Accepted Manuscript

Composite Modification Mechanism of Blended Bio-asphalt Combining Styrene-

Butadiene-Styrene with Crumb Rubber: A Sustainable and Environmental-friendly
Solution for Wastes

Ze-jiao Dong, Tao Zhou, Hai Luan, R. Christopher Williams, Peng Wang, Zhen Leng

PII: S0959-6526(19)30004-6

DOI: 10.1016/j.jclepro.2019.01.004

Reference: JCLP 15391

To appear in: Journal of Cleaner Production

Received Date: 30 August 2018

Accepted Date: 01 January 2019

Please cite this article as: Ze-jiao Dong, Tao Zhou, Hai Luan, R. Christopher Williams, Peng Wang,
Zhen Leng, Composite Modification Mechanism of Blended Bio-asphalt Combining Styrene-
Butadiene-Styrene with Crumb Rubber: A Sustainable and Environmental-friendly Solution for
Wastes, Journal of Cleaner Production (2019), doi: 10.1016/j.jclepro.2019.01.004

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 ACCEPTED MANUSCRIPT

Composite Modification Mechanism of Blended Bio-asphalt Combining Styrene-

Butadiene-Styrene with Crumb Rubber: A Sustainable and Environmental-
friendly Solution for Wastes
Ze-jiao Donga,*, Tao Zhoua, Hai Luanb, R. Christopher Williamsc, Peng Wangd, Zhen Lenge

a School of Transportation Science and Engineering, Harbin Institute of Technology, Harbin 150090, P. R. China
b Department of Road Engineering, Jilin Provincial Transportation Planning and Design Institute, Changchun
130021, P. R. China
c Department of Civil, Construction and Environmental Engineering, Iowa State University, Ames, IA 50011,
USA
d School of Transportation Engineering, Shandong Jianzhu University, Jinan 250101, P. R. China
e Department of Civil and Environment Engineering, Hong Kong Polytechnic University, Hong Kong, P. R. China
* Corresponding author: +86 158-4653-3166, hitdzj@hit.edu.cn (Ze-jiao Dong)

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1 Abstract

2 Using bio-asphalt from bio-waste to replace petroleum-based asphalt could decrease the

3 dependence on petroleum and shift toward more environmental-friendly and sustainable

4 development of pavement. This study investigates the composite modification mechanism of

5 blended bio-asphalt (BBA) combining styrene-butadiene-styrene (SBS) with crumb rubber (CR)

6 through a comprehensive procedure. Chemical characteristics proposed by Fourier-transform

7 infrared (FTIR) spectroscopy and gel permeation chromatography (GPC) show that the

8 blending and modification was a physical process. Morphological features conducted by atomic

9 force microscopy (AFM) and fluorescence microscopy (FM) indicate that the bio-asphalt could

10 promote the swelling and homogeneous distribution of the polymers, and thus strengthens the

11 polymer’s cross-linked network. Rheological properties implemented by multiple stress creep

12 and recovery (MSCR), bending beam rheometer (BBR) and frequency sweep (FS) tests indicate

13 that composite modification could enhance both the high and low-temperature performance of

14 the BBA. Moreover, the Han curves illustrate that the compatibility between the asphalt and

15 polymers was improved by the bio-asphalt addition. Furthermore, performances of modified

16 asphalt processing on industry-scale are superior to that in the laboratory due to the high-

17 effective equipment. In summary, the composite modification not only enhances the

18 comprehensive performances of the BBA, but also makes it possible to reuse bio-waste and

19 scrap tire.

20 Keywords: Bio-asphalt; Composite modification mechanism; Styrene-Butadiene-Styrene;

21 Crumb rubber; Rheology; Morphology.

22 1. Introduction

23 With the rapid and large-scale construction and maintenance of highway and airfield

24 pavements, the demand for asphalt binder has increased sharply over the past several years.

25 However, conventional asphalt binder is derived from the crude oil refining process which is

26 non-renewable. Hence, seeking substitutes for petroleum-based asphalt to decrease the strong

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1 dependence of petroleum adhesives, conserve the shrinking stock of fossil fuel, and reduce the

2 cost of pavement construction is desirable. Thus moving pavement engineering away from

3 petroleum-based economy, shifting the former toward more environment-friendly and energy-

4 efficient, and achieving sustainable and cleaner development in pavement engineering has

5 brought increased attention.

6 As a promising and potential substitute for petroleum-based asphalt, bio-asphalt which could

7 be derived from the sustainable bio-waste, such as the bio-oil of bio-mass thermochemical

8 liquefaction (TCL), also called pyrolysis (Yang and Suciptan, 2016; Dhasmana et al., 2015),

9 by-products from agricultural crops processing (Uzun et al., 2010; Jalkh et al., 2016), or

10 residues from the oil industry (Sun et al., 2017; Wen et al., 2013), could replace conventional

11 asphalt partially or even fully by utilizing the former as a modifier, extender, or alternative

12 substitution (Raouf and Williams, 2010). Previous studies of chemical analysis indicated that

13 the elemental distribution, functional groups, typical compositions of bio-asphalt had some

14 similarities with petroleum-based asphalt (Mullen and Boateng, 2008; Fini et al., 2011; Yang

15 et al., 2017). Adding bio-asphalt into base asphalts could modify the temperature susceptibility

16 (Dong et al., 2018; Zargar et al., 2012) as well as decrease the viscosity of the binder (Sun and

17 Zhou, 2018; Mills-Beale et al., 2014), which may have an adverse impact on the rutting

18 resistance and cause inappropriate permanent deformation of the pavement under traffic loading.

19 However, Yang et al. (2013) indicated that bio-oil made from waste wood could enhance the

20 high-temperature performance of the binder with the higher rutting resistance factor (G*/sinδ)

21 while decrease the low-temperature performance with the higher stiffness (S) and lower m-

22 value. Research conducted by Mills-Beale et al. (2014) pointed out that the addition of bio-

23 binder from swine manure leads to lower phase angle (δ) and complex modulus (G*) compared

24 with the PG 64-22, and showed improved rutting and thermal cracking resistance of asphalt

25 binders and mixtures. In addition, Dhasmana et al. (2015) illustrated that the bio-binder behaved

26 like a Newtonian material (lower modulus) before aging and behaved like solid elastic material

27 (higher modulus) after aging, also, the bio-binder obtained from algae feedstocks was relatively

28 harder than that derived from swine manure. Moreover, Chen et al. (2014) found that waste

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1 edible vegetable oil could effectively rejuvenate aged asphalt by increasing the rutting

2 resistance factor, phase angle, complex modulus and creep recovery to the virgin level, also

3 improving the fatigue life of the binder and decreasing the fatigue cracking of mixture.

