Lignocellulosic fibers classification [13].
Abstract
In this chapter, a review is made on the processing and properties of hybrid composites based on a polymer matrix and a blend of different natural (lignocellulosic) fibers. In particular, the processing methods are described and comparisons are made between the general properties with a focus on physical, mechanical and thermal properties. A discussion is presented on the effect of the polymer and fiber types, as well as reinforcement content. Properties improvement is also discussed using fiber surface treatment or the addition of coupling agents. Finally, auto‐hybrid composites are presented with conditions leading to a positive deviation from the rule of hybrid mixture (RoHM) model.
Keywords
- hybrid composites
- polymer matrices
- natural fibers
- fiber concentration
- mechanical properties
1. Introduction
Composites are materials containing at least two constituents, each one with different chemical composition. Their combination provides a new material with better functional properties than each of the components separately [1].
The main component in the composite is the matrix, which can be a metal, ceramic or polymer, while the other part is a reinforcement which can be in particulate, laminate, short fiber or long fiber form [2]. Composite materials are widely used in construction, aerospace, aircraft, medicine, electrical and automotive industries [2–5]. Here, a focus is made on fiber reinforced composites made from a polymer matrix reinforced with fibers having a natural origin [6].
2. Natural fibers
Natural fibers are biosourced materials extracted from plants (lignocellulosic) or animals [7]. Lignocellulosic fibers are produced by plants for which, on a dry basis, the cell walls are mainly composed of cellulose, with hemicelluloses, lignins, pectins and extractives in lower amounts. Chemical composition and distribution mostly depend on fiber source and varies within different parts even of the same type or family [7, 8]. According to their source, lignocellulosic fibers can be classified as bast fibers, leaf fibers, fruits‐seeds fibers, grass‐reed fibers and wood fibers [7, 9–12]. Table 1 presents some examples of each category [13].
Fiber type | Characteristics | Examples |
---|---|---|
Bast | High cellulose content, flexible, obtained from plants phloem | Kenaf, hemp, flax |
Seed | Fibers that have grown around seeds | Cotton, kapok |
Fruit | Obtained from fruit shells | Coir, oil palm |
Stalk | Cereal stalks byproducts | Wheat and corn straw |
Grass | Obtained from grass plants | Bamboo, wild cane, esparto grass |
Leaf | Obtained by decortication of plants leaves | Banana, sisal, pineapple, agave |
Wood | Extracted from flowering and conifers trees | Maple, pine |
Due to natural fibers’ strength, stiffness, availability, low cost, biodegradability and lower density (1.2–1.5 g/cm3) compared to synthetic fillers such as talc (2.5 g/cm3) and glass fiber (2.5 g/cm3) [14–16], they can be effectively used in lightweight composites production [8, 9, 17].
3. Natural fiber composites
Natural fiber composites are materials based on a polymer matrix reinforced with natural fibers [9]. The polymer matrix can be a thermoplastic or a thermoset, the main difference being that once thermoplastics are molded they can be remelted and reprocessed by applying heat and shear, while this is not the case for thermosets [14, 15]. But thermoset matrices generally provide higher rigidity and are more chemically stable. This is why they are more difficult to recycle. The main thermoset matrices used for natural fiber composite production are polyester, vinyl ester, phenolic, amino, derived ester and epoxy resins. Thermoset composites are commonly processed via resin transfer molding (RTM), sheet molding compound (SMC), pultrusion, vacuum‐assisted resin transfer molding (VARTM) and hand lay‐up. All these manufacturing processes do not need high pressure requirements. Another advantage of thermoset matrices is that fiber loading can be higher than for thermoplastics since the resin is initially in a liquid form. So, lower viscosity improves fibers introduction and dispersion via different mixing equipment [18–22]. Fiber orientation as well as fiber content might improve mechanical properties in thermoset composites. Grass, leaf and bast fibers are more effective to increase the matrix mechanical properties, while surface treatment improves interfacial interactions. Table 2 summarizes some work on natural fiber thermoset composites with their manufacturing process, fiber content, fiber treatments and fiber source, as well as the main results obtained from each work.
