16
A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN IN DIFFFERENT MOLAR RATIOS A.M.Al-sabagh (1) , F.Abdel_Hai (2) , A.M.M.Abd El Rhman (1) , M.EL-Shafie (1) I. M. Ibrahim, I. M. Ibrahim and M.M.Mohammedy. (1)* (1) Egyptian Petroleum Research Institute (EPRI), Cairo, Egypt (2) Faculty of Science, AL-Azhar University, Cairo, Egypt ABSTRACT Polymer modified asphalt is increasingly used in road surfacing. Unmodified asphalt is sensitive to changes in temperature, it becomes brittle and cracks in cold weather and soften in high temperature, causing rutting and surface deformation. This research aims to prepare hot mix asphalt (HMA) for paving using polymer prepared from stearyl acrylate and methyl methac- rylate and styrene in molar ratios: 0.5:0.5:0.2 and 0.5:0.5:0.5, respectively. The solid materials in the mix include normal and highly porous aggregates. 4,6,8% of two polymers by weight of asphalt were used to prepare special binders. The samples were tested for physical, chemical, ageing, SEM and TGA. The results revealed that the prepared hot mix asphalt (HMA) polymer had high performance as compared to ordinary one and the two polymer prepared could be used in road construction. Key words: Asphalt,ester, hot mix asphalt, modified asphalt, polymer, Marshall. INTRODUCTION The addition of polymeric chains of repeated small molecules, to asphalt has been shown to improve performance. Pavement with polymer modification exhibits greater resistance to rutting and thermal cracking, and decreases fatigue dam- age, stripping, and temperature susceptibility[1]. Bitumen, residue from crude oil distillation, is a complex mixture of four main families of com- pounds, referred to as SARAs fractions (satu- rates, aromatics, resins and asphaltenes)[2]-[3]. Polymers that are used for asphalt modification can be grouped into three main categories: ther- moplastic elastomers,plastomers and reactive polymers. Thermoplastic elastomers are obvi- ously able to confer good elastic properties on thermo modified binder; while plastomers and reactive polymers are added to improve rigidity, and reduce deformations under load. Belong- ing to the first category, styrene-butadiene-sty- rene block (SBS) copolymers are probably the most frequently used asphalt modifiers for pav- ing applications [4]-[7]. Examples of the plas- tomeric types of polymers were studied since asphalt modifications are polyethylene (PE), and ethylene-butyl acrylate (EBA) random co- polymers [8]-[11]. Due to its low compatibility with asphalt, PE is not widely used for paving applications, and thus ethylene copolymers are preferred. Recently, reactive polymers have been introduced as asphalt modifiers. Their “reactiv- ity” is due to the presence of functional groups supposedly able to bond with asphalt molecules. Polarity of the polymer can enhance its solubil- ity and compatibility with base bitumen. Polar groups present in the polymer molecules can re- act with the polar constituents of bitumen. Sub- sequently, phase separation is prevented, which in turn enhances the materials consistency,and decreases oxidative ageing [12]-[15]. Among polar polymers, a very limited number of studies discuss the fundamental properties of modified bitumens with acrylate polymers.Most frequent- ly used acrylates as bitumen modifying agents in road applications are ethylene vinyl acetate. (EVA) glycidyl methacrylate (EA) terpolymer, ethylene butyl acrylate (EBA) copolymer, etc. [16]-[18]. In this work, use prepare the octadec- ylacrylate, then polymerized it with styrene and methyl methacrylate . This polymer was added to asphalt for improving the performance of bi- tumen in pavement. 2. EXPERIMENTAL 2.1. Materials Used Methyl methacrylate monomer and styrene was supplied by Navol, and stearyl alcohol from SASOL,,Acrylic acid from BASF, benzoyl per- Al Azhar Bulletin of Science Vol.(25) No.1, June, 23 - 38, 2014,.

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

  • Upload
    others

  • View
    1

  • Download
    0

Embed Size (px)

Citation preview

Page 1: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN

IN DIFFFERENT MOLAR RATIOS

A.M.Al-sabagh(1), F.Abdel_Hai (2), A.M.M.Abd El Rhman(1), M.EL-Shafie (1) I. M. Ibrahim, I. M.

Ibrahim and M.M.Mohammedy.(1)*

(1) Egyptian Petroleum Research Institute (EPRI), Cairo, Egypt

(2) Faculty of Science, AL-Azhar University, Cairo, Egypt

ABSTRACT

Polymer modified asphalt is increasingly used in road surfacing. Unmodified asphalt is sensitive to changes in temperature,

it becomes brittle and cracks in cold weather and soften in high temperature, causing rutting and surface deformation. This

research aims to prepare hot mix asphalt (HMA) for paving using polymer prepared from stearyl acrylate and methyl methac-

rylate and styrene in molar ratios: 0.5:0.5:0.2 and 0.5:0.5:0.5, respectively. The solid materials in the mix include normal and

highly porous aggregates. 4,6,8% of two polymers by weight of asphalt were used to prepare special binders. The samples were

tested for physical, chemical, ageing, SEM and TGA. The results revealed that the prepared hot mix asphalt (HMA) polymer

had high performance as compared to ordinary one and the two polymer prepared could be used in road construction.