4 Similarly, environmental problem caused by scrap tires from auto industry is another

5 challenge around the world. Researches have proved that using crumb rubber (CR) from scrap

6 tires to improve the ultimate pavement performance of the asphalt binder is effective and

7 environmental-friendly (Wang et al., 2017; Oliveira et al., 2013). Meanwhile, the environment

8 concerns of waste tires in landfills also could be reduced (Yu et al., 2017). However, due to the

9 higher viscosity, the production of rubberized asphalt needs a complex modification process

10 with high temperature, as well as in mixing and compaction of asphalt mixture during the

11 pavement construction, that may result in energy waste and more greenhouse gas (GHG)

12 emission compared with more normal asphalt mixtures (Wen et al., 2018; Katman et al., 2015),

13 that undesirable consequence may decrease by the combined utilization of bio-oil materials

14 considering their lower viscosity generally, meanwhile, the performance of the bio-oil also

15 could be improved. This kind of work has been conducted by Peralta et al. (2013; 2014), related

16 results showed that using the crumb rubber from different manufacturing methods (cryogenic

17 and ambient) to modify the bio-oil from wood fast pyrolysis directly could obtain a binder, it

18 performs as well or even better than petroleum-based asphalt binder. Furthermore, styrene-

19 butadiene-styrene (SBS) conjugated copolymer is a commonly used polymer modifier to

20 enhance the performance of asphalt and has shown noticeable benefits (Tayfur et al., 2007;

21 Wen et al., 2002), which also was used for composite modification of base asphalt combining

22 with crumb rubber to update the pavement performance grade, thus meeting the requirement of

23 the high-grade pavements (Xiang et al., 2010; Zhang and Hu, 2017).

24 Through the current literature review related to bio-asphalt, it could be concluded that the

25 research topics mainly focus on the chemical characteristics of the original bio-asphalt, physical

26 and rheological properties of the blended bio-asphalt by simply physical mixing with base

27 asphalt. In other words, the previous studies usually concentrated on the performance

28 evaluation rather than the performance improvement. Remember that the effects of different

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1 sourced or processed bio-asphalts when blended with an asphalt binder might vary greatly. The

2 inherent limitations of original bio-asphalt and the performance degradation of binder caused

3 by the addition of bio-asphalt, which prevent the application of the bio-asphalt from the

4 laboratory to pavement construction. Although there is handful research to address these issues

5 by modification approach, e.g., adding crumb rubber, it is still far from being using as the high-

6 performance binder that could meet the requirement of the high-grade pavement. Therefore,

7 composite modification of blended bio-asphalt combining styrene-butadiene-styrene with

8 crumb rubber may not only enhance the comprehensive performance of bio-asphalt, but also

9 could improve the workability of the rubberized asphalt. Meanwhile, the problem of waste

10 management is addressed, and the sustainable and cleaner development of pavement

11 engineering was achieved by introducing the renewable and environment-friendly bio-asphalt

12 and crumb rubber, thus increasing the efficiencies in the uses of resources and realizing the

13 economic, social and environmental benefits.

14 This research was conducted to investigate and reveal the composite modification

15 mechanism of blended bio-asphalt with SBS and CR by analyzing its chemical characteristics

16 (Fourier-transform infrared spectroscopy and gel permeation chromatography), morphological

17 features (atomic force microscopy and fluorescence microscopy) and rheological properties

18 (dynamic shear rheometer and bending beam rheometer) through laboratory tests, thus

19 promoting application of bio-asphalt in high-grade pavements.

20 2. Materials and Methods

21 2.1. Materials

22 This study selected a conventional PEN 90 asphalt from Panjindali Petrochemical Company

23 (Panjin, Liaoning, China) as the petroleum-based asphalt (PEN 90), and the original bio-asphalt

24 (OB) is the residue of pressing castor oil after refining fatty acids from castor, which was

25 dehydrated before use as the binder, Fig. 1 shows the processing technologies for OB. The

26 fundamental properties of PEN 90 and OB are given in Table 1. The linear Styrene-butadiene-

27 styrene (SBS) conjugated copolymer of YH-791H from SINOPEC Baling Petrochemical

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1 Branch (Yueyang, Hunan, China) with the styrene content of 30%, and crumb rubber (CR) from

2 waste radical tire by ambient mechanical-shredding with a particle size of 40 mesh or less were

3 introduced as the modifiers of the asphalt binder. Table 2 presents the physical properties and

4 chemical compositions of the crumb rubber.

5 2.2. Modification and processing technology of binders

6 The PEN 90 blended with OB was done first to produce the blended bio-asphalt (BBA). Then,

7 the BBA was modified by SBS or CR solely (BBA+SBS or BBA+CR), or SBS and CR in

8 combination (BBA+SBS+CR), thus producing the modified blended bio-asphalt. Meanwhile,

9 the PEN 90 also was modified by SBS and CR solely or in combination (PEN 90+SBS, PEN

10 90+CR or PEN 90+SBS+CR) as the control group. The contents of OB, SBS and CR were

11 15%, 2.5% and 18% wt, respectively, which was determined from the results of previous studies

12 to ensure the modified asphalt had the best performance. The modification process could be

13 divided into three phases: (a) swelling phase, polymers swelled by absorbing the light

14 components in asphalt; (b) grinding shear phase, swelled polymers were sheared into fine

15 particles; (c) development phase, the mix of asphalt and polymers were stirred on low speed at

16 to facilitate the formation of cross-linked polymer network structure, which also known as

17 breeding phase. The blending and modification processes were implemented by employing a

18 low-speed mixer (using for swelling and development) of BME-100L (Weikang Machinery

19 Manufacturing Company, Shanghai, China) and a high-speed mechanical shearing equipment

20 (using for blending and grinding shear) of Ross-100L (Charles Ross & Son Company, New

21 York, USA). The control parameters (e.g., temperature, mixing speed and time) during a

22 completed blending and modification processes, and some necessary details are presented in

23 Fig. 2 (a). These parameters were determined to ensure enough flowability of the binder and

24 swelling of the polymer modifiers. The processing technology of the modified asphalt samples

25 were same whether modified solely or in combination. Furthermore, the composite modified

26 blended bio-asphalt, i.e., BBA+SBS+CR, was processed on industrial-scale (CMBBA) at a

27 modified asphalt processing plant with a purpose of verifying this modification technology on

28 the practical engineering application. In this process, the blending between the base asphalt and

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1 bio-asphalt, and the shearing of the polymers (CR and SBS) were implemented by a three-stage

2 high-speed shearing machine, the swelling of the polymers and development of the modified

3 asphalt were implemented in the swelling and development tank, respectively, which associated

4 with several sets of stirring blades. The control parameters on industrial-scale and in the lab are

5 same, the equipment diagram used on industrial-scale is presented in Fig. 2 (b).

6 In order to differentiate the asphalt binders used in this research, the labels of binders that

7 will be referred to hereafter as well as their definition and description were given in Table 3.