Matrix | Natural fiber source |
Manufacturing process |
Fiber content (%) |
Fiber treatment |
Mechanical properties | References | ||||
---|---|---|---|---|---|---|---|---|---|---|
E (GPa) |
TS (MPa) |
FM (GPa) |
FS (MPa) |
IS (J/m) |
||||||
Epoxy | Banana | Hand lay-up | 10 | NaOH solution | 0.6–1.4 | 12.1–33.6 | 15–34 | 26–69 | 2–12 | [23] |
Recycled cellulose | RTM | 19, 28, 40, 46 | – | – | – | 0.5–5.5 | 60–140 | 5–22 | [21] | |
Flax | RTM | 40–50 | – | 17.3–33.6 | – | – | – | – | [19] | |
Hand lay-up | 50 | – | 8.6 | – | – | – | – | [24] | ||
Compression molding and pultrusion | 40 | NaOH solution | 2.7–32 | 50–283 | 8–27 | 0.4–4.1 | – | [25] | ||
Oil palm | Compression molding | 5, 10, 15, 20 | NaOH solution | – | 11–17 | – | – | – | [26] | |
Hemp | Hand lay-up | 30 | H2PO3 solution NH4OH Geniosil GF-9 Toluene solution aminosilane | 3–4.8 | 49.1–66.5 | 3–5.2 | 69–92.8 | – | [27] | |
Date palm | Hand lay-up | 10 | NaOH solution | 1.5–2.5 | 10–40 | – | – | – | [28] | |
|
Molding | 1, 5, 7, 9 | NaOH solution | – | 98.3–114.9 | – | 17–26 | – | [29] | |
Polyester | Jute | Hand lay-up | NA | – | – | – | – | – | 3.8–4.1 | [30] |
Macadamia nut shell | Hand lay-up | 10, 20, 30, 40 | – | – | – | 4.1–4.6 | 26–38 | – | [31] | |
Flax | VARTM | 20 | – | 15.3–20.3 | 188.6–230.7 | 2.1–2.3 | 16.3–17.5 | – | [32] | |
Curaua | RTM | 0–40 | – | – | – | 0.1 | – | 20–190 | [33] | |
Wild cane grass | Hand lay-up | 0–40 | NaOH solution KMnO4 solution |
– | – | 1.8–7 | – | – | [34] | |
Sisal | Mixing and compression molding | 10, 20, 30, 40 | NaOH solution | – | – | 1.49–2.68 | – | – | [35] | |
Typha leaf | Compression molding | 7.3, 10.3, 12.6 | NaOH solution Sea water | – | – | 3.5–6 | 25–70 | – | [36] | |
Rice husk | Mixing and compression molding | 57 | GMAMAHSAH solutions | 0.4–1.6 | 2.5–19 | 0.1–1.9 | 3–42 | 9.5–40 | [22] | |
Elephant grass | Hand lay-up | 30.4, 31.3, 31.5 | NaOH KMnO4 solutions |
0.6–2.2 | 31.5–118.1 | – | – | – | [37] | |
Bamboo | Mixing and compression molding | NA | H2O2 +DTPA +Na2O3Si +NaOH solution, IEM +DBTDL | – | 39–65 | – | 75–105 | – | [38] | |
Coir | Hand lay-up | NA | NaOH solutions | – | 17.9–23.6 | – | 18.7–48 | – | [39] | |
10, 20, 30 | – | – | 10.6–15.6 | – | 25.9–38.5 | 25.6–161.9 | [40] | |||
Polyurethane | Kraft cellulose | Compression molding | 5, 10, 15, 20 | – | 0–0.2 | – | – | – | – | [41] |
Phenolic | Bagasse | Compression molding | 17.6 | HClO2 solution Furfuryl alcohol |
– | – | – | – | 17–28 | [42] |
Curaua | Compression molding | 17.6 | HClO2 solution Furfuryl alcohol |
– | – | – | – | 39–88 | [42] | |
Cellulose eucalyptus |
Molding | 1, 3, 5, 7 | NaOH solution, propyl-trimethoxy-silane | 0.7–0.9 | 9.5–16.5 | 5.1–1.0 | 18.5–28.0 | – | [43] | |
Ramie | Compression molding | 40.4 | – | 3.3, 1.2 | 72.3,158 | – | 90–145 | – | [44] | |
Jute | Pultrusion | N/A | – | – | 25–38 | – | 28–63 | – | [45] | |
Bamboo | Compression molding | 15 | – | 21.2–30.1 | – | – | 210–320 | – | [46] | |
Vinyl ester | Silk | Hand lay-up | 0–15 | – | 0.9–1.3 | 40–71 | – | – | – | [47] |
Cellulose | VARTM | 20, 30, 40, 50 | – | 3–7 | – | – | 40–160 | – | [20] | |
Sisal | RTM | 10, 15, 20, 25, 30 | NaOH solution | 1.7–2.9 | 38–75 | 2.1–4.5 | 75–180 | – | [48] | |
Kenaf | Pultrusion | 40 | – | 9–12.5 | 135–145 | 1.6–1.9 | 150–190 | – | [49] | |
Pineapple leaf |
Molding | 20 | NaOCl solution | 1.9–3.9 | 68–119 | 19–105 | [50] |
The most common thermoplastic matrices used for natural fiber composites production are the different grades of polypropylene (PP) and polyethylene (PE), as well as polycarbonate (PC), nylon (PA), polysulfones (PSU), polyethylene terephthalate (PET) and polystyrene (PS). More recently, biopolymers such as polylactic acid (PLA) have gained interest to produce 100% biosourced materials [51–55]. Typical manufacturing processes for these composites are extrusion, injection, calendering, compression molding and thermoforming. Some advantages of using thermoplastic matrices are their recyclability and the production can be continuous [56–61]. Depending on the matrix, fiber and additives content, fiber treatment and manufacturing process, the mechanical and thermal properties of these composites can be adjusted as presented in Table 3, with the main results obtained.
