Development of Modified

Binders and future Perspectives

Dr.-Ing. Volker Hirsch

Federal Highway Research Institute

08.09.2008

Modified Bitumen

Road Construction - a simple matter ?

Aggregates

Filler

Bitumen

08.09.2008

Modified Bitumen

Asphalt

Facts of Life:
Lack of Compaction
Thermal
and Oxidative
Damages
Cracking
Rutting
Ravelling

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Modified Bitumen

Historical Development
17th of September, 1823
Hancock, T.
British Patent No. 4768:
An Improvement in the
Preparation of Pitch and of Tar
Ludwig van Beethoven

(Mixture of rubber, terpentine and tar, used as protective

coating)
08.09.2008

Modified Bitumen

Historical Development
1844
Cassell, E.E.
British Patent No. 10327:
A Material suitable for Paving,
Piping, Roofing
De Fontainemoreau, P.A.
Charles
Goodyear
British Patent No. 10187:
Samuel
Morse
A new and improved mode or method of paving and covering
roads

08.09.2008

Modified Bitumen

Historical Development
14th of December, 1916
Ilcken, C.A.
British Patent No. 111.906:
An Improved Process for the
Manufacture of Rubber
Albert Einstein

(Mixture of bitumen and rubber.

Use of recycled rubber)
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Modified Bitumen

Historical Development
16th of January, 1917
De Caudemberg, Ch.-A.C.:
French Patent
No. 484.258:
Foundation of DIN
Perfectionementcombinaisons
dasphalte et de bitumen avec du
caoutchouc

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Modified Bitumen

Historical Development
1931-34 Niederlndisch-Indien:
Straenbelge aus Naturkautschuk

1937

Netherland, (Leeuwarden near Bussum)

Bitumen/Rubber

Starting in 1949 USA, UK, France:

Bitumen/Rubber
synth. Polymers

(e.g. Polychloroprene)

In the early 1950th Germany:

Bitumen/Rubber
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Modified Bitumen

Modification by Polymers
Styreneol-Butadiene-Styrene (SBS)
Styrene-Butadiene-Rubber (SBR)
Ethylvinylacetate (EVA)
Polyoctenamer-Rubber (TOR)

Modifier

08.09.2008

Polymers

Recycled-Rubber
Elastomers
Natural Rubber (NR)
Isoprene Rubber (IR)
Polychloroprene-Rubber (CR)
Acrylic-Rubber (ACM)
Ethylene-Acrylate-Rubber (AECM)
Ethylene-Propylene-Diene-Monomere (EPDM)
Polyethylene (PE)
Plastomers
Polypropylene (PP)
Polyepoxide
Polyester
Resins
Polyurethane (PUR)

Modified Bitumen

Temperature and mechanical Stress

Plastic
Deformation

Loading
Loading-Time

Stress crack

Enlargment of plasticity

Peak load
crack
Temperature

Positive:

08.09.2008

Temperature

Viscosity

Temperature

Viscosity
Modified Bitumen

Combination
is difficult

10

Modification by Additives

Elastomers

Polymers
Plastomers

Modifier

Styrene-Butadiene-Styrene (SBS)
Styrene-Butadiene-Rubber (SBR)
Ethylvinylacetate (EVA)
Polyoctenamer (TOR)
Recycled-Rubber
Polyethylene (PE)
Polypropylene (PP)

Resins
Sulphur

"Additives"

Special

Poly-phosphorous acid
Synthetic Resins

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Modified Bitumen

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Special Modifiers
Sulphur (approx. 1980)
Content: 10-15%
Effects: Increase of viscosity, better resistance
against rutting
Problem: Emission of Sulphurdioxide and
Hydrogen Sulphide during storage and
handling

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Modified Bitumen

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Special Modifiers
Poly-Phosphorous Acid
Content: ca. 0,5%
Effekte: Resistance against rutting
adhesive effect
Problem: also negative experiences (cracking ?)

