Chemical and Physical Properties of Poly (Lactic) Acid Modified Bitumen

Ain Shams Engineering Journal
Chemical and Physical Properties of Poly(Lactic) Acid (PLA) Modified Bitumen

--Manuscript Draft--
Manuscript Number: ASEJ-D-19-00656R2
Article Type: Full Length Article
Section/Category: Civil Engineering
Keywords: Chemical interaction; Compatibility; Dispersity; Modified bitumen; Physical

properties; Poly(Lactic) Acid.
Corresponding Author: Nur Izzi Md Yusoff, PhD

Universiti Kebangsaan Malaysia
Bangi, MALAYSIA
First Author: Nashriq Jailani, MSc
Order of Authors: Nashriq Jailani, MSc
Ahmad Nazrul Hakimi Ibrahim, PhD
Abdur Rahim, PhD
Ahmad Kamil Arshad, PhD
Norhidayah Abdul Hassan, PhD
Nur Izzi Md Yusoff, PhD
Abstract: This study investigates the feasibility and effect of poly(lactic) acid (PLA) on bitumen
modification. The chemical and physical properties were evaluated for the modified
bitumen produced with varying percentages of PLA ranging from 3 to 9%. Several
testings such as the nuclear magnetic resonance (NMR), Fourier Transform Infrared
Spectroscopy (FTIR), Gel permeation chromatography (GPC), penetration, softening
and ductility, and thermal storage stability were evaluated. The results show that
chemical interaction exists between PLA and bitumen. The GPC analysis indicates
high compatibility of the bitumen with the PLA modifier. Moreover, the results indicated
that the addition of PLA increased the consistency of modified bitumen. The storage
stability and segregation of phases were positively affected in the PLA modified
bitumen. The PLA and base bitumen interact at physical and chemical levels which
results in enhancement of performance of modified bitumen to produce a high-quality
binding material for pavement construction.
Response to Reviewers: List of comments and response
Point 1: More suitable title should be selected for the article.

Response 1: The authors has changed the manuscript title to “Chemical and Physical
Properties of Poly (Lactic) Acid Modified Bitumen”.
Point 2: The abstract should state briefly the purpose of the research, the principal
results and major conclusions. An abstract is often presented separately from the
article, so it must be able to stand alone.
Response 2: The abstract in the revised manuscript has been rewritten and restructure
based on suggested outline by Reviewer 4.
Point 3: It is suggested to present the structure of the article at the end of the
introduction.
Response 3: The structure of article was presented at the end of the introduction.
Point 4: The major defect of this study is the debate or Argument is not clear stated in
the introduction session. Hence, the contribution is weak in this manuscript. I would
suggest the author to enhance your theoretical discussion and arrives your debate or
argument.
Response 4: The authors has revised and restructured the whole introduction section
in the revised manuscript. The revised introduction provided a well discuss related the
theoretical and finding of the previous related works. In addition, the limitation of the
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previous works is well derived and identified as the main reason this study was
conducted.
Point 5: The necessity and innovation of the article should be presented to the
introduction.
Response 5: Based on limitation of the previous works, this study was conducted to
bridge the gap of knowledge. The necessity of this study is presented in the
introduction and the innovation of this study is described as well in the revised
manuscript.
Point 6: More suitable title should be presented for the figure 11 instead of "Softening
point value of PLA-modified bitumen".
Response 6: The title of Figure 11 and Figure 12 in the revised manuscript has been
revised.
Point 7: It is suggested to compare the results of the present research with some
similar studies which is done before.
Response 7: The findings of this study was compared to the results of the related
previous studies. The discussion of this can be seen in Section 3 (Results) and Section
4 (Discussion).
Point 8: A flowchart should be added to the article to show the research methodology.
Response 8: The flow chart was added in Figure 1 to summarize the flow of research
protocol.
Point 9: Following, you will find some new related references which should be added to
literature review:
Saedi & Oruc. The Effects of Nano Bentonite and Fatty Arbocel on Improving the
Behavior of Warm Mixture Asphalt against Moisture Damage and Rutting;
Shihab et al. Effects of Temperature in Different Initial Duration Time for Soft Clay
Stabilized by Fly Ash Based Geopolymer;
Nhabih et al. Study a Structural Behavior of Eccentrically Loaded GFRP Reinforced
Columns Made of Geopolymer Concrete.
Response 9: The relevant information from these suggested studies have been used to
enhance the sentence and discussion in the revised manuscript. In addition, these
suggested studies were added in the revised manuscript.
Point 10: Page 11: the following paragraph is unclear, so please reorganize that:
"Lower indexes were observed for the area under the band of C-O with C-C for the
unwashed (11.0 to 7.0%) and washed (10.6 to 5.1%) samples. On the other hand, an
increasing index pattern was observed for both the C=O bond with C-C (unwashed=
4.7 to 17.9%; washed=12.1 to 16.9%) and the C=O with C=C (unwashed=1.0 to 7.3%;
washed=9.0 to 18.9%).".
Response 10: This sentence has been revised.
Point 11: Much more explanations and interpretations must be added for the Results,
which are not enough.
Response 11: The authors has extended the explanations and interpretations of the
findings in this study. See Result and Discussion section.
Point 12: It is suggested to add articles entitled "Iqbal et al. Improving the Aging
Resistance of Asphalt by Addition of Polyethylene and Sulphur", "Kadhim & Al-
Mutairee. An Experimental Study on Behavior of Sustainable Rubberized Concrete
Mixes" and "Trang et al. The Study of Dynamics Heterogeneity in SiO2 Liquid" to the
literature review.
Response 12: The relevant information from these suggested studies have been used
to enhance the sentence and discussion in the revised manuscript. In addition, these
suggested studies were added in the revised manuscript.
Point 13: Please make sure your conclusions' section underscore the scientific value
added of your paper, and/or the applicability of your findings/results, as indicated
previously. Please revise your conclusion part into more details. Basically, you should
enhance your contributions, limitations, underscore the scientific value added of your
paper, and/or the applicability of your findings/results and future study in this session.
Response 13: The authors has rewritten and restructure the conclusion of this study. In
addition, the suggestion for future research also listed in the same section.
Point 14: "Notation" should be added to the article.

Response 14: The “notation” was added in the figure and text in the revised
manuscript.
Point 15: DOI of the references must be added (you can use "https://crossref.org/").
Response 15: The DOI number was added for all references in the revised manuscript.
Thank you for your suggestion of using "https://crossref.org/". See Reference section.
Cover Letter
Fakulti Kejuruteraan dan Alam Bina Faculty of Engineering and Built Environment
Chief-in-Editor
Ain Shams Engineering Journal
26th December 2020
Dear Prof,
SUBMISSION OF A REVISED MANUSCRIPT – R2 FOR POSSIBLE PUBLICATION IN

AIN SHAMS ENGINEERING JOURNAL
Hereby I have attached a revised manuscript entitled “Effects of Chemical and Physical
Properties of Poly(Lactic) Acid (PLA) Modified Bitumen” co-authored by Nashriq Jailani,
Ahmad Nazrul Hakimi Ibrahim, Abdur Rahim, Ahmad Kamil Arshard, Norhidayah Abdul
Hassan and Nur Izzi Md Yusoff for a possible publication in the Ain Shams Engineering
Journal.
Please do not hesitate to get in touch with me if you have any questions and I look forward to
hearing from you very soon.
Thank you very much indeed.
Kind regards,
Izzi
Assoc Prof. Ir. Dr. Nur Izzi Md. Yusoff
Dept. of Civil Engineering
Faculty of Engineering and Built Environment
Universiti Kebangsaan Malaysia
43600 UKM Bangi
Selangor, Malaysia
Tel: +603-8921 6447 (office), +6019-289 1221 (mobile)
Fax: + 603-8921 6147
Email: izzi@ukm.edu.my, izzi.alkutani@gmail.com
MS ISO 9001:2008 Cert. No. : AR 5779

JABATAN KEJURUTERAAN AWAM, FAKULTI KEJURUTERAAN DAN ALAM BINA,
Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan
Telefon: +603-8921 6447 Faksimili: +603-8911 8344 E-mel: izzi@ukm.edu.my Laman Web: http://www.eng.ukm.my
Detailed Response to Reviewers
CORRECTION REPORT
TITLE:
Chemical and Physical Properties of Poly (Lactic) Acid Modified Bitumen
(REF: ASEJ-D-19-00656R1)
We are very pleased to have been given the opportunity to revise our manuscript, which is entitled,
“Chemical and Physical Properties of Poly (Lactic) Acid Modified Bitumen” for the Ain Shams
Engineering Journal. We have carefully considered those offered by a reviewer. Here, we explain how
we have revised the paper based on those comments and recommendations. We would like to extend our
gratitude all parties for taking the time and making the effort to provide such insightful guidance.
The response to all comments from Reviewer 4 is shown in the list of comments and response
and attached revised manuscript.
In conclusion, we appreciate all the insightful comments. We have done our best to make the
recommended amendments. Thank you for the time and effort to help us improve the writing
of this paper. We hope that you will approve the revised version of this paper.
Thank you.
List of comments and response
Point 1: More suitable title should be selected for the article.