The main objective of adding natural fibers in polymer matrices is to increase mechanical properties regardless of polymer and fiber type [21, 26, 31, 40, 52, 54, 55, 61–68]. Since natural fibers have lower density (1.2–1.5 g/cm3) compared to synthetic/inorganic reinforcement such as glass fibers (2.5 g/cm3), lightweight composites can be produced [28, 69, 70]. Nevertheless, lignocellulosic fibers are hydrophilic and polar which causes some incompatibility with the most common polymer matrices which are hydrophobic and nonpolar. This effect leads to poor mechanical properties due to a lack of interfacial adhesion between the fibers and the matrix. Furthermore, the high amount of hydroxyl groups available on the fiber surface is increasing water absorption, even when inside a composite [65, 71, 72]. These problems can be resolved by modification of the fibers surface such as mercerization (treatment in sodium hydroxide solution to remove lignins and hemicellulose) with subsequent addition of coupling agents [22, 73–75]. There is also the possibility to combine thermomechanical refining with coupling agent addition [71, 72]. More recently, fiber treatment with a coupling agent in solution has been proposed [76].
Matrix | Fiber source | Processing | Fiber content (%) |
Fiber surface treatment |
Additive | Mechanical properties |
TD (°C) | References | |||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
CA | BA | E (MPa) |
TS (MPa) |
FM (MPa) |
FS (MPa) |
IS (J/m) |
|||||||
HDPE | Flax | Injection molding |
0, 15, 30 | – | – | ACA | 220–470 | 14–24 | 500–1600 | 15–26 | 60–230 | – | [66] |
Wood | Compression molding |
0–40 | Thermo‐ mechanical refining |
MAPE | ACA | – | – | 0.9–3.9 | – | – | – | [72] | |
Wood | Extrusion | 20, 30, 40 | – | MAPE | – | 2300–2900 | – | 1900–3400 | – | – | – | [56] | |
Wood | Extrusion | 50, 60, 70, 80 | – | MAPE | – | 3130–4600 | 11.1–30.2 | 2470–3370 | 25.0–58.8 | – | – | [77] | |
Wood | Injection molding | 40 | Ethanol and toluene extraction NaClO2 treatment NaOH solution |
MAPE | – | 3570–4940 | 23.8–48 | – | – | – | – | [78] | |
Wood | Injection molding | 25, 35, 45 | – | – | – | 1200–2000 | 18.5–27.5 | 1200–2700 | 27.5–43 | – | – | [59] | |
Oil palm | Compression molding | 30, 40 | – | MAPP | – | 650–1050 | 10–15 | [65] | |||||
Hemp | Compression molding | 0–40 | – | – | ACA | – | – | 1093–1634 | 18.8–23 | – | – | [55] | |
Agave | Injection molding | 0–20 | – | – | ACA | 225–550 | 15–24 | 1–2.7 | – | – | – | [79] | |
Hemp | Compression molding | 40 | Thermo‐mechanical refining | MAPE MAH |
– | – | – | 2–2.6 | – | – | – | [71] | |
Argan nut shell | Injection molding | 5, 10, 15, 20, 25 | NaOH solution | – | – | 1136–1795 | 27.2–29.3 | – | – | – | – | [80] | |
UHMWPE | Wood powder | Compression molding | 0–30 | – | – | – | 195–280 | – | 650–1260 | – | – | – | [67] |
LMDPE | Agave | Rotomolding | 5, 10, 15 | – | – | – | 255–440 | 13–18.8 | 495–590 | 12.5–16.5 | 0.9–7.5 | – | [81] |
Agave | Rotomolding | 15 | Solutions of: MAPE NaOH Aldehyde Acrylic acid Methyl methacrylate Silane |
– | 167–217 | 13–18 | 420–520 | 13–17.8 | 83.8–148.5 | – | [76] | ||
Hemp | Injection molding | 30 | Solutions of: NaOH MAPE |
MAPE | – | 241–668 | 13.1–17.9 | – | – | – | – | [73] | |
LLDPE | Maple wood | Rotomolding | 0–20 | – | – | ACA | 26–184 | 3–16.4 | 119–680 | – | – | – | [52] |
Wood | Injection molding | 47 | – | MAPP | – | – | 30.2 | – | – | – | – | [82] | |
Agave | Compression molding | 0–40 | Solutions of: NaOH MAPE |
– | – | 224–381 | 10–22 | 389–1027 | 14–31 | 123–260 | – | [75] | |
PS | Agave | Compression molding | 10, 20, 30 |
– | – | ACA | 3345–4929 | 30–62 | – | – | – | 400 | [83] |
Wood fiber | Extrusion | 10, 20, 30, 40 |
MAPS | – | – | – | 31–49 | – | 54–94.5 | – | – | [84] | |