Key words: Asphalt,ester, hot mix asphalt, modified asphalt, polymer, Marshall.

INTRODUCTION

The addition of polymeric chains of repeated

small molecules, to asphalt has been shown to

improve performance. Pavement with polymer

modification exhibits greater resistance to rutting

and thermal cracking, and decreases fatigue dam-

age, stripping, and temperature susceptibility[1].

Bitumen, residue from crude oil distillation, is a

complex mixture of four main families of com-

pounds, referred to as SARAs fractions (satu-

rates, aromatics, resins and asphaltenes)[2]-[3].

Polymers that are used for asphalt modification

can be grouped into three main categories: ther-

moplastic elastomers,plastomers and reactive

polymers. Thermoplastic elastomers are obvi-

ously able to confer good elastic properties on

thermo modified binder; while plastomers and

reactive polymers are added to improve rigidity,

and reduce deformations under load. Belong-

ing to the first category, styrene-butadiene-sty-

rene block (SBS) copolymers are probably the

most frequently used asphalt modifiers for pav-

ing applications [4]-[7]. Examples of the plas-

tomeric types of polymers were studied since

asphalt modifications are polyethylene (PE),

and ethylene-butyl acrylate (EBA) random co-

polymers [8]-[11]. Due to its low compatibility

with asphalt, PE is not widely used for paving

applications, and thus ethylene copolymers are

preferred. Recently, reactive polymers have been

introduced as asphalt modifiers. Their “reactiv-

ity” is due to the presence of functional groups

supposedly able to bond with asphalt molecules.

Polarity of the polymer can enhance its solubil-

ity and compatibility with base bitumen. Polar

groups present in the polymer molecules can re-

act with the polar constituents of bitumen. Sub-

sequently, phase separation is prevented, which

in turn enhances the materials consistency,and

decreases oxidative ageing [12]-[15]. Among

polar polymers, a very limited number of studies

discuss the fundamental properties of modified

bitumens with acrylate polymers.Most frequent-

ly used acrylates as bitumen modifying agents

in road applications are ethylene vinyl acetate.

(EVA) glycidyl methacrylate (EA) terpolymer,

ethylene butyl acrylate (EBA) copolymer, etc.

[16]-[18]. In this work, use prepare the octadec-

ylacrylate, then polymerized it with styrene and

methyl methacrylate . This polymer was added

to asphalt for improving the performance of bi-

tumen in pavement.

2. EXPERIMENTAL

2.1. Materials Used

Methyl methacrylate monomer and styrene

was supplied by Navol, and stearyl alcohol from

SASOL,,Acrylic acid from BASF, benzoyl per-

Al Azhar Bulletin of Science Vol.(25) No.1, June, 23 - 38, 2014,.

Page 2: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A.M.Al-sabagh, et al.24

oxide (DBPO) was obtained from Merck, Tolu-

ene and methanol were obtained from Carloerba

reagents. Local asphalt of penetration grade 60/

70, produced by El-Nasr Petroleum Company,

Suez-Egypt. The crushed limestone aggregate,

limestone mineral filler, and crushed sand were

originally obtained from Ataka Suez-Egypt. The

physical properties of the asphalt binder and the

aggregates are given in Table(s) 1, 2 and 3 re-

spectively.

2.2.1. Preparation of Octadecyl acrylate :

Octadecyl acrylate was prepared by the reac-

tion of acrylic acid and stearyl alcohol in a molar

ratios: 1.2:1, using toluene as solvent, p-toluene

sulfonic acid (PTSA) as catalyst, hydroquinone

as inhibitor, water was separated a zeotropically

using Dean–Stark apparatus [19]. The alcohol,

toluene and hydroquinone were mixed in a four-

necked flask, then heated to 60 °C. After the mix-

ure completely mixed, acrylic acid and PTSA

were added, and the mixure is gradually heating

to 115–120 °C. The reaction was stopped after a

theoretical amount of water is separates. Reac-

tion products were washed several times with an

aqueous solution of Na2CO

3 (5 %) until the low-

er layer became clear, then washed by distilled

water, vacuum distilled using a rotary evaporator

and them vacuum dried.

2.2.2 Polymerization of additives

All additive samples were prepared by free

radical solution polymerization in xylene us-

ing benzoyl peroxide as the initiator[20]. Po-

lymerization was performed in a reaction flask

equipped with a condenser, mechanical stirrer,

and temperature controller. Polymerization reac-

tion was carried out in nitrogen atmosphere at

90°C for 5 h. During that time, more than 95%

of monomer was polymerized. The resulting

homogeneous product was then cooled to room

temperature and used as additive without any

further treatment.

3. Experimental Procedure:

3.1. Characterization of raw materials

- Penetration, softening point, specific

gravity and Brookfield viscosity were determined

for the virgin asphalt samples (AC 60/70). The

results are illustrated in Table (1). The polymer

costituent illustrated in Table (2) and molecular

weight in Table (15)and FTIR spectra were re-

ported as shown in figure (2).