8 2.3. Experimental procedures

9 2.3.1 Chemical analysis

10 Fourier-Transform Infrared Spectroscopy (FTIR) Fourier-transform infrared spectroscopy

11 was employed herein to determine the functional groups, thus analyzing the chemical

12 composition of the asphalt binders. Because of the high viscosity of the binders as compared

13 with the standard liquid, the asphalt samples were smeared to be a film to meet the test

14 requirement. The test procedure was conducted by Thermo Scientific Nicolet iS 5 (Thermo

15 Fisher Scientific, Waltham, Massachusetts, USA) with the scan frequency of 32 times/min

16 under the wave numbers from 4000 cm-1 to 500 cm-1.

17 Gel Permeation Chromatography (GPC) The molecular size or weight of materials are

18 closely related to their chemical characteristics. Gel permeation chromatography is a practical

19 way to determine the molecular size distribution of the materials. Herein, Waters 1515 gel

20 filtration chromatography (Waters Corporation, Milford, Massachusetts, USA) with a

21 differential refractive index (RI) detector was used to measure the molecular weight. The

22 particle size of the chromatographic column is 5 µm with porosity of 10 Å. Polystyrene (PS)

23 was chosen as the reference material and tetrahydrofuran (THF) was selected as the mobile

24 phase at a flow rate of 1 ml/min. The test was completed at 30°C with a column pressure of 329

25 PSI.

26 2.3.2 Morphological analysis

27 Atomic Force Microscopy (AFM) Atomic force microscopy was widely utilized to study the

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1 morphological characteristics of modified asphalts by analyzing the difference of the

2 topography at the micro-scale. This study proposed the AFM of Dimension FastScan from

3 Bruker (Bruker Corporation, Billerica, Massachusetts, USA) to investigate the morphology of

4 the binders under ambient conditions at room temperature by applying a silicon nitride probe

5 in tapping mode. The asphalt samples of AFM were prepared by a heat-casting method, i.e., the

6 binders were heated to approximately 160°C for a better flow, then cast into glass slides to form

7 films. These analyses followed the Dimension FastScan User Guide.

8 Fluorescence Microscopy (FM) The improved swelling between the asphalt and polymer

9 could would likely result in the polymer modified binder (PMB) having improved performance.

10 Fluorescence microscopy is commonly used to investigate the swelling property of the PMB

11 because of the different fluorescence of asphalt and polymer. In this research, the DVM5000

12 HD fluorescence microscopy from Leica Microsystems (Buffalo Grove, Illinois, USA) was

13 used to analyze the micromorphology of the binder. To prepare the samples, the hot asphalt

14 binders (approximately 160°C) were cast into glass slides first and then moved into an oven at

15 160°C for five minutes. Finally, the samples were naturally cooled down to room temperature.

16 2.3.3 Rheological analysis

17 Multiple Stress Creep and Recovery Test (MSCR) The Multiple stress creep and recovery

18 test was developed based on the creep and recovery concept, which was used to determine the

19 percent recovery (R) and non-recoverable creep compliance (Jnr) of asphalt binders, and is used

20 to evaluate the permanent deformation resistance under repeated loading. 0.1 kPa and 3.2 kPa

21 were chosen as the constant creep stress to load the specimen of one second and followed with

22 a zero-stress recovery of nine seconds for a total of ten cycles. The MSCR test procedure

23 followed ASTM D7405-15 by a DHR-2 Dynamic Shear Rheometer (DSR) manufactured by

24 TA Instruments (New Castle, Delaware, USA) at 60°C.

25 Frequency Sweep Test (FS) The frequency sweep conducted with a DSR to measure the

26 complex modulus (G*), storage modulus (G’) and loss modulus (G’’) at different temperatures

27 and frequencies, and these data could be used to evaluate the rheological properties of the

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1 asphalt binder. The frequencies were chosen from 0.1 Hz to 30 Hz with the temperature ranging

2 from 6°C to 80°C. The geometries of parallel-plate with 2 mm thickness and 8 mm diameter

3 was selected for intermediate temperatures (6°C, 20°C and 35°C), and 1 mm in thickness with

4 a 25 mm diameter was selected for high temperatures (50°C, 65°C and 80°C). The strain sweep

5 tests were conducted first to obtain the linear viscoelastic (LVE) region for each kind of binder

6 at selected testing temperatures at a frequency of 1.6 Hz (10 rad/s) by referring to the Superpave

7 specification (Anderson et al., 1994), the LVE strain limit was established as the strain at which

8 the modulus decreased to 95 percent of its initial value. Then, the frequency sweep test under

9 controlled strain loading mode was conducted at strains that were in 50 percent of LVE limit.

10 All the tests were carried out by using a DHR-2 Rheometer and following the ASTM D7175-

11 15.

12 Bending Beam Rheometer Test (BBR) Bending beam rheometer testing was carried out to

13 evaluate the low-temperature performance of the asphalt binders before and after Pressure

14 Ageing Vessel (PAV) condition by measuring the creep stiffness (S) and m-value. The PAV

15 was implemented by using Model 82A Thin Film Oven Test (TFOT) System from Wuxi

16 Petroleum Instrument Co., LTD. (Wuxi, Jiangsu, China) and Prentex Model 9300 PAV System

17 from Alloy Fabricators, Inc. (Dallas, Texas, USA) with the conditions of 100°C, 2.1 MPa, 20

18 h in accordance with ASTM D6521-18 The BBR test was conducted by using the TE-BBR

19 from Cannon Instrument (State College, Pennsylvania, USA) at -12°C, -18°C and -24°C. The

20 preparation of specimens and testing procedure followed ASTM D6648-16.

21 A flowchart presented in Fig. 3 is used to illustrate the experimental procedures in this

22 research.

23 3. Results and Discussion

24 3.1 Chemical characteristics

25 3.1.1 Functional groups analysis by FTIR

26 Functional groups are responsible for the characteristic of the materials in the chemical

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1 reaction, which can be determined by infrared absorption under special wave number ranges

2 using an infrared spectrometer. Analyzing and comparing the functional groups of the asphalt

3 binders before and after modification can assist on determining whether some chemical

4 reactions occurred during the composite modification, or the composite modification was just

5 a physical process. Fig. 4 shows the FTIR spectrum of asphalt samples. Generally, the middle

6 infrared region (wave numbers range from 4000 cm-1 to 400 cm-1) was usually split into

7 functional group region (FGR, wave numbers range from 4000 cm-1 to 1330 cm-1) and

8 fingerprint region (FPR, wave numbers range from 1330 cm-1 to 400 cm-1) (Weng and Xu,

9 2016). The functional group region is used to identity the functional groups thus to determine

10 the structure in the material. However, the fingerprint region is difficult to interpret because the

11 bands in this region are different for each molecule with many absorptions which present the

12 infrared characteristics of compounds, similar to the fingerprints of the humans. As shown in

13 Fig. 4 (a), the binders before and after adding bio-asphalt or modification had a similar spectrum

14 in the FTIR test. In the functional group region, the strong absorption peaks located at 2930

15 cm-1 and 2857 cm-1 are attributed to the ─CH2 and ─CH3 stretching vibrations in Alkanes, the

16 absorption peak located at 1720 cm-1 is the C═O stretching vibrations in Aldehydes and

17 Ketones, at 1613 cm-1 is the C═C stretching vibrations in Aromatics, at 1464 cm-1 and 1378

18 cm-1 are the ─CH3 deformation vibrations in Alkanes. In the fingerprint region, 1032 cm-1 is

19 the S═O stretching vibrations in Sulfoxides, 966 cm-1 is the C═C bending in SBS (Fig. 4 (b))

20 and ─C─H bending vibrations in Aromatics are observed from 900 cm-1 to 700 cm-1. It is

21 obvious that there is no new absorption peak occurring in the functional group or fingerprint

22 region during the blending and modification process. Hence, it was deduced that the

23 modification of the asphalt binder was a physical process, and the modifiers of SBS and CR

24 were sheared and grinded to be fine enough and separated in the base asphalt homogeneously.