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Modified Bitumen

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Modification by Additives
Elastomers

Polymers
Plastomers

Styrene-Butadiene-Styrene (SBS)
Styrene-Butadiene-Rubber (SBR)
Ethylvinylacetate (EVA)
Polyoctenamer (TOR)
Recycled-Rubber
Polyethylene (PE)
Polypropylene (PP)

Resins

Modifier

Special

"Additives"

Sulphur
Poly-phosphorous acid
Synthetic Resins
Hydrated Lime

"Filler"

synth. silicic acid

Natural rubber

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Modified Bitumen

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Filler a Modifier?
Hydrated Lime:
Effects: Stiffening effect,
Chemical reaction with acid
components of bitumen
Problem: Optimal dosage

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Modified Bitumen

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Filler a Modifier?
Synth. silicic acid
Content: 0,5-1%
Effekte: Better resistance against rutting
without cracking
Problem: No practical application is
documented

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Modified Bitumen

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Modification by Additives
Elastomers

Polymers
Plastomers

Styrene-Butadiene-Styrene (SBS)
Styrene-Butadiene-Rubber (SBR)
Ethylvinylacetate (EVA)
Polyoctenamer (TOR)
Recycled-Rubber
Polyethylene (PE)
Polypropylene (PP)

Resins

Modifier
Special

"Additives"

"Filler"

Sulphur
Poly-phosphorous acid
Synthetic Resins
Hydrated Lime
synth. silicic acid
Natural rubber

"Anti-stripping agents"

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Modified Bitumen

Amines
Amides

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Anti-Stripping Agents
H3C H3C H3C H3C H3C H3C H3C H3C H3C H3C H3C

Bitumen

H2N H2N H2N H2N H2N H2N H2N H2N H2N H2N H2N

Aggregate

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Modified Bitumen

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Modification by Additives
Elastomers

Polymers
Plastomers

Styrene-Butadiene-Styrene (SBS)
Styrene-Butadiene-Rubber (SBR)
Ethylvinylacetate (EVA)
Polyoctenamer (TOR)
Recycled-Rubber
Polyethylene (PE)
Polypropylene (PP)

Resins

Modifier

"Additives"

Sulphur
Poly-phosphorous acid
Special
Synthetic Resins
Hydrated Lime
synth. silicic acid
"Filler"
Natural rubber
Amines
"Anti-stripping agents"
Amides

"Warm mix asphalt"

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Modified Bitumen

Paraffins
Amides
(Zeolithes)
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Warm Mix Asphalt

1,00E+07

Komplexer Schubmodul [Pa]

1,00E+06

1,00E+05

Bitumen 50/70
Bitumen 50/70 + Modifier

1,00E+04

Level of equiviscosity

1,00E+03

1,00E+02

1,00E+01

T0

Tm

1,00E+00
0

20

40

60

80

100

120

140

160

180

Temperatur [C]

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Modified Bitumen

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Fundamental Basis
Polymers

Modifier

"Additives"

Elastomers
Plastomers
Resins
Special
"Filler"
"Anti-Stripping Agents"
"Warm mix asphalt"
Napthene-base

Bitumen

Crude Oil

Mixed-base
Paraffin-base

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Modified Bitumen

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Selection of Crude Oil:

Naphthene-base crude oil was preferred
(Mexico, Venezuela)
Due to the altered situation of availability,
mixed-base or paraffin-base crude oil are
frequently used (Middel-East, GUS)

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Modified Bitumen

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Fundamental Basis
Polymers

Elastomers
Plastomers
Resins
Special
"Filler"
"Anti-Stripping Agents"
"Warm mix asphalt"

"Additives"

Modifier

Crude Oil

Napthene-base
Mixed-base
Paraffin-base

Bitumen
Refinery Process

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Modified Bitumen

Destillation
"Air-Blowing"
"Precipitation"
"Blending"

23

Bitumeneinsatz in Deutschland (2007)

German Consumption of Bitumen in 2007

Dach-/
Dichtungsbahnen
14%

davon PmB
18%

Sonstiges
6%

davon Bitumen
62%
Asphaltstraenbau
80%

Mainly: Styrene-Butadiene-Styrene (SBS)