- TGA analysis was carried out using SDTQ

600 thermo-gravimetric analyzer (TA-USA) to

test the thermal stability of the virgin asphalt

sample and all polymers in the temperature range

of 25o to 500oC and a heating rate of 10oC/min

under dynamic nitrogen gas Table (3).

- The temperatures susceptibility of virgin

and modified asphalt sample was expressed in

term of penetration index (P.I) using the penetra-

tion at 25ºC(pen25) and softening point (soft.

pt)values.

P.I. can be calculated from the following

equation[21]:

P.I. = 1 952-500x log (pen 25) - 20x soft. Pt

50- log (pen 25) – soft. pt – 120

3.2. Preparation and Characterization of poly-

mer modified asphalt samples (PMAs).

Blends of virgin asphalt and three types of

polymer modifiers (4, 6 and 8% w/w of asphalt)

were prepared. The blending conditions were

conducted at 163oC with stirring for 2 hours with

complete addition of polymer into asphalt. The

prepared samples were tested for compatibility

test using Shell method[22], and then charac-

terized physically and chemically. The charac-

terization of PMAs are illustrated in Tables (7-

13).

3.3. Evaluation of Best Polymer Modified As-

phalt Samples :

FTIR (figure 2), SEM (figure 3) , TGA(figure

4) and analysis were carried out on virgin as-

phalt and modified AC with 4,8% of each poly-

mer which gave a suitable physical and chemi-

cal characteristics. SEM photographs have been

observed using scanning electron microscope

(SEM; Philips). Infrared spectra of all samples

were recorded via FTIR spectrophotometer

(Model 960 Mooog, ATI Mattson Infinity Series,

USA).

3.4. Preparation of hot mix asphalt :

Hot mix asphalt samples were prepared us-

ing virgin asphalt and modified binders and

Page 3: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN 25

�2�

0��� ��,�(�$&"�$��"�&�����C�$������!��"���!����*�������

@�"�$������!$��"�$�,����!��"�

C�$������# �

#���"$"���� "��3K(����22����3�����2�����

���"������!���"��K(� $�����������

#���"$"��������1� ���

�!�&���&��$+�"��%������!�&����"�$�� "��3K(��

����������$��!���"�� (��+�����E!���(%!���K(�

@%&"���"��� &��� "��3K(��3�&�F�������

R����"�&�+��&���"�� &�"�� "��<3K(�����

;$��.������+��&���"��(#� "�52�(K����

0��$���8$+���"$�&��������� 08���

� ��'��"������$�"����"��!�$"%$���K(�

� ����������$�"����"��!�$"%$���K(�������������������������

� �0�"��/����"������ /"��7��

��"��&��"��",�

�C���%�� !!���

�D�&.��� !!���

5<�

32�

�2�H?�

��2�6�

S�32�

S�32�

<<��

��2�?�

�45��6�

3�2�4��

65��2�

�4��2�

�<4�2�

52F?2�

43F33�

��,�S��

D� �

S�32�

S�32�

T<�2�

D� �

D� ��

D� ��

D� �

D� �

D� �

D�;,�� ���"��$���!�&���&"������$�U8���$���%"��$�"����$�������;$���������

�������0$��!�$""����������!"��'"���D���2����

����������� ��D�"��!�&��������

������ �����$�$"��62�������!������D���42Q��#�L��2�%�����;$��.����������

+��&���"�$� ������@C�����S�!$��$�����$�����"�$��

����������� ����&&�$�����"����"�$"%$����1��%�������$��&�����9�:

0��� ��,����$���������"���!�����$��

� �

0��� <�,��C�%������08����$��!�����$������;�

������������

#�����$�&����

������������(��!�%�������������������

������

E&"��&��&$��"��

��������"������"��&$��"�� ������ �"�$���� ������

�� 2�3�� 2�3� 2���

;� 2�3� 2�3� 2�3�

Page 4: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A.M.Al-sabagh, et al.26� �

