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The Quasi-static and Dynamic Mechanical Behavior of Epoxy Matrix Composites Reinforced with Curaua Fibers

Abstract

The research of natural fiber composites is growing due to the fact that the green materials combine low weight with good mechanical properties. Curaua fiber arises as a competitive natural fiber due to its abundance, low cost and a variety of applications. In this work, different weight fractions of Curaua fiber were used in order to obtain this natural composite material. Specimens of Curaua/Epoxy composites were tested in tensile and in flexion to observe the quasi-static mechanical properties and its physical properties due to temperature variation were evaluated by Dynamic Mechanical Analyses (DMA) analyses. An increase in fiber quantity showed an increase in both the modulus and the strength, leading to a stiff and less ductile material. The results also showed an increase in the viscoelastic stiffness of the epoxy matrix by the incorporation of Curaua fibers. The interaction between Curaua fibers and epoxy matrix affects segmental mobility of the epoxy chains.

Keywords:
Natural Fibers; Mechanical Properties; Composite Materials


1. Introduction

The applications of lignocellulosic fibers in reinforcement of composite structures are growing. Curaua fiber (Ananas erectifolius) is a Brazilian fiber development in the Amazon region (Para state) cultivated by small farmers. With an accelerated industrialization process the search for materials that can respond market needs is more often. Due to the fact that the industries are strongly competitive these new materials shall meet low cost, good mechanical and chemical properties.

Raw materials based on sustainability issues are a great solution for development of biocomposities considering the fact that they have an origin from renewable resources and ally some advantages such as biodegradability, high production and non-toxicity. Considering the properties of curaua, among natural fibers is the most competitive11 Spinacé MAS, Lambert CS, Fermoselli KKG, De Paoli MA. Characterization of lignocellulosic curaua fibres. Carbohydrate Polymers. 2009;77(1):47-53.. This fiber is replacing glass and carbon fiber in some applications. Green materials gain attention for several applications from aerospace to the building industry because it combines some special features like low weight and price with good physical properties11 Spinacé MAS, Lambert CS, Fermoselli KKG, De Paoli MA. Characterization of lignocellulosic curaua fibres. Carbohydrate Polymers. 2009;77(1):47-53.

2 Bispo SJL, Freire Junior RCS, de Aquino EMF. Mechanical Properties Analysis of Polypropylene Biocomposites Reinforced with Curaua Fiber. Materials Research. 2015;18(4):833-837.

3 Hosokawa MN, Darros AB, Moris VAS, Paiva JMF. Polyhydroxybutyrate Composites with Random Mats of Sisal and Coconut Fibers. Materials Research. 2017;20(1):279-290.

4 Morais JA, Gadioli R, De Paoli MA. Curaua fiber reinforced high-density polyethylene composites: effect of impact modifier and fiber loading. Polímeros. 2016:26(2):115-122.
-55 Corrêa AC, Teixeira EM, Pessan LA, Mattoso LHC. Cellulose nanofibers from curaua fibers. Cellulose. 2010;17(6):1183-1192..

Automobile industries in a constant search of reduction of weight and CO2 emissions are making panels and others interior parts with natural fibers66 Holbery J, Houston D. Natural-fiber-reinforced polymer composites in automotive applications. JOM. 2006;58(11):80-86.,77 Joshi SV, Drzal LT, Mohanty AK, Arora S. Are natural fiber composites environmentally superior to glass fiber reinforced composites? Composites Part A: Applied Science and Manufacturing. 2004;35(3):371-376..

Natural fiber polymer composites are materials that consist of a polymeric matrix with immersed fibers. The polymeric matrix can be in two types thermofixes and thermoplastics having the main function of ensuring the fiber integrity against chemical and environmental factors. The fibers, with over mechanical strength, endure the load. An important mechanical aspect of composites is the load transfer by the matrix to the fibers.

The reduction in interfacial mechanical properties between fiber and polymer matrix commonly decreases the fibers ability of to be a reinforcing component considering the hydrophilic character of lignocellulosic fibers.

Some disadvantages of Curaua, as all natural fiber, are related to the composition (cellulose, hemicellulose, lignin and waxes) and the elevated capacity of moisture absorption, which contribute to the poor adhesion between the polymeric matrix and fibers. The properties of natural fibers have a hard dependency of its chemical composition88 Mohammed L, Ansari MNM, Pua G, Jawaid M, Saiful Islam M. A review on Natural Fiber Reinforced Polymer Composites and Its Applications. International Journal of Polymer Science. 2015;2015:243947.