Wood flour | Extrusion | 10, 20, 30, 40 |
MAPS | – | – | – | 31–41.5 | – | 55–68 | – | – | ||
PP | Argan nut shell | Injection molding | 0–30 | – | SEBS‐g‐MA | – | 1034–1593 | 26.5–30 | – | – | – | 339.4–350 | [85] |
Flax | Compression molding | 10, 20, 26, 30 |
– | MAPP PPAA |
– | 1000–3200 | – | – | – | – | – | [86] | |
Abaca | Injection molding | 10, 15, 20, 25 |
Benzene diazonium treatment, NaOH solution | – | – | 800–2700 | 24.5–31 | 800–3100 | 43–55 | 22.5–50 | – | [87] | |
Coir bagasse | Injection molding | 5, 10, 15, 20, 25, 30 |
NaOH solution | – | – | 1100–1700 | 27.5–34.7 | 1400–2000 | 35–53 | – | – | [88] | |
Wood | Compression molding | 10, 20, 30, 40 | – | MAPP | – | 600–1600 | – | 2100–2400 | 44–52 | 10–17 | – | [89] | |
NNC | Compression molding | 1 | – | MAPP | – | 450–663 | 32.3–39.1 | 1809–2238 | – | – | – | [90] | |
Sisal | Injection molding | 10, 20, 30 |
NaOH solution | MAPP | – | 500–1100 | 23–28 | – | – | – | 363.2–434.5 | [91] | |
Pine cone | Injection molding | 5, 10, 15, 20, 25, 30 |
NaOH solution | SEBS‐g‐MA SBS |
– | 1020–1550 | 21–27.5 | – | – | – | 321–355 | [92] | |
Wood cotton | Compression molding | 10, 20, 30 |
– | MAPP | – | – | 28–50 | – | 37–152 | – | – | [93] | |
PLA | Flax | Injection molding | 15, 25, 40 |
– | – | – | – | – | 2500–6000 | – | – | 282–340 | [54] |
Maple wood | Injection molding | 15, 25, 40 |
– | – | – | – | – | 2400–5900 | – | – | 282.3–342.7 | [62] | |
Maple wood | Injection molding | 5, 10, 15, 20, 25 |
– | – | – | 1250–1890 | 59.8–61.5 | 3650–5260 | 96.6–107 | 21.7–34.3 | 250–360 | [94] | |
Wood | Injection molding | 20, 30, 40, 50, 55, 60, 65 |
– | – | – | 5270–10300 | 56.8–64.6 | 5400–1088 | 77–91.8 | – | – | [58] | |
Cotton | Injection molding | 10, 20, 30, 40, 50 |
– | – | – | 1260–2500 | 58.1–62.6 | 3690–8220 | 97.9–106.2 | 17.5–24.3 | 250–360 | [94] | |
Agave Coir Pine |
Injection molding | 10, 20, 30 |
– | – | – | 1242–1865 | 43–60 | 2300–3110 | 55–96 | 30–49 | – | [95] | |
Post consumer PP+HDPE | Wood flour | Compression molding | 0–40 | – | MAPP MAPE |
– | 247–394 | 12.7–15.3 | 950–1889 | – | 38–65.6 | – | [61] |
Wood flour | Compression molding | 0–40 | – | POE MAPP MAPE |
– | – | – | 1073–1958 | 16.6–22.4 | – | – | [96] | |
Flax | Injection molding | 30 | – | MAPP EO‐g‐MAH – |
– | 608 | – | 3090 | – | – | – | [97] | |
– | 579 | – | 2921 | – | – | – | [98] | ||||||
– | 332–608 | – | 1114–3090 | – | – | – | [99] | ||||||
Post consumer HDPE | Pine wood | Compression molding | 30 | – | MAPE CAPE TDM |
– | – | 21.4–30.6 | – | – | – | 341.3–342.4 | [60] |
Bagasse | Compression molding | 30 | – | MAPE CAPE TDM |
– | – | 22.3–36.1 | – | – | – | 348.5–353.3 | [60] | |
Wood | Compression molding | 50, 60 | – | MAPE | – | – | 9–18 | – | – | 20–35 | – | [100] | |
Post consumer PP | Wood | Extrusion | – | – | MAPP | – | 450–490 | 27.3–29.8 | 2230–2940 | 43–51 | – | 285–499 | [101] |
Oil palm | Extrusion | – | – | MAPP | – | 340–380 | 18.7–19 | 1870–2150 | 30.1–33.8 | – | 268–495 | [101] |
Coupling agents are usually copolymers containing functional groups compatible with the fibers (hydroxyl groups) and the polymer matrix [74]. These reactions (chemical or physical) are increasing interfacial adhesion leading to improved mechanical properties and water absorption reduction [22, 65, 71–73, 75, 76, 99, 102, 103]. Coupling agents can be mixed with the polymer matrix by extrusion previously to fibers addition [65, 74, 92] but can also be added during composite compounding, i.e. mixing the matrix, fiber and coupling agent all together [55, 72, 83, 90, 97–99, 102–104]. Likewise, natural fibers can be functionalized by treating them with a coupling agent in solution, to increase compatibility with the polymer matrix [22, 71, 73–76].