Response 1: The authors has changed the manuscript title to “Chemical and Physical Properties
of Poly (Lactic) Acid Modified Bitumen”.
Point 2: The abstract should state briefly the purpose of the research, the principal results and
major conclusions. An abstract is often presented separately from the article, so it must be able
to stand alone.
Response 2: The abstract in the revised manuscript has been rewritten and restructure based
on suggested outline by Reviewer 4.
Point 3: It is suggested to present the structure of the article at the end of the introduction.
Response 3: The structure of article was presented at the end of the introduction.
Point 4: The major defect of this study is the debate or Argument is not clear stated in the
introduction session. Hence, the contribution is weak in this manuscript. I would suggest the
author to enhance your theoretical discussion and arrives your debate or argument.
Response 4: The authors has revised and restructured the whole introduction section in the
revised manuscript. The revised introduction provided a well discuss related the theoretical and
finding of the previous related works. In addition, the limitation of the previous works is well
derived and identified as the main reason this study was conducted.
Point 5: The necessity and innovation of the article should be presented to the introduction.
Response 5: Based on limitation of the previous works, this study was conducted to bridge the
gap of knowledge. The necessity of this study is presented in the introduction and the
innovation of this study is described as well in the revised manuscript.
Point 6: More suitable title should be presented for the figure 11 instead of "Softening point
value of PLA-modified bitumen".
Response 6: The title of Figure 11 and Figure 12 in the revised manuscript has been revised.
Point 7: It is suggested to compare the results of the present research with some similar studies
which is done before.
Response 7: The findings of this study was compared to the results of the related previous
studies. The discussion of this can be seen in Section 3 (Results) and Section 4 (Discussion).
Point 8: A flowchart should be added to the article to show the research methodology.
Response 8: The flow chart was added in Figure 1 to summarize the flow of research protocol.
Point 9: Following, you will find some new related references which should be added to
literature review:
Saedi & Oruc. The Effects of Nano Bentonite and Fatty Arbocel on Improving the Behavior of
Warm Mixture Asphalt against Moisture Damage and Rutting;
Shihab et al. Effects of Temperature in Different Initial Duration Time for Soft Clay Stabilized
by Fly Ash Based Geopolymer;
Nhabih et al. Study a Structural Behavior of Eccentrically Loaded GFRP Reinforced Columns
Made of Geopolymer Concrete.
Response 9: The relevant information from these suggested studies have been used to enhance
the sentence and discussion in the revised manuscript. In addition, these suggested studies were
added in the revised manuscript.
Point 10: Page 11: the following paragraph is unclear, so please reorganize that:
"Lower indexes were observed for the area under the band of C-O with C-C for the unwashed
(11.0 to 7.0%) and washed (10.6 to 5.1%) samples. On the other hand, an increasing index
pattern was observed for both the C=O bond with C-C (unwashed= 4.7 to 17.9%; washed=12.1
to 16.9%) and the C=O with C=C (unwashed=1.0 to 7.3%; washed=9.0 to 18.9%).".
Response 10: This sentence has been revised.
Point 11: Much more explanations and interpretations must be added for the Results, which
are not enough.
Response 11: The authors has extended the explanations and interpretations of the findings in
this study. See Result and Discussion section.
Point 12: It is suggested to add articles entitled "Iqbal et al. Improving the Aging Resistance
of Asphalt by Addition of Polyethylene and Sulphur", "Kadhim & Al-Mutairee. An
Experimental Study on Behavior of Sustainable Rubberized Concrete Mixes" and "Trang et al.
The Study of Dynamics Heterogeneity in SiO2 Liquid" to the literature review.
Response 12: The relevant information from these suggested studies have been used to
enhance the sentence and discussion in the revised manuscript. In addition, these suggested
studies were added in the revised manuscript.
Point 13: Please make sure your conclusions' section underscore the scientific value added of
your paper, and/or the applicability of your findings/results, as indicated previously. Please
revise your conclusion part into more details. Basically, you should enhance your contributions,
limitations, underscore the scientific value added of your paper, and/or the applicability of your
findings/results and future study in this session.
Response 13: The authors has rewritten and restructure the conclusion of this study. In
addition, the suggestion for future research also listed in the same section.
Point 14: "Notation" should be added to the article.

Response 14: The “notation” was added in the figure and text in the revised manuscript.
Point 15: DOI of the references must be added (you can use "https://crossref.org/").
Response 15: The DOI number was added for all references in the revised manuscript. Thank
you for your suggestion of using "https://crossref.org/". See Reference section.
Title Page (with AU credentials)
Chemical and Physical Properties of Poly (Lactic) Acid Modified Bitumen
Nashriq Jailani1, Ahmad Nazrul Hakimi Ibrahim2, Abdur Rahim3, Ahmad Kamil Arshad4,
Norhidayah Abdul Hassan5 and Nur Izzi Md. Yusoff6*
1
PhD Student, Dept. of Civil Engineering, Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia, Selangor, Malaysia
Email: nashriqjailani@yahoo.com
2
PhD Student, Dept. of Civil Engineering, Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia, Selangor, Malaysia
Email: ahmadnazrulhakimi@gmail.com
3
Senior Lecturer (Dr.), Dept. of Transportation Engineering and Management, University of
Engineering and Technology, Lahore, Pakistan
Email: rahim@uet.edu.pk
4
Prof. (Ir. Dr.), Institute for Infrastructure Engineering and Sustainable Management,
Universiti Teknologi MARA, Shah Alam, Selangor, Malaysia
Email: drahmadkamil@uitm.edu.my
5
Senior Lecturer (Dr.), School of Civil Engineering, Universiti Teknologi Malaysia, Johor,
Malaysia
Email: hnorhidayah@utm.my
6
Associate Prof. (Ir. Dr.), Dept. of Civil Engineering, Faculty of Engineering and Built
Environment, Universiti Kebangsaan Malaysia, Selangor, Malaysia
Email: izzi@ukm.edu.my
*Corresponding author: izzi@ukm.edu.my

Manuscript text (without AU credentials)
1 Chemical and Physical Properties of Poly (Lactic) Acid Modified Bitumen