25 This means the processing technology is key to the performance of the modified asphalt.

26 Furthermore, the absorption peaks near 720 cm-1 in the binders containing bio-asphalt move to

27 the higher wave number region as compared with the binders without the bio-asphalt (Fig. 4

28 (c)). Considering the absorption peak of -(CH2)n located at 724 cm-1 to 722 cm-1 while n is

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1 greater than 4, and the smaller n, the farther movement of the peak to the higher wave number

2 (Weng and Xu, 2016), This means the alkanes with branched long-chain molecules in bio-

3 asphalt are shorter than those in the base asphalt, which has been shown in previous research

4 (Dong et al., 2018), and is in good agreement with the GPC analysis.

5 3.1.2 Molecular size distribution by GPC

6 Generally, three different statistical average molecular weights, e.g., number-average
7 molecular weight (Mn), weight-average molecular weight (Mw) and Z-average molecular weight
8 (Mz) were calculated to study the properties of the materials. As defined in Equation (1) to
9 Equation (3).
10
11 (1)
Mn 
 N M  W
i i i

N N i i

12 (2)
Mw 
N M i i
2


W M i i

N M i i W i

13 (3)
Mz 
N M
i i
3


W M i i
2

N M
i i
2
W M i i

14 where Ni is the mole number of molecules with molecular weight of Mi, Wi is the weight of
15 molecules having molecular weight Mi.
16
17 Fig. 5 and Table 4 presented the GPC chromatogram and molecular size distribution of the
18 asphalt samples. Jennings et al. (1982) portioned chromatogram is separated into three groups
19 by elution time: large molecular size (LMS), medium molecular size (MMS) and small
20 molecular size (SMS). As for the unmodified asphalts (PEN 90, BBA and OB), there were two
21 peaks (Fig. 5 (a)) that occurred in the GPC chromatogram (except the OB) which tends to the
22 SMS, and the corresponding molecular weights also have two values (Table 4). It could be
23 observed that the molecular size of the OB was obviously lower than that of the PEN 90, thus
24 the molecular size of the blend (BBA) also was reduced. After modification (Fig. 5 (b)), there
25 were three peaks in the GPC chromatogram from left to right (except BBA+CR), which
26 corresponded to the polymer modifier, primarily asphaltenes and primarily maltenes,
27 respectively (Ruan et al., 2003). As the polymer modifier of SBS has a higher molecular weight
28 as compared with the base asphalt, its Mw is in the range of 1,000,000 to 19,000 Das, while the
29 typical petroleum-based asphalt has a molecular weight ranging from 19,000 to 200 Das (based

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1 on the polystyrene molecular weights) (Daly et al., 2013; Gao et al., 2013). Combining the
2 molecular size distribution in Table 4, these differences in GPC chromatogram and molecular
3 weight (peak Ⅰ in Fig. 5 (b) and Table 4) make it easy to identify the SBS in the modified
4 asphalt. However, since the BBA+CR did not contain the SBS polymer, hence, the LMS peak
5 did not occur in its chromatogram. In addition, as some of the rubber particles were filtered out
6 by the syringe filter before injection during the GPC test and partial degradation of the rubber
7 particles which had been released in the asphalt, the chromatogram of CR modified asphalts
8 (BBA+CR, PEN 90+SBS+CR, BBA+SBS+CR and CMBBA) were similar in the MMS and
9 SMS regions (peak Ⅱ and Ⅲ in Fig. 5 (b)), this result also was consistent with their molecular
10 size distribution in Table 4 and has been shown in prior research (Baek et al., 2009; Lin et al.,
11 2017). Furthermore, it also could be deduced that the bio-asphalt was beneficial to the swelling
12 of the polymer modifier by comparing the Mw and Mz of PEN 90+SBS+CR, BBA+SBS+CR
13 and CMBBA, based on the truth that the Mw and Mz was largely determined by the number of
14 the large molecular which could be concluded from the definition of the statistical average
15 molecular weight by Equations (2) and (3).

16 3.2. Morphological features

17 3.2.1 Homogeneity by AFM

18 The microphotographs captured by the AFM is presented in Fig. 6. The scanning area of

19 panel (a) to (f), and (g) to (i) is 30 μm×30 μm and 10 μm×10 μm, respectively. It is observed

20 that a small number of bee-like structures appeared in the PEN 90, as seen in panel (a), which

21 is usually believed to be related to the content of wax and asphaltene of asphalt, also to the

22 interaction between the former and other components of asphalt (Pauli et al., 2011; Lyne et al.,

23 2013). After adding bio-asphalt into the base asphalt (panel (b)), the number of the bee-like

24 structures decreased, together with the sharp size reduction, this is because the dilution effect

25 caused by the light components of the bio-asphalt. If one compares panel (c) with panel (d), and

26 panel (e) with panel (f), it is concluded that the bio-asphalt could swell the polymers of SBS

27 and CR, which is displayed by the size increase of the SBS as well as the uniform distribution

28 of the different particle size (panel (d)), at the same time, the network in the CR modified asphalt

29 became denser after adding bio-asphalt (panel (f)). Another noteworthy phenomenon is the

30 Nano topography decreases when joining the two polymers together (CR and SBS) comparing

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1 to the addition of single polymer (CR or SBS), which attributes to the preparation process of

2 the binder samples. As we presented in the Fig. 2 (a), the polymer (CR or SBS) need to be

3 grinded and sheared only one time while the asphalt binder was modified solely, and two times

4 while the asphalt binder was composite modified. The longer that the grinding and shearing

5 time continues, the finer that the polymer particle was, naturally, the Nano topography

6 decreases when combining the CR and SBS together. In addition, the network in the composite

7 modified asphalt using BBA as the base asphalt was more compact than that using PEN 90 as

8 the base asphalt (panel (g) and (h)), and the composite modified asphalt processing in the

9 asphalt factory (panel (i)) had a homogeneous and dense topography than that processing in

10 laboratory (panel (h)), again, there was some heterogeneous areas that existed in the latter,

11 which indicated that the strength and effect of shearing and grinding in the laboratory were not

12 as good as at the industrial-scale.