Since natural fibers start to degrade at lower temperature (150–275°C) than most polymer matrices (350–460°C) [60, 63, 74, 83, 105], fiber mercerization and coupling agent addition were shown to improve the thermal stability of the fibers and therefore of the final composites [24, 29, 73, 75, 85, 91, 92].
4. Hybrid composites
To improve on the properties of natural fiber composites and/or overcome some of their limitations such as moisture absorption, thermal stability, brittleness and surface quality, the concept of hybrid composite was developed. The idea is to combine natural fibers with other fibers or particulate reinforcements, which can be of natural or synthetic origin such as glass fibers or rubber particles [15, 51, 63, 106–109]. The main purpose of blending different reinforcements is to obtain a material with better properties than using a single reinforcement. Assuming there is no chemical/physical interaction between each type of fibers, the resulting properties of hybrid composites (
where
Naturally, the model can be generalized for more than two types of reinforcement.
Natural and synthetic reinforcements combination has showed to improve several composite characteristics such as thermal stability [106, 112–114], impact strength [63, 115–117] and water uptake [70, 112–114, 118, 119]. But the combination of two different types of lignocellulosic fibers was shown to control water absorption [53, 103, 110] and increased impact strength [103, 120], especially when using coupling agents.
The final properties of hybrid composites depend are function of different factors [53, 74, 104, 120], and Table 4 summarizes some of the most important mechanical and thermal properties of hybrid composites based on thermoset matrices. The effect of fiber and matrix type, as well as fiber surface treatment is reported with their mechanical properties and thermal degradation temperature. Similarly, Table 5 reports the corresponding information for hybrid composites based on thermoplastic matrices. In general, it is observed that combining natural fibers with inorganic reinforcements leads to improved thermal stability and impact strength, as well as higher flexural and tensile moduli. Moreover, Table 6 shows that water uptake decreases by combining two natural fibers from different sources, or using natural fibers with inorganic reinforcements in hybrid composites based on thermoplastics matrices.
Matrix | Fibers | Manufacturing process | Fiber treatment | Mechanical properties | TD (°C) | References | ||||
---|---|---|---|---|---|---|---|---|---|---|
E (GPa) | TS (MPa) | FS (MPa) | FM (GPa) | IS (kJ/m2) | ||||||
Polyester | Hemp/wool | Pultrusion | – | 16.84 | 122.12 | 180 | 11 | – | [18] | |
Palmyra palm leaf/jute |
Compression molding | NaOH solution | 2.3–5.1 | 15.3–19.3 | 24.7–36.4 | – | [121] | |||
Banana/sisal | Hand lay‐up + compression molding | – | 1.1–1.5 | 2.7–4.2 | ∼16–37 | – | [122] | |||
Coir/silk | NaOH solution | 11.4–17.4 | 37.4–42 | – | [123] | |||||
Oil palm/glass | Compression molding | – | ∼2.5–5.5 | ∼20–75 | ∼30–138 | ∼1.5–8 | ∼7–16 | – | [124] | |
Banana/kenaf | Hand lay‐up | Solutions of: NaOH SLS |
– | 45–139 | 75–172.2 | – | ∼15–28 | – | [125] | |
Ramie/cotton | Compression molding | – | – | 24.2–118 | – | 6.3–27.4 | – | [126] | ||
Sisal/roselle | RTM | – | – | 30.1–58.7 | 48.4–63.5 | – | 1.39–1.41 | – | [127] | |
Sisal/glass | Hand lay‐up | – | – | ∼78–95 | ∼70–265 | ∼2.1–11 | ∼66–88 | – | [128] | |