1
2 2
3
4 3 Abstract
5
4
6
7 5 This study investigates the feasibility and effect of poly(lactic) acid (PLA) on bitumen
8
9 6 modification. The chemical and physical properties were evaluated for the modified bitumen
10
11 7 produced with varying percentages of PLA ranging from 3 to 9%. Several testings such as the
12
13 8 nuclear magnetic resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), Gel
14
15 9 permeation chromatography (GPC), penetration, softening and ductility, and thermal storage
16 10 stability were evaluated. The results show that chemical interaction exists between PLA and
17
18 11 bitumen. The GPC analysis indicates high compatibility of the bitumen with the PLA modifier.
19
20 12 Moreover, the results indicated that the addition of PLA increased the consistency of modified
21
22 13 bitumen. The storage stability and segregation of phases were positively affected in the PLA
23
24 14 modified bitumen. The PLA and base bitumen interact at physical and chemical levels which
25
26 15 results in enhancement of performance of modified bitumen to produce a high-quality binding
27 16 material for pavement construction.
28
29 17
30
31 18 Keywords: Chemical interaction; Compatibility; Dispersity; Modified bitumen; Physical
32
33 19 properties; Poly(Lactic) Acid
34
35 20
36
37
21 1. Introduction
38 22
39
40 23 Bitumen is produced by refining crude oil through a series of distillation processes and it is
41
42 24 composed of heavy hydrocarbons, which are classified into saturates, aromatics, resins and
43
44 25 asphaltenes (Günay & Ahmedzade 2020). It is used in various engineering applications such
45
46 26 as highway and airfield pavement due to its physical and rheological characteristics as well as
47
27 impermeability and adhesive properties (Farias et al., 2016; Mohammadiroudbari et al., 2016).
48
49 28 However, being a viscoelastic material, bitumen is easily affected by seasonal temperature and
50
51 29 rain as well as loading factors including increasing traffic volumes and continuous heavy loads
52
53 30 (Ibrahim et al. 2016; 2017; Iqbal et al. 2020). The viscoelastic properties of bitumen are time
54
55 31 and temperature dependant. This effect changes in its physical properties, which are reflected
56
57 32 in the mechanical properties of asphalt mixtures. Therefore, bitumen should be sufficiently stiff
58
33 to resist rutting at high temperatures and soft at low temperatures to prevent the occurrence of
59
60 34 thermal cracking (Lesueur, 2009; Saedi & Oruc 2020).
61
62 1
63
64
65
35
1
2 36 The performance bitumen is, traditionally, enhanced with different types of modifiers
3
4 37 including; nanomaterial (Omar et al., 2018; Yusoff et al., 2019), geopolymer (Ali et al., 2017;
5
38 Ibrahim et al., 2016; Rosyidi et al. 2020; Shihab et al. 2018), waste materials such as glass and
6
7 39 plastic (Zakaria et al., 2018), and rubber (Al Mansoob et al., 2017). The previous studies
8
9 40 indicate that the addition of modifier improves the performance of the binder in terms of
10
11 41 elasticity and stiffness, and also reduces the permanent deformation of the pavement resulting
12
13 42 from environmental effects and repetitive traffic loading (Braseileiro et al., 2014; Giavarini et
14
15 43 al., 1996; Panda & Mazumdar, 1999). However, amongst the different types of bitumen
16 44 modifiers, the polymers are the frequently used as modifiers and have demonstrated to be good
17
18 45 modifying agents in the production of high-performance binder (Brasileiro et al., 2019; Polacco
19
20 46 et al., 2005; Padhan & Gupta, 2018; Sengoz et al., 2009; Zhu et al., 2014).
21
22 47
23
24 48 The evidence for performance enhancement with polymers is demonstrated by Jiang et
25
26 49 al. (2020) and Laukkanen et al. (2018). According to the studies, the modification of bitumen
27 50 with SBS enhances the engineering properties of the bitumen for reduced temperature
28
29 51 dependence, increased elasticity, as well as an enhanced performance at low and high service
30
31 52 temperature. This is due to the excellent mechanical properties of SBS such as high fatigue
32
33 53 resistance, elastic recovery and high resistance at extreme temperatures (Airey, 2004; Chen et
34
35 54 al. 2007; Schaur et al. 2017). Another thermoplastic modifier that has been widely used for
36
37
55 bitumen modification is crumb rubber (CR). According to Poovaneshvaran et al. (2020), Wang
38 56 et al. (2020a, 2020b, 2020c) and Yao et al. (2018) CR can modify the physical and mechanical
39
40 57 properties of bitumen to produce improved resistance to fatigue and thermal cracking, ageing,
41
42 58 and rutting. Loderer et al. (2018) reported that, unlike SBS-modified bitumen, CR-modified
43
44 59 bitumen has a high resistance to rutting and low-temperature cracking. Moreover, other studies
45
46 60 on bitumen modification with natural rubber show enhancement of physical and rheological
47
61 properties of the modified bitumen (Al-Mansob et al. 2014) and improvement in resistance to
48
49 62 shear stress (Poovaneshvaran et al. 2020). Furthermore, the modification of bitumen with
50
51 63 polymers has demonstrated to improve the binder properties, for instance, enhanced stiffness
52
53 64 at high temperatures, cracking resistance at low temperatures, moisture resistance, and longer
54
55 65 fatigue life (Alata et al., 2013; Gardiner et al., 1995; Al Mansoob et al., 2017). The promising
56
57 66 potential of using polymers such as rubber and geopolymer is not limited to the bituminous
58
67 materials only. Numerous evidences were found related to the promising effect of using these
59
60
61
62 2
63
64
65
68 polymers in other applications including as structural and concrete materials (Nhabih et al.
1
2 69 2020; Kadhim & Al-Mutairee 2020).
3
4 70
5
71 The findings of the previous studies related to the polymer modified bitumen are
6
7 72 promising and establish the applicability of polymer in bitumen. Within this scope, this
8
9 73 research explores the potential of PLA as a modifier. PLA is a bio-based green thermoplastic
10
11 74 polyester which can be derived from renewable resources such as sugarcane or cornstarch
12
13 75 (Auras et al., 2004; Rasal et al., 2010). Furthermore, PLA is an attractive substitute for
14
15 76 conventional polymers due to its excellent biocompatibility, high tensile strength, and high
16 77 modulus. The simplicity of the PLA structure with esters as the repeating unit and carboxyl
17
18 78 group as the end chain can explain the chemical reaction that occurs between PLA and bitumen.
19
20 79
21
22 80 The pavement engineering field, traditionally, has remained less focused on the
23
24 81 chemical reaction occurring between the polymers and bitumen. Since the past several years,
25
26 82 the major concern in literature is enhancing the stability and compatibility of bitumen-polymer
27 83 blends and optimizing the formulation of the blends (Wang et al. 2020). Most reported works
28
29 84 on the utilization of polymers as a modifier focus on describing the physical dispersion of
30
31 85 polymers in bitumen while ignoring the chemical reaction that occurs in the blend (Yusoff et
32
33 86 al. 2014; Rosyidi et al. 2020).
34
35 87
36
37
88 In view of the limitations of previous works, this study aims to investigate the chemical
38 89 and physical performance of modified bitumen with a new bitumen modifier known as
39
40 90 poly(lactic) acid (PLA). This research examines the chemical interaction occurring between
41
42 91 the PLA and the base bitumen by using multiple spectroscopic techniques. The relationship of
43
44 92 the interactions is then confirmed using the sequential dissolution approach, where a reaction
45
46 93 mechanism between PLA and bitumen is also proposed. The PLA-bitumen compatibility and
47
94 the dispersion of PLA in bitumen are also discussed. The current study will be useful to
48
49 95 understand the behaviour and properties of PLA in bitumen modification for its potential
50
51 96 utilization in pavement engineering. The remainder of this paper is structured as follows.
52
53 97 Section 2 describes the materials, blending and testing protocol. Section 3 presents the results
54
55 98 and discussion of the outcome in this study. The paper ends with conclusion and
56
57 99 recommendations for future research in Section 4.
58
100
59
60 101
61
62 3
63
64
65
102 2. Material and Methods
1
2 103
3
4 104 2.1. Materials
5
105
6
7 106 Poly(lactic) acid (PLA) in pellet form with a melt flow index (MFI) of 20 g/10 min (190
8
9 107 °C/2.16 kg) and a density of 1.24 g/cm3 was purchased from Shenzhen Bright China Industrial
10
11 108 Co, while the chloroform was obtained from Merck Pvt Ltd, Selangor, Malaysia. The filter
12
13 109 paper (Whatman, 150mm, Catalog Number 1001-150) was purchased from a local supplier,
14
15 110 and the 60/70 penetration grade bitumen was supplied by a refinery in Port Klang, Malaysia.
16 111 The physical properties of the 60/70 penetration grade bitumen used in this study are presented
17
18 112 in Table 1.
19
20 113
21
22 114 Table 1: Physical properties of 60/70 penetration grade bitumen
23
24 Parameter Standard Unit Specification
25 Penetration at 25°C ASTM D5 mm/10 60/70
26 Softening point ASTM D36 °C 49/56
27
28
Ductility at 25°C ASTM D113 cm 100 min
29 Loss of heating ASTM D6 wt. % 0.2 max
30 Drop in penetration after heating ASTM D5-D6 % 20 max
31 115
32
33 116 2.2. Preparation of bitumen blends
34
35 117
36
37 118 Aluminum cans (500 cm3) were filled with 200 g of 60/70 penetration grade bitumen and put
38
119 in a 150 °C oven until they are ready for use. The PLA was dissolved in an appropriate volume
39
40 120 of chloroform to obtain a final concentration of 3, 5, 7 and 9 wt. % by base bitumen (250g).
41
42 121 The semi-liquid PLA was gradually added (2 mL/min) to the base bitumen at 180 ± 2 °C and
43
44 122 a high-shear mixer to blend at 1000 ± 10 rpm for two hours to obtain a homogenous mixture.
45
46 123 After this step, the mixture was aliquoted into different cans for subsequent physical and
47
48 124 chemical testing. The experimental process of the development of PLA modified bitumen is
49
125 presented in Figure 1.
50
51 126
52
53 127
54
55 128
56
57 129
58
59 130
60
61
62 4
63
64
65
131
1
Materials selection and
2 132 characterisation
3
4 133
5
134
6 Blending process
7 135
8
9 136
10
11 137 Chemical characterization
12 of PLA modified bitumen
13 138
14
15 139
16
140 Physical characterization
17 of PLA modified bitumen
18 141
19
20 142 Figure 1: Research methodology
21
22 143
23
24 144 2.3. Characterization of reactive polymer with bitumen
25
26 145
27 146 Proton (1H)-nuclear magnetic resonance (NMR) spectra was used to study the structural
28
29 147 distribution of PLA and their interaction with the bitumen. The analysis was carried out using
30
31 148 the Brucker Advance III HD 400MHz 1-Dimensional NMR spectroscopy with
32
33 149 tetramethylsilane (TMS) as the internal standard. Each sample was dissolved in deuterated
34
35 150 chloroform (CDCl3) to a final concentration of 10% w/v and the run time was 10 minutes.
36
37
151 Fourier-Transform Infrared spectroscopy (FT-IR) was carried out to determine the functional
38 152 groups and the chemical bonds in the PLA-modified bitumen. All samples were tested in
39
40 153 triplicate using the Perkin Elmer Spectrum 400-FT-IR spectrometer.
41
42 154
43
44 155 The compatibility of PLA with base bitumen was determined by analyzing the
45
46 156 asphaltenes using sequential dissolution via staged extraction approach. The 100 mg samples
47
157 of bitumen and modified bitumen with 3, 5, 7 and 9% PLA, were washed three times with 10
48
49 158 mL of chloroform. Each layer was then filtered with using a filter paper. The residue (in the
50
51 159 form of asphaltenes) retained on the filter paper was weighed and compared with the control
52
53 160 bitumen. Next, the extracted asphaltenes from the third wash of each sample were recovered
54
55 161 and characterized using FT-IR spectroscopy.
56
57 162
58
163 Gel permeation chromatography (GPC) was employed to analyze the dispersity of PLA
59
60 164 in the base bitumen. Dispersity was determined based on molar mass and molar-mass
61
62 5
63
64
65
165 distribution of the polymer obtained from GPC (Waters 1515) equipped with differential
1
2 166 refractive index (RI 2410) and ultraviolet (UV 2487) detectors. The molar masses were
3
4 167 separated using Waters Styragel columns in a series with the molar mass ranging from 100-
5
168 500 000 gmol-1. The samples were dissolved in chloroform and analyzed using tetrahydrofuran
6
7 169 (THF) as the eluent at a flow rate of 1.0 mL/min (30 °C) for 40 minutes.
8
9 170
10
11 171 2.4. Characterization of PLA-modified bitumen
12
13 172
14
15 173 The physical characterization of PLA-modified bitumen includes performing the penetration
16 174 test at a fixed temperature (25 °C) according to ASTM D5 while the softening point was
17
18 175 measured with ring and ball approach as per ASTM D36-06 standard. The stability test was
19
20 176 carried out by placing the bitumen in an aluminum-covered tube with a diameter of 3.5 cm and
21
22 177 a height of 30 cm in a 180 °C oven for three days. The samples were then cooled at ambient
23
24 178 temperature and then cut into three sections. The upper and lower sections of each sample were
25
26 179 subjected to softening temperature test. The degree of homogeneity of the mixture is indicated
27 180 by differences in softening temperature between the two sections, where a smaller difference
28
29 181 indicates high compatibility of the PLA with bitumen. The ductility test was carried out
30
31 182 according to ASTM D113 standard at 25 °C.
32
33 183
34
35 184 3. Results and Discussion
36
37
185
38 186 3.1. Characterization of PLA-bitumen reaction
39
40 187
41
42 188 3.1.1. 1-Dimensional Nucleus Magnetic Resonance Proton (1H 1D-NMR) analysis
43
44 189
45
46 190 In order to demonstrate the interaction between PLA and bitumen, a representative 1H NMR
47
191 spectrums and the assigned signals of the control and the bitumen modified with varying
48
49 192 percentages of PLA (Figure 2-4). The results in Figure 2 show that there are multiple signals
50
51 193 from the chemical shift from 0.8 to 3.5 ppm. The signals were assigned as two parts, the part
52
53 194 ‘a’ ranges from 0.8 to 1.4 ppm and represents the signals of the aliphatic proton from alkanes.
54
55 195 The ‘b’ ranges from 1.5 to 3.5 ppm and represents the protons from alkenes, alkynes or aliphatic
56
57 196 with carbonyl such as ketone, aldehyde, ester and carboxyl group. The chemical structure for
58
197 poly(lactic) acid is shown in Figure 3, where two signals have been detected. The doublet peak
59
60 198 absorbed at a chemical shift from 1.58 to 1.60 ppm (labelled c) indicates a proton from methyl
61
62 6
63
64
65
199 group (-CH3), and the quartet peak at 5.15-5.20 ppm (labelled d) indicates a proton from the
1
2 200 ester side chain (-OCH(CH3)-) of the repeating unit of PLA. Figure 4 shows the stacked NMR
3
4 201 of the bitumen modified with 3, 5, 7 and 9% PLA. The four detected signals (a, b, c and d)
5
202 indicate the occurrence of a chemical interaction between the PLA and the bitumen. The
6
7 203 increase in the intensity of the doublet and quartet (peaks c and d) corresponds with the high
8
9 204 percentage of PLA in the samples. A comparison with the control bitumen shows the
10
11 205
men + Rh-WMA.001.001.1r.esp
suppression of the signals in the ‘b’ region (Figure 4B) of the PLA-modified bitumen.
12
13 206 Nashriq_bitumen + Rh-WMA.001.001.1r.esp
1.00
14
15 0.95
16
0.90
17
18 0.85
19 0.80
20
0.75
21
22 0.70
23
0.65
24
25 0.60 b
Normalized Intensity
26 0.55
27
0.50
28
29 0.45
30 0.40
31
32 0.35
a
33 0.30
34
0.25 CDCl3
35
8.0 36 7.5 0.207.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
37 0.15
38
39 0.10 b
40 0.05
41
0
42
43 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
44 207
Chemical Shift (ppm)
45 208 Figure 2: 1H-NMR spectrum of control bitumen.

