Asphalt

Asphalt ( or, occasionally ), also known as bitumen ,  is a sticky, black and highly viscous liquid or semi-solid form of petroleum. It may be found in natural deposits or may be a refined product; it is a substance classed as a pitch. Until the 20th century, the term asphaltum was also used. The word is derived from the Ancient Greek asphaltos, which in turn was borrowed from an Eastern word.

The primary use (70%) of asphalt/bitumen is in road construction, where it is used as the glue or binder mixed with aggregate particles to create asphalt concrete. Its other main uses are for bituminous waterproofing products, including production of roofing felt and for sealing flat roofs.

The terms asphalt and bitumen are often used interchangeably to mean both natural and manufactured forms of the substance. In American English, asphalt (or asphalt cement) is the carefully refined residue from the distillation process of selected crude oils. Outside the United States, the product is often called bitumen. Geologists often prefer the term bitumen. Common usage often refers to various forms of asphalt/bitumen as "tar", such as at the La Brea Tar Pits. Another archaic term for asphalt/bitumen is "pitch".

Naturally occurring asphalt/bitumen is sometimes specified by the term "crude bitumen". Its viscosity is similar to that of cold molasses while the material obtained from the fractional distillation of crude oil boiling at 525 C is sometimes referred to as "refined bitumen".

Composition
The components of asphalt are classified into four classes of compounds: The naphthene aromatics and polar aromatics are typically the majority components. Additionally, most natural bitumens contain organosulfur compounds, resulting in an overall sulfur content of up to 4%. Nickel and vanadium are found in the <10 ppm level, as is typical of some petroleum.
 * saturates, saturated hydrocarbons, the % saturates correlates with softening point of the material
 * Naphthene aromatics, consisting of partially hydrogenated polycyclic aromatic compounds.
 * Polar aromatics, consisting of high molecular weight phenols and carboxylic acids
 * Asphaltenes, consisting of high molecular weight phenols and heterocyclic compounds

The substance is soluble in carbon disulfide. It is commonly modelled as a colloid, with asphaltenes as the dispersed phase and maltenes as the continuous phase. and "it is almost impossible to separate and identify all the different molecules of asphalt, because the number of molecules with different chemical structure is extremely large".

Asphalt/bitumen can sometimes be confused with "coal tar", which is a visually similar black, thermoplastic material produced by the destructive distillation of coal. During the early and mid-20th century when town gas was produced, coal tar was a readily available byproduct and extensively used as the binder for road aggregates. The addition of tar to macadam roads led to the word tarmac, which is now used in common parlance to refer to road-making materials. However, since the 1970s, when natural gas succeeded town gas, asphalt/bitumen has completely overtaken the use of coal tar in these applications. Other examples of this confusion include the asphalt/bitumen of the La Brea Tar Pits and the Canadian oil sands. Pitch is another term sometimes used at times to refer to asphalt/bitumen, as in Pitch Lake.

Occurrence


The great majority of asphalt used commercially is obtained from petroleum. Nonetheless, large amounts of asphalt occur in concentrated form in nature. Naturally occurring deposits of asphalt/bitumen are formed from the remains of ancient, microscopic algae (diatoms) and other once-living things. These remains were deposited in the mud on the bottom of the ocean or lake where the organisms lived. Under the heat (above 50 °C) and pressure of burial deep in the earth, the remains were transformed into materials such as asphalt/bitumen, kerogen, or petroleum.

Natural deposits of asphalt/bitumen include lakes such as the Pitch Lake in Trinidad and Tobago and Lake Bermudez in Venezuela. Natural seeps of asphalt/bitumen occur in the La Brea Tar Pits and in the Dead Sea.

Asphalt/bitumen also occurs as impregnated sandstones known as bituminous rock and the similar "tar sands" such as in Athabasca, Canada and Utah, US. The Athabasca tar sands are located in the McMurray Formation, Alberta. This formation is from the early Cretaceous, and is composed of numerous lenses of oil-bearing sand with up to 20% oil. Isotopic studies attribute the oil deposits to be about 110 Ma old. Heavy oil or bitumen deposits also occur in the Uinta Basin in Utah, US. The Tar Sand Triangle deposit, for example, is roughly 6% bitumen.