13 3.2.2 Swelling property by FM

14 Fig. 7 presented the fluorescence micrographs of asphalts samples with the continuous phase

15 of the asphalt and the dispersed phase of the polymer. Since the PEN 90 and the BBA had no

16 fluorescence (panel (a) and (b)) while the polymer of SBS and CR had a fluorescence (panel

17 (c) to (i)), thus the spots emerged under the irradiation of the light source and can be used to

18 distinguish the distribution and the particle size of the polymers. From panel (c) and (d), it is

19 observed that bio-asphalt had a significant improvement on the swelling property of the SBS

20 with the larger size and uniform distribution of the polymer. In addition, the size of the dispersed

21 phase in the PEN 90+CR was much larger than that in the PEN 90+SBS. Meanwhile, the size

22 of dispersed phase in CR modified asphalt was less effected by the bio-asphalt, but the number

23 of the swelling polymer had a slight increase by comparing panel (e) with (f). Moreover, the

24 area of the dispersed phase in the composite modified asphalt containing bio-asphalt was larger

25 with different size of particles, at the same time, the small particles filled and embed in the gaps

26 of large particles (panel (h)). In addition, the dispersed phase in the CMBBA was more well-

27 distributed and with higher dispersity, which could be attributed to the high-effective equipment

28 used in the modified asphalt processing plant, the polymer modifiers were swelled enough due

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1 to the sufficient contact between the asphalt and polymers by the constant stirring with several

2 sets of blades, and the three-stage high-speed shearing machine makes the swelled polymers

3 cut into the finer particles more easily. The conclusions from the FM were consistent with the

4 results of the AFM.

5 3.3. Rheological Properties

6 3.3.1 Permanent deformation resistance by MSCR

7 The MSCR test (creep and recovery) results are shown in Fig. 8 with the corresponding non-

8 recoverable compliance (Jnr) and recovery (R) of binders were given in Fig. 9. It is observed

9 that the accumulated strain of unmodified and solely modified asphalt samples (Fig. 8 (a) and

10 (c)) were higher than that of the composite modified asphalt samples (Fig. 8 (b) and (d)).

11 Considering the results in Fig. 9, it could be noted that the addition of bio-asphalt could increase

12 the accumulated strain of the binder noticeably, at the same time, the Jnr was increased, and R

13 was decreased. This is because the addition of the bio-asphalt with low-molecular weight

14 components corresponds to an increase in the maltenes content of the binder, which lead to a

15 degradation of high-temperature performance due to the lower viscosity, this conclusion also

16 could be proved by the comparison among the solely modified asphalts (PEN 90+SBS vs

17 BBA+SBS, or PEN 90+CR vs BBA+CR). As for the solely modified asphalts, the BBA+CR

18 had a lower Jnr and higher R, also, the corresponding accumulated strain was lower than that of

19 the BBA+SBS. The reason for the differences is that the content and particle size of CR were

20 larger than that of the SBS, the particles were packed between each other and increased the

21 viscosity thus to enhancing the capability for the deformation of the binder system. Comparing

22 PEN 90+SBS+CR with BBA+SBS+CR, the composite modified asphalt had little difference in

23 the Jnr and R values between using PEN 90 as the base asphalt and using BBA as the base

24 asphalt. However, the R of the CMBBA was far greater than that of the BBA+SBS+CR, and

25 also had the lowest Jnr. In conclusion, the high-temperature performance of composite modified

26 asphalt was favorable.

27 3.3.2 Low-temperature cracking resistance by BBR

28 The stress relaxation capability of the binder is related to the low-temperature cracking

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1 resistance of the asphalt pavement, which was evaluated by the BBR test and characterized by

2 the creep stiffness (anti-cracking capacity) and m-value (creep rate). A lower creep stiffness (S)

3 and a higher m-value is favorable to the cracking resistance of binder at low temperatures. The

4 BBR test results before and after PAV aging are given in Table 5. It is found that the addition

5 of bio-asphalt could decrease the stiffness as well as increase the m-value of both base asphalt

6 and modified asphalt by comparing the PEN 90 with BBA, and PEN 90+SBS+CR with

7 BBA+SBS+CR, which is beneficial to its low-temperature performance. Combing the results

8 of Fig. 8, Fig. 9 and Table 5, the high and low-temperature performance of modified asphalts

9 using BBA as the base asphalt (BBA+SBS+CR and CMBBA) were superior to that of using

10 PEN 90 as the base asphalt (PEN 90+SBS+CR), meanwhile, the high and low-temperature

11 performance of CR modified asphalt (BBA+CR) also were superior to SBS modified asphalt

12 (BBA+SBS). This improved performance is due to the following two facts: 1. the addition

13 proportion of the CR was higher than that of the SBS, and 2. the lighter components in the bio-

14 asphalt could promote the swelling of the rubber particles, and the swelling rubber particles

15 behaved like elastic micro-balls which had a greater recovery capability for the deformation

16 caused by the load. However, the addition proportion of the SBS was lower and the strength of

17 the network decreased significantly due to the excessive swelling of the SBS, and thus the

18 performance of the binder was also poor. In addition, the BBR test for CMBBA could not be

19 conducted at -12°C because the binder was too soft to meet the instrument measurement range,

20 but the CMBBA had the lowest S and highest m-value at -18°C and -24°C, which means the

21 performance of the composite modified asphalt processing on industrial-scale was better than

22 that prepared in the laboratory. After PAV aging, it is concluded that the incorporation of bio-

23 asphalt did not weak the aging resistance by comparing the S and m-value of PEN 90 with that

24 of BBA, also, the modified asphalt binders showed good aging resistance, especially for the

25 composite modified asphalt, previous research have pointed out that the polymers could

26 decrease the effects of the aging on asphalt binder (Peralta et al., 2009; Subhy et al., 2018).

27 Overall, the addition of bio-asphalt could enhance the comprehensive performance of the

28 petroleum-based asphalt and its modified products.

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1 3.3.3 Master curves of complex modulus

2 The complex modulus (G*) of the binders from frequency sweep tests were used to plot the

3 master curves according to the Time-Temperature Superposition Principle (TTSP) by

4 employing the Christensen-Anderson-Marasteanu (CAM) model (Marasteanu and Anderson,

5 1996), as given in Equations (4) to (6):

6
Gg*  Ge*
7 G G 
* *
e me / k (4)
1  ( f c / f ) k 

8 f   f   T( T ) (5)
C1 (T - Tref )
9 log T (T )   (6)
C2  (T - Tref )
10 where G* is the complex modulus at reduced frequency f ’; Gg* is the glass complex modulus
11 when the frequency approaches infinity; Ge* is the equilibrium complex modulus when the
12 frequency is close to zero, for binders, Ge* =0; fc is the location parameter, also called crossover
13 frequency, corresponds to the frequency at a given temperature where the storage and loss
14 modulus are equal; f ’ is the reduced frequency obtained from Equation (5); f is the original
15 frequency; αT(T) is the shift factors which can be fitted by the Williams-Landel-Ferry (WLF)
16 function (Williams et al., 1955), as given in Equation (6). Tref is the standard reference
17 temperature; C1, C2 are the model parameters; k and me are the shape parameter.
18
19 Fig. 10 presents the master curves of G* for asphalt samples at a reference temperature of

20 35°C. It is found that addition of bio-asphalt could shift the master curve to a lower G* value in

21 both the low and high-frequency regions by comparing BBA with PEN 90, and BBA+SBS+CR

22 with PEN 90+SBS+CR. Also, the G* of the BBA+CR was higher than that of the BBA+SBS in

23 the low-frequency region, while lower than that of the BBA+SBS in the high-frequency region.