46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 7
63
64
65
1.60
1.58
Nashriq_PLA only.001.001.1r.esp
1.00
0.95
1
01.001.1r.esp CH3 d O CH3
2 0.90
H
3 0.85 O OH
4 HO O
0.80
5
6 0.75 c
1.60
1.58
Nashriq_PLA only.001.001.1r.esp
O CH3 O
7 1.00 c n
0.70
0.95
8 0.90
0.65
9
5.16
0.85
5.18
10 0.60
0.80
11 0.55
0.75
0.70
12 0.50
d
13
0.65
CDCl3
0.60
0.45
14
7.27
0.55
15 0.40 0.50
5.16
5.18
16 0.35
0.45
0.40
17 0.35
0.30
18 0.30
5.20
19
5.15
0.25 0.25
20 0.20
0.20
21 0.15
0.15 0.10
22
5.20
5.15
0.05
23 0.10
0
5.5524 5.50 5.45 5.40 5.35

2.35 5.30
2.30 5.25
2.25 5.20
2.20 5.15
2.15 5.10
2.10 5.05
2.05 5.00
2.00 4.95
1.95 4.90
1.90 4.85
1.85 4.80
1.80 1.75 1.70 1.65 1.60 1.55 1.50 1.45 1.40 1.35 1.30 1.25 1
0.05 Chemical Shift (ppm) Chem ical Shift (ppm)
25
0
26
27 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
28
209 Chemical Shift (ppm)
29 210 Figure 3: 1H-NMR spectrum of PLA

