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Rheological Properties of Asphalt Binders Modified with Natural Fibers and Oxidants Journal of Multidisciplinary Engineering Science and Technology (JMEST) ISSN: 2458-9403 Vol. 4 Issue 10, October - 2017 Rheological Properties of Asphalt Binders Modified With Natural Fibers and Oxidants T. M. F. Cunha G. Cardoso C. A. Frota Petrobras – REMAN Federal University of Sergipe Federal University of Amazonas Manaus - AM, Brazil Aracaju - SE, Brazil Manaus - AM, Brazil E-mail: [email protected] E-mail: [email protected] E-mail: [email protected] Abstract—The thermal and rheological A. Objective and Scope behaviors of asphalt binder modified with natural The aim of the present work is to improve the fibers and antioxidants obtained from the Amazon rheological characteristics (complex modulus, phase rain forest are analyzed through angle and viscosity) of the asphalt binder AC 50/70, Thermogravimetry (TG), Differential Scanning modifying it with raw materials from the Ama-zon Calorimetry (DSC) and Dynamical Shear biodiversity, with the perspective of sustainable use of Rheometer (DSR) tests. The addition of modifiers natural resources. The mechanical properties of AC alters considerably the physical and rheological 50/70 modified with those materials were compared properties of the modified binders. The main with those of pure AC 50/70 and that modified with results are: a good thermal stability and styrene-butadiene-styrene (SBS) copolymer. miscibility with asphalt cement (AC), significant increase of G* at low frequencies, decrease of As one of the natural modifier material we used and increase of the viscosity. The results are natural fiber obtained from the shell of a fruit compared with that of asphalt binder modified popularly known as Cutia-Chesnut (Couepia Edulis - with SBS polymer. Prance), with fibrous characteristics, found in the western Amazon (Figure 1). Its shell has high level of Keywords — Asphalt binder; SBS copolymer; lignin, a polymer of aromatic nature with high cutia-chesnut fiber; ucuúba fat; rheology molecular weight, with great potential for use as I. INTRODUCTION asphalt binder modifier. The lignin behaves as an asphalt antioxidant and gives to the asphalt binder Asphalt cements has been used successfully in large compressive strength [30]. Its capability as an highways and airport pavements worldwide due to asphalt oxidant comes from their phenolic structures their viscoelastic and adhesion properties [1]. In order (benzene rings with attached hydroxyl groups), which to improve the mechanical properties of these has the ability to neutralize the free radicals contained materials, modifiers such as polymers [2-4] including on oxygen [31], by donating either a proton (positive plastics, elastomers, extenders, antioxidants and hydrogen ions H+, which technically is just a proton) fibers [5-9] are under intense investigation. The or an electron [32]. asphalt modification by polymers improves their mechanical properties, as for example, the reduction of the thermal susceptibility, the permanent deformation and the enhancement of the resistance to cracking at low temperatures [10,11]. Particularly, the addition of antioxidant and fiber minimize the negative effects of oxidation and act as reinforcement and prevent the yielding, respectively [12]. It has been observed that fibers improve the Fig. 1. (a) Cross-section of the Cutia-Chesnut (Couepia rheological characteristics of asphalt: the creep Edulis - Prance) shell; (b) Fiber obtained from the Cutia- compliance and rutting resistance [13,14]; the low- Chesnut shell. temperature anti-cracking properties, fatigue life, and Additionally we used a second natural modifier durability of AC mixtures [15-17]; dynamic modulus material as an antioxidant to minimize the negative [20] and elasticity [21]. Since 1960 different effects of the oxidative aging, which causes the approaches have been used to incorporate crumb asphalt to become hardened and brittle. The additive rubber modifier (CRM) in road paving materials. After is a fat that was extracted from the ucuúba (Virola seminal research works by [22], Bahia and Davies Surinamensis) fruit almond, a natural species from the [23,24], the application of CRM to improve the Amazon forest (Figure 2). The addition of ucuúba fat rheological characteristics of the asphalt pavement yields a mixture which is more homogeneous, without has attracted a lot of interest of the scientific segregation of the Cutia-Chesnut fibers. community worldwide [24-29]. www.jmest.org JMESTN42352424 8332 Journal of Multidisciplinary Engineering Science and Technology (JMEST) ISSN: 2458-9403 Vol. 4 Issue 10, October - 2017 the almond by pressing. Then the shells were triturated using a knife mill. Finally, the granularity of the triturated material was set to values near those of SBS polymer, separating the material retained on the sieve # 0.297 mm, whose particle size distribution is shown in Figure 3. Their dry and