24 According to the TTSP, the high service temperature corresponds to the low loading frequency

25 and vice versa, which means both the high and intermediate-temperature performance of CR

26 modified asphalt were superior to that of the SBS modified asphalt, this conclusion was in

27 agreement with the results of the MSCR and BBR tests with the aforementioned explanation in

28 the previous section. Furthermore, the G* of CMBBA was high than that of the BBA+SBS+CR

29 in both low and high-frequency regions, this is because the shearing, grinding and swelling in

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1 the asphalt production was effective than in laboratory, and the three-dimensional cross-linked

2 polymer network structure formed in the binders also was stronger, and thus increased the G*

3 of the modified asphalt.

4 3.3.4 Compatibility prediction by Han curves

5 The Han curve was developed to predict the linear viscoelastic properties of the compatible

6 polymer mixtures having dissimilar chemical structures and phases by using the viscoelastic

7 parameters in the oscillatory shearing flow state. This is based on the concept of tube model of

8 Doi and Edwards, which was defined as the plots of log (elastic modulus, G’) versus log

9 (viscous modulus, G’’) (Han and Kim, 1989a). The effect of polydispersity on log G’ versus

10 log G’’ plots for linear entangled homopolymers in the terminal region can be expressed as

11 Equation (7). The slope in the terminal region of log G’ versus log G’’ plots is equal to 2 for

12 the linear entangled homopolymers, and less than 2 for polydisperse polymers, which decreases

13 from 2 with increasing polydispersity, as given in Equation (8) (Han and Kim, 1989b).
14
6 M
15 logG=2logG+log( GN0 )+3.4log( z ) (7)
5 MW

8GN0
16 logG=xlogG+(1-x)log( ) (8)
π2

17 where G0 N is the plateau modulus of polymer; MZ and MW are the Z-average and weight-
18 average molecular weights, respectively; x is the slope of the log G’ versus log G’’ plot.
19
20 The data from the frequency sweep test (in the oscillatory shearing flow state) were used to

21 plot the Han curves as shown in Fig. 11. At the lower temperatures (6°C, 20°C and 35°C), the

22 log G’ and log G’’ of the binders had a strong linear relationship and the binders were closer to

23 behaving like homopolymers. However, with the temperature increasing to 50°C (Fig. 11 (a))

24 and 65°C (Fig. 11 (b)), a plateau occurred in the Han curves, which means the linear relationship

25 between log G’ and log G’’ has disappeared. A significant temperature dependence exists in

26 the polydisperse polymers once the temperature goes beyond a critical temperature, the

27 different phases of the blend will separate, and this critical temperature was defined as the

28 critical temperature of phase separation (Tc). Below the Tc, the polymer mixtures (as the blend

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1 systems) were in an ordered state and showed a linear viscoelastic behavior (significantly

2 increasing elasticity, longer relaxation time, and invalid of TTSP) (Wang et al., 2017). Above

3 the Tc, the linear relationship between log G’ and log G’’ had disappeared due to the phase

4 separation in the polymer blends. As for the binders, the Tc for PEN 90, BBA, and BBA+SBS

5 was 50°C and for BBA+CR, PEN 90+SBS+CR, BBA+SBS+CR, and CMBBA was 65°C.

6 Apparently, the swelling CR was beneficial to facilitating the modified asphalt maintaining an

7 ordered state and improve the Tc thus to slow the phase separation in the modified asphalts.

8 Comparing the slopes in the terminal region of the Han curves, it is found that the compatibility

9 between the bio-asphalt and base asphalt was desirable that can be illustrated by the higher

10 slope value of BBA. Furthermore, the slope in the terminal region of BBA+SBS was higher

11 than that of the PEN 90 and BBA, that is because the incorporation of the SBS polymer formed

12 a three-dimensional cross-linked polymer network structure in the binder and created a more

13 homogeneous blend. The facilitates make the polymer blends tend to behave as the

14 homopolymers (with a higher slope value). Nevertheless, comparing the CR with SBS, the CR

15 was harder to shear and grind into the small size particles and thus disperse in the binder

16 homogeneously. Similarly, the slopes in the terminal region of the Han curves decreased to

17 varying degrees, which means the asphalt and polymer blends tended to behave as the

18 polydisperse polymers, but this tendency was very weak. Moreover, the slope value of

19 BBA+SBS+CR was higher than that of PEN 90+SBS+CR, but lower than that of CMBBA,

20 which signifies that the bio-asphalt could enhance the compatibility between base asphalt and

21 polymers. Also, processing the modified asphalt on industrial-scale could result in a better

22 grinding effect and facilitate the polymers dispersing into the binder more homogeneously.

23 4. Conclusions

24 The research investigation involved the composite modification mechanism of the blended

25 bio-asphalt combining SBS with CR. Based on the analysis of chemical characteristics,

26 morphological features and rheological properties of the binders, the following findings can be

27 stated:

28 (1) In chemical characteristics analysis, FTIR testing indicated that there was no new

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1 absorption peak in the FTIR spectrum of the modified asphalts, which means the functional

2 groups in the binder were not changed. Meanwhile, the molecular size distribution via GPC

3 showed that the SBS modifier (about 250,000 Das), primarily asphaltenes (including the

4 swelling rubber, about 1500 Das) and primarily maltenes (about 200 Das) in the binders

5 corresponded to the three peaks in the GPC chromatogram. Hence, this modification was

6 proved to be a physical process.

7 (2) Morphological features via AFM and FM illustrated that the bio-asphalt could promote

8 the swelling properties of the modifiers and also enhance the density and strength of three-

9 dimensional cross-linked polymer network structure formed in the binders. This is illustrated

10 by the size increase of the SBS and the uniform distribution of the different particle size both

11 in AFM and FM images, as well as the mutual filling and embedding between the small and

12 large particles of polymers observed in the FM images.

13 (3) As for the rheological properties, the MSCR and BBR tests demonstrated that both the

14 permanent deformation resistance at high temperature and thermal-cracking resistance at low

15 temperature of the binder were improved through the composite modification using SBS with

16 CR. This is shown by the lower accumulated strain, Jnr, S and the higher R and m-value, which

17 was in agreement with the higher G* in low-frequency region and lower G* in high-frequency

18 region from FS test. In addition, the Han curves illustrated that the Tc was increase from 50°C

19 to 65°C by the modification, and the compatibility between the asphalt and polymers was

20 improved with the bio-asphalt with the higher slope in the terminal region in the Han curves.

