ASPHALT AND ASPHALTENE

Neither One is a Single Material

 

Asphalt and asphaltenes are names that show up in articles and papers discussing paving and roofing materials. Especial with people not very familiar with technical field, discussions often sound like each is a single well define material such as salt or water. However that is far from the fact. Some may even feel that asphaltenes are something in the way that needs to be isolated or corralled. Yet they are vital in controlling the properties of an asphalt. Also researchers may reach conclusions on an asphalt from a particular crude source and believe that those conclusions pertain to all asphalts.

Asphalt.

Asphalt is the part of crude oil that is left when all the other hydrocarbons have been removed. There are two main ways of separating the asphalt from the gasoline, kerosene and oils; distilling, and solvent extraction.

Source. The properties of a particular unmodified asphalt are controlled by the source of the crude oil. The differences can be profound. In California there are three crude sources that produce entirely different asphalts: California Valley, Coastal and LA Basin. Within those broad designations are subgroups such as the coastal crudes; Santa Maria and San Ardo. A specification can be developed such that it can be met by asphalts from all three sources however they will perform differently. There are some asphalts that have very poor cold temperature performance and others that perform very badly in hot weather.

Distillation. In the distillation of crude oil, one pipe goes into the distillation towers, and a number of pipes come out. Each tower system is designed for a particular crude or crude blend and there are pumps removing the products. What is left over is asphalt on the bottom of the tower also. Some crude oils have no asphalts while others may contain as much as 65% asphalt. If any one of the storage tanks gets full, the refinery has to shut down.

Propane Extraction. The other method is to extract the non-asphalt portion with propane.

Asphaltene

One of the components of asphalt is the asphaltenes. Here we have two problems: the misconception that asphaltenes are significantly different than other asphalt components, and the basic definition. While some methods define asphaltenes as n-pentane insoluble material, other methods use hexane or heptane or even iso-octane as the solvent. n-Pentane will produce the largest amount. Because certain asphaltenes are precipitated by a solvent doesn’t mean that there aren’t still other materials in the asphalt that are very similar to asphaltenes. Asphaltenes give body to the asphalt. If the asphaltenes are completely solvated, the asphalt won’t perform well. On the other hand, if they are in a second phase, again the asphalt may cause problems. In some cases, the asphaltenes will be at least solvated sufficiently at ambient temperatures for a single phase to be present, however they may form two phases in cold conditions, resulting in cracking in winter.

Modification

The addition of polymer modifiers further complicates the situation. Adding a polymer to any asphalt will result in two phases no matter how well the asphaltenes are solvated. When polymer modification was young problems with phase separation was a problem that had to be resolved. It can be seen that with a wide range of properties in asphalts, polymer modification can be more of an art than a science. One question I have is how well modified asphalts will perform in low temperatures even though they pass all of the low temperature test. For pavements to resist low temperature cracking the binder must be able to stress relax faster than thermal stresses build up. If the binder becomes more like a plastic with a yield force necessary, the pavement will crack.

Robert L. Dunning, chemistdunning@gmail.com, www.petroleumsciences.com

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WATER CAUSED PAVEMENT DISTRESS

Raveling

Raveling is the loss of the mastic matrix in the surface of a pavement. This would be expected to occur with time but is aggravated by the presence of water. If the aggregate surface is not protected from water, traffic will cause raveling. This can be seen near curbs where often water is flowing. The asphalt is not pulled off but is floated off.

Water, a blessing and a bane! To get compaction in a subgrade or base, the water content must be at an option. A blessing. Even with cold recycling systems, the total liquid content (including water) must be optimum to get proper compaction. A blessing again. Obviously we love water, especially on a hot day. If we had a choice of a cool glass of water or a glass of warm lard, we would obviously choose water. Most aggregates are no different. If they have a choice, they would choose water to imbibe into their pores, not asphalt.

Our production system forcibly removes water from aggregate and equally forcibly makes the aggregate accept asphalt. That doesn’t make the aggregate happy and if it has the chance it will invite water back in through any defect in the coating and gleefully kick the asphalt off. Many aggregates have hydroxyl groups sticking out on the surface, which attracts water. In addition there may be water loving sodium and potassium exchangeable ions on the surfaces. These ions are the result of defects in the silicate and aluminate structure in the aggregate. In the silicate structure there may be an aluminum atom instead of silicon resulting in a structural negative charge. Likewise a magnesium atom may replace aluminum in the aluminate structure.