30
31 211
32
33 212
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 8
63
64
65
(A) (B)
c a
1
2
d
3
4 0.19
Nashriq_3% PLA.001.001.1r.esp
5 0.18
CDCl3
6 0.17
7 0.16
8 0.15
9 0.14
0.19
Nashriq_3% PLA.001.001.1r.esp
10 0.13 0.18
b
11 0.12
0.17
0.16
12
0.11 0.15
13 0.10 0.14
0.13 9% PLA
14 0.09
0.12
15
0.08 0.11
0.10
16 0.07
17 0.06
0.09
0.08
7% PLA
18 0.05 0.07
0.06
19 0.04
0.05
0.03
5% PLA
20 0.04
0.03
0.02
21 0.02
0.01
22 0.01
0
3% PLA
0
23 8.0
8.0
7.5 7.0
7.5
6.5 6.0
7.0
5.5 5.0
6.5
4.5
6.0
4.0 3.5
5.5
3.0 2.5
5.0
2.0 1.5
4.5
1.0
4.0
Chem
0.5 ical Shift
0
3.5
(ppm )
3.0 2.5 2.0 1.5 1.0 0.5 0
24 Chemical Shift (ppm)
25 Bitumen
26
27 213
28 214 Figure 4: (A) 1H-NMR spectrum of the bitumen modified with 3, 5, 7 and 9% PLA. (B)
29
30 215 Zoom 1H-NMR spectrum between 0.5 to 3.0 ppm of the bitumen modified with 3, 5, 7 and
31
32 216 9% PLA
33
34 217
35
36
218 3.1.2. Fourier-Transform Infrared (FT-IR) analysis
37 219
38
39 220 Figure 5 shows a comparison of the FT-IR spectrum of the control bitumen, PLA and the
40
41 221 bitumen modified with 3, 5, 7 and 9% PLA. The spectrum shows that the bitumen modified
42
43 222 with different percentages of PLA have similar overlapping profiles. A comparison of the
44
45 223 spectrum for samples modified with PLA with control bitumen and PLA shows an almost
46
47
224 similar profile except for the additional bands at 1098 cm-1 (region i) and 1749 cm-1 (region ii)
48 225 in the modified bitumen. This indicates the simultaneous presence of the carbon-oxygen (C-O)
49
50 226 and carbonyl (C=O) functional groups. A comparison with the PLA spectrum shows a
51
52 227 decreased transmittance percentage in the PLA-modified bitumen in region iii (3600-3650 cm-
53 1
54 228 ) for the band representing the hydroxyl group (OH).
55
56
57
58
59
60
61
62 9
63
64
65
Region iii Region ii Region i
1
2 100
3
4
5
6 80
3600- 3650 cm-1
7
% Transmittance
8
1749.985 cm-1
9 60
10 Bitumen control
11
12 PLA
13 40
14 1098.9 cm-1
3, 5, 7 and 9% PLA
15
16
17 20
18
19
20
0
21
4000 3500 3000 2500 2000 1500 1000 500
22
23 229 wavenumbers (cm-1)
24
25 230 Figure 5: FT-IR spectrum of the control bitumen, PLA and bitumen modified with 3, 5, 7
26
231 and 9% PLA
27
28 232
29
30 233 The compatibility of PLA with bitumen was investigated using sequential dissolution
31
32 234 technique via the staged extraction method. The asphaltenes from each sample (the third wash)
33
34 235 were extracted and sent for FT-IR analysis to determine their carbonyl index. Figure 6 shows
35
36 236 the percentage of asphaltenes for bitumen modified with 3, 5, 7 and 9% PLA. The results are
37 237 comparable with the percentage of the control bitumen (~14.4%), except for higher asphaltenes
38
39 238 content observed in the bitumen modified with 9% PLA (18.1%). Based on the FT-IR
40
41 239 spectrum, the carbonyl index (CI) was determined by calculating the area under the carbonyl
42
43 240 band absorbed at wavelength 1695 cm-1 and the saturated C-C band at 1455 cm-1 (Eq. 1). The
44
45 241 same asphaltenes residue shows that the carbonyl index of the bitumen modified with 3, 5 and
46
47
242 7% PLA are slightly higher (~16.3%) than that of the control bitumen (14.5%). Similar to the
48 243 asphaltenes content, bitumen modified with 9% PLA has a high carbonyl index of 19.7%
49
50 244 (Figure 6).
51
52 245
53
54 area of carbonyl at 1695 cm-1
55 246 CI = x 100 (1)
56 area of saturated C-C at 1455 cm-1
57 247
58
59
60
61
62 10
63
64
65
25 25
1 asphaltenes
2 19.72
3 20 Carbonyl Index 18.1 20
Carbonyl index (%)