21 (4) Processing the composite modified blended bio-asphalt on an industry-scale is more

22 effective than that in the laboratory due to the more efficient swelling, shearing, grinding and

23 breeding. The polymer modifiers were swelled enough due to the sufficient contact between

24 the asphalt and polymers by the constant stirring with several sets of blades in the professional

25 swelling tank, and the three-stage high-speed shearing machine makes the swelled polymers

26 cut into the finer particles more easily, thus forming the strong and stable network structure in

27 the modified asphalt binder.

28 Overall, the composite modification is and effective method to improve the comprehensive

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1 performance of the bio-asphalt and prompt the reuse of the waste. However, the findings

2 presented above may not be applicable to any kind of materials, due to the variety of the bio-

3 asphalt origin, also, this is a biggest challenge of the application of the bio-asphalt at large-

4 scale. Hence, the reproduction of this modification technology on other sourced bio-asphalt

5 from different region is under way. In addition, other issues of possibility of bio-asphalt

6 production for the pavement demand, and environmental impact during the materials

7 transportation should be addressed to facilitate the large-scale application of this sustainable

8 material in pavement.

9 Acknowledgments

10 This research work was sponsored by National Natural Science Foundation of China (Grant

11 Nos.51478154 and 51478152) and Science & Technology Project of DOT of Jilin Province

12 (Grant No. 2018-1-2). Also, special appreciation is given to Analysis & Test Center of Harbin

13 Institute of Technology and Jilin Provincial Transportation Planning and Design Institute for

14 their generous assistances during the laboratory tests.

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Fig. 1. Processing technology of bio-asphalt.

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(a)

(b)

Fig. 2. Processing technology of modified asphalt samples: (a) processing flowchart of modified

asphalt in lab; (b) equipment diagram used on industrial-scale.

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blending
PEN 90 Petroleum-based asphalt (PEN 90) Bio-asphalt Castor Refined fatty acids
modifier modifier
Styrene-butadiene-styrene (SBS) Blended bio-asphalt (BBA) Crumb rubber (CR)

Asphalt binders were modified solely or in combination

Experimental group Control group

BBA, BBA+SBS, BBA+CR BBA+SBS+CR, CMBBA PEN 90, PEN 90+SBS, PEN 90+CR, PEN 90+SBS+CR

Chemical characteristics Morphological features Rheological properties

FT-IR GPC AFM FM MSCR FS BBR

Fig. 3. Flowchart of the experimental procedures.

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Functional Group Region (FGR) Fingerprint Region (FPR)

100
FPR Ⅰ
FPR Ⅰ
80
Transmittance (%)

PEN 90 C=O stretching

BBA (Aldehydes, Ketones)
60
BBA+SBS C=C stretching
BBA+CR (Aromatics) S=O
40 PEN 90+SBS+CR
stretching
(Sulfoxides)
BBA+SBS+CR -CH2 &-CH3 -CH3 asymmetric
-CH3 symmetric
20 CMBBA stretching deformation deformation
(Alkanes) (Alkanes) -C-H bending
(Alkanes) (Aromatics)
0
4000 3500 3000 2500 2000 1500 1000 500
-1
Wave numbers (cm )

(a)

80 80

70
Transmittance (%)

Transmittance (%)
70 C=C
bending (SBS) 60
720 cm-1
50
60
40
50
966 cm-1 30

1100 1050 1000 950 900 780 750 720 690 660
-1 -1
Wave numbers (cm ) Wave numbers (cm )

(b) (c)

Fig. 4. FTIR spectrum of asphalt samples: (a) major functional groups; (b) enlarged detail of FPR

Ⅰ; (c) enlarged detail of FPR Ⅱ.

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LMS MMS SMS LMS MMS SMS

Ⅰ Ⅰ
20 20 BBA+SBS
BBA+CR
PEN 90+SBS+CR
RI response (mV)

RI response (mV)
15 15 BBA+SBS+CR
CMBBA
Ⅰ
10 10
PEN 90
Ⅰ
5 BBA 5
OB Ⅰ

0 0
5 6 7 8 9 10 11 12 5 6 7 8 9 10 11 12
Elution time (min) Elution time (min)

(a) (b)

Fig. 5. GPC chromatogram of asphalt samples: (a) unmodified asphalt samples; (b) modified

asphalt samples.

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Fig. 6. AFM images of asphalt samples: (a) PEN 90; (b) BBA; (c) PEN 90+SBS; (d) BBA +SBS;

(e) PEN 90+CR; (f) BBA+CR; (g) PEN 90+SBS+CR; (h) BBA+SBS+CR; (i) CMBBA.

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Fig. 7. Fluorescence micrographs of asphalt samples (objective 20X with eyepiece 20X): (a) PEN

90; (b) BBA; (c) PEN 90+SBS; (d) BBA +SBS; (e) PEN 90+CR; (f) BBA+CR; (g) PEN

90+SBS+CR; (h) BBA+SBS+CR; (i) CMBBA.

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7 0.36
PEN 90 PEN 90+SBS+CR
6

Accumulated Strain (%)

Accumulated Strain (%)

BBA 0.30 BBA+SBS+CR

PEN 90+SBS CMBBA
5
BBA+SBS 0.24
4 PEN 90+CR
BBA+CR 0.18
3
0.12
2
1 0.06

0 0.00
0 20 40 60 80 100 0 20 40 60 80 100
Time (s) Time (s)

(a) (b)
250 18
PEN 90 PEN 90+SBS+CR
BBA
Accumulated Strain (%)
Accumulated Strain (%)

200 15 BBA+SBS+CR
PEN 90+SBS CMBBA
BBA+SBS 12
150 PEN 90+CR
BBA+CR 9
100
6
50 3

0 0
0 20 40 60 80 100 0 20 40 60 80 100
Time (s) Time (s)

(c) (d)

Fig. 8. MSCR test of asphalt samples (60°C, 1000 um gap): (a) unmodified and solely modified

asphalt samples at 0.1 kPa; (b) composite modified asphalt samples at 0.1 kPa; (c) unmodified and

solely modified asphalt samples at 3.2 kPa; (d) composite modified asphalt samples at 3.2 kPa.

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9 100
8 @ 0.1 kPa @ 3.2 kPa @ 0.1 kPa @ 3.2 kPa
7 80
6
Jnr (1/kPa)

5 60

R (%)
4
3
40
0.5
20

0.0 0
90 A S S R R R R A 90 A S S R R R R A
N BB 0+SB +SB 90+C A+C S+C S+C BB N BB 0+SB +SB 90+C A+C S+C S+C BB
PE 9 B A N B
B 0+ SB SB C M PE 9 B A N B
B 0+ SB SB C M
PE
N B PE 9 A+ PE
N B PE 9 A+
E N BB E N BB
P P

(a) (b)
Fig. 9. The non-recoverable compliance (Jnr) and recovery (R) of binders at 0.1 kPa and 3.2 kPa:
(a) Jnr; (b) R.