Asphalt/bitumen occurs in hydrothermal veins. An example of this is within the Uinta Basin of Utah, in the US, where there is a swarm of laterally and vertically extensive veins composed of a solid hydrocarbon termed Gilsonite. These veins formed by the polymerisation and solidification of hydrocarbons that were mobilized from the deeper oil shales of the Green River Formation during burial and diagenesis.

Asphalt/bitumen is similar to the organic matter in carbonaceous meteorites. However, detailed studies have shown these materials to be distinct.

Ancient times
The use of asphalt/bitumen for waterproofing and as an adhesive dates at least to the fifth millennium BC in the early Indus community of Mehrgarh, where it was used to line the baskets in which crops were gathered.

In the ancient Middle East, the Sumerians used natural asphalt/bitumen deposits for mortar between bricks and stones, to cement parts of carvings, such as eyes, into place, for ship caulking, and for waterproofing. The Greek historian Herodotus said hot asphalt/bitumen was used as mortar in the walls of Babylon.

A 1 km tunnel beneath the river Euphrates at Babylon in the time of Queen Semiramis (ca. 800 BC) was reportedly constructed of burnt bricks covered with asphalt/bitumen as a waterproofing agent.

Asphalt/bitumen was used by ancient Egyptians to embalm mummies. The Persian word for asphalt is moom, which is related to the English word mummy. The Egyptians' primary source of asphalt/bitumen was the Dead Sea, which the Romans knew as Palus Asphaltites (Asphalt Lake).

Approximately 40 AD, Dioscorides described the Dead Sea material as Judaicum bitumen, and noted other places in the region where it could be found. The Sidon bitumen is thought to refer to asphalt/bitumen found at Hasbeya. Pliny refers also to asphalt/bitumen being found in Epirus. It was a valuable strategic resource; the object of the first known battle for a hydrocarbon deposit, between the Seleucids and the Nabateans in 312 BC.

In the ancient Far East, natural asphalt/bitumen was slowly boiled to get rid of the higher fractions, leaving a thermoplastic material of higher molecular weight which when layered on objects became quite hard upon cooling. This was used to cover objects that needed waterproofing, such as scabbards and other items. Statuettes of household deities were also cast with this type of material in Japan, and probably also in China.

In North America, archaeological recovery has indicated asphalt/bitumen was sometimes used to adhere stone projectile points to wooden shafts.

Early use in Europe
One hundred years after the fall of Constantinople in 1453, Pierre Belon described in his work Observations in 1553 that pissasphalto, a mixture of pitch and bitumen, was used in Dubrovnik for tarring of ships from where it was exported to a market place in Venice where it could be bought by anyone. An 1838 edition of Mechanics Magazine cites an early use of asphalt in France. A pamphlet dated 1621, by "a certain Monsieur d'Eyrinys, states that he had discovered the existence (of asphaltum) in large quantities in the vicinity of Neufchatel", and that he proposed to use it in a variety of ways – "principally in the construction of air-proof granaries, and in protecting, by means of the arches, the water-courses in the city of Paris from the intrusion of dirt and filth", which at that time made the water unusable. "He expatiates also on the excellence of this material for forming level and durable terraces" in palaces, "the notion of forming such terraces in the streets not one likely to cross the brain of a Parisian of that generation". But it was generally neglected in France until the revolution of 1830. Then, in the 1830s, there was a surge of interest, and asphalt became widely used "for pavements, flat roofs, and the lining of cisterns, and in England, some use of it had been made of it for similar purposes". Its rise in Europe was "a sudden phenomenon", after natural deposits were found "in France at Osbann (BasRhin), the Parc (l'Ain) and the Puy-de-la-Poix (Puy-de-Dome)", although it could also be made artificially. One of the earliest uses in France was the laying of about 24,000 square yards of Seyssel asphalt at the Place de la Concorde in 1835.

