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Polyphosphoric acid (PPA) in road asphalts modification

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 Polyphosphoric acid (PPA) in road asphalts

science • technique
modification
Hanna JAROSZEK – Fertilizers Research Institute, Inorganic Chemistry Division “IChN” in
Gliwice

Please cite as: CHEMIK 2012, 66, 12, 1340-1345

Introduction Asphalt’s composition and its colloidal structure determines its

Asphalt binders are commonly used in the pavement construction. physical and rheological properties. The penetration increases with
To meet the raising requirements for durability of the road surface, increasing share of saturates and decreases with increase of asphaltenes
alternative methods of improving binder have been developed. The and resins; changes in softening point and ductility are opposite. High
wide range of viscoelasticity is essential to achieve long-lasting road content of asphaltenes increases viscosity, whereas resins contribute
surface, as it ensures consistency of asphalt’s rheological state in to the adhesion of asphalt to aggregate [3].
extreme service temperatures. Modifiers applied for improving asphalt’s
viscoelasticity are [1]: elastomers, plastomers, synthetic resins, crumb Asphalts classification
rubber, metal-organic compounds, sulfur, natural asphalts and paraffins. In the USA until 1970s asphalts were classified due to their
Also polyphosphoric acid can be used for this purpose – pros and cons penetration at 25ºC, (ASTM D946), during 1980÷90s due to their
of its application are subject of this paper. viscosity at 60ºC (ASTM Standard D3381). From 1990s Superpave
Performance Grade (PG) classification is introduced. It is based on
Bituminous binders relation between the binder’s properties and the conditions under
Bituminous binders are materials of organic origin whose binding which it is used. Asphalts are reported as PG X-Y, where X is the
and hardening is caused by the temperature-related change of adhesion average seven-day maximum pavement temperature, Y is minimum
and cohesion of their molecules [1]. Those thermoplastic materials are pavement design temperature [1]. Introduction of this classification
divided into tars and asphalts due to their origin. Tars are produced system has forced changes in the design of asphalt binders. To meet
by destructive distillation under pyrolysis from the organic materials stiffness requirements in regions with extreme climatic conditions
(coal, lignite, wood, peat). Because of their toxicity and low quality they is not possible without asphalt binder modification. In Poland, as in
are not used in construction industry. many other European countries, the base of asphalt classification is
Asphalt, also known as bitumen, is the mixture of hydrocarbons their penetration at 25ºC. Road bitumens are classified according
which are naturally occurring or obtained from crude oil distillation. to PN-EN 12591.
The composition of asphalt is very complex and depends both on the Polymer modified bitumen (PMB) are classified according
origin and on the method of crude oil processing. Asphalts, especially to PN-EN 14023:2011. Polymer modified bitumens are reported
modified, are also thixotropic – they flow like a liquid when a sideways as PMB X/Y-Z, where X/Y-penetration range at 25ºC, Z- lowest
force is applied. The properties of asphalt are function of temperature softening point.
and duration of load.
Bitumens are used as binders in asphalt concrete, a composite Modification of asphalts, polymer modificators
material used in the construction of road layers. It also contains mineral Modified bitumen is asphalt whose chemical or rheological
aggregate, filler and additives. All compounds are glued together properties were modified by addition of chemical compound [3].
by asphalt, so despite its low content (ca. 5%) its effect on properties First polymer modified bitumens were produced in first half of the
of concrete and, therefore, on the pavement performance is critical. XX century; in Poland – in 1990s. Earliest modifiers were natural
The physical and rheological properties of asphalt are dependent rubber latex, sulfur and rubber; firstly synthetic modifiers were
on its composition, chemical structure and colloidal structure. polychloroprene (CR) and styrene-butadiene copolymer (SBS), which
is most commonly used nowadays.
Colloidal structure of asphalt Increased attention in asphalt modifiers can be attributed to the
Due to the complexity and a large number of molecules with following factors [6]:
different chemical structure, the structure of asphalt is divided • increasing traffic volume, loads and tire pressures, causing increased
into fractions of similar properties. There are several methods for pavement rutting and cracking
extracting those asphalt group components [1÷3]. Bitumen is often • environmental and economic issues – possibility of recycling waste
characterized by its chromatographic fractions, the maltenes and the and industrial byproducts (tires, roofing shingles, glass, ash) with
asphaltenes, soluble and insoluble in n-heptane, respectively. The achieving benefit in pavement properties
maltenes can be fractionated further into saturates, aromatics and • public agency willingness to fund higher-cost asphalt additives for
resins [2]. The asphaltenes consist mainly of highly condensed polycyclic longer service life of pavement and its less maintenance.
aromatic hydrocarbons of average molecular weight 2-15 kDa [2]. • Bitumen is modified to enhance the functional properties of asphalt
Asphalt is commonly modeled as a colloid, with maltenes as the concrete and the lifetime of pavement. Most important issue is
continuous phase and micelles of asphaltenes stabilized by associated to extend the range of viscoelasticity.
resins as the dispersed phase [4]. There is no evident border between Binder and polymer have to be miscible to form homogeneous
dispersed and continuous phase. mixture, without destroying colloidal structure of asphalt. Compatibility