To combat this, amines or lime can be added to change the nature of the aggregate surface. Unfortunately, the protection may not last, especially if salt or magnesium chloride is used for deicing. The chemical principle of mass action can reverse the action of these antistrips. One solution has been to graph onto the aggregate surface an organosilicon material that actually becomes an integral part of the aggregate and thus cannot be dislodged. The aggregate then changes allegiance so strongly that it actually forcibly rejects water and opens its pores to the asphalt.

So to control raveling, the adverse affect of water must be controlled. This is especially important with raveling as it occurs on the surface where the pavement will be often in contact with water. The best solution is to persuade the aggregates to distain the advances of their first love and turn to a new one that is not so transparent.

Robert L. Dunning, chemistdunning@gmail.com, www.petroleumsciences.com

LOW COST ROADS

Using Local Materials

Roads are absolutely necessary for economies to succeed. Yet in these perilous economic times, funds are not available to build them to luxury standards. However there is technology available that allows the construction of very usable roads using materials already in-place.

Asphalt Emulsion Stabilized Bases. With soils with a plasticity index of 6 or less asphalt emulsions could be considered for base stabilization. This technology has been around for decades. I published a paper in the 1965 Proc. Asphalt Paving Technology on asphalt emulsion stabilized bases which included a mix design. We had found that one inch of stabilized base could replace about 1 ¼” of crushed aggregate base. For roads with low truck traffic a chip seal might be used as a wearing surface. A word of caution, the same care must be taken for compaction as with soils, and in calculating the maximum density; the liquid would be the sum of the emulsion and added water. There are some sophisticated emulsion formulations in which the emulsion “sets” and kicks out water, however they are not available everywhere.

Another caution. Just because an emulsion is labeled “slow set” does not mean it will necessarily mix with all in-place soils. We once were working with a particular slow set emulsion that was working quite well. On this project we first treated the soil with lime then stabilized it with a slow set emulsion. To save money, the contractor switched to another slow set emulsion, which didn’t work. In emulsion stabilization the mixed soil should be brown. In this case it came out the same color as it was before mixing, indicating that then emulsion was coagulating and balling up rather than coating.

Emulsion Based Macadams. When I was in Panama many years ago I witnessed the construction of a macadam using CRS-2 asphalt emulsion. The emulsion was manufactured by a company for whom I was doing consulting on asphalt emulsion manufacturing. A typical macadam construction technique was used. First a layer of large stone was place followed by a layer of asphalt emulsion. Following that were consecutive layers of aggregate and emulsion with each aggregate size ½ the size of the proceeding one. The last layer was sand. Since CRS-2 emulsions break as soon as it contacts the aggregate, it appeared to work in the tropics.

Lime Stabilization. For soils too plastic for using asphalt emulsions, lime stabilization might be the selection.

Cold In-Place Recycling.  Cold in-place recycling is being used in the United States especially in place of hauling new aggregate base. For low truck traffic the wearing surface could be a single or double chip seal. For heavier traffic, however, hot mix should be used.

This short piece was to suggest that there may be lower cost options for constructing roads in rural areas. For any question contact me at chemistdunninng@gmail.com in English or Spanish. (I have also had a couple of years of Russian but that was a lifetime ago, but I can read the Cyrillic alphabet. Although my knowledge of Russian has retreated to the far reaches of my brain, we do have a large Russian population here so we can accept Russian inquiries.)

Robert L. Dunning. www.petroleumsciences.com

Recycled Pavement or Black Rocks

I have been working with recycled asphalt since presenting an AAPT paper in 1975 on 100% asphalt recycling. I have always considered all of the asphalt was acting as binder. I am not so sure anymore. As more and more RAP is being used the question comes up whether all of the asphalt in the mix should be considered truly asphalt or actually be part of the aggregate.  We have noticed that mixes that require, say, 5.1% asphalt  with no RAP may require 5.5-5.7% asphalt. The next question is whether the formation of the “black rocks” is actually the true condition of the RAP, or whether coking of the asphalt happened during the mix design phase because the technician added the RAP too soon in the mix cycle, such as leaving it in the aggregate in the oven overnight. This would not be happening in cold-in-place recycling. If part of the asphalt is not working as binder, perhaps we should change the mix design criteria as to how we calculate VMA etc.