0��� <�,��C�%������08����$��!�����$������;�

<��;��!�=��#�����$,��

�<��

4H?�H�

H?�?�

�<4�?��

322�4�������������������������������

H6�4���

#�����$� ���

���'��"������$�"����"��!�$"%$���<��

����������$�"����"��!�$"%$���<�������������������������

��/����"�7���&��!������

#�����$� ;��

���'��"������$�"����"��!�$"%$���<��

����������$�"����"��!�$"%$���<���������������������������������

��/����"�7���&��!������

�0��� 4�,�#����&��#$�!�$"�����������������!��"���!�����

#$�!�$"��

C�$����

�!��"�

�(��

����������!��"�%�����

#�����$� ��� #�����$� ;��

47� 57� 67� 47� 57� 67�

�#���"$"���� �"��3�K(���22����3�������

�����"������!���"� $������������K(�

��!�&���&��$+�"�� "��3�K(��

��.����"�&�+��&���"�� "��<3�K(���&�"�

��!���"$"��������1� #�'��

5��

3��

��2��

<63�

�2�42�

46�

36�

��2?�

�662�

2�HH6�

44�

5��

���<�

��?2�

��5�5�

<?�

53�

���5�

�<<2�

��3H4�

3?�

52�

��23�

�H32�

��<55�

3��

5<�

�����

��22�

��?26�

4��

5?�

���4�

�<32�

��633�

Page 5: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN 27

0��� 3�,�(�&%�"��������"���N����1���$�%�����"����%$�&��&�%$����!��"���1���3����1���

���+��

��)���

����

(�������

�3��,�H���

(�������

�H��,4�?3���

�����$� ($%���������� �

N���

�7#������ 7#������ 7#������ 7#������

�22� �4� �22� �5� �22� 3� �22� 43� �

�3�4� �22� �4� �22� �5� �22� 3� �22� 43� �22�

�H� H��H� ���<� �22� �5� �22� 3� �22� 43� H6�<�

H�3� 6��� ��H� 56�H� �?�H� �22� 3� �22� 43� 5H�H�

4�?3� ��2� 2�5� ���2� ��H� �22� 3� �22� 43� 3<�3�

��<5� 2� 2� ���� 2�3� �22� 3� ?2��� <��3� <?���

2�5� 2� 2� 2� 2� �22� 3� 3��?� �<�<� �6�<�

2�<� 2� 2� 2� 2� �22� 3� <2�H� �<�H� �6�H�

2��3� 2� 2� 2� 2� H3� 4�6� 6�?� <�H� 6�?�

2�2?3� 2� 2� 2� 2� 62� 4�2� 3�H� ��?� 5�?�

�(�����,���)�������$��"������ � � N��,����)�����&�$�������������$��"����

������������$����

������$,�(�&�"�� ((E<�� � � � ���

7�!�����,����$�"��!�������$������+��

Page 6: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A.M.Al-sabagh, et al.28

0��� 5�,������8$�����Q�0���$�&�����"����%$�&��(�%$�����!��"���1���3����1�������

��)���

���+����)��� ���� #$�!�����

N����

7�#������

N���0���$�&��

N��� ��/�$�

����"�

*!!�$�

����"�

� �3�4�� �22� �22� �22�

<F4 �H�� H6�<� 62� �22�

<F6 H�3�� 5H�H� 52� 62�

DE�6 4�?3�� 3<�3� 46� 53�

DE�6 ��<5�� <?��� <3� 32�

DE�<2 2�5�� �6�<� �H� <2�

DE�32 2�<�� �6�H� �<� �<�

DE��22 2��3�� 6�?� ?� �3�

DE��22 2�2?3�� 5�?� �� 6�

N��,��)�����&�$�������������$��"����������������$����

�������������'5/���0&1��>��5����!'�"�)/�,�

Page 7: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN 29

�$�����@������!$��"�$�,�

��!��"��

&��"��"��

/"7��

;%�.��!�&���&�

���8$+�"��

��F�&�<��

�"���"���� D��� ���/��

����

��$�

+�����

������1��

7��

��$�+��������

������

�"�$�����

7�

�$�����

�"���������

DF����

4� ���66� �6?2� <�3� ?� �3�4� 3<4�<�

3� ��<�3� ��22� <�6� 4�<� �3��� 3?6�H3�

5���<<6� �442� 4��� ��5� �3�3� 3H3����

?���<�H� ���2� 4�4� ��?� �5�5� 4?H�3�

0��� ?�,��$�����(�$&"�$��"�&�����!+������1"%$��D�� ���%�����+�$�����!��"��

0��� 6�,��$�����!$��"�$����$���1"%$��D�� 4����"���1��!��"�%��������������

�!��"�/�"��47����!�����$� �����

�$�����@������!$��"�$�,�

��!��"��

&��"��"��

/"7��

;%�.�

�!�&���&�

��8$+�"��

��F�&�<��

�"���"�

��� D���

���/��

����

��$�+�����

������1��

7��

��$�+�����

���������

�"�$�����

7��

�$������"���������

DF����

4� ��<�<� �?32� <�<3� 3�H� �4�4� 6�2�H�

3� ��<42� �H�2� <�5�� <�5� �4��� 62<�H�

5� ��<3H� �652� <�6� ��5� �4�<� ?3��5�

?���<43� �?42� 4��� ���� �3�5� 556�<�

Page 8: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A.M.Al-sabagh, et al.30

0��� H�,��$�����#$��"�$P�������1"%$���D�� <��57�#�����$� ���

�$�����@������!$��"�$�,�

��!��"��

&��"��"��

/"7��

;%�.�

�!�&���&�

���8$+�"��

��F�&�<��

�"���"����

D���

���/��

����

��$�+�����

������1��

7��

��$�+�����

���������

�"�$�����

7��

�$�����

�"���������

DF����

4� ��<�2� <�22� ��?� 5��� �4��� ��63���

3� ��<43� <5�2� <�<� 4��� �4�� �2H?�

5���<52� <4?2� <�6� ��<� �4�<� H�<���

?���<32� <��2� 4�3� ��5� �3�3� ?�3�5�

0��� �2�,��$�����#$��"�$P�������1"%$���D�� <��67�#�����$� ���

�$�����@������!$��"�$�,�

��!��"��

&��"��"��

/"7��

;%�.�

�!�&���&�

���8$+�"��

��F�&�<��

�"���"