nr 12/2012 • tom 66 • 1343

 affects the long-term storage behavior as it prevents polymer phase • Facilitated processing: ease of pumping, operating at lower
science • technique
separation. Miscibility depends on structure and properties both temperatures, reduced emissions from asphalt operations
asphalt’s and polymer’s. • In addition with polymers: lower polymer consumption, possible
Asphalt can be modified with elastomeric or plastomeric polymers. lower temperature processing, synergetic effect of both additives,
The first results in improved elastic recovery after removing applied stress, cost reduction.
broaden range of viscoelasticity, reduced risk of rutting and reduced Since 1990s, researches on using PPA in conjunction with
prone to thermal and fatigue cracking. Plastomers make bitumen stiffer polymers to improve quality of road bitumens are conducted. The
but more prone to permanent deformation; low-temperature properties major benefit of this particular combination is synergistic effect
of such modified asphalt are not better than base asphalt [3]. – possible reinforcement of both modificators effects on asphalt. It has
The most popular polymer modifiers suitable for mixing with been observed for binder elasticity, thermal cracking resistance, and
asphalt are: atactic polypropylene (APP), polychloroprene (CR), resistance to permanent deformation [9]. Moreover, PPA improves
ethylene-vinyl-acetate (EVA), polybutylene (PB), styrene-butadiene- adhesion and may eliminate the need for antistripping agents. In
styrene (SBS), synthetic styrene-butadiene-rubber (SBR), natural addition, the stability of binder during long-time storage in elevated
rubber latex, ethylene-propylene-diene terpolymer (EPDM), ethylene- temperatures is increased. Overall cost of using modified asphalt
methyl acrylate and ethylene-butyl acrylate (EMA, EBA) and styrene- binders is reduced by using less modifier, possible elimination of anti-
isoprene-styrene (SIS). strips, and energy savings from lowering operating temperatures [9].
Addition of PPA may reduce reaction time with some polymers [9].
Polyphosphoric acid (PPA) Polymers linked with PPA are: SBS [12÷15], EVA [12, 14, 16] and
Polyphosphoric acid (CAS 8017‒16‒1) is a polymeric product ethylene terpolymer [17].
of thermal dehydration and polycondensation of orthophosphoric Effect of PPA on crumb rubber modified asphalt has been
acid (H3PO4). Beside orthophosphoric forms, it contains a mixture investigated since 2003, with good results [9]. PPA improves viscosity,
of polymeric forms whose content increases with increasing acid stability during storage, elastic recovery and reduces the amount of
concentration. Commercially available PPA is a mixture of linear asphalt needed to create the blend. Binder containing 5-8% gum and
polyacids of general formula Hn+2PnO3n+1, where n ≥ 2. Those acids are 0.5-1% PPA has a similar characteristics to asphalt modified with PPA
produced either from the dehydration of H3PO4 at high temperatures and polymer [18].
or by heating P2O5 dispersed in H3PO4. In the latter method, longer
chains are obtained. Polyphosphoric acid is highly hydroscopic and Mechanism of PPA modification
easily hydrolyze in moist air. Its viscosity and physical form at room Modification of asphalt with PPA is a complex physicochemical
temperature depends on the content of P2O5 [6]. PPA main’s application process. Investigation of reaction occurring between the components
is production of high quality liquid fertilizers, but it is also a substrate of of the binder and the PPA is difficult, due to the great number
numerous chemical synthesis. of molecules with different chemical structure and their possible
PPA is available in various grades, the naming of which can be interactions. It has been proven that PPA acts on functional groups with