9 Sain M, Panthapulakkal S. Green fibre thermoplastic composites. In: Baillie C, ed. Green Composites - Polymer composites and the environment. Oxford: Woodhead Publishing; 2004. p. 181-206.
-1010 Spinacé MAS, Fermoseli KKG, De Paoli MA. Recycled polypropylene reinforced with curaua fibers by extrusion. Journal of Applied Polymer Science. 2009;112(6):3686-3694.. Good interfacial adhesion initially requires a good wetting between the fiber and the matrix, to achieve an extensive and proper interfacial contact. In order to improve the adhesion between Curaua/Polypropylene, chemical treatment with 5 wt% aqueous NaOH solution for many hours at 23 °C is applied to the natural fibers1010 Spinacé MAS, Fermoseli KKG, De Paoli MA. Recycled polypropylene reinforced with curaua fibers by extrusion. Journal of Applied Polymer Science. 2009;112(6):3686-3694.. Other treatment of natural fiber involves the exposure in hot water at 80°C for 1h and then after both treatments dried in air for 48h. These procedures improve the mechanical interaction between hydrophobic epoxy resin and hydrophilic fibers, removing the waste components (lignin, hemicellulose) from the fibers1111 Almeida Júnior JHS, Amico SC, Botelho EC, Amado FDR. Hybridization effect on the mechanical properties of curaua/glass fiber composites. Composites Part B: Engineering. 2013;55:492-497.

12 Cardoso PHM, Bastian FL, Thiré RMSM. Curaua Fibers/Epoxy Laminates with improved Mechanical Properties: Effects of Fiber Treatment Conditions. Macromolecular Symposia. 2014;344(1):63-70.

13 Gomes A, Matsuo T, Goda K, Ohgi J. Development and effect of alkali treatment on tensile properties of curaua fiber green composites. Composites Part A: Applied Science and Manufacturing. 2007;38(8):1811-1820.
-1414 Leão RM, Luz SM, Araujo JA, Novack K. Surface Treatment of Coconut Fiber and its Application in Composite Materials for Reinforcement of Polypropylene. Journal of Natural Fibers. 2015;12(6):574-586..

The degradation of natural fiber is strongly connected with moisture and climatic conditions. Green fibers are mainly composed of sugar (cellulose and hemicellulose)1515 Faruk O, Bledzki AK, Fink HP, Sain M. Biocomposites reinforced with natural fibers: 2000-2010. Progress in Polymer Science. 2012;37(11):1552-1596.. The chemical composition is distributed layer by layer and varies from fiber to fiber.

In this work, the mechanical properties, tensile and flexural properties of Curaua/Epoxy composites with different amount of Curaua fibers are investigated and also its viscoelastic behavior from very low temperatures, -50ºC, to elevated ones, 180ºC. Viscoelastic behavior was evaluated by Dynamic Mechanical analysis and also the glass transition temperature.

2. Materials and Methods

2.1. Materials

To manufacture Curaua/Epoxy composites the natural fibers and polymer resin were manually mixed, poured in a 200 mm x 200 mm x 4 mm steel mold cured for one week at room temperature prior to testing. The composite resultant was post-cured for 8h at 80°C in order to accelerate the curing process and improve some properties of composites. After the curing process, specimens were cutted according the specific standards.

The epoxy resin used in this work was provided by Epoxyfiber®. Based on diglycidyl ether of bisphenol A and an aliphatic amine hardener. The epoxy resin has low viscosity and the mix ratio to hardener of 4:1. Resin properties by the manufactures are shown in Table 1.

Table 1
Properties of Epoxy resin at room temperature.

Curaua fiber (Ananas erectifolius) from Para state is a type of lignocellulosic fiber. The fiber has a diameter of 50 µm, a length of 6 mm and the aspect ratio (L/D) is 120. The Curaua fibers are shown in Figure 1.

Figure 1
Curaua fibers.

Curaua fibers were manually sifted, rinsed with water and dried in an electric oven. There was not any kind of pre-treatment on the fibers, they were used as it was collected from the nature. The fibers were chopped and blended with the polymer epoxy resin by 30%, 40% and 50% of the total weight.