���� D���

���/��

����

��$�+�����

������1��

7��

��$�+�����

���������

�"�$����

7��

�$�����

�"���������

DF����

4� ��<�4� �622� <�32� 5��� �4� 622�

3� ��<4?� <�42� <�?4� 4��� �<�H� 6<H�52�

5� ��<53� <<?2� 4�22� ��4� �4��<� 64��3�

?� ��<3�� <�22� 4�<2� ��?� �4�5� ?�2�H�

Page 9: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN 31

0��� ���,��$�����#$��"�$P�������1"%$���D�� 3��47�#�����$� ;��

�$�����@������!$��"�$�,�

��!��"��

&��"��"��

/"7��

;%�.�

�!�&���&�

���8$+�"��

��F�&�<��

�"���"����

D���

���/��

����

��$�+�����

������1��

7��

��$�+�����

���������

�"�$����

7��

�$�����

�"���������

DF����

4� ��<�6� �622� <�<� 5�5� �4��� 646�3�

3� ��<4<� <222� <�3� 4�5� �4��� 63?��4�

5� ��<36� <�22� <�6� <� �4�4� 6�3�?�

?� ��<46� �H�2� 4��� ���� �3�3� 5H3���

0��� ���,��$�����#$��"�$P�������1"%$���D�� 5��57�#�����$� ;��

�$�����@������!$��"�$�,�

��!��"��

&��"��"��

/"7��

;%�.�

�!�&���&�

���8$+�"��

��F�&�<��

�"���"����

D���

���/��

����

��$�

+�����

������1��

7��

��$�+��������

������

�"�$�����

7��

�$�����

�"���������

DF����

4� ��<�5� �?22� <��� 5�6� �4�5� 644�

3� ��<4�� <232� <�5� 4�H� �4��� 64?���

5���<3� �H32� <�H� <�<� �4�3� ?35�4��

?���<44� �H22� 4�<� ��4� �3��� 5?4�4��

Page 10: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A.M.Al-sabagh, et al.32

0��� �<�,��$�����#$��"�$P�������1"%$���D�� ?��67�#�����$� ;��

�$�����@������!$��"�$�,�

��!��"��

&��"��"�� /"�

7��

;%�.�

�!�&���&�

���8$+�"��

��F�&�<��

�"���"����

D���

���/��

����

��$�+�����

������1��

7��

��$�+�����

���������

�"�$����

7��

�$�����

�"���������

DF����

4� ��<�H� <<22� <�5?� 5�4� �4��� 6HH���

3� ��<4?� <632� <�6<� 4�3� �<�?3� �223����

5���<3�� <3H2� 4�� <�4� �4�3� 6H?�3�

?���<<?� <<32� 4��� ��3� �3�H� ?H?�5�H�

0��� �4�,��$�����(�$&"�$��"�&�����"���!$�!$���!+������1���

�������������������������

(�$&"�$��"�&��C�$����

�!��"�

����������!��"�/�"�,� �

��� ��� ;�

47� 57� 67� 47� 57� 67�

�E!"��%��

�!��"�

&��"��"7�

3�?<� 3��5� 3�<<� 3�?�� 3�?3� 3�4?� 3�3� �

�"���"�����

"�����1�

�!��"�

D��

�<H2� �H�2� <522� <<�2�� <262� �<622� <?<2� T��22���

;%�.��!�&���&�

���8$+�"��

��F�&�<���

��<5� ��<43� ��<3� ��<5� ��<5� ��<34� ��<3� �

����/����"���

��1� ������

4� <�53� <�44� <�63� <�?�� <�H�� <�H�� ��

4 �����

���$�+��������

"�����1� 7���

<��3� <��3� <�43� <�2� <�<3� <�H� 4�2�� <�3�

���$�+��������

������

�"�$����7�

�3�<�� �4���� �4�23�� �4�� �4�<�� �4�� �<�H6� T�<�3��

�$�����

�"���������

DF����

?45�H� ?H<��� �2�?��� 63��<� 632�� H?4�<� ?H6�<�� �

����,�����!"����"���$����!�����&"����

� �

Page 11: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN 33�

����� �

���������0'������&"��&���&$��"��� �������������������������0'�����!�����$� ����

��������� �

�����������0'���!��"�+�$���� ��������������������������������������������0'�������1"%$���!��"�/�"��57�!�����$����

��� ��,��0'������&"��&���&$��"���!�����$�����!��"�+�$����Q��1�

�!��"�/�"��57�!�����$����

0�� �3�,��+$�������&%�$�/����"�����"���!$�!$���!�����$�,���

��,��+�$����%��$������&%�$�/���"=�

�� �/,�+�$���/����"������&%�$�/���"=�

�!,����&%�$�/���"����"���������"�!�.�=�

�),���������������� ����������=�

�)S�,������$���������������� �����������=�

�����

������ <��,�����!��"�����+�$�����!��"�Q����������/�"�� 4��6�7�!�����$��

&����

!�����$�

��"��"����

"������� �/� �!� �)�

��"�����

�)S��

��"�����

#����

���!�$��"��

�� �4��44� ??6H� �4643� �4�2�� 3�H5�� ?6456� <��H�

;� �4��3�� �2?35� �?4��� �4226� 3��66� ?34<4� ��3�3�

������!���(�*��'('���

����� !��'!��?�=����������������

������!���(�*��'('���

����� !��'!��2�=��

������!���(�

,'�5'"������ !��

Page 12: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A.M.Al-sabagh, et al.34

�'5$021���7��)/�,����(�*��'('�������� !���*� ���)�"!�'"'"5�?��!�=�

�� �*����9��

��

� �

�'5�081������� �)/�,����(����/�'"5�,'�5'"��"��*��'('�������� !���'!��

�� �*����9�$���

���!��"�(��"��"�7�

��!��"�(��"��"�7�

��!��"�(��"��"�7�

��!��"�(��"��"�7�

��!��"�(��"��"�7�

Page 13: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN 35

��

��

�'50@1������� ������)!��'�!')���(�� ������������,'"5�*'.�����������������

Page 14: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A.M.Al-sabagh, et al.36

evaluated using Marshall Test method (ASTM

D-6927). The mixes were designed according to

the standard limits of surface (wearing) course

4c. The job mix was formulated(JMF) (%wt)

using coarse and fine aggregates, sand and filler

as 33, 30, 32, 5 wt %, respectively.

Tables (5-6) and figer (1) illustrates the tech-

nical propertes of solid materials according to

ASTM standard test methods.

• The mixtures were tested for maximum load

and flow. Density and air voids in mix and solid

materials were determined:

HMA Table(7) mixture of aggregate type

and virgin asphalt samples .

HMA tabels (8,9,10) are mixture of aggre-

gate type and modified asphalt using 4,6,8% of

polymer A.

HMA Tables (11,12,13) are mixture of aggre-

gate type and modified asphalt using 4,6,8% of

polymer B.

4. RESULTS AND DISCUSSION

4.1- Characteristics of Virgin and Modified As-

phalt Samples:

4.1.1.Physical characteristics and Molecular

type composition of asphalt samples

Generally, data in Tables (8-13) indicated

that the modified samples are more hard than

the virgin one. There was an increase in soften-

ing point, specific gravity and dynamic viscosi-

ties and decrease in penetration value using an

increasing values of the polymer content from

4,6,8 wt %. This is attributed to either and the

chemical molecular composition of the polymer

used. Asphalt modification, modify both cohe-

sion and elasticity. At higher temperatures, the

stiffness modulus of polymer phase is higher

than that of the matrix. These reinforcing prop-

erties of the polymer phase contribute to the

increase in viscosity. At low temperatures, the

stiffness modulus of the dispersed phase is low

compered with that of the matrix, which reduces

its brittleness. Consequently, the dispersed poly-

mer phase enhances the engineering properties

of asphalt in terms of viscosity, softening point

and toughness[23].

4.1.2. Infrared spectroscopy analysis

The FTIR spectrum of octadecylacrylate

disappearance of the characteristic absorption

band (OH) of the carboxylic acids at about 3200

cm_1,appearance of the carbonyl group of ester

band around (1729.57) cm_1,two bands for (C-O-

C) appear at 1192.21 cm_1 and 1278.8 cm_1and

the band for C=C which appear at1631 cm_1.The

FTIR spectrum of the base AC asphalt illustrated

that, the strong peaks within 2850–2960 cm_1 re-

gions were typical C-H stretching vibrations in

aliphatic chains. The peak at 1607.91 cm_1 was

attributed to C=C stretching vibrations in aromat-

ics. The asymmetric deforming in -CH2 and CH

3,

and the C-H symmetric deforming in CH3 vibra-

tions were observed at 1458.2 cm_1 and 1375.2

cm_1 respectively. The peak at 1047.2 cm_1 was

ascribed to S=O stretching vibrations. The small

peaks within 740–910 cm_1 regions were typical

C-H vibrations in benzene structure.

Comparing the spectrum of asphalt modi-

fied with (6% polymer A) with that of the base

AC asphalt, a new peak appeared at 723 cm_1

illustrating the bending vibration of C-H in the

double bonds –CH=CH- in aromatics. the FTIR

spectrum fig(2) showed the same characteristic

peaks of asphalt spectrum except the appear-

ance of C=O group at 1733 cm-1 and this was

due to the presing of polymer which have ester

group (octadecylacrylate).

4.1.3. Determination of molecular weight of the

prepared polymer:

The molecular weights of the prepared poly-

mer were determind by using vapoar pressure os-

mometr. The molecular weight (Mn) of the pre-

pared polymers were determined by Gel perme-

ation Chromatography (GPC), model 510 using

polystyrene standerd. Ultra-Styragel column,and

tetrahydrofuran as solvent Table 15.