Photography and art
Asphalt/bitumen was used in early photographic technology. In 1826 or 1827, it was used by French scientist Joseph Nicéphore Niépce to make the oldest surviving photograph from nature. The asphalt/bitumen was thinly coated onto a pewter plate which was then exposed in a camera. Exposure to light hardened the asphalt/bitumen and made it insoluble, so that when it was subsequently rinsed with a solvent only the sufficiently light-struck areas remained. Many hours of exposure in the camera were required, making asphalt/bitumen impractical for ordinary photography, but from the 1850s to the 1920s it was in common use as a photoresist in the production of printing plates for various photomechanical printing processes.

Asphalt/bitumen was the nemesis of many artists during the 19th century. Although widely used for a time, it ultimately proved unstable for use in oil painting, especially when mixed with the most common dilutents, such as linseed oil, varnish and turpentine. Unless thoroughly diluted, asphalt/bitumen never fully solidifies and will in time corrupt the other pigments with which it comes into contact. The use of asphalt/bitumen as a glaze to set in shadow or mixed with other colours to render a darker tone resulted in the eventual deterioration of a good many paintings, those of Delacroix being just one notable example. Perhaps the most famous example of the destructiveness of asphalt/bitumen is Théodore Géricault's Raft of the Medusa (1818–1819), where his use of asphalt/bitumen caused the brilliant colors to degenerate into dark greens and blacks and the paint and canvas to buckle.

Early use in the United Kingdom
Among the earlier uses of asphalt/bitumen in the United Kingdom was for etching. William Salmon's Polygraphice (1673) provides a recipe for varnish used in etching, consisting of three ounces of virgin wax, two ounces of mastic, and one ounce of asphaltum. By the fifth edition in 1685, he had included more asphaltum recipes from other sources.

The first British patent for the use of asphalt/bitumen was Cassell's patent asphalte or bitumen' in 1834. Then on 25 November 1837, Richard Tappin Claridge patented the use of Seyssel asphalt (patent #7849), for use in asphalte pavement, having seen it employed in France and Belgium when visiting with Frederick Walter Simms, who worked with him on the introduction of asphalt to Britain. Dr T. Lamb Phipson claims that his father, Samuel Ryland Phipson, a friend of Claridge, was also "instrumental in introducing the asphalte pavement (in 1836)". Indeed, mastic pavements had been previously employed at Vauxhall by a competitor of Claridge, but without success.

In 1838, Claridge obtained patents in Scotland on 27 March, and Ireland on 23 April, and in 1851 extensions were sought for all three patents, by the trustees of a company previously formed by Claridge. This was Claridge's Patent Asphalte Company, formed in 1838 for the purpose of introducing to Britain "Asphalte in its natural state from the mine at Pyrimont Seysell in France", and "laid one of the first asphalt pavements in Whitehall". Trials were made of the pavement in 1838 on the footway in Whitehall, the stable at Knightsbridge Barracks, "and subsequently on the space at the bottom of the steps leading from Waterloo Place to St. James Park". "The formation in 1838 of Claridge's Patent Asphalte Company (with a distinguished list of aristocratic patrons, and Marc and Isambard Brunel as, respectively, a trustee and consulting engineer), gave an enormous impetus to the development of a British asphalt industry". "By the end of 1838, at least two other companies, Robinson's and the Bastenne company, were in production", with asphalt being laid as paving at Brighton, Herne Bay, Canterbury, Kensington, the Strand, and a large floor area in Bunhill-row, while meantime Claridge's Whitehall paving "continue(d) in good order".

In 1838, there was a flurry of entrepreneurial activity involving asphalt/bitumen, which had uses beyond paving. For example, asphalt could also used for flooring, damp proofing in buildings, and for waterproofing of various types of pools and baths, with these latter themselves proliferating in the 19th century. On the London stockmarket, there were various claims as to the exclusivity of asphalt quality from France, Germany and England. And numerous patents were granted in France, with similar numbers of patent applications being denied in England due to their similarity to each other. In England, "Claridge's was the type most used in the 1840s and 50s"

In 1914, Claridge's Company entered into a joint venture to produce tar-bound macadam, with materials manufactured through a subsidiary company called Clarmac Roads Ltd. Two products resulted, namely Clarmac, and Clarphalte, with the former being manufactured by Clarmac Roads and the latter by Claridge's Patent Asphalte Co., although Clarmac was more widely used. However, the First World War impacted financially on the Clarmac Company, which entered into liquidation in 1915. The failure of Clarmac Roads Ltd had a flow-on effect to Claridge's Company, which was itself compulsorily wound up, ceasing operations in 1917, having invested a substantial amount of funds into the new venture, both at the outset, and in a subsequent attempt to save the Clarmac Company.