2.2. Methods

Mechanical tensile and flexural tests at different weight % were performed by Shimadzu®AG-X universal testing machine according to ASTM D3039/D3039M-141616 ASTM International. ASTM D3039/D3039M-14 - Standard Test method for Tensile Properties of Polymer Matrix Composite Materials. West Conshohocken: ASTM International; 2014. and ASTM D790-101717 ASTM International. ASTM D790-10 - Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Material. West Conshohocken: ASTM International; 2010., respectively. The tensile tests were performed with a cross-head speed of 2 mm/min and the three-point bending with a speed of 1.5 mm/min. Four specimens were tested for each type of mechanical testing. Figure 2 shows the tensile and three-point bending set-up for Curaua/Epoxy tests.

Figure 2
Tensile and flexural test set-up

The dynamic mechanical analysis (DMA) was used for measuring the temperature influence in elastic properties of all formulations of natural fiber composite. Tests were performed with three-point bending configuration and the span of the supports was 40 mm, according to ASTM D70281818 ASTM International. ASTM D7028-07 - Standard Test Method for Glass Transition Temperature (DMA Tg) of Polymer Matrix Composites by Dynamic Mechanical Analysis (DMA). West Conshohocken: ASTM International; 2007.. The samples were scanned from -50°C to 180°C with a heating rate of 2°C/min at 0.01, 0.1, 1, 10 and 100 Hz.

3. Results and Discussion

3.1. Tensile and Flexural Experiments

The tensile and three-point bending test results of composite manufactured with different content of Curaua fibers are presented in Table 2.

Table 2
Tensile and three-point bending test results of Curaua fibers composite

From table 2 it can be seen the tensile and flexural maximum strength and stiffness are dependent of fiber quantity. As fiber content increases the tensile and flexural modulus increase improving stiffness. Although the fibers improve the strength of the studied composite, with the addition of fiber the tensile and flexural strength decrease compared to the epoxy matrix. Increasing the quantity of Curaua fiber from 30% to 40%, an increase of 28.5% in the tensile strength is calculated and 50% higher tensile strength is reported for composites manufactured with 50% of Curaua fibers. Stiffness, as previously mentioned, increased overall, is elevated 31.2% when 30% of Curaua fibers are used to produce this natural fiber composite and an elevation of 99.4% and 145% is calculated when 40% and 50% of Curaua fibers are used. Similar behavior is observed when Curaua/Epoxy composites are evaluated in flexion. Elevating the quantity of Curaua fiber from 30% to 40% at 13.4% improve on the flexural strength is observed and 29.7% higher values of flexural strength is calculated when 50% of Curaua fibers is used as matrix reinforcement. Again, the flexural stiffness increased in all composite configurations tested. Using 30% of Curaua fibers, stiffness increased 8.5%. Higher values, 49.8% and 61.3%, are calculated when the content of Curaua fibers is elevated to 40% and 50%, respectively. These results show that Curaua fibers can be an attractive natural fiber to be used as reinforcement due to its high specific strength and stiffness.

Figure 3 shows the typical tensile stress vs. strain curves for Curaua/Epoxy composites with 0, 30, 40 and 50% of fiber.

Figure 3
Typical tensile stress vs. strain curves of Curaua/Epoxy composites.

Figure 3 shows that Curaua fiber hardly influences the tensile behavior of Curaua fiber composites. Despite the decrease in the maximum tensile strength when Curaua fibers are introduced in the epoxy matrix, it can be seen a significant increase in the stress vs. strain slope representing a higher stiffness for higher values of Curaua fiber content. Both modulus of elasticity and maximum strength are fiber-dependent. The stress-strain curve becomes nonlinear for all Curaua fiber composites. This nonlinear behavior can be explained considering that short shredded Curaua fibers results in limited interaction between fibers and matrix, the presence of extensive voids and poor bonding; this reduces the effect of fiber reinforcement in the composite1919 Tran LQN, Yuan XW, Bhattacharyya D, Fuentes C, Van Vuure AW, Verpoest I. Fiber-matrix interfacial adhesion in natural fiber composites. International Journal of Modern Physics B. 2015;29:1540018.. Further improve on the fiber surface preparation should be performed in the future.