Quelle: ARBIT
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Modified Bitumen

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Parameter

Tailor-made Polymers :
Polymertype/-structure
Chain-Length / Molecular Weight
Cross-Linking
Distribution

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Modified Bitumen

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Styrene-Butadiene-Styrene (SBS)
CH2

CH3

H3C

Segment 1:n
Polystyrol

Segment 2:n

H2C

H3C

CH3

CH2

1.4-Polybutadien

Variant:

H2C

H3C

H2C

H2C

n
H2C

H2C

H2C

H2C

H2C

1.2-Polybutadien

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Modified Bitumen

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Shortening of Polymers
1,4-Polybutadiene:
H3C
CH3

Decomposition
1,2-Polybutadiene:
H3C
CH3

H2C

H2C

H2C

H2C

H2C

H2C

H2C

H2C

H2C

H2C

Preservation !

08.09.2008

Modified Bitumen

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Polymer-Design
SBS (1.4-linked)

Styrene

Butadiene
Sequence

SBS (1.2-linked)

Styrene

Butadiene
Sequence

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Molecular Weight Distribution

4,4 % linear SBS
1.4- and 1.2- Butadiene
Styrene/Butadiene (1: 2,7)

Concentration d(Wf
Wf) / d(LogM)

6,83

5,12

5,4 % radial SBS

1.2- Butadiene
Styrene/Butadiene (1: 2,4)

3,42

1,71

0,00

4,26

4,60

4,94

5,28

5,62

5,96

6,30

Log (Molecularweight)

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Modified Bitumen

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Cross-Linking

Radial Structure

Comb-Structure

Network

Accidentally branched
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Modified Bitumen

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Distribution

Quelle: Benninghoven

High performance shear-mixer

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Modified Bitumen

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Specification of PmB
(EN 14023)
Problem:
EN 14023 only of limited use for the selection of
suitable products.
PmBs with the same specification can have
different physical properties.

08.09.2008

Modified Bitumen

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90

b
c
a

30/45

85

50/70 (a)

50/70 (b)
50/70 (c)

80

Phasenwinkel [Grad]

30/45

75
PmB 45 (3)

1
70

PmB 45 (2)

b
c

PmB 45 (1)
65

60

3
30/45

55

50
1,00E+01

1,00E+02

1,00E+03

1,00E+04

1,00E+05

1,00E+06

1,00E+07

Komplexer Schubmodul [Pa]

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Modified Bitumen

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Tensile Strength of Asphalt

Maximale Zugfestigkeitsreserve [MPa]

7
ohne Alterung
mit Alterung
H PmB
6

5
PmB 25A
PmB 45A
(3)
4

PmB 45A
(2)
PmB 45A
50/70 (1)

3
4

-2

-4

-6

-8

-10

-12

-14

Temperatur der max. Zugfestigkeitsreserve [C]

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Modified Bitumen

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70

Force Ductility Curves of PmB 45

(T=10C; 50mm/min; EN-mould)

60

Kraft [N)

50

40
PmB 45A (1)
PmB 45A (2)
PmB 45A (3)

30

20

10

0
0

100

200

300

400

500

600

700

800

900

Weglnge [mm]
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Consequences
More knowledge is necessary !
Correlation: Bitumen-Asphalt
Consideration of
performance-related test methods
Validation !

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Future Developments
Improving resistance of ageing
(e.g. Oxidation of porous asphalt pavements)
Cold curing resins for special applications
But:
The handling is more difficult than of elastomers

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Future Developments

Supermodifier are very unlikely

An efficient tool-box with modifying agents is

already existing.

Potential benefit:
Specific system optimization:
Aggregate/Filler/Bitumen/Modifier

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Conclusions
Modified bitumens are no panacea.
But:
Modified bitumens may substantially contribute to a
better durability of roads.

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Conclusions
Bitumen is for the most part a good-natured
material and forgives some mistakes.
Whoever is producing modified bitumens or is
processing it, must know a great deal more.

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Road Construction a simple matter

?
Definitely not !

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Baustoff Bitumen, Dr. Hirsch

S6