Early use in the United States
The first use of asphalt/bitumen in the New World was by indigenous peoples. On the west coast, as early as the 13th century, the Tongva, Luiseño and Chumash peoples collected the naturally occurring asphalt/bitumen that seeped to the surface above underlying petroleum deposits. All three used the substance as an adhesive. It is found on many different artifacts of tools and ceremonial items. For example, it was used on rattles to adhere gourds or turtle shells to rattle handles. It was also used in decorations. Small round shell beads were often set in asphaltum to provide decorations. It was used as a sealant on baskets to make them watertight for carrying water. Asphaltum was used also to seal the planks on ocean-going canoes.

Roads in the US have been paved with materials that include asphalt/bitumen since at least 1870, when a street in front of the Newark, NJ City Hall was paved. In many cases, these early pavings were made from naturally occurring "bituminous rock", such as at Ritchie Mines in Macfarlan in Ritchie County, West Virginia from 1852 to 1873. In 1876, asphalt-based paving was used to pave Pennsylvania Avenue in Washington, DC, in time for the celebration of the national centennial. Asphalt/bitumen was also used for flooring, paving and waterproofing of baths and swimming pools during the early 20th century, following similar trends in Europe.

Rolled asphalt concrete
The largest use of asphalt/bitumen is for making asphalt concrete for road surfaces and accounts for approximately 85% of the asphalt consumed in the United States. Asphalt concrete pavement mixes are typically composed of 5% asphalt/bitumen cement and 95% aggregates (stone, sand, and gravel). Due to its highly viscous nature, asphalt/bitumen cement must be heated so it can be mixed with the aggregates at the asphalt mixing facility. The temperature required varies depending upon characteristics of the asphalt/bitumen and the aggregates, but warm-mix asphalt technologies allow producers to reduce the temperature required. There are about 4,000 asphalt concrete mixing plants in the U.S., and a similar number in Europe.

When maintenance is performed on asphalt pavements, such as milling to remove a worn or damaged surface, the removed material can be returned to a facility for processing into new pavement mixtures. The asphalt/bitumen in the removed material can be reactivated and put back to use in new pavement mixes. With some 95% of paved roads being constructed of or surfaced with asphalt, a substantial amount of asphalt pavement material is reclaimed each year. According to industry surveys conducted annually by the Federal Highway Administration and the National Asphalt Pavement Association, more than 99% of the asphalt removed each year from road surfaces during widening and resurfacing projects is reused as part of new pavements, roadbeds, shoulders and embankments.

Asphalt concrete paving is widely used in airports around the world. Due to the sturdiness and ability to be repaired quickly, it is widely used for runways dedicated to aircraft landing and taking off.

Mastic asphalt
Mastic asphalt is a type of asphalt which differs from dense graded asphalt (asphalt concrete) in that it has a higher asphalt/bitumen (binder) content, usually around 7–10% of the whole aggregate mix, as opposed to rolled asphalt concrete, which has only around 5% added asphalt/bitumen. This thermoplastic substance is widely used in the building industry for waterproofing flat roofs and tanking underground. Mastic asphalt is heated to a temperature of 210 °C and is spread in layers to form an impervious barrier about 20 mm thick.

Asphalt emulsion
A number of technologies allow asphalt/bitumen to be mixed at much lower temperatures. These involve mixing with petroleum solvents to form "cutbacks" with reduced melting point, or mixtures with water to turn the asphalt/bitumen into an emulsion. Asphalt emulsions contain up to 70% asphalt/bitumen and typically less than 1.5% chemical additives. There are two main types of emulsions with different affinity for aggregates, cationic and anionic. Asphalt emulsions are used in a wide variety of applications. Chipseal involves spraying the road surface with asphalt emulsion followed by a layer of crushed rock, gravel or crushed slag. Slurry seal involves the creation of a mixture of asphalt emulsion and fine crushed aggregate that is spread on the surface of a road. Cold-mixed asphalt can also be made from asphalt emulsion to create pavements similar to hot-mixed asphalt, several inches in depth and asphalt emulsions are also blended into recycled hot-mix asphalt to create low-cost pavements.