Figure 4 displays the three-point bending stress vs. strain curves for Curaua/Epoxy composite with 0, 30, 40 and 50% of Curaua fiber.

Figure 4
Typical flexural stress vs. strain curves of Curaua/Epoxy composites.

The curves showed in figure 4 present the strong influence of quantity of fiber with modification in stiffness and strength of composite. Accordingly to what is observed in tension, when Curaua fibers are inserted in the epoxy matrix the composite has lower deflection and therefore fails for lower strain. Despite that, it can be seen a significant improvement in bending stiffness. This can be observed by the increase in the angle of the bending stress vs. strain slope. Increasing Curaua fiber content bending stress also increases, but strain at failure is around the same range.

3.2. Thermal Analysis of Curaua/Epoxy Composites by DMA

The DMA results of 1Hz analysis are presented in figure 5. The specimens were tested from -50°C to 180°C.

Figure 5
DMA test results of Curaua/Epoxy composites at 1 Hz

Figure 5 presents complete sets of DMA curves (E', E'' and tan δ) for the pure epoxy and Curaua/Epoxy composite specimens. It can be seen an increase in the dynamic bending properties of Curaua/Epoxy composites when compared to unreinforced epoxy matrix. The degree of fiber adhesion affects the mobility of the epoxy molecular chains and hence its temperature transition to an amorphous structure. It can be seen from the peak of tan δ that as Curaua fibers are introduced in the epoxy polymer matrix, the glass transition temperature also increases. It should be noticed that all composite loss modulus (E'') peaks are displaced higher temperatures in comparison to the pure epoxy peak, indicating a reduction in the chain flexibility. A low interfacial strength will not allow the chains to move without much restriction at the contact with the Curaua fibers. Table 3 shows the storage modulus (E'), Tan Delta and glass transition temperature (Tg) of composite Curaua/Epoxy with different content of fiber.

Table 3
DMA test results of Curaua fiber composites.

From table 3 it can be seen that the increase in Curaua fiber quantity improves the Tg of the composite and also improves the storage modulus. The decrease in the tan δ values indicates a reduction in the epoxy chain mobility.

Figure 6 shows the viscoelastic behavior of composite material when it exhibits a dependency of test frequency.

Figure 6
Curaua/Epoxy composites storage modulus (E') at different frequencies.

Figure 6 shows a strong dependency of Curaua/Epoxy composites from test frequencies revealing the viscoelastic property is these composites. For all tested composites, as test frequency increases, the storage modulus also increases. This means that the Curaua fibers increase the epoxy matrix capacity to support mechanical constraints with recoverable viscoelastic deformation. In particular the composite stiffness is substantially increased with Curaua fiber incorporation, which is also comparable to a result found in quasi-static tensile and flexural tests.

4. Conclusions

In this research, different mechanical and dynamic characterizations of a natural fiber composite manufactured with Curaua fibers are presented, directed toward the exploration of possible composite materials for structural and non-structural applications. It is shown by the mechanical test results that despite the decrease in tensile and flexural strength when compared to pure epoxy, incorporating Curaua fibers higher stiffness in both tensile and flexural behavior is observed. Higher values are reported for higher fiber quantities. The glass transition temperature assessed by DMA analysis displayed that the results have a strong relation with rigidity of the chemical structure of the matrix. Extreme temperatures -50°C to 180°C were used to evaluate stiffness and phase change of the composite. Also, increasing Curaua fiber content, it is observed an elevation in the glass transition temperature. The composite material exhibited the viscoelastic behavior showing the dependency of test rate. The elastic characteristics related to storage modulus (E') are more evident at higher frequencies. These results show that Curaua/Epoxy composites have a potential to be used instead of conventional synthetic composites in engineering applications where low weight, easily recyclable and environmental friendly materials are desirable.

5. Acknowledgments

The authors would like to thank the United States Air Force (through the SOARD grant FA9550-16-1-0482).