4.1.4. TGA Analysis

From Fig. (4) it was found that, addition

of polymers to asphalt produces PMA samples

haveing lower decomposition ability percentages

compared to polymers themselves. This maybe

attributed to the increase of asphaltene content

for PMA as compared to virgin one. Either virgin

and PMA samples have nearly the same thermal

Page 15: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED BITUMEN 37

stability. This may be attributed to the nature of

each addition as well as to the partial compat-

ibility between virgin asphalt and polymers as

illustrated in SEM photos fig.(3)

4.1.5. SEM of PMAs

SEM is used to predict the shape of bitu-

men, surface texture even polymer distribution

in modified bitumen. The typical morphology of

base bitumen with SEM is shown in Figure (3)

In SEM photos of the virgin and polymers modi-

fied blends the light phase in the picture repre-

sents the swollen polymer while the dark phase

is the asphalt. Small polymer spheres swollen by

asphalt compatible fractions (e.g., aromatic oils)

spread (dispersed phase) homogeneously in a

continuous asphalt phase.

Polymer particles extensively spreading on

PMA’s surface lead to a decrease in technical

properties such as toughness and tenacity. This

may be attributed to differences in molecular

weight, polarity and structure of the used poly-

mers. A chemical dissimilarity asphalt and poly-

mer showed. The morphology of PMA samples

is the result of the mutual interaction polymer

and asphalt, and, consequently, is influenced by

both asphalt composition, polymer content and

structure. There is a good compatibility between

asphalt and polymers.

4.2- Characteristics of the Prepared asphalt

Paving Mixes:

All mixtures prepared (tables 7 and 13) com-

ply with the standard specification of HMA for

surface course in roads having high traffic vol-

ume.

Comparing to mixture (1), it was noticed that

for all prepared mixtures there was a decrease in

asphalt content, accompanied by increasing sta-

bility and higher Marshall stiffness. The asphalt

for virgen 5.75 decreased to 5.16, 5.33,5.72 for

asphalt modified by polymer A additive (4,6,8%

) respectively in percentages of 10.26, 7.3& 0.52

from Tables (8, 9,10) respectively while the sta-

bility increased from 2390 (N) to 2390 (N) to

3600 (N) and 3310(N). asphalt content for ad-

ditive polymer B for 4% increase to 0.35%

and 6,8% decrease to4.5%,4% respectively

and the stability increase to3080(N), 3800(N)

and3730(N),This may be attributed to different

molar ratios of polymer, and high absorptive

aggregate. asphalt absorbed by inter and intra

aggregate particles. So, there was an increase in

stability, flow at and Marshall Stiffness. Increase

in air voids and solid aggregates caused by in-

creasing viscosity of PMA samples. On the other

hand, the unit weight decreased.

4.2.1 Effect of using modified asphalt in HMA

containing HA aggregate (mixes 2(a,b), 3(a,b)

and 4(a,b)):

The use of modified asphalt in mixes prepara-

tions lowered the asphalt content as compared to

HMA (mix(1). This is attributed to the increase

in asphalt viscosity resulting in adecrease in the

absorbed partiton by the aggregate.

HMA was found to have the most hardnened

pration of modified mixtures, as it had highest

stability and air voids in mix and solid aggre-

gates as well as lowest flow value. This may be

attributed to the observed toughness in polymer.

The Marshall stiffness increased for vir-

gin asphalt 597.5(N/mm) to HMA polymer A

(4,6,8%) to HMA polymer B(4,6,8%) in percent-

ages of 33.4, 75.14& 43.9% and of 38.6, 62.65&

60.06%.

CONCLUSION

The aim of this work is to prepare and char-

acterica a special type of HMA consisting of

spicial materials having the property of decreas-

ing the cost of paving and maintenance, keep-

ing the premium aggregates for a longe period

. To achieve this, 4,6,8% of polymer prepared

from synthesis of octadecylacrylate from stearyl

alcohol and acrylic acid in presence of P- toluene

sulphonic acid as a catalyst and then polymer-

izing with styrene and methyl methacrylate in

different molar ratios . The polymer was used in

modification asphalt. High absorptive aggregate

and marble fillers were used in mixtures prepara-

tions. The obtained results showed that:

A mixtures of polymers and solid materials

are suitable in road paving.

The mixtures comply with the standards and

have reduced temperature susceptibility.

The best modifier was either 6% polymer A

and B

Page 16: A STUDY ON MARSHALL PROPERTIES FOR POLYMER MODIFIED

A.M.Al-sabagh, et al.38

REFERENCES1-Zhang, H.L., Jia, X.J., Yu, J.Y. and Xue, L.H. (2013) Ef-

fect of Expanded Vermiculite on Microstructures and

Ageing Properties of Styrene-Butadiene-Styrene Co-

polymer Modified Bitumen. Construction and Building

Materials, 40,224-230.

2- Traxler R. “Asphalt: its composition, properties and

uses.” New York: Reinhold Publishing Corporation;

1961.

