner
polymer materials. The boundary moves at a constant speed and the core decreases until the penetration
balance of the entire polymer is reached.
Non-Fick diffusion or anomalous type occurs when the penetrator mobility and relaxation of the
polymer segment are comparable. It is therefore an intermediate behavior between case I and case II.
Distinction between these three mechanisms can be done using theoretical considering the shape
of the absorption curve, which can be modeled using Equation (4).

Mt
= ktn (4)
Mm

where Mt is the moisture content, Mm is the moister content at saturation, and k an n are constant. The
parameter n is associated with the diffusion mode and takes different values, depending on the specific
case: for Fick’s diffusion n = 0.5, type II n = 1, and for type III (anomalous diffusion) 0.5 < n < 1. The
values of n and k can be determined from the slope and intersection of Mt/Mm vs. t on a logarithmic
graph obtained from experimental data (Figure 11) according to the Equation (5):

Mt
log = log(k) + nlog(t) (5)
Mm
Materials 2020, 13, x FOR PEER REVIEW 16 of 19

Figure 11. Calculated

Figure 11. Calculated experimental
experimental data
data to
to estimate
estimate parameter n associated
parameter n associated with
with the
the diffusion
diffusion mode.
mode.

Table 6 summarizes
Table 6.the values parameters
Estimated of the parameter n thatcoefficient
for diffusion resulted and
from
itsmatching
kinetics. all samples. The
n-values for composites were close to each other and indicated a value of 0.3–0.7, thus suggested Fick’s
Samples ID D (m2/s) Parameter k Parameter n
PE 4.0 × 10−12 0.00003 1.0000
PE6W 3.2 × 10−12 0.0004 0.4792
PE6K 2.5 × 10−12 0.0004 0.4342
PE6F 3.2 × 10−12 0.0004 0.5633
PE6B 7.8 × 10−13 0.00004 0.3001
Materials 2020, 13, 2595 16 of 18

diffusion mechanism in composites, but this calculation is devoted to materials that do not absorb water,
hence the deviation from the theoretical value can be attributed to the occurrence of other mechanisms
in fiber composites such as swelling, weakening of the fiber/matrix interface, micro-cracking of the
matrix. Lower values of the parameter n were obtained for materials with 6 wt.% of fibers at which the
diffusion rate was probably slower than the segment mobility of the polymer.

4. Conclusions
The introduction of natural fibers in a small amount of 6% by weight increased the stiffness
of the material, without changing its tensile strength. Doubling the fiber content to 12% by weight
affected both the strength and stiffness of the material at tensile and bending stresses. From natural
fibers, the greatest potential when reinforcing polyethylene was flax fiber, which increased strength
properties, ensuring relatively good plastic properties, eliminated the brittle cracking of the composite
in comparison with other tested materials. The introduction of fibers into bio-polyethylene caused the
water to be absorbed by the composites, and the strength properties after water and thermal aging are
reduced as opposed to the unfilled material. The conducted research allowed for an initial assessment
of the effectiveness and mechanisms of strengthening individual natural fibers in composites based on
bio-polyethylene, and the further direction of research will be the production of hybrid composites
using the potential of natural fibers. Such materials could be a good alternative to glass fiber materials
used in elements of rehabilitation equipment for humans or animals, as well as in household and
automotive articles.

Author Contributions: Conceptualization, S.K. and P.B.; methodology, P.B. and D.M.; formal analysis, P.B.;
investigation, P.B.; writing—original draft preparation, P.B.; writing—review and editing, S.K.; visualization, P.B.
and R.B.; supervision, S.K. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

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