natural densities in g/cm3 are 1.100 and 1.200, respectively. The composition by mass of CEF (cellulose, lignin, extractive-free, humidity, ashes and silica) are presented in Table 2. Fig. 2. Fat extracted from ucuúba (Virola surinamensis). II. MATERIALS AND METHODS The materials used in the present study are the following: the asphalt binder AC 50/70, the SBS copolymer, a natural fiber of Cutia-Chesnut (Couepia Edulis - Prance) (CEF) and a fat extracted from ucuúba (Virola Surinamensis) (UF). We analysed the Fig. 3. Grain size curve for SBS and CEF. rheological properties of four mixtures of asphalt binder AC with SBS, CEF and UF, named as ACSBS, TABLE II. COMPOSITION OF CUTIA-CHESNUT (CEF) FIBER MS3.0, MS2.5 and MS2.0, whose proportions by CEF Composition % (mass) mass are presented in subsection II.E. Cellulose 56.78 ± 0.1 A. The Asphalt Binder Lignin 33.26 ± 0.2 Extractive-Free 6.24 ± 0.4 The asphalt binder AC 50/70 was obtained from Humidity 10.30 ± 0.3 the Brazilian oils Campo Fazenda Alegre and Ceara- Ashes 0.87 ± 0.01 Mar, presenting the following physical properties: a) o Silica 0.15 ± 0.02 Penetration 58.0 (100g, 5s, 25 C, 0.1 mm - ASTM o D5); b) Fire and Flash Point 300 C (ASTM D92); c) Softening Point 49:8 oC (ASTM D36). D. Ucuúba (Virola Surinamensis) Fat (UF) B. SBS Copolymer The ucuúba fat, used as a binder extender agent, As a polymeric material we used the styrene- was extracted by mechanical pressing of the almond butadiene-styrene (SBS) copolymer (34% stirene and fruit of Virola Surinamensis, whose physicochemical 66% butadiene). The rheological properties of the characteristics are presented in Table 3 [34]. asphalt binder modified with natural fibers and oxidants will be compared with those of SBS. This TABLE III. PHYSICOCHEMICAL CHARACTERISTICS OF UCUÚBA FAT. copolymer is classically used as an AC modifier, Ucuúba Fat(UF) Gross whose elastomeric characteristic and thermoplastic Acid index (mg KOH/g oil) 32.60.3 behavior enhance the resistance of the mixture to Saponification index (mg KOH/g oil) permanent deformations. The SBS copolymer 259.60.4 molecular weight are presented in Table 1 [33]. P eroxide index (meq/kg oil) 8.60.1 Io dine index (g I2/100 g sample) 0.790.09 Unsa ponication (%) 3.00.2 3 TABLE I. CHARACTERISTIC OF SBS COPOLYMER Densi ty(g/cm ) 0.930.02 Numerical molar mass (Mn) 1.1 x 105 Weight molar mass (Mw) 1.4 x 102 E. Modified Asphalt Binder (AC 50/70)) Average molar mass (Mz) 1.7 x 102 The asphalt binder AC 50/70 was mixed with the Polydispersion 1.3 SBS polymer, Cutia- Chesnutfiber and ucuúba fat using a mechanical mixer model Fisato 647. In Table C. Cutia-Chesnut (Couepia Edulis - Prance) 4 we present the modifier levels for three modified Fiber (CEF) samples (MS), which are called MS3.0, MS2.5 and MS2.0. The cutia-chesnut is originally from Amazon forest. In order to obtain the fiber of its nut the following steps were performed. Initially the shell was separated from www.jmest.org JMESTN42352424 8333 Journal of Multidisciplinary Engineering Science and Technology (JMEST) ISSN: 2458-9403 Vol. 4 Issue 10, October - 2017 TABLE IV. LEVELS OF SBS POLYMER, CUTIA-CHESNUT FIBER content represents approximately 4.2% of the initial AND UCUÚBA FAT IN THE MODIFIED ASPHALT BINDER AC 50/70. mass. Sample SBS (%) CEF(%) UF(%) The CEF thermogravimetric curve presents three o ACSBS 5.0 0.0 0.0 decomposition events. Until the temperature of 100 C there is a mass reduction of approximately 10%, as is MS2.0 2.0 3.0 1.0 MS2.5 2.5 2.5 1.0 shown by the left arrow in Figure 4. This mass MS3.0 3.0 2.0 1.0 reduction, which occurs at the boiling-water temperature, is attributed to the loss of moisture of the vegetable fibers (dehydration intramolecular and In the preparation of the mixtures the binder was intermolecular reactions). The moisture content of heated to facilitate the addition of the modifiers, and 103 % for natural CEF exhibited in Table II then it was transferred to the mixer. The materials corroborates this assertion. As there is no water previously homogenized were subjected to an angular content in SBS at room temperature, this event is velocity of 560 rpm for 2 hours at a temperature of absent in the SBS thermogravimetric curves. A 1605 oC. pronounced mass reduction of 43% occurs above 255 oC, due to the decomposition of hemicelluloses and F. Thermal Analysis the breaking of the chemical bonds of the cellulose. o The thermogravimetric curves for the SBS The last step occurs above 375 C due to the copolymer, Cutia-Chesnut fiber, ucuúba fat and for the decomposition of the final cellulose and lignin, with asphalt binder samples, pure (AC 50/70) and modified final waste content being equal to 20% of the initial (MS3.0, MS2.5 and MS2.0), were obtained according mass. The thermal behavior displayed by the CEF to ASTM-E537, using the equipment DTG 60H from fibers is similar to that of the main natural fibers used Shimadzu Corporation, under an air flux of 50 ml/min.
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