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Procedia Engineering 172 (2017) 1297 – 1304

Modern Building Materials, Structures and Techniques, MBMST 2016

Impact of chemical and physical modification on thermoplastic

characteristics of bitumen
Krzysztof Zielińskia, Michał Babiaka, Maria Ratajczaka*, Jacek Kosnob
a
Poznań University of Technology, Piotrowo 5, 60-965 Poznan, Poland
b
Institute of Heavy Organic Synthesis „Blachownia”, Enegetyków 9, 47-225 Kedzierzyn-Koźle, Poland

Abstract

In spite of strong competition of synthetic materials (including PVC, EPDM), bitumen remains the major component of most
waterproofing materials. It makes up approx. 80% by weight of the final product. The characteristics of bitumen mix have
a decisive impact on the quality of the final product. During storage, transport, manufacturing and installation of waterproofing
materials, bitumen is subject to ageing. As a result of the ageing process the characteristics of bitumen waterproofing materials
deteriorate, roofing membrane becomes more rigid and cracks. The damaged waterproofing layer ceases to perform its function;
it does not protect the building envelopes against water penetration. The development of organic chemistry allowed the synthesis
of a number of modifying substances used for chemical modification of bitumen. Among the most promising are heterocyclic
organic compounds belonging to the group of imidazolines. The article presents the results of preliminary laboratory tests of
bitumen modified jointly by SBS and imidazoline. The objective of the study was to find a new type of bitumen modifier (hybrid
modifier) synergically combining the advantages of both types of presented modifications.

© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2016 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of MBMST 2016.
Peer-review under responsibility of the organizing committee of MBMST 2016
Keywords: bitumen; imidazoline; styrene-butadiene-styrene; waterproofing.

1. Introduction

Moisture in walls, damp stains on internal walls, poorly insulated foundations and leaking roofs can be found in
various types of building structures. It is mostly due to errors made during the design and construction phase of

* Corresponding author. Tel.: +48 665 21 68; fax: +48 665 20 59.
E-mail address: maria.ratajczak@put.poznan.pl

1877-7058 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of MBMST 2016
doi:10.1016/j.proeng.2017.02.159
1298 Krzysztof Zieliński et al. / Procedia Engineering 172 (2017) 1297 – 1304

buildings or the effect of the use of defective waterproofing material. Improper waterproofing allows water
penetration into a building. Damp parts lose their heat insulation properties. The process of biological corrosion is
initiated and the likelihood of fungi and mould growing on building elements increases.
In spite of strong competition of synthetic materials (including PVC, EPDM), bitumen remains the major
component of most waterproofing materials. It makes up approx. 80% by weight of the final product. The bitumen
price derives from the price of crude oil. In the last year the bitumen price decreased by as much as 50%.
It considerably increased the price competitiveness of materials manufactured with its use. Due to this, clearly
marginalized waterproofing materials produced with bitumen have again become commonly used products.
The characteristics of bitumen mix have a decisive impact on the quality of the final product [1,2]. During
storage, transport, manufacturing and installation of waterproofing materials, bitumen is subject to ageing [3,4]. This
term defines changes that occur over time in the structure and chemical composition of bitumen. Bitumen ageing is
a complex issue which is difficult to assess and is not fully recognized [2,5]. It depends on the chemical structure of
bitumen and external factors [6].
As a result of the ageing process the characteristics of bitumen waterproofing materials deteriorate, roofing
membrane becomes more rigid and cracks. The damaged waterproofing layer ceases to perform its function; it does
not protect the building envelopes against water penetration. In winter conditions the accumulated water freezes, due
to which the waterproofing layer is destroyed. Numerous transitions of temperature through 0 degrees Celsius (up to
120 times per year), characteristic for the climate in Poland, shorten the lifetime of the membrane and make
investors carry out costly repairs. The destroyed membrane is non-biodegradable material and becomes a hazardous
waste for the environment.
From the point of view of a user and for the protection of the environment, extended lifetime of waterproofing
materials is of high importance. For this purpose various types of bitumen modifiers are used. These are substances
that improve the in –use performance of waterproofing materials, increase their durability and increase their
resistance to high and low temperatures.
The first attempts to modify bitumen were made at the beginning of the twentieth century. At that time bitumen
and sulphur emulsion (chemical modification) and bitumen with the addition of mineral powder (physical
modification) were developed. Modern materials for bitumen modification started to be used in mid-seventies of the
twentieth century. The increase of oil price (due to the oil crisis in 1973) and rapid development of organic
chemistry contributed to the common use of modern technologies of bitumen modification [1,2,7].
Currently the most common physical modifiers of bitumen belong to the group of polymers - macromolecular
organic compounds of natural origin or being the result of planned chemical synthesis. They are produced by
modification of natural compounds (e.g. rubber) or obtained as a result of polymerization of micromolecular
compounds. A polymer production process is harmful to the environment and energy-consuming. The resulting
waste is toxic and non-biodegradable. Polymers are substances which do not react chemically with bitumen; they act
as a filler or form a spatial network inside bitumen (the so called physical cross-linking) [5]. Currently the most
commonly used bitumen modifier is SBS (styrene-butadiene-styrene). It has a significant impact on improving the
rheological properties of bitumen at both low and high temperatures. This method, however, has several
disadvantages. It is energy and time consuming process [8]. To achieve the desired effect, it is necessary to modify
bitumen by adding 12% of SBS (by weight). A large amount of polymer deteriorates bitumen adhesion to substrate.
The development of organic chemistry allowed the synthesis of a number of modifying substances used for
chemical modification of bitumen. Among the most promising are heterocyclic organic compounds belonging to the
group of imidazolines. These substances have dispersing characteristics, they modify bitumen thermoplastic
properties [9,10]. The reaction of imidazoline with bitumen cause blocking of aromatic compound cyclization
processes and blocking the transition of naphthene aromatic fractions to resins and resins to asphaltenes. They
significantly improve bitumen resistance to ageing. Both physical modification of bitumen (SBS) and chemical
modification (imidazoline) have advantages and disadvantages. The article presents the results of preliminary
laboratory tests of bitumen modified jointly by SBS and imidazoline. The objective of the study was to find a new
type of bitumen modifier (hybrid modifier) synergically combining the advantages of both types of presented
modifications.
 Krzysztof Zieliński et al. / Procedia Engineering 172 (2017) 1297 – 1304 1299