Other uses
Roofing shingles account for most of the remaining asphalt/bitumen consumption. Other uses include cattle sprays, fence-post treatments, and waterproofing for fabrics. Asphalt/bitumen is used to make Japan black, a lacquer known especially for its use on iron and steel, and it is also used in paint and marker inks by some graffiti supply companies to increase the weather resistance and permanence of the paint or ink, and to make the color much darker. Asphalt/bitumen is also used to seal some alkaline batteries during the manufacturing process.

Production
About 40,000,000 tons were produced in 1984. It is obtained as the "heavy" (i.e., difficult to distill) fraction. Material with a boiling point greater than around 500 °C is considered asphalt. Vacuum distillation separates it from the other components in crude oil (such as naphtha, gasoline and diesel). The resulting material is typically further treated to extract small but valuable amounts of lubricants and to adjust the properties of the material to suit applications. In a de-asphalting unit, the crude asphalt is treated with either propane or butane in a supercritical phase to extract the lighter molecules, which are then separated. Further processing is possible by "blowing" the product: namely reacting it with oxygen. This step makes the product harder and more viscous.

Asphalt/bitumen is typically stored and transported at temperatures around 150 °C. Sometimes diesel oil or kerosene are mixed in before shipping to retain liquidity; upon delivery, these lighter materials are separated out of the mixture. This mixture is often called "bitumen feedstock", or BFS. Some dump trucks route the hot engine exhaust through pipes in the dump body to keep the material warm. The backs of tippers carrying asphalt/bitumen, as well as some handling equipment, are also commonly sprayed with a releasing agent before filling to aid release. Diesel oil is no longer used as a release agent due to environmental concerns.

From oil sands
Naturally occurring crude asphalt/bitumen impregnated in sedimentary rock is the prime feed stock for petroleum production from "Oil sands", currently under development in Alberta, Canada. Canada has most of the world's supply of natural asphalt/bitumen, covering 140,000 square kilometres (an area larger than England), giving it the second-largest proven oil reserves in the world. The Athabasca oil sands is the largest asphalt/bitumen deposit in Canada and the only one accessible to surface mining, although recent technological breakthroughs have resulted in deeper deposits becoming producible by in situ methods. Because of oil price increases since 2003, upgrading bitumen to synthetic crude oil has become highly profitable. As of 2006, Canadian crude asphalt/bitumen production averaged about 1.1 Moilbbl per day and was projected to rise to 4.4 Moilbbl per day by 2020. The total amount of crude asphalt/bitumen in Alberta which could be extracted is estimated to be about 310 Goilbbl, which at a rate of 4400000 oilbbl/d would last about 200 years.

Alternatives and bioasphalt
Although uncompetitive economically, asphalt/bitumen can be made from nonpetroleum-based renewable resources such as sugar, molasses and rice, corn and potato starches. Asphalt/bitumen can also be made from waste material by fractional distillation of used motor oil, which is sometimes otherwise disposed of by burning or dumping into landfills. Use of motor oil may cause premature cracking in colder climates, resulting in roads that need to be repaved more frequently.

Nonpetroleum-based asphalt/bitumen binders can be made light-colored. Lighter-colored roads absorb less heat from solar radiation, and have less surface heat than darker surfaces, reducing their contribution to the urban heat island effect.

Natural bitumen
Selenizza is a naturally occurring solid hydrocarbon bitumen found in the native asphalt deposit of Selenice, in Albania, the only European asphalt mine still in use. The rock asphalt is found in the form of veins, filling cracks in a more or less horizontal direction. The bitumen content varies from 83% to 92% (soluble in carbon disulphide), with a penetration value near to zero and a softening point (ring & ball) around 120 °C. The insoluble matter, consisting mainly of silica ore, ranges from 8% to 17%. The Albanian bitumen extraction has a long history and was practiced in an organized way by the Romans. After centuries of silence, the first mentions of Albanian bitumen appeared only in 1868, when the Frenchman Coquand published the first geological description of the deposits of Albanian bitumen. In 1875, the exploitation rights were granted to the Ottoman government and in 1912, they were transferred to the Italian company Simsa. Since 1945, the mine was exploited by the Albanian government and from 2001 to date, the management passed to a French company, which organized the mining process for the manufacture of the natural bitumen on an industrial scale.