Sisal/jute/glass | Hand lay‐up | – | – | 111.2–232.1 | 214.1–308.6 | – | – | – | [118] | |
Hemp/glass fibers | Hand lay‐out + compression molding | NaOH solution | – | – | – | – | – | 345 | [107] | |
Epoxy | Banana/jute | Hand lay‐up + compression molding | – | 0.6–0.7 | 16.6–19 | 57.2–59.8 | 8.9–9.1 | 13.44–18.23 | 376.5–380 | [108] |
Banana/sisal | Hand lay‐up | – | 0.6–0.7 | 16.1–18.6 | 57.3–62 | 8.9–9.3 | 13.2–17.9 | – | [129] | |
Jute/bagasse | Hand lay‐up | NaOH HCl solution |
0.3–0.7 | 0.6–1.7 | 6.9–15.9 | 0.6–1.7 | 6.9–15.9 | 438.2–475.9 | [109] | |
Jute/coir | Hand lay‐up | NaOH Cyclohexane/ethanol Furfuryl alcohol |
∼0.3–0.7 | ∼8.5–35 | ∼39–37 | ∼0.5–1.5 | – | – | [130] | |
Banana/silica | Hand lay‐up | – | 6.5–9.1 | – | – | – | – | – | [111] | |
Sisal/silica | Hand lay‐up | – | 4.7–6.1 | – | – | – | – | – | [111] | |
Polyurethane | Hemp/wool | Pultrusion | – | 18.91 | 122.66 | ∼142 | ∼12 | – | – | [18] |
Vinyl ester | Hemp/wool | Pultrusion | – | 15.27 | 112.54 | ∼143 | ∼13 | – | – | [18] |
Jute/ramie | VARTM | – | 6.7–6.8 | 6.2–6.7– | – | –– | 18–19 | – | [131] | |
Coconut/sisal/ glass |
Molding | – | – | – | – | – | 1993–16373 | – | [117] | |
Vetiver/glass | Hand lay‐up | NaOH solution | 1–2.4 | 53.2–69.8 | 97.3–131.9 | 2–3.6 | – | – | [116] | |
Jute/vetiver | Hand lay‐up | NaOH solution | 1.7–1.9 | 63.3–71.7 | 114.8–133.1 | 2.9–3.6 | – | – | [116] |
Manufacturing process |
Composite | Coupling agent | Filler content (%) |
Filler surface treatment |
Mechanical properties |
TD (°C) | References | ||||
---|---|---|---|---|---|---|---|---|---|---|---|
E (MPa) |
TS (MPa) |
FS (MPa) |
FM (GPa) |
IS (J/m) |
|||||||
PP‐glass /flax fibers |
MAPP (5%) | 40 (vol) | – | 522–629 | 21.9–25.5 | – | – | 37.9–49.6 | – | [106] | |
MAPE‐GTR rubber /hemp fiber |
– | 10, 30 50, 60 |
– | 120–243 | 9.8–14.3 | – | 363–781 | 139.6–239.8 | 294–465 | [63] | |
PP‐Kenaf/coir/MMT | MAPP (5%) |
30 | – | 300–360 | 11–12 | – | – | – | – | [132] | |
PP‐NNC/Maple fibers | MAPP (2%) |
21 | – | 444.9 | 25.4 | – | 1735.2 | – | – | [104] | |
PP‐wood/SiO2 PP‐wood/CaCO3 PP‐wood/milled glass fibers |
MAPP (4.5%) | 50 | – | – | 32–45 | 48–65 | 2400–3540 | – | 348 | [133] | |
PP‐sisal/glass fibers | MAPP (1%, 2%, 3%) |
30 | – | 41.75–55.1 | 970–1686 | 47.4–67.5 | 1900–2800 | 59.3–81.6 | 346–384 | [70] | |
PP‐jute/flax fibers | MAPP (19.12%) | 25.96% | PP/jute and MAPP/flax woven fabrics were treated with NaOH solution | 29.7–42.6 | 2437.3–2852.4 | 50.1–68.8 | 1399.7–2331.8 | – | – | [134] | |
LDPE‐banana/coir fibers | MAPP (5%) |
15 | Solutions of: NaOH Acetylation bleaching with H2SO4 |
36.2–50 | 29.5–52.4 | 9.3–13.6 | 473 | [135] | |||
HDPE‐coir/Oil palm fibers |
MAPE (2%, 4%) |
40 | Hot water and soap |
8–13.5 | 550–630 | 17–27 | 1570–2380 | – | – | [120] | |
HDPE‐kenaf/pineapple leaf fibers (PALF) | – | 40 | – | 27–30 | 550–680 | 23–28 | 1700–2100 | – | – | [110] | |
PS‐banana/glass fibers | – | 20 | Solutions of: NaOH Benzoyl chloride PSMA |
29–38.8 | 1462.2–1558.3 | 7.9–11.3 | 489.7–698.8 | – | – | [136] | |
Injection + compression | PP‐SBR rubber/ birch wood |
MAPP (3%, 5%) |
0–40 | – | 10.5–25 | 520–1560 | – | – | – | – | [51] |
Injection molding | PP‐sisal/glass fiber | N/A (3.5%) |
10, 20, 30 |
Boiled in methanol and benzene mixture and with NaOH solution | – | – | – | – | 100 | 190–230 | [112] |
PP‐sisal/glass fibers | MAPP (3%) |
30 | – | 29.2–31.6 | 2330–2430 | 66.7–68.8 | 4.03–4.14 | 16.7–20 | 331.3–464.7 | [113] | |