3- Partal P., Martı´nez-Boza F., Conde B., and Gallegos C.

“Rheological characterization of synthetic binders and

unmodified bitumens”. Fuel, 78 (1999) 1–10.

4- Zhang, F. and Yu, J.Y. (2010) Research for High-Per-

formance SBR Compound Modified Asphalt. Construc-

tion and Building Materials, 24, 410-418.

5- Martin, J., Dusan, B., Daryl, M. and Ludo, Z. (2013)

Preparation and properties of conventional asphalt

modified by physical mixtures of Linear SBS and

Montmorillonite Clay. Construction and Building Ma-

terials, 38, 759-765.

6- Al-Hadidy, A.I., Tan, Y.Q. and Ayman, T.H. (2011) Starch

as a Modifier for asphalt Paving Materials. Construc-

tion and Building Materials, 25, 14-20.

7- Peiliang, C., Peijun, X., Mingliang, X. and Shuanfa,

C. (2013) Investigation of asphalt Binder Containing

Various Crumb Rubbers and asphalts. Construction and

Building Materials, 40, 632-641.

8- Karim, G., Azam, J.A. and Mahsa, N. (2012) Statisti-

cal Investigation on Physical-Mechanical Properties of

Base and Polymer Modified Bitumen Using Artificial

Neural Network. Construction and Building Materials,

37, 822-831.

9-Moatasim, A., Cheng, P.F. and Al-Hadidy, A.I. (2011)

Laboratory Evaluation of HMA with High Density-

Polyethylene as a Modifier. Construction and Building

Materials, 25, 2764-2770.

10- Zhang, H.Y., Wu, X.W., Cao, D.W., Zhang, Y.J. and

He, M. (2013) Effect of Linear Low Density-Polyethyl-

ene grafted with Maleic Anhydride (LLDPE-g-MAH)

on Properties of High density-Polyethylene/Styrene-

Butadiene-Styrene (HDPE/SBS) Modified Asphalt.

Construction and Building Materials, 47, 192-198.

11- Esmaeil, A., Majid, Z., Mohamed, R.K., Mahrez, A.

and Payam, S. (2011) Using Waste Plastic Bottles as

Additive for Stone Masticasphalt. Materials & Design,

32, 4844-48493- Redelius P. “Solubility parameters and

bitumen”, Fuel, 79 (2000) 27–35.

12-Polacco, G., Berlincioni, S., Biondi, D., Stastna, J. and

Zanzotto, L. (2005) Asphalt Modification with Differ-

ent Polyethylene- Based Polymers. European Polymer

Journal, 41, 2831-2844.

13- Kim, H., Lee, S.J. and Amirkhanian, S.N. (2011) Rhe-

ology of Warm Mix Asphalt Binders with Aged Bind-

ers. Construction and Building Materials, 25, 183-189.

14- Edwards, Y., Tasdemir, Y. and Isacsson, U. (2007) Rhe-

ological Effects of Commercial Waxes and Polyphos-

phoric Acid in Bitumen 160/220—High and Medium

Temperature Performance. Construction and Building

Materials, 21, 1899-1908.

15- Merusi, F. and Giuliani, F. (2011) Rheological Char-

acterization of Wax-Modified Asphalt Binders at High

Service Temperatures. Materials and Structures, 44,

1809-1820.

16- Fawcett, A.H. and McNally, T. (2001) Studies on Blends

of Acetate and Acrylic Functional Polymers with Bitu-

men. Macromolecular Materials and Engineering, 286,

126-137.

17- Airey, G.D. (2002) Rheological Evaluation of Ethylene

Vinyl Acetate Polymer Modified Bitumens. Construc-

tion and Building Materials, 16, 473-487.

18- Iqbal, M.H., Hussein, I.A., Wahhab, H. and Amin,

M.B. (2006) Rheological Investigation of the Influence

of Acrylate Polymers on the Modification of Asphalt.

Journal of Applied Polymer Science, 102, 3446-3456.

19-H.P. Soni, D.P. Bharambe. (2006) Synthesis and evalua-

tion of polymeric additives as flow improvers for Indian

crude oil .Iranian Polymer Journal, 15 pp. 943–954.

20- Evdokia, K.O., Aikaterini, B., Georgios, B. and Joan-

nis, K.K. (2011) Poly (Sodium styrene sulfonate) Poly

(methyl methacrylate) Diblock Copolymers through

Direct Atom Transfer Radical Polymerization: Influ-

ence of Hydrophilic Hydrophobic Balance on Self-

Organization in Aqueous Solution. European Polymer

Journal, 47, 752-761.

21- Wielend H. and Richter D., “Mechanism of oxidation

processes.”XXVIII. Autoxidation of aldehyde. Amn,

486 (1931) 226- 242.

22- Shaker M., “ Evaluation and improvement of local as-

phalt, Ph.D thesis, Faculty of engineering, Cairo Uni-

versity, 1993.

23- Daranga C., “Characterization of aged polymer modi-

fied asphalt cements for recycling purposes.”, Ph.D,

Tunisiena State Univeristy, 2005.