Today the mine is predominantly exploited in an open pit quarry but several of the many underground mines (deep and extending over several km) still remain viable. The bitumen Selenizza is produced primarily in granular form, after melting the asphalt pieces selected in the mine. Selenizza is mainly used as an additive in the road construction sector. It is mixed with traditional bitumen to improve both the viscoelastic properties and the resistance to ageing. It may be blended with the hot bitumen in tanks, but its granular form allows it to be fed in the mixer or in the recycling ring of normal asphalt plants. Other typical applications include the production of mastic asphalts for sidewalks, bridges, car-parks and urban roads as well as drilling fluid additives for the oil and gas industry. Selenizza is available in powder or in granular material of various particle sizes and is packaged in big bags or in thermal fusible polyethylene bags.

A Life Cycle Assessment (LCA) study of the natural bitumen Selenizza compared with petroleum bitumen, has shown that the environmental impact of the natural bitumen is about half the impact of the road bitumen produced in oil refineries in terms of carbon dioxide emission.

Etymology
The word asphalt is derived from the late Middle English, in turn from French asphalte, based on Late Latin asphalton, asphaltum, which is the latinisation of the Greek ἄσφαλτος (ásphaltos, ásphalton), a word meaning "asphalt/bitumen/pitch", which perhaps derives from ἀ-, "without" and σφάλλω (sfallō), "make fall". Note that in French, the term asphalte is used for naturally occurring bitumen-soaked limestone deposits, and for specialised manufactured products with fewer voids or greater bitumen content than the "asphaltic concrete" used to pave roads. It is a significant fact that the first use of asphalt by the ancients was in the nature of a cement for securing or joining together various objects, and it thus seems likely that the name itself was expressive of this application. Specifically Herodotus mentioned that bitumen was brought to Babylon to build its gigantic fortification wall. From the Greek, the word passed into late Latin, and thence into French (asphalte) and English ("asphaltum" and "asphalt").

The expression "bitumen" originated in the Sanskrit, where we find the words jatu, meaning "pitch," and jatu-krit, meaning "pitch creating", "pitch producing" (referring to coniferous or resinous trees). The Latin equivalent is claimed by some to be originally gwitu-men (pertaining to pitch), and by others, pixtumens (exuding or bubbling pitch), which was subsequently shortened to bitumen, thence passing via French into English. From the same root is derived the Anglo Saxon word cwidu (mastix), the German word Kitt (cement or mastic) and the old Norse word kvada.

Neither of the terms asphalt or bitumen should be confused with tar or coal tars.

Modern usage
In British English, the word 'asphalt' is used to refer to a mixture of mineral aggregate and asphalt/bitumen (also called tarmac in common parlance). The earlier word 'asphaltum' is now archaic and not commonly used. In American English, 'asphalt' is equivalent to the British 'bitumen'. However, 'asphalt' is also commonly used as a shortened form of 'asphalt concrete' (therefore equivalent to the British 'asphalt' or 'tarmac'). In Australian English, bitumen is often used as the generic term for road surfaces. In Canadian English, the word bitumen is used to refer to the vast Canadian deposits of extremely heavy crude oil, while asphalt is used for the oil refinery product used to pave roads and manufacture roof shingles and various waterproofing products. Diluted bitumen (diluted with naphtha to make it flow in pipelines) is known as dilbit in the Canadian petroleum industry, while bitumen "upgraded" to synthetic crude oil is known as syncrude and syncrude blended with bitumen as synbit. Bitumen is still the preferred geological term for naturally occurring deposits of the solid or semi-solid form of petroleum. Bituminous rock is a form of sandstone impregnated with bitumen. The tar sands of Alberta, Canada are a similar material.