RPP‐date palm wood/glass fiber | – | 30 | – | 19.5–21 | 1100–1300 | – | – | – | 361.8–479.4 | [114] | |
PP‐hemp/glass fibers | MAPP (5%) |
40 | – | 52.5–59 | 3800–4300 | 97–101 | 5000–5400 | 49–55.4 | 360–474 | [57] | |
PP‐wood flour/glass fiber | MAPP PP‐g‐MA POE‐g‐MA SBS‐g‐MA (3%, 6%) |
40 | – | 28–45.4 | – | 39.7–62.8 | 2680–3497 | – | 345–363 | [137] | |
PP‐wood/kenaf fibers | MAPP (1%) |
40 | – | 39–44 | 2771–3008 | – | – | – | – | [138] | |
PLA‐kenaf/corn husk | – | 30 | NaOH solution Sodium lauryl sulfate solution Silane and potassium permanganate |
– | 1547 | – | – | – | – | [139] | |
PLA‐banana /nano‐clay |
– | 33 | – | 67 | 4965–5577 | 105–108 | 7715–7725 | 119–120 | 295–397 | [140] | |
HDPE‐Pine /agave fibers |
MAPE (3%) |
20, 30 | – | 20.5–26.5 | 415–650 | 24–32 | 670–1180 | 37–47 | – | [53] | |
HDPE‐coir/agave fibers | MAPE (3%) |
20, 30 | NaOH solution | 19.5–25.9 | 355–500 | 23.3–31.9 | 890–1190 | 42–68 | – | [103] | |
HDPE‐sisal/hemp | MA solution (10%) | 25, 30 | NaOH solution | 15.7–19.2 | – | – | – | – | – | [141] | |
PP‐coir shell/coir fibers |
SEBS‐g‐ MA (8%) |
20 | NaOH solution Benzoyl peroxide solution |
26.5–29.5 | 1050–1300 | – | – | – | 344–349 | [74] | |
PLA‐banana/sisal fibers | – | 30 | – | 57–79 | 1700–4100 | 91–125 | 4200–5600 | – | – | [142] | |
PLA‐hemp/lyocell | – | 40 | – | 41.4–71.5 | 4643–7035 | – | – | – | – | [143] | |
PLA‐hemp/kenaf fibers | – | 40 | – | 34.4–61 | 4920–7039 | ||||||
HDPE‐wood/hollow glass microspheres | – | 50 | – | 26.2–31 | 3300–3600 | – | – | – | – | [119] | |
Extrusion | HDPE‐wood/bast fibers | – | 60 | Vinyl triethoxysilane | 42–44 | 650–700 | 73–77 | 4900–5250 | – | – | [144] |
HDPE‐wood/Kevlar | – | 60 | Allyl and 3–trimethoxy silyl‐propyl |
13.8–19.8 | 3050–4100 | 24.5–3600 | 2200–3400 | – | – | [145] | |
Extrusion calendering | PP‐jute/glass | – | 20, 30, 40 | – | 42–63 | 4660–7170 | 72.8–102.5 | 3550–5950 | – | – | [69] |
Matrix | Reinforcements | Observations | References |
---|---|---|---|
MAPE | GTR rubber/hemp fiber | GTR decreases water uptake | [63] |
PP | Kenaf/coir/MMT | Water uptake is reduced by hybridization | [132] |
Wood/SiO2 Wood/CaCO3 Milled glass fibers |
SiO2, CaCO3 and milled grass decreased water uptake | [133] | |
Hemp/glass fibers | Glass fiber reduced water uptake | [57] | |
Wood/glass fibers | Increasing fiber glass weight ratio, water uptake was reduced. | [146] | |
HDPE | Pine/agave fibers | Pine fiber decreased water uptake in hybrid composites | [53] |
Coir/agave fibers | Coir reduced water uptake in hybrid composites | [103] |
5. Auto‐hybrid composites
Composites reinforced with two sizes of the same type of reinforcement are referred to as auto‐hybrid composites. As these composites only have a single type of reinforcement, they are easier to recycle. But most importantly, these materials were shown to exhibit a positive deviation from the RoHM depending on fiber concentration, weight ratio, size and type [64, 102, 147]. Nevertheless, the auto‐hybridization effect seems to be more influenced by the total fiber content than coupling agent addition [64, 147]. However, coupling agent addition is always important to improve tensile strength [102]. As total fiber content, fiber type and coupling agent content, all affect the level of deviation from the RoHM, and optimization of these parameters is a new challenging field of research to develop better composite performances. Table 7 summarizes the limited amount of work on auto‐hybrid composites using natural fibers as reinforcement.