2. Materials and methods

Samples of bitumen 160/220, which is often used for the production of waterproofing materials, were analysed.
The basic physical characteristics of bitumen used are as follows:

x Softening point (ring and ball): 39.4⁰C

x Fraass breaking point: -13⁰C
x Penetration P25⁰C/100g/5s : 157
x Penetration index IP: -1.3.

Bitumen was modified with:

x oleic imidazoline type I, the respective content of imidazoline was 1%, 2%, 3% (by weight),
x SBS elastomer, the SBS content reached 3%, 6%, 9%, 12% (by weight),
x and a mixture of SBS and imidazoline.

The following measurements were taken:

x Softening point by ring and ball method, according to [11]

x Fraass breaking point according to [12]
x Needle penetration according to [13].

On the basis of these results the index of penetration was calculated. This is a measure of thermal sensitivity of
bitumen in terms of viscoelasticity. The index was calculated according to the formula included in [14]:

 20 ˜ TRB  500 ˜ log P  1952 

Ip (1)
TRB  50 ˜ log P  120

where: TRB – softening point by ring and ball method (ͼC); logP – logarithm of penetration value at 25ͼC (0.1 mm).

4. Results and discussion

Table 1 and Figure 1 show the results of the determination of the softening point of bitumen by ring and ball
method for binders modified with SBS and imidazoline. It was found that the addition of SBS elastomer causes
a proportional increase of the softening point. The highest softening point was obtained for samples of bitumen
modified with SBS content of 9% - 12% (160% to 180% increase compared to the samples without modification).
The addition of oleic imidazoline type I caused a slight decrease of the softening point (by approx. 10% for the
modifier content of 3% compared to pure bitumen). Bitumen modified with a mix of SBS and imidazoline retained
the properties of polymer bitumen. For samples of bitumen modified with 11% of SBS + 1% of imidazoline, the
highest value of the softening point was achieved. For the remaining bitumen samples (modified with SBS and
imidazoline) a slight decrease of the parameter was achieved compared to bitumen modified with 12% SBS content.

Table 1. Softening point of bitumen modified with SBS and imidazoline.