4 16.03 16.23 16.42
Asphaltene (%)
5 14.50 14.4 14.7 14.5

15 13.8 15
6
7
8 10 10
9
10
11 5 5
12
13
0 0
14
bitumen control 3% PLA 5% PLA 7% PLA 9% PLA
15
16 248
17
18
249 Figure 6: Compatibility and sequential dissolution of different percentages of PLA and
19 250 bitumen
20
21 251
22
23 252 The FT-IR spectrum presented in Figure 5 and the sequential dissolution technique
24
25 253 were used as a basis for further investigation of the correlation between the additional C-O
26
27 254 band at 1098 cm-1 (region i) and C=O band at 1749 cm-1 (region ii) in the PLA-modified
28
255 bitumen. The spectrum in Figure 5 which were PLA-modified bitumen was labelled as
29
30 256 unwashed (UW) and the PLA-modified bitumen that underwent sequential dissolution notated
31
32 257 as washed samples sequential dissolution (WSD). The results were compared to understand the
33
34 258 interaction between the PLA and the bitumen. Figure 7 shows the percentage index of C-O
35
36 259 bond (region i) while Figure 8 shows the result of C=O (region ii) divided with the area of (A)
37
38 260 unsaturated C=C at 1650 cm-1 and (B) saturated C-C at 1455 cm-1. The index pattern of the C-
39
261 O bond is observed to be different from that of C=O when divided with the unsaturated and
40
41 262 saturated carbon-carbon interaction. Figure 7 indicates that the UW showed a simultaneous
42
43 263 increase from control bitumen in the index of C-O and C=O with C=C from 11.0 to 26.3% and
44
45 264 4.7 to 17.9% respectively and C=O with C-C index from 1.0 to 7.3%. While a decreasing
46
47 265 pattern of UW sample for C-O bond with C-C index from 11.0 to 7.0% observed. On the other
48
49 266 hand, for WSD samples, the result did not show any significant difference in the index of C-O
50 267 with C=C (~11.1%) except for the 9% PLA (12.7%). Together with UW samples, WSD also
51
52 268 showed a decreasing index pattern of C-O bond with C-C from 10.6 to 5.1%. However, an
53
54 269 increasing indexes pattern showed for WSD samples of C=O with C=C and C-C each from
55
56 270 12.1 to 16.9% and 9.0 to 18.9% respectively.
57
58
59
60
61
62 11
63
64
65
A.
1
2 30
unwashed washed 26.3
3
25 23.5
4
5 20.4
20 18.5
6
Index (%)
7
8 15 12.7
11.0 11.0 11.1 11.2 11.1
9
10 10
11
12 5
13
14 0
15 bitumen control 3% 5% 7% 9%
271
16
17 B.
18
30
19
20 25
21 unwashed washed
22 20
23
Index (%)
24 15
25 11.010.6 10.09.7 9.0 8.1
26 10 8.0
27 6.5 7.0
5.1
28 5
29
30 0
32 272
33 273 Figure 7: Comparison of washed and unwashed indexes of C-O bond at 1749 cm-1 (region i)
34
35 274 with (A) C=C, and (B) C-C bonds using FT-IR analysis
36
37 275
38
39 276
40
41 A.
42 25
43
44 unwashed washed
45 20 17.9
16.9
46 14.6 15.4
14.5
Index (%)
47 15 13.4
48 12.1 11.4
49 9.9
10
50
51 4.7
52 5
53
54 0
56 277
57
58
59
60
61
62 12
63
64
65
B.
1
2 25
3
unwashed washed 18.9
4 20
5 15.8
6
Index (%)
15 13.2
7 11.1
8 9.0
9 10
7.3
10 5.1
11 5 3.2
12 1.0 1.8
13
0
14
bitumen control 3% 5% 7% 9%
15 278
16
17 279 Figure 8: Comparison of washed and unwashed indexes of carbonyl at 1749 cm-1 (region ii)
18 280 with (A) C=C, and (B) C-C bonds using FT-IR analysis
19
20 281
21
22 282 3.1.3. Gel Permeation Chromatography (GPC) analysis
23
24 283
25
26 284 The molar mass and molar-mass distribution or dispersity of PLA throughout the bitumen were
27
28
285 examined using GPC. Figure 9 is the stacked GPC chromatograms of the control bitumen and
29 286 the PLA-modified bitumen, while Figure 10 shows the zoom chromatograms of the distribution
30
31 287 and dispersity of PLA in bitumen. Two peaks can be seen in the control bitumen sample eluted
32
33 288 at retention times of 25.0 and 30.3 minutes. The two major peaks represent bitumen and are
34
35 289 present in all PLA-modified bitumen samples (Figure 9). However, Figure 10 shows that, when
36
37 290 PLA is added to the bitumen, the increase in the numbers of peaks correspond with the
38
291 increasing percentage of PLA (from 3, 5, 7 to 9% PLA). The distribution of PLA peaks at a
39
40 292 retention time of 25 minutes varies between samples while the major peak (at 30.3 mins) is not
41
42 293 affected. The large fragments of PLA peaks eluted at retention time 25 minutes indicate the
43
44 294 poly-dispersity of PLA within the samples. Thus, the properties of all peaks at the 25.0-minute
45
46 295 retention time were further investigated and the results are shown in Table 2. The table shows
47
48 296 that the retention time of the second major peak in all samples shifted about ± 0.1 minutes, the
49
297 effect of the size of exclusion column separation. The values of peak molecular weight, average
50
51 298 molecular weight, average molar mass and molar distribution (dispersity) increased with PLA
52
53 299 modification (Table 2). The varying dispersity for the 3 and 5% (1.089 and 1.136) and the 7
54
55 300 and 9% (1.653 and 1.984) bitumen-PLA indicate that the dispersity of PLA is enhanced when
56
57 301 7% and 9% of PLA were added to the bitumen.
58
59 302
60
61
62 13
63
64
65
1
2
3 Bitumen
4
5
6
7
8
9
10 3% PLA
11
12
13
14
15
16
17
18 5% PLA
19
20
21
22
23
24
25
26
7% PLA
27
28
29
30
31
32
33
34 9% PLA
35
36
37
38
39
40
41 303
42
43 304 Figure 9: Gel permeable chromatography (GPC) of the control and modified bitumen
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 14
63
64
65
1
2
3
4
Bitumen control
5
6
7
8
9
10
11
12
13 3% PLA
14
15
16
17
18
19
20
21 5% PLA
22
23
24
25
26
27
28
29 7% PLA
30
31
32
33
34
35
36
37 9% PLA
38
39
40 305
41
42 306 Figure 10: Zoom GPC of the control and modified bitumen
43 307
44
45 308 Table 2: Molecular properties of bitumen modified with PLA
46
47 Peak Average
48 Average
Retention Molecular Molecular Dispersity
49 Sample molar mass
50 time (min) Weight Weight (Mw/Mn)
(Mn)
51 (MP) (Mw)
52 Control
53 25.063 1633 1253 1205 1.039
Sample
54
3% PLA 25.047 1659 1331 1222 1.089
55
56 5% PLA 25.154 1701 1456 1281 1.136
57 7% PLA 25.157 1786 2161 1307 1.653
58 9% PLA 25.134 1805 2749 1385 1.984
59 309
60
61
62 15
63
64
65
310 3.2. Performance of PLA-modified bitumen
1
2 311
3
4 312 The effect of PLA on the properties of modified bitumen was evaluated based on the physical
5
313 performance including; penetration, softening point, ductility and storage stability. Figure 11
6
7 314 presents the result of the penetration values of the binders. The penetration is an indication of
8
9 315 bitumen consistency, which is an empirical measure of the resistance of bitumen to continuous
10
11 316 deformation. The addition of PLA to bitumen changes the penetration value of the binders
12
13 317 (Figure 11). The bitumen added with more quantity of PLA (7% and 9%) shows low
14
15 318 penetration values as compared to the base bitumen. This indicates the ability of the PLA
16 319 modifier to enhance bitumen stiffness. The penetration result shows a peculiar trend, where the
17
18 320 addition of 3% of PLA increases the penetration value up to 18.5% in comparison to the base
19
20 321 bitumen, after which penetration gradually decreases with high PLA content. This is due to the
21
22 322 dispersion level of PLA in bitumen. Based on dispersity reported earlier, the dispersity of 3%
23
24 323 PLA in bitumen is low, and this has the effect of softening the binder. The gradual decrease of
25
26 324 the value observed with the addition of high amounts of PLA (5% to 9%) is due to the high
27 325 dispersity of PLA in bitumen. Furthermore, the high fatigue resistance and elastic recovery of
28
29 326 PLA are similar to other thermoplastic materials such as SBS, crumb rubber and natural rubber
30
31 327 and contribute to the improvement of bitumen’s consistency (Chen et al. 2007; Schaur et al.
32
33 328 2017 Airey, 2004; Chen et al. 2007; Schaur et al. 2017; Poovaneshvaran et al. 2020; and Yao
34
35 329 et al. 2018). High amounts of PLA in bitumen results in improved mechanical properties (from
36
37
330 PLA) of the modified bitumen, and as a result increases the stiffness of the binder. This increase
38 331 may also be due to the enhanced structural chain mobility properties of the modified bitumen.
39
40
90
41
42 80
43
Penetration value (dmm)
44 70
45 60
46
47 50
48 40
49
50 30
51
52 20
53 10
54
55 0
56 Control Sample 3% PLA 5% PLA 7% PLA 9% PLA
57 Type of Sample
58 332
59
60 333 Figure 11: Penetration values at 25 °C
61
62 16
63
64
65
334
1
2 335 The softening point value of PLA-modified bitumen (Figure 12) is directly proportional
3
4 336 to the amount of PLA in bitumen. The high PLA content in bitumen increased the asphaltene
5
337 ratio in modified binders and this contributes to improving the stiffening properties of modified
6
7 338 bitumen. As a result, it reduces the susceptibility of the modified binder to temperature changes.
8
9 339 The less susceptibility of bitumen such as PLA modified bitumen indicated the high
10
11 340 performance of bitumen at high temperature (Zakaria et al., 2018; Al Mansoob et al., 2017).
12
13 341 This is congruent with the observation made by Poovaneshvaran et al. (2020), Rosyidi et al.
14
15 342 (2020) and Yusoff et al., (2019) about the ability of modified bitumen to withstand high
16 343 temperatures as compared to base bitumen. In addition, the ductility value of PLA-modified
17
18 344 bitumen is >100 cm, which is similar to the value for the base bitumen (See Table 3). The
19
20 345 physical properties of PLA-modified bitumen reported in this study are comparable with those
21
22 346 reported in earlier studies, including Al-Mansob et al. (2017), Ibrahim et al. (2016),
23
24 347 Poovaneshvaran et al. (2020) and Ali et al. (2015).
25
26 348
27
28 80
29
70
30
Softening point value (°C)
31 60
32
33 50
34
35 40
36
37 30
38 20
39
40 10
41
42 0
43 Control Sample 3% PLA 5% PLA 7% PLA 9% PLA
44 Type of sample
45
349
46
47 350 Figure 12: Softening point values
48
49 351
50
51 352 On the other hand, the main concern with polymer modified bitumen is the storage
52
53
353 stability of the modified bitumen. According to Yu et al. (2015), the modified bitumen is
54 354 considered stable when the difference between the softening point of the upper and lower
55
56 355 sections of the samples after storage under certain condition is less than 2.5 °C. The difference
57
58 356 in softening points of the top and bottom sections of the samples determines the degree of phase
59
60 357 separation. During high-temperature storage, the phase separation occurs when the modifier is
61
62 17
63
64
65
358 not dissolved in the modified bitumen and result in the non-homogeneous mixture.
1
2 359 Hosseinnezhad et al. (2019) argued that the occurrence of phase separation is influenced by the
3
4 360 solubility and particle size of the modifier and density of both the modifier and bitumen.
5
361 According to the literature, polymer-modified bitumen with poor storage stability is not
6
7 362 suitable for paving, roofing, and industrial specialty product applications (Isacsson et al., 1995;
8
9 363 Becker et al., 2001; Wahhab et al., 2016).
10
11 364
12
13 365 Bitumen modified with functionalized polymers, such as PLA, have high thermal
14