Processing | Composite | Coupling agent | Fiber diameter (µm) |
Fiber content (%) |
Crystallinity index (%) | Main results | References |
---|---|---|---|---|---|---|---|
Injection | PP‐hemp fibers | MAPP (3%, 5%)* |
Fiber: 300–710 Powder: 45–180 |
20, 30 | – | Hybridization more effective at 20 wt.% reinforcement Optimum weight ratio of 20/80 (powder/fibers) 3% of coupling agent was more efficient Ductility and impact strength decreased with fiber content Tensile and flexural modulus increased with fiber content |
[147] |
HDPE‐ pine fibers |
MAPE (3%) |
Short fiber: 40–105 Long fiber: 300–425 |
10, 20, 30 |
56.2–61.1 | Coupling agent increased tensile strength, and decreased tensile modulus, flexural strength and impact strength of auto‐hybrids Total fiber concentration affected hybridization being more effective at 20 and 30 wt.% Higher values of mechanical properties were obtained at 30/70 (short/long) weight ratio (without coupling agent) in auto‐hybrids Crystallinity index decreased with coupling agent addition |
[102] | |
HDPE‐ agave fibers |
53.3–57.4 | ||||||
PP‐pine fiber | – | Short fiber: 50–212 Long fiber: 300–425 |
10, 20, 30 | – | Hybridization did not affect flexural and tensile strength Hybridization was more effective at 30/70 (short/long) and 50/50 (short/long) weight ratio Positive hybridization effect was higher at 20 and 30 wt.% fiber content Impact strength was higher at 20 wt.% with a 30/70 (short/long) weight ratio Water absorption was not affected by fiber size |
[64] | |
PP‐agave fibers | |||||||
Compression molding | LLDPE‐maple fibers | MAPE (3%) |
Short fibers: 0–45 Medium fibers: 125–250 Long fibers: 355–450 |
5, 10, 15, 20 | 13–32 | Positive deviation of RoHM at 30/70 (smaller/longer) weight ratio, regardless of fiber size 20 wt.% showed higher RoHM positive deviation and auto‐hybridization was more effective Positive deviation of RoHM is affected by fiber size and total fiber content Tensile and flexural modulus increased with fiber content, but not with fiber size Impact strength and torsion modulus of hybrid composites are affected by fiber weight ratio |
[148] |
6. Conclusion
Natural fibers are now interesting alternative to replace synthetic fibers due their good specific properties (per unit weight). They have been used to develop different composites based on thermoset and thermoplastic matrices. As for any composite, their mechanical, thermal and physical properties are function of the properties of the matrix and the reinforcement, as well as fiber loading, fiber source and manufacturing process. Nevertheless, interfacial conditions are always important to optimize the general properties.
The main disadvantages of using natural fibers are water uptake, low thermal stability, as well as low mechanical properties due to fiber agglomeration and poor interfacial adhesion, especially at high concentration. The problem is usually more important in thermoplastics than thermosets due to their difference in initial resin viscosity. But most of the limitations associated to natural fiber composites can be controlled or overcome by the addition of coupling agents and/or fiber surface modifications.
Finally, another possibility to improve the properties of natural fiber composites is to add a second reinforcement to produce hybrid composites. These materials were shown to have improved mechanical and thermal properties over neat natural fiber composites as they follow the rule of hybrid mixture (RoHM) regardless of the matrix, manufacturing processing and fiber combination. Based on this concept, different class of materials was also developed such as all natural fiber hybrid composites (combination of two different natural fibers) and auto‐hybrid composites (combination of two different sizes of the same fiber). The latter is highly interesting as positive deviations from the RoHM were reported. This is usually the case around 20 wt.% of total fiber content with around 30/70 short/long fiber ratio regardless of coupling agent addition, fiber type and processing method. This opens the door to a new field of investigation as several parameters can be controlled to optimize the final properties of the materials and to design new applications for these multi‐functional composites.
Acknowledgments
The authors would like to thank the financial support of the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Research centre for high performance polymer and composite systems (CREPEC), as well as Centre de recherche sur les matériaux avancés (CERMA) and Centre de recherche sur les matériaux renouvelables (CRMR) of Université Laval for technical help.
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