Sample number Content of modifier (%) TRB (⁰C) Δ TRB in relation to bitumen 160/220 (⁰C)
1 0 39,4 0,0
2 3% of SBS 47,8 8,4
3 6% of SBS 97,5 58,1
4 9% of SBS 103,5 64,1
5 12% of SBS 110 70,6
1300 Krzysztof Zieliński et al. / Procedia Engineering 172 (2017) 1297 – 1304

6 1% of Imidazoline 38,6 -0,8

7 2% of Imidazoline 37 -2,4
8 3% of Imiadzoline 35,8 -3,6
9 3% of SBS + 3% of Imiadazoline 45,4 6,0
10 6% of SBS + 3% of Imiadazoline 95,5 56,1
11 9% of SBS + 3% of Imiadazoline 103,5 64,1
12 10% of SBS + 2% of Imiadazoline 103 63,6
13 11% of SBS + 1% of Imiadazoline 108 68,6

120

100

80
TRB (ͼͼC)

60
110

108
103,5

103,5

103
97,5

95,5
40
47,8

45,4
39,4

38,6

35,8

20
37

0
3% SBS + 3% Imiadzoline

6% SBS + 3% Imiadzoline

9% SBS + 3% Imiadzoline
3% SBS

6% SBS

9% SBS
160/220

12% SBS

1% Imidazoline

3% Imiadzoline
2% Imidazoline

10% SBS + 2% Imiadzoline

Modifier content (%) 11% SBS + 1% Imiadzoline

Fig. 1. Softening point of bitumen modified with SBS and imidazoline.

Table 2 and Figure 2 show the results of the determination of breaking point by Fraass for binders modified with
SBS and imidazoline. It was found that the addition of SBS elastomer causes a proportional decrease of the breaking
point. The lowest value was achieved for bitumen samples modified with 12% SBS content. The addition of oleic
imidazoline type I caused a slight decrease of the breaking point compared to pure bitumen. For samples modified
with SBS and imidazoline there was a decrease of breaking point, proportional to the content of particular modifiers.
For samples of bitumen modified with 9% of SBS + 3% of Imidazoline and 10% of SBS + 2% of Imidazoline, the
lowest values of the parameter were achieved.

Table 2. Breaking point for bitumen modified with SBS and imidazoline.
Sample number Content of modifier (%) TFraass (⁰C) Δ TFraass in relation to bitumen 160/220 (⁰C)
1 0 -13 0
2 3% of SBS -16 -3
3 6% of SBS -20 -7
 Krzysztof Zieliński et al. / Procedia Engineering 172 (2017) 1297 – 1304 1301

4 9% of SBS -38 -25

5 12% of SBS -43 -30
6 1% of Imidazoline -15 -2
7 2% of Imidazoline -17 -4
8 3% of Imiadzoline -18 -5
9 3% of SBS + 3% of Imiadazoline -18 -5
10 6% of SBS + 3% of Imiadazoline -22 -9
11 9% of SBS + 3% of Imiadazoline -42 -29
12 10% of SBS + 2% of Imiadazoline -42 -29
13 11% of SBS + 1% of Imiadazoline -35 -22

-5
-13

-15
-16

-17

-18

-18
-20

-10

-22
-15

-35
-38

-20

-42

-42
-43
TFraass (ͼͼC)

-25

-30

-35

-40

-45

-50
3% SBS + 3% Imiadzoline

6% SBS + 3% Imiadzoline

9% SBS + 3% Imiadzoline
160/220

3% SBS

6% SBS

9% SBS

12% SBS

3% Imiadzoline

10% SBS + 2% Imiadzoline

11% SBS + 1% Imiadzoline

1% Imidazoline

2% Imidazoline

Modifier content (%)

Fig. 2. Breaking point for bitumen modified with SBS and imidazoline.

Table 3 and Figure 3 show the results of the determination of bitumen penetration P 25ͼC/100g/5s for binders
modified with SBS and imidazoline. It was found that the addition of SBS elastomer causes a proportional decrease
of the parameter. The lowest value of penetration was achieved for bitumen samples modified with SBS content
between 9% - 12% (a decrease by approx. 160% to 180% in relation to samples without modification). The addition
of oleic imidazoline type I caused an increase of bitumen penetration (by approx. 10% for the modifier content of
3% compared to pure bitumen). Bitumen modified with a mixture of SBS and imidazoline retained the properties of
polymer bitumen, however, due to the impact of imidazoline we can observe a clear increase of the parameter in
relation to bitumen modified only with SBS. For samples of bitumen modified with 3% of SBS 3% + 3% of
Imidazoline the highest penetration values were achieved. The higher the degree of bitumen modification with SBS,
the lower the penetration, but a beneficial phenomenon of polymer bitumen liquefaction continues to occur –
bitumen modified with 9% of SBS + 3% of Imidazoline has approx. 40% higher penetration than bitumen
containing only 9% of SBS.
1302 Krzysztof Zieliński et al. / Procedia Engineering 172 (2017) 1297 – 1304

Table 3. Penetration of bitumens modified with SBS and imidazoline.