15 366 stability and no phase separation. This is indicated by the small temperature difference (<2.5
16 367 °C) between the top and bottom sections of the sample, except for the bitumen modified with
17
18 368 9% PLA (See Table 3). The poor thermal storage stability of the bitumen modified with 9%
19
20 369 PLA is due to the less compatibility between PLA and bitumen.
21
22 370
23
24 371 Table 3: Ductility and storage stability of base bitumen and PLA-modified bitumen
25
26 *Storage Stability
27
28 Ductility at
29 Sample
25 °C (cm)
30 Top (°C) Bottom (°C) Difference (°C) Status
31
32
33 Control
34 >100 - - - -
Sample
35
36 3% PLA >100 50 51 1 Good
37 5% PLA >100 58 60 2 Good
38 7% PLA >100 59 61 2 Good
39
40
9% PLA >100 68 72 4 Poor
41 372 *difference between the softening point of the top and bottom sections
42
373
43
44 374 3.3 Discussion of the Results
45
46 375
47
48 376 In this study, polymer modification of bitumen involves the physical blending of the polymer
49
50 377 with bitumen as well as the chemical reactions between the two materials as recommended by
51
52 378 Brasileiro et al., (2019) and Cardone et al., (2014). Nuclear magnetic resonance (NMR) is a
53
379 spectroscopic method that can provide information about the number of magnetically distinct
54
55 380 atoms such as hydrogen nuclei (protons). NMR differs from Infrared (IR) related to the
56
57 381 approach of NMR reveals the type of functional groups present in a molecule. By combining
58
59 382 the utilization of NMR and IR spectroscopies, this study is able to gather sufficient evidence
60
61
62 18
63
64
65
383 on the chemical interactions between the bitumen and poly(lactic) acid (PLA). In NMR
1
2 384 analysis, different types of protons (H) are represented as peak signals in the spectrum having
3
4 385 different chemical shifts. The NMR of the control bitumen (Figure 2) shows that signals are
5
386 absorbed at a different range of chemical shift. The signals from 0.8 to 1.4 ppm in the region
6
7 387 (a) represent the protons from aliphatic alkanes. It can be concluded that most of the protons in
8
9 388 the base bitumen are alkanes, whether they are from the primary (R-CH3), secondary (R-CH2-
10
11 389 R) or tertiary alkanes (R3CH). The two singlet peaks in this region indicate that these protons
12
13 390 are bonded with other functional groups (R), for instance, oxygen. The signals in the region (b)
14
15 391 are protons which represent alkenes, alkynes, aliphatic carbonyl functional group or protons
16 392 bonded with phenyl (aromatic as side chain). In addition, no other signals are observed in the
17
18 393 spectrums. This indicated the occurrence of other chemical shift (between 6.5 and 8.0 ppm)
19
20 394 which represented the aromatic protons. However, it is known that bitumen contains a lot of
21
22 395 aromatic compounds (Polacco et al., 2006), thus, it can be deduced that the aromatic group in
23
24 396 the bitumen is present as the phenyl group and no free protons are attached at the aromatic
25
26 397 structure.
27 398
28
29 399 The NMR spectrum of PLA (Figure 3) shows two signals, where one of the peaks is a
30
31 400 doublet, indicating the protons from the methyl group (assigned as c), and the second peak is a
32
33 401 quartet, which indicates the proton assigned as (d). Proton (d) is more shielded (appears at a
34
35 402 high chemical shift) compared to the methyl group and more electronegative when interacting
36
37
403 closely with two oxygen atoms next to each other. The results of NMR analysis of the bitumen
38 404 modified with 3, 5, 7 and 9% PLA (Figure 4) show that all signals from the bitumen and PLA
39
40 405 (a, b, c, and d) appear at each chemical shift. The increase in the observed intensity of the
41
42 406 signals for PLA corresponds with the increasing concentration of PLA in the samples.
43
44 407 However, the signals in the region (b) of the modified samples seem to be suppressed. The
45
46 408 suppression of the signals in this area indicates the loss of the proton absorbed at this chemical
47
409 shift. This is because one of the functional groups (either carbonyl groups or aliphatic
48
49 410 alkenes/alkynes) from this region interacts with PLA; this is later confirmed by the result of
50
51 411 the FT-IR analysis.
52
53 412
54
55 413 FT-IR analysis of the base bitumen, PLA and PLA modified bitumen (Figure 5) show
56
57 414 two additional bands at wavenumbers 1098.9 (region i) and 1749.9 cm-1 (region ii) and the
58
415 PLA-modified bitumen show a decrease in a band at 3600-3650 cm-1 relative to PLA. The new
59
60 416 functional groups in the PLA-modified bitumen sample (carbon-oxygen bonding (C-O) in
61
62 19
63
64
65
417 region i and carbonyl group (C=O) in region ii) support the result of NMR analysis. The
1
2 418 occurrence of new functional groups in the PLA-modified bitumen represented the PLA is
3
4 419 compatible with the base bitumen. The PLA and bitumen are chemically interacting with the
5
420 base bitumen during blending. The disappearance of the band in region iii, represented by the
6
7 421 hydroxyl group (OH), shows the reaction between the base bitumen and PLA occurring at the
8
9 422 OH group; this has resulted in the formation of new C-O and C=O bonding. However, the result
10
11 423 is not sufficient for predicting the functional group in the base bitumen reacting with the OH
12
13 424 group of the PLA. Thus, sequential dissolution was carried out to to determine the compatibility
14
15 425 of PLA with the bitumen.
16 426
17
18 427 The approach for investigating sequential dissolution was formulated by Corbett (1969)
19
20 428 and has been utilized by many researchers. Sequential dissolution is carried out to evaluate the
21
22 429 oxidation process that occurs between the binder and the bitumen. Generally, there is a net
23
24 430 reduction of maltenes fraction during an oxidation reaction, which occurs simultaneously with
25
26 431 an increase in asphaltene fraction. The formation of carbonyl functionalities within the binder
27 432 is linked with the increase in asphaltene during a sequential dissolution. Thus, an increase in
28
29 433 carbonyl functionalities is anticipated during the later stages of the extraction process when a
30
31 434 binder is being sequentially dissolved. In this study, sequential dissolution was used to
32
33 435 investigate the compatibility of PLA as a modifier for bitumen, thereby determining the
34
35 436 interaction of asphaltene with PLA. All samples (base bitumen and bitumen modified with 3,
36
37
437 5, 7 and 9% PLA) were washed with the same volume of chloroform (w/v). The result presented
38 438 in Figure 6 shows that the standard deviation does not exceed 1. The fractionation of the
39
40 439 bitumen modified with 3, 5 and 7% PLA with chloroform yielded 14.4 ± 0.8% asphaltenes,
41
42 440 slightly higher than the amount produced by the control bitumen (13.8 ± 0.2%). The lack of
43
44 441 significant difference in the value indicates absence of sequential dissolution and PLA in
45
46 442 concentrations of 3, 5 and 7% are compatible with the base bitumen.
47
443
48
49 444 The bitumen modified with 9% PLA show a ±5 % change in asphaltene content in
50
51 445 comparison to the control sample, indicating the compatibility of PLA with bitumen base does
52
53 446 not exceed 7%. A sufficient degree of polymer-bitumen compatibility is required to prevent
54
55 447 separation during storage, pumping and application of the asphalt mixture, as well as to ensure
56
57 448 required properties for pavements. Polymer modified bitumen with poor storage stability is not
58
449 suitable for applications such as paving binder, roofing, and other industrial speciality products
59
60 450 (Isacsson et al., 1995; Becker et al., 2001; Wahhab et al., 2016). The results of NMR and FTIR
61
62 20
63
64
65
451 are supported by the carbonyl index shown in Figure 6, where the carbonyl index is directly
1
2 452 proportional to the release of asphaltenes. It should be noted that the solvent used in this study,
3
4 453 i.e. chloroform, has never been reported to be one of the solvents with good compatibility with
5
454 bitumen. The amount of asphaltenes released due to the utilization of chloroform (13.8 ± 0.2%)
6
7 455 is lower than most of the solvents tested, such as TCE (16.7%), THF (22.5%), toluene (19.7%)
8
9 456 and decalin (22.6%) (Bowers et al. 2014). The low percentage of asphaltenes released by
10
11 457 chloroform is an indication of its high solubility.
12
13 458
14
15 459 FT-IR analysis of sequential dissolution was carried out to further investigate the
16 460 interaction between PLA and bitumen observed in the IR spectrum shown in Figure 5. The
17
18 461 washed (sequential dissolution) (WSD) and unwashed (PLA-modified bitumen) (UW) samples
19
20 462 were compared to determine the inter-correlation between the existing functional group and
21
22 463 the changes after blending. Based on the comparison of the washed and unwashed samples, it
23
24 464 can be concluded that the interaction bond between asphaltenes and PLA is dependent on the
25
26 465 carbonyl functionalities index. There is a different index pattern shown in addition to the band
27 466 at region i (C-O) and region ii (C=O) when divided with C=C and C-C bonds (Figure 5).
28
29 467 Overall, the C=C bond decreases while the C-C bond remains unchanged in the UW samples
30
31 468 of the control bitumen and the PLA modified bitumen. However, an increase in both the C=C
32
33 469 and C-C bonds was observed in all WSD in comparison to the control bitumen. The increase
34
35 470 in the amount of both alkenes and alkanes in the WSD is expected since both are a part of
36
37
471 asphaltene, which is the product of sequential dissolution. The difference in the number of
38 472 alkenes and alkanes in the UW indicates that one of them is probably involved in the chemical
39
40 473 interaction between the bitumen and the PLA.
41
42 474
43
44 475 From the analysis of the C-O bond in region i, the 11.2% increase in the cumulative
45
46 476 index of C-O with C=C relative to the control compared with the 2.5% decrease in that for C-
47
477 O with C-C indicated the C-O bond formed in the PLA modified bitumen samples is related
48
49 478 to the C=C interaction. This data is supported by the result of the WSD analysis, the index for
50
51 479 C-O with C=C values remains unchanged (except for 9% PLA) while the C-O shows a decrease
52
53 480 when divided with C-C area. The same index value for C-O with C-C in the WSD indicate that
54
55 481 no C-O bond is detected in PLA because of its high compatibility with bitumen after the
56
57 482 extraction process for sequential dissolution evaluation. Analysis of the carbonyl in region ii
58
483 shows that the decrease in the carbonyl index of the WSD corresponds with the amount of
59
60 484 asphaltenes dissolved in chloroform. The difference in the values of both carbonyl index
61
62 21
63
64
65
485 between C=C (average, 15.1%) and C-C (average, 4.4%) in all PLA-modified bitumen samples
1