6. References

  • 1
    Spinacé MAS, Lambert CS, Fermoselli KKG, De Paoli MA. Characterization of lignocellulosic curaua fibres. Carbohydrate Polymers 2009;77(1):47-53.
  • 2
    Bispo SJL, Freire Junior RCS, de Aquino EMF. Mechanical Properties Analysis of Polypropylene Biocomposites Reinforced with Curaua Fiber. Materials Research 2015;18(4):833-837.
  • 3
    Hosokawa MN, Darros AB, Moris VAS, Paiva JMF. Polyhydroxybutyrate Composites with Random Mats of Sisal and Coconut Fibers. Materials Research 2017;20(1):279-290.
  • 4
    Morais JA, Gadioli R, De Paoli MA. Curaua fiber reinforced high-density polyethylene composites: effect of impact modifier and fiber loading. Polímeros 2016:26(2):115-122.
  • 5
    Corrêa AC, Teixeira EM, Pessan LA, Mattoso LHC. Cellulose nanofibers from curaua fibers. Cellulose 2010;17(6):1183-1192.
  • 6
    Holbery J, Houston D. Natural-fiber-reinforced polymer composites in automotive applications. JOM 2006;58(11):80-86.
  • 7
    Joshi SV, Drzal LT, Mohanty AK, Arora S. Are natural fiber composites environmentally superior to glass fiber reinforced composites? Composites Part A: Applied Science and Manufacturing 2004;35(3):371-376.
  • 8
    Mohammed L, Ansari MNM, Pua G, Jawaid M, Saiful Islam M. A review on Natural Fiber Reinforced Polymer Composites and Its Applications. International Journal of Polymer Science 2015;2015:243947.
  • 9
    Sain M, Panthapulakkal S. Green fibre thermoplastic composites. In: Baillie C, ed. Green Composites - Polymer composites and the environment Oxford: Woodhead Publishing; 2004. p. 181-206.
  • 10
    Spinacé MAS, Fermoseli KKG, De Paoli MA. Recycled polypropylene reinforced with curaua fibers by extrusion. Journal of Applied Polymer Science 2009;112(6):3686-3694.
  • 11
    Almeida Júnior JHS, Amico SC, Botelho EC, Amado FDR. Hybridization effect on the mechanical properties of curaua/glass fiber composites. Composites Part B: Engineering 2013;55:492-497.
  • 12
    Cardoso PHM, Bastian FL, Thiré RMSM. Curaua Fibers/Epoxy Laminates with improved Mechanical Properties: Effects of Fiber Treatment Conditions. Macromolecular Symposia 2014;344(1):63-70.
  • 13
    Gomes A, Matsuo T, Goda K, Ohgi J. Development and effect of alkali treatment on tensile properties of curaua fiber green composites. Composites Part A: Applied Science and Manufacturing 2007;38(8):1811-1820.
  • 14
    Leão RM, Luz SM, Araujo JA, Novack K. Surface Treatment of Coconut Fiber and its Application in Composite Materials for Reinforcement of Polypropylene. Journal of Natural Fibers 2015;12(6):574-586.
  • 15
    Faruk O, Bledzki AK, Fink HP, Sain M. Biocomposites reinforced with natural fibers: 2000-2010. Progress in Polymer Science 2012;37(11):1552-1596.
  • 16
    ASTM International. ASTM D3039/D3039M-14 - Standard Test method for Tensile Properties of Polymer Matrix Composite Materials West Conshohocken: ASTM International; 2014.
  • 17
    ASTM International. ASTM D790-10 - Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Material West Conshohocken: ASTM International; 2010.
  • 18
    ASTM International. ASTM D7028-07 - Standard Test Method for Glass Transition Temperature (DMA Tg) of Polymer Matrix Composites by Dynamic Mechanical Analysis (DMA) West Conshohocken: ASTM International; 2007.
  • 19
    Tran LQN, Yuan XW, Bhattacharyya D, Fuentes C, Van Vuure AW, Verpoest I. Fiber-matrix interfacial adhesion in natural fiber composites. International Journal of Modern Physics B 2015;29:1540018.

Publication Dates

  • Publication in this collection
    12 Mar 2018
  • Date of issue
    May-Jun 2018

History

  • Received
    14 Sept 2017
  • Reviewed
    07 Jan 2018
  • Accepted
    09 Feb 2018
ABM, ABC, ABPol UFSCar - Dep. de Engenharia de Materiais, Rod. Washington Luiz, km 235, 13565-905 - São Carlos - SP- Brasil. Tel (55 16) 3351-9487 - São Carlos - SP - Brazil
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