Sample number Content of modifier (%) P25ͼC/100g/5s (0.1 mm) P25ͼC/100g/5s in relation to bitumen 160/220 (0.1 mm)
1 0 157 0
2 3% of SBS 121 -36
3 6% of SBS 88 -69
4 9% of SBS 69 -88
5 12% of SBS 48 -109
6 1% of Imidazoline 186 29
7 2% of Imidazoline 209 52
8 3% of Imiadzoline 229 72
9 3% of SBS + 3% of Imiadazoline 171 14
10 6% of SBS + 3% of Imiadazoline 115 -42
11 9% of SBS + 3% of Imiadazoline 95 -62
12 10% of SBS + 2% of Imiadazoline 80 -77
13 11% of SBS + 1% of Imiadazoline 71 -86

250

200
Penetration (0.1 mm)

150
229
209

100
186

171
157

121

115

50
95
88

80

71
69

48

0
3% SBS + 3% Imiadzoline

6% SBS + 3% Imiadzoline

9% SBS + 3% Imiadzoline
160/220

3% SBS

6% SBS

9% SBS

10% SBS + 2% Imiadzoline

11% SBS + 1% Imiadzoline

12% SBS

1% Imidazoline

3% Imiadzoline
2% Imidazoline

Modifier content (%)

Fig. 3. Penetration of bitumen modified with SBS and imidazoline.

Figure 4 shows the value of penetration index for the bitumen tested. For bitumen modified with imidazoline the
penetration index was similar to that of non-modified bitumen and ranged between -1.5 and -1.0). For SBS modified
bitumen the penetration index increased. The highest value of the parameter was achieved for bitumen modified
with 6% SBS content. For higher quantity of modifier a slight decrease of the parameter was observed. Bitumen
modified with a mixture of SBS and imidazoline maintained the characteristics of polymer bitumen. For bitumen
 Krzysztof Zieliński et al. / Procedia Engineering 172 (2017) 1297 – 1304 1303

samples modified with 6% of SBS and 3% of Imidazoline the highest values of the parameter were achieved. For the
remaining samples of bitumen (modified with SBS + Imidazoline) a slight decreased of penetration index was
observed.
10,0

8,0

6,0
Penetration index

8,9
8,8

8,4
8,3
8,1

7,9
4,0

7,5
2,0
0,7

1,3
0,0
-1,3

-1,0

-1,3

-1,5
-2,0

-4,0

3% SBS + 3% Imiadzoline

6% SBS + 3% Imiadzoline

9% SBS + 3% Imiadzoline
3% SBS

6% SBS

9% SBS
160/220

3% Imiadzoline
12% SBS

1% Imidazoline

2% Imidazoline

10% SBS + 2% Imiadzoline

11% SBS + 1% Imiadzoline

Modifier content (%)

Fig. 4. Penetration index for bitumen modified with SBS and imidazoline.

5. Conclusions

The analysis of the test results showed a significant impact of the addition of SBS and imidazoline on the
improvement of thermoplastic characteristics of bitumen. Synergistic effects of the both modifiers were
demonstrated. It was found that there were no adverse reactions between the substances used.
From the tested samples two were selected for further studies: bitumen containing 9% of SBS and 3% of
imidazoline and bitumen containing 10% of SBS and 2% of imidazoline. For both mixes the softening point
increased while the breaking point decreased. Products manufactured with the use of such binders will be
characterized by higher flexibility and resistance to cracking, which will result in their increased durability.
Reducing SBS content and increasing the amount of imidazoline addition will allow the reduction of the costs of
bitumen mix production (imidazoline is twice cheaper than SBS). Due to the addition of imidazoline, bitumen
penetration increases, liquefaction of bitumen takes place, which in turn facilitates the production process of
waterproofing materials (lower costs of production). The mutual compatibility of modifiers is also worth noticing
(ease of mixing).

Acknowledgements

This research was supported by research grant Applied Research Programme III (PBS3/B2/17/2015) from the
National Centre of Research and Development.
1304 Krzysztof Zieliński et al. / Procedia Engineering 172 (2017) 1297 – 1304

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