2 486 is due to the significantly low C=C content in the samples after modification. Based on these
3
4 487 values, it can be concluded that the interaction of bitumen with PLA is between C=C and not
5
488 C-C. The result of NMR analysis (Figure 4B) supports this conclusion since there is a
6
7 489 suppression of signals at a chemical shift of between 1.5 and 3.5 ppm; these signals represent
8
9 490 the alkene (C=C) group. Finally, the loss of OH group in region iii (Figure 5) in the PLA-
10
11 491 modified bitumen samples seems to indicate the following reaction mechanism between PLA
12
13 492 and bitumen (Figure 13).
14
15 493
16
CH3 O CH3
17 H
18 O OH
Asphaltene H HO O
19
20 O CH3 n O H Asphaltene
C C
21 Asphaltene C C
22 H
PLA H Asphaltene
23
24
25
26
27
28 CH3 O CH3
H H H Asphaltene
29 Asphaltene O O
30 C C O O C C
31 O CH3 n O H
Asphaltene H H Asphaltene
32 H
33
34
35
36
37
38 CH3 O CH3 Asphaltene
39 Asphaltene H
O O C
40 C O O
41 Asphaltene
Asphaltene CH3 O CH3 n O CH3
42 494
43
44 495
45 496 Figure 13: Proposed reaction mechanism between PLA and bitumen
46
47 497
48
49 498 Generally, all the supporting data from NMR and FT-IR suggest that the reaction
50
51 499 between PLA and bitumen is an addition reaction. This reaction occurred when the hydroxyl
52
53 500 group of PLA reacts with the alkenes in bitumen, where the formation of bridge C-O bonding
54
55
501 found in the region based on FT-IR analysis. The finding is supported by the previous studies,
56 502 indicating the certain chemical reactions between the functional groups of the components of
57
58 503 the blends. This reaction or chemical compatibilization creates in-situ copolymers formation
59
60 504 during processing (Polacco et al., 2015; Mancini et al., 1991). This proposed mechanism is
61
62 22
63
64
65
505 important since the structure of PLA has high compatibility with bitumen. The finding of new
1
2 506 mechanism potentially provided the fundamental information related to the chemical
3
4 507 interaction of PLA and bitumen which lead to the discovery of new modifiers that are better
5
508 bitumen enhancer.
6
7 509
8
9 510 In addition to FT-IR analysis to determine the compatibility of PLA with bitumen, the
10
11 511 dispersity of PLA throughout the base bitumen was also examined with Gel Permeation
12
13 512 Chromatography (GPC). GPC was used to determine the molecular weight average of PLA
14
15 513 modified bitumen. The profile of GPC varies between bitumen modified with 3, 5, 7 and 9%
16 514 PLA relative to the control bitumen. It is worth noting that the peak eluted at ± 25.1 minutes,
17
18 515 differentiates the bitumen from the bitumen-PLA samples. The molecular properties of this
19
20 516 peak are presented in Table 2, and it shows a decline in the number of MP. The Mw, Mn and
21
22 517 polydispersity index of the samples were compared to the control sample. Mn is the statistical
23
24 518 average molecular weight of all PLA chains in the sample. Unlike Mn, Mw takes into account
25
26 519 the molecular weight of a chain in determining its contributions to the average molecular
27 520 weight.
28
29 521
30
31 522 Figure 10 and Table 2 show that there is a significant difference in bitumen modified
32
33 523 with 5% PLA (1456 gmol-1) and 7% PLA (2161 gmol-1). The heavier the chains have more
34
35 524 contribution to Mw; therefore, a better PLA-bitumen interaction is observed with 7% PLA
36
37
525 modification as compared to 3 and 5%. Polydispersity index is a measure of the distribution of
38 526 PLA’s molecular weight in the samples and is defined as Mw/Mn. The large polydispersity
39
40 527 index indicates the broad distribution of molecular weight. The difference in polydispersity
41
42 528 index of 5% (1.136) and 7% (1.653) PLA modification indicates that the bitumen showed the
43
44 529 best chemical interaction with the incorporation of up to 7% PLA. However, from the data of
45
46 530 sequential dissolution, the 9% PLA showed a sequential dissolution effect resulting in reduced
47
531 compatibility. In summary, based on the GPC and sequential dissolution data, the best
48
49 532 modification of bitumen is achieved with 7% PLA. This result is supported by the
50
51 533 characterization of the physical performance of PLA-modified bitumen. This research shows
52
53 534 that the properties of modified bitumen with 7% of PLA is the good quality in terms of
54
55 535 hardness, stiffness, ductility and storage stability ability. This is consistent with the previous
56
57 536 discussion of the chemical interaction, compatibility and dispersity test.
58
59 537
60
61
62 23
63
64
65
538 4. Conclusions and Suggestion for Future Study
1
2 539
3
4 540 This study aims to comprehensively evaluate the chemical and physical properties of PLA
5
541 modified bitumen. The chemical properties were monitored using NMR, FTIR and GPC, while
6
7 542 the physical properties of modified bitumen were measured by several empirical indexes in
8
9 543 terms of penetration, softening point and ductility grading. Furthermore, the storage stability
10
11 544 of the modified bitumen was also investigated in this study. The main conclusions of this
12
13 545 research are:
14
15
16
546  The addition of PLA into the base bitumen indicates the existence of chemical
17 547 interaction between these materials. The findings of this study have shown the
18
19 548 chemically cross-link at the alkene group (C=O) of PLA and hydroxyl group (OH) of
20
21 549 bitumen.
22
23 550  The results from GPC analysis shows high compatibility between the bitumen and
24
25 551 PLA. The dispersion of PLA in the bitumen is found to be directly proportional with
26
27 552 the amount of PLA, which results in the enhanced molecular properties of the PLA-
28 553 modified bitumen.
29
30 554  The physical properties of PLA modified bitumen obtained from the conventional
31
32 555 bitumen tests show that the consistency of modified bitumen has increased as
33
34 556 compared to the base bitumen with the low penetration and high softening point value.
35
36 557 Also, ductility properties of modified bitumen indicate the permitted value as that of
37
38 558 base bitumen.
39
40
559  The modification of bitumen with up to 7% PLA is storage stable except for the
41 560 modified bitumen with 9% of PLA content.
42
43 561  In summary, the use of PLA in bitumen modification has a significant effect on the
44
45 562 chemical and physical properties of modified bitumen. Based on the results, 7% PLA
46
47 563 is recommended as the optimum amount for modifying base bitumen.
48
49
564 For future studies, a more comprehensive characterization of PLA modified bitumen for
50
51 565 rheology properties can be carried out. There is a need to investigate the ageing of the PLA
52
53 566 modified bitumen for the effect of oxidation and UV radiation on the rheological properties
54
55 567 and the potential deterioration over time. Moreover, further research is recommended to
56
57 568 investigate the application of PLA-modified bitumen in asphalt mixtures.
58
59 569
60
61
62 24
63
64
65
570 Acknowledgement
1
2 571
3
4 572 The authors would like to express their gratitude to Universiti Kebangsaan Malaysia (UKM)
5
573 for the financial support of this work (DIP-2020-003).
6
7 574
8
9 575 Conflicts of Interest Statement
10
11 576
12
13 577 The authors declare that there is no conflict of interest in the publication of this paper.
14
15 578
16
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Author Biography
AUTHOR BIOGRAPHY
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Nashriq Jailaini is a research assistant at the Department of Civil Engineering, Universiti
5 Kebangsaan Malaysia (UKM), Malaysia. His research interests are mainly in the area of
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7 pavement engineering and pavement materials.
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13 Ahmad Nazrul Hakimi Ibrahim is a PhD student at the Department of Civil Engineering,
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Universiti Kebangsaan Malaysia (UKM), Malaysia. His research interests are mainly in the area
16 of highway and transportation engineering.
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22 Dr. Abdur Rahim is a senior lecturer in the Department of Transportation Engineering and
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24 Management, University of Engineering and Technology, Lahore, Pakistan. His research
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interests are mainly in the area of pavement engineering and pavement materials.
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31 Ir. Dr. Ahmad Kamil Arshad is a professor in the Institute for Infrastructure Engineering and
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33 Sustainable Management, Universiti Teknologi MARA (UiTM), Shah Alam, Malaysia. His
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35 research interests are mainly in the area of pavement engineering and pavement materials.
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40 Ts. Dr. Norhidayah Abdul Hassan is a senior lecturer in the School of Civil Engineering,
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42 Universiti Teknologi Malaysia (UTM), Malaysia. Her research interests are mainly in the area
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44 of pavement engineering and pavement materials.
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49 Ir. Dr. Nur Izzi Md. Yusoff is an associate professor in the Department of Civil Engineering,
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51 Universiti Kebangsaan Malaysia (UKM), Malaysia. His research interests are mainly in the area
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53 of pavement engineering and pavement materials.
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Author Photo
*Conflict of Interest
Conflicts of Interest Statement
The Authors declare that there is no conflict of interest regarding the publication of this paper.

Chemical and Physical Properties of Poly (Lactic) Acid Modified Bitumen

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Chemical and Physical Properties of Poly (Lactic) Acid Modified Bitumen

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Ain Shams Engineering Journal

Chemical and Physical Properties of Poly(Lactic) Acid (PLA) Modified Bitumen

Manuscript Number: ASEJ-D-19-00656R2

Article Type: Full Length Article

Section/Category: Civil Engineering

Keywords: Chemical interaction; Compatibility; Dispersity; Modified bitumen; Physical

Corresponding Author: Nur Izzi Md Yusoff, PhD

First Author: Nashriq Jailani, MSc

Order of Authors: Nashriq Jailani, MSc

Ahmad Nazrul Hakimi Ibrahim, PhD

Abdur Rahim, PhD

Ahmad Kamil Arshad, PhD

Norhidayah Abdul Hassan, PhD

Nur Izzi Md Yusoff, PhD

Response to Reviewers: List of comments and response

Point 1: More suitable title should be selected for the article.

Point 14: "Notation" should be added to the article.

26th December 2020

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