confusing as the percentage often exceed 100%. It is effect of calculation high dielectric constants – hence studies are conducted on bitumen
of H3PO4 concentration on the base of P2O5 content in this inorganic model compounds. As a result of reaction between asphalt and PPA,
polymer. For the asphalt’s modification, concentration of 105, 110 and a decrease in molar weight distribution and a change in asphalt’s
114% H3PO4 are used (75.9, 79.8 and 82.6% P2O5, respectively). morphology is observed [10, 19]. Explanation of this phenomenon is
PPA is produced mainly in China and in the USA. One of very based on colloidal structure of asphalt.
few in Europe and Poland’s only producer of PPA is Inorganic According to recently proposed mechanism [10], asphalt’s weak
Chemistry Division “IChN” of Fertilizers Institute, located in bases (pyridines and amphoteric quinolones) form ionic pairs with
Gliwice. PPA production is based on their own, original solution strongly acidic PPA, thus, PPA displace weak acids such as phenols in
of multi-sectional electrothermal evaporator [7], which provides their interaction with those bases. The loss of the hydrogen bonds and
a controlled production of 100-114% H3PO4 acid (73-82% wt. the release of an alkylated phenol from a larger aromatic structures
P2O5). The plant’s production capacity total is 30-45 kg per hour. results in compounds with lower molecular mass. Those lower
Obtained PPA has very good quality parameters, making it suitable molecular weight components enrich maltens fraction. PPA is also
for many applications. a catalyst in indole bridge formation. Formed large, covalently linked
and therefore, stiffer molecules remain in fraction of asphaltenes.
PPA as an asphalt modifier As a result, a decrease in average molecular weight of asphalt
First patent on use of PPA in asphalt modification was published components and change in its morphology is observed, due
in 1973 [8]. Addition of PPA to binder results in increase of to disintegration of asphaltenes resulting in smaller domains and
softening point with no effect (or sometimes small decrease) in amplification of the natural segregation of maltenes and asphaltenes.
low-temperature brittleness [10], as PPA does not oxidize asphalt. Low molecular weight compounds migrate to maltenes and decrease
This leads to improve maximum service temperature (or useful its Tg, and higher molecular weight covalently linked compounds raise
temperature range). However, also decrease in low-temperature the Tg of the asphaltenes [10].
properties was observed [11], it seems to be depending on base Reactions of PPA with bitumen is strongly dependent on its chemical
asphalt composition. composition, which is related to its type and origin; thus properties of
Main advantages on use of PPA in asphalt modification are: modified asphalt can slightly vary [19].
• Good compatibility of PPA with asphalt: no phase separation during Main heteroatom in asphalt is sulfur, however, both aliphatic
the long-term storage and aromatic sulfide groups, were proven to be inert when heated
• Modified bitumen characteristics: increased viscosity without with PPA at 150°C for 1 hour [19]. Other studies [10] showed that
oxidation, softening point improvement, lower penetration at reactivity of PPA with asphalt increases with increasing nitrogen
room temperature, improved stiffness and oxygen content. Given that indoles are found in higher
• Pavement characteristics: reduced rutting, increased resistance concentrations than other functional groups (on second place there
to thermal and fatigue cracking, increased resistance on moisture, are pyridines), its content is expected to play a crucial role in the
increased durability due to better binder adhesion to aggregate reaction of binders with PPA.