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109 109
PEN 90 PEN 90
108 108
BBA
Complex modulus (Pa)

Complex modulus (Pa)

PEN 90+SBS+CR
107 BBA+SBS 107 BBA+SBS+CR
106 BBA+CR 106 CMBBA
105 105
10
3
104
104 104
103 102 103
103
102 102
101
101 10-4 10-3 10-2
101 10-3 10-2

100 -5 100 -5
10 10-3 10-1 101 103 105 107 10 10-3 10-1 101 103 105 107
Reduced frequency (Hz) Reduced frequency (Hz)

(a) (b)

Fig. 10. Master curves of complex modulus (Tref=35°C): (a) unmodified and solely modified asphalt

samples; (b) composite modified asphalt samples.

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109
108 6°C PEN 90
20°C BBA Tc=50°C
107
Elastic Modulus (Pa)

35°C BBA+SBS
106 50°C
105 65°C
80°C
104
103
Slope (PEN 90)=1.1098
102
Slope (BBA)=1.3250
101 Slope (BBA+SBS)=1.3599
100
10-1 1
10 102 103 104 105 106 107 108
Viscous Modulus (Pa)
(a)

109
108 6°C BBA+CR
107 20°C PEN 90+SBS+CR Tc=65°C
Elastic Modulus (Pa)

35°C BBA+SBS+CR
106 50°C CMBBA
105 65°C
80°C
104
103 Slope (BBA+CR)=0.8274
Slope (PEN 90+SBS+CR)=0.8144
102
Slope (BBA+SBS+CR)=0.9281
101 Slope (CMBBA)=0.9953
100 1
10 102 103 104 105 106 107 108
Viscous Modulus (Pa)
(b)

Fig. 11. Han curves of asphalt samples: (a) unmodified and SBS modified asphalt samples; (b) CR

modified and composite modified asphalt samples.

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Highlights
 Blended bio-asphalt was modified by Styrene-Butadiene-Styrene and Crumb.
 Bio-asphalt could promote the swelling properties of the polymer modifiers.
 Bio-asphalt could enhance the compatibility between base asphalt and polymers.
 Composite modification could improve the high and low temperature performance.
 Modification processing on industry-scale is more effective than laboratory.
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Table 1. Fundamental properties of the PEN 90 and OB.

Properties PEN 90 OB

Specific Gravity 1.030 0.987

Needle Penetration @ 25°C (0.1 mm) 84 >300

Ring & Ball Softening Point (°C) 46.5 —a

Ductility @ 15°C (cm) >100 >100

@ 90°C 5.362 3.480

Brookfield Viscosity (Pa·s) @ 135°C 0.277 0.414

@ 165°C 0.099 0.146

Note: aRing & Ball Softening Point of original bio-asphalt used herein could not be obtained because the sample
was too soft to prepare a standard specimen.

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Table 2. Physical properties and chemical compositions of crumb rubber used.

Properties Value

Density (g/cm3) 1.18

Break Strength (MPa) 15.2

Elongation at Break (%) 521

Ash Content (%) 4.2

Moisture Content (%) 0.4

Metal Content (%) 0.03

Rubber Hydrocarbon Content (%) 48

Carbon Black Content (%) 30

Acetone Extract (%) 8

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Table 3. List of the asphalt binders used.

Labels Extender Modifier Definition and Description of Asphalt Binders

PEN 90 None None Base asphalt.

BBA Bio-asphalt None Blended bio-asphalt, i.e., base asphalt blended with bio-asphalt.

PEN 90+SBS None SBS Base asphalt modified by SBS.

BBA+SBS Bio-asphalt SBS Blended bio-asphalt modified by SBS.

PEN 90+CR None CR Base asphalt modified by CR.

BBA+CR Bio-asphalt CR Blended bio-asphalt modified by CR.

PEN 90+SBS+CR None SBS+CR Base asphalt modified by SBS and CR.

BBA+SBS+CR Bio-asphalt SBS+CR Blended bio-asphalt modified by SBS and CR.

Composite modified blended bio-asphalt, i.e., BBA+SBS+CR
CMBBA Bio-asphalt SBS+CR
processing on industrial-scale.a
Note: aThe CMBBA was processed at the asphalt plant, and other asphalt samples were prepared in the laboratory.

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Table 4. Molecular size distribution of asphalt samples.

Asphalt Samples Peak Mn Mw Mz Mpa PDI b

OB Ⅱ 526 2260 9729 441 4.30

Ⅰ 179 259 316 382 1.45

PEN 90
Ⅱ 1416 4595 22426 805 3.24

Ⅰ 166 241 293 439 1.45

BBA
Ⅱ 1295 3893 17622 828 3.01

Ⅰ 193 274 329 383 1.42

BBA+CR
Ⅱ 1452 8568 86446 807 5.90

Ⅰ 182 262 318 392 1.44

BBA+SBS Ⅱ 1381 4235 17725 823 3.07

Ⅲ 206223 224350 248797 205412 1.09

Ⅰ 183 261 316 389 1.42

BBA+SBS+CR Ⅱ 1551 15852 249007 764 10.22

Ⅲ 220359 310240 454621 210589 1.41

Ⅰ 182 261 317 385 1.44

PEN 90+SBS+CR Ⅱ 1450 6848 37146 807 4.72

Ⅲ 219436 288041 432935 207651 1.31

Ⅰ 195 278 335 374 1.42

CMBBA Ⅱ 1477 7130 40756 788 4.83

Ⅲ 250579 355552 564369 203199 1.42

Note: aMp is molecular weight at the peak.

bM
w/Mn is the polydispersity index, PDI.

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Table 5. Creep stiffness and m-value of asphalt samples.

Creep Stiffness (MPa) m-value

Asphalt Samples Virgin PAV Aged Virgin PAV Aged

-12°C -18°C -24°C -12°C -18°C -24°C -12°C -18°C -24°C -12°C -18°C -24°C

PEN 90 174.0 404.0 682.0 205.0 460.0 1025.0 0.392 0.298 0.211 0.370 0.283 0.206

BBA 135.0 321.0 547.0 149.0 359.0 721.5 0.427 0.328 0.240 0.422 0.299 0.237

BBA+SBS 87.1 242.0 553.0 95.0 275.5 631.5 0.461 0.361 0.273 0.440 0.352 0.258

BBA+CR 39.5 108.0 287.0 40.3 123.5 322.5 0.480 0.370 0.298 0.423 0.354 0.278

PEN 90+SBS+CR 46.9 113.0 291.0 52.4 134 346.5 0.460 0.347 0.311 0.456 0.358 0.273

BBA+SBS+CR 37.2 97.9 233.0 41.1 100.6 245.0 0.465 0.397 0.317 0.444 0.334 0.296

CMBBA —a 84.0 226.0 42.7 93.0 246.5 —a 0.452 0.347 0.446 0.349 0.341

Note: aThe BBR test for Virgin CMBBA could not be conducted at -12°C because the binder was too soft to meet
the instrument measuring range.