1344 • nr 12/2012 • tom 66

 national manufacturer. PPA used in correct way, in the appropriate

science • technique
amount and according to technological guidelines, can significantly
improve asphalt properties, thus, improve pavement’s performance,
its durability and application range. Also using PPA in conjunction
with polymer or with crumb rubber is possible and beneficial. On the
other hand, incorrect application of PPA technology, as in case of many
other polymer modificators, can result in construction or performance
Fig 1. Diagram of a chemical modification of asphaltene through problems. The effect of PPA on asphalts of various origin and on other
polyphosphoric acid, leading to break down into smaller domains components of asphalt concrete should be carefully considered during
and formation of indole bridges
formulation.

Technical guidelines for PPA asphalt modification Literature

The following guidelines are based on Best Practices for PPA 1. Piłat J., Radziszewski P.: Nawierzchnie asfaltowe. Wydawnictwa
Modification of Asphalt [20] prepared by the Polyphosphoric Acid Komunikacji i Łączności 2004.
Subcommittee in cooperation of the PPA producers in USA and 2. Masson J-F.: A brief review of the chemistry of polyphosphoric acid (PPA)
on materials from 2009 PPA Workshop in Minneapolis [21]. Useful and bitumen. Energy & Fuels 2008, 22, 2637-2640.
information on asphalt technology and requirements can also be found 3. Gaweł I., Kalabińska M., Piłat J.: Asfalty drogowe. Wydawnictwa
in the Poradnik Asfaltowy 2011, developed by PKN Orlen [5]. Komunikacji i Łączności 2001.
Acid selection: it is very important to distinguish between 4. Nellensteyn F.J.: The Constitution of Asphalt. Journal of Institute
polyphosphoric and orthophosphoric acid, the latter confusingly is Petroleum Technology 1924, 10, 311-325.
sometimes named PPA, from purified phosphoric acid. Orthophosphoric 5. Błażejowski K., Olszacki J., Peciakowski H.: Poradnik asfaltowy 2011.
acid contains free water, which lowers miscibility with asphalt and ORLEN Asfalt 2011.
leads to phase separation during storage, asphalt foaming and steel 6. Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., vol.15.
tanks corrosion. Polyphosphoric acid contains no free water and is John Wiley & Sons 1986.
completely miscible with asphalt. It is also less corrosive to steel and 7. Patent PL 308863
stainless steel. 8. Patent US 3751278
Acid concentration of 105 and 115% H3PO4 is mostly used in 9. Use of Polyphosphoric Acid in Asphalt Binders. Phosphate Forum of the
asphalt modification. The amount of PPA required is different for Americas 2009.
each base asphalt, typically from 0.25% up to 1.5%. There are no 10. Masson J-F., Collins P., Woods J.R., Bundalo-Perc S., Margeson J.C.:
recommendations for PPA grade. Chemistry and effects of polyphosphoric acid on the microstructure,
Masson et al. [10] proposed an equation to predict the stiffening molecular mass, glass transition temperatures and performance grades
effect of PPA on asphalt binders with 1% PPA or less. It can be used of asphalts. Journal of the Association of Asphalt Paving Technologists
as a first approximation in the design and production of binders with 2009, 78, 403-430.
specific PGs. 11. Aflaki S., Tabatabaee N.: Proposals for modification of Iranian bitumen
Properties of prepared asphalt blend have to be tested for each to meet the climatic requirements of Iran. Construction and Building
composition, after adding all additions. Materiale 2009, 23, 2141-2150.
Aggregate and anti-strips: PPA can react with components 12. Patent WO 9958600
of asphalt binder. Neutralization reaction that occurs depends on 13. Patent US 5880185
the type of asphalt, aggregate and antistripping agent and may lead 14. Patent US 5070123
to a reduction in elasticity of asphalt and its adhesion to aggregate. PPA 15. Patent US 5451621
does not react with limestone. Reaction with acidic aggregates (e.g. 16. Patent US 6136898
granite) leads to enhance moisture resistance and can eliminate the 17. Patent US 6117926
need for using anti-strip additives. 18. Patent US 2006/0250886
When required, the anti-strip additives used should be compatible 19. Masson J-F., Collins, P.: FTIR study of the reaction of polyphospheric
with PPA, otherwise neutralization may occur. Strongly recommended acid and model bitumen sulfur compounds. Energy & Fuels 2008, 23,
are phosphate esters, due to its proven compatibility. Adhesives based 440-442.
on amines react with PPA, leading to decrease of mixture properties. 20. Best Practices for PPA Modification of Asphalt. Phosphate Forum of the
Technology: in a plant, PPA should be stored in a dedicated tank, Americas 2009.
it is recommended that a nitrogen blanket be placed over the material 21. https://engineering.purdue.edu/NCSC/PPA%20Workshop/2009/
to prevent moisture absorption from air. Preferred tank construction index.html, 2009 PPA Workshop Minneapolis, 10.01.2012
material is 316SS. Laboratory tests proven that the PPA modified asphalt
and the head space above the modified binder are not corrosive. Translation into English by the Author
The storage tank, pump, and acid process lines should be heated
to maintain PPA in a fluent state. The required handling temperature is
approximately 38ºC for 105% PPA is and 94ºC for 115% PPA.
Safety: asphalt is classified as hazardous due to high temperature
required during transport. PPA modified asphalt is as safe as neat
Hanna JAROSZEK – M.Sc., graduated from the Faculty of Chemistry
asphalt, PPA is not leached and does not migrate from asphalt’s mass.
Raw polyphosphoric acid is corrosive and should be treated according of Silesian University of Technology (2011). Currently, she is employed at
to MSDS. Fertilizers Research Institute, Inorganic Chemistry Division “IChN” in Gliwice.
Research interest: high purity substances.
Summary
e-mail: hanna.jaroszek@ichn.gliwice.pl; phone: +48 32 231 30 51 ext.203
Polyphosphoric acid has been successfully used in the USA for over
10 years. However, it does not gain any interest in Poland, despite

nr 12/2012 • tom 66 • 1345

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