Galatin ized asphalt cement and method for manufacturing thereof

The present invention relates to a method for producing asphalt cement. This new gelled multi-grade cement As a beneficial substitute for traditional asphalt cements for roads and roof constructions as well as special asphalt cement products, where reduced sensitivity to temperature and reduced hardening due to aging are sought after among important properties.

Pavement asphalt surfaces make up over 90% of pavement in the United States of America. Natural asphalts obtained from deposits in the Lakes have been used since 1874. Later, rock asphalt deposits were discovered in some southern and western states, which were ground, applied and rolled to form road surfaces. However, since the early 1900s, bitumens produced in the oil refining process have dominated the use of road surfaces and roof surfaces.

Asphalt Is a dark brown to black material with a high viscosity, containing Bitumen as the main component, which are found in various proportions in most crude petroleum. Asphalt residue from oil refining, essentially free of light initial fractions, is commonly called asphalt.

163 713

Topcoats are classified as asphalt cement, fluxed cement and asphalt emulsions. In this case, it is asphalt cement, although further mention is made of asphalt emulsions and fluxed asphalt.

Asphalt cement is asphalt in properties suitable for roads and roofing as well as specialized products. In road construction, the asphalt is heated to a free flowing consistency and mixed with the aggregate heated to approximately 9am (usually 120-160 ° C) and applied to the prepared surface, compacted and hardened to form asphalt concrete. In the long history of asphalt surfaces, the hot mixing process of asphalt cement and aggregate has remained a constant method, as it provides the best balance of costs and quality. In the hot mixing process heated liquefied asphalt cement is brought into contact with the heated aggregate to form the entrusted aggregate ready for leveling and hardening.

Asphalt cement grades used for pavements are determined according to three clear parameters! viscosity, viscosity after aging and penetration. The most common species assessment system in the United States is based on viscosity measured at 60 ° C / AASHTO M-226 /. / AASHTO stands for American Association ot State Hignway and Transportation Ufficiais /. Thus, asphalt cement having a viscosity of 25 Pa.at 60 ° C is designated AC-2.5 and is considered as soft asphalt. From the other end, asphalt cement with a viscosity of 400 Pa.s at 60 ° C, designated AC-40, is considered as hard asphalt. In the middle are bitumen marked AC-5, AC-10, AC-20 and AC-30. In addition, AC-50 is used in some areas in hot climates and AC-1 is used in cold climates. Standard bitumen grades are compiled in tables and discussed in the Principles of construction of Hot-Mix Asphalta Pavements, The Asphalt Institute, Manual Series No. 22 / MS-22 /, January 1983, p. 14.

Some western states have used a species determination system based on viscosity after aging. This system is intended to more accurately reflect the surface's viscosity after it has been put in place. The test simulates asphalt aging by accelerated oxidation of a thin asphalt film at 60 ° C / AASHTO M-226 /. The results are given, for example, as AR-10 for a viscosity of 100 Pa.s considered as soft asphalt and AR-160 for a viscosity of 1600 Pa.s considered as hard asphalt. This species identification system is discussed in the abovementioned publication on page 15.

Bitumen grades can also be determined with the standard penetration test / AASHTO M-20 /. In these tests, the distance at which a standard needle loaded with a certain weight penetrates into the asphalt at a specified time at 25 ° C indicates the hardness or softness of the asphalt. This test is discussed on page 16 of the abovementioned publication.

When used for roofing, asphalt cement is used in the construction of layered roofs, roof tiles and fillers when applying asphalt with rollers. The grade of asphalt cement used in layered roofs is defined by the softening point according to ASTM 0 312. / ASTM stands for American society for Testing Materials /. Type I bitumen, which has a low softening temperature, is considered to be soft asphalt. Bitumen for roofing type IV has a high softening point and is considered as hard asphalt. This and intermediate grades are based on asphalt susceptibility to flow at given temperatures and roof slopes. Laminated roofs are built by rolling asphalt saturated felt and then grinding asphalt cement on it. This process is repeated several times to form a waterproof sandwich roof.

There are other specialized applications for asphalt cement including, for example, joint and crack fillings, circulation and waterproofing and moisture resistance measures that have different requirements depending on the intended use.

Fluxed asphalt is used where liquid asphalt is desired at temperatures below those normally used for asphalt cement or emulsification bases / see below /. Fluxed bitumens are usually applied by spraying. They are prepared by dissolving asphalt in a petroleum solvent such as naphtha.

163 713 kerosene or heating oil. Both when using fluxed asphalt by spraying as well as cold mixing, problems of environmental pollution and safety arise due to the evaporation of the solvent into the atmosphere. Also in the energy crisis of the 1970s, the use of petroleum solvents for this purpose was contrary to the moderation demanded at the time, resulting in a significant reduction in the use of fluxed asphalt today.

Solvents are normally not used to make asphalt emulsions, although fluxed asphalt may be used as the asphalt component (usually water-in-oil emulsions). The asphalt softener is liquefied by heating. The asphalt globules are dispersed and ground with surfactants to form a stable water-in-oil emulsion. Asphalt emulsions can be one of several types including anionic, cationic or nonionic emulsions depending on the surfactant used to make them. Emulsjo is used to seal existing roads by applying a thin layer of asphalt emulsion to the road surface and then covering with an aggregate to obtain a waterproof road. Asphalt emulsions can also be used to mix with the aggregate on site in the road bed or mixed with the aggregate in a clay mixer and then spread along the road using a sliding road concrete mixer. Emulsions are usually associated with the cold mixing process, and when used in the hot mixing process, lower temperatures are usually used compared to the traditional hot process.

Asphalt emulsions can be used in the hot mixing process for the production of asphalt concrete, but inherent production difficulties generally lead to the use of more favorable asphalt cement. Some of the problems associated with emulsions in the Hot Mixing process are discussed below.

During the periodic hot mixing process, when venting the steam emitted during heating of the emulsion (usually containing 30% water by weight), there are sometimes explosive forces when the aggregate is brought to a relatively high temperature creating safety and environmental problems. In continuous processes of hot mixing in drums, short mixing times are insufficient to obtain adequate water evaporation.

In both hot-mixing manufacturing processes, additional energy is required to evaporate the water contained in the emulsion. Oil-in-water emulsions freeze if stored at sufficiently low temperatures and, consequently, premature destruction of the emulsion. If for some reason the emulsion is overheated, water may be prematurely lost and the emulsion inverted, potentially causing serious handling problems and, as a result, the product may become unusable.

The most important from the point of view of quality is the need to remove water as soon as possible and most completely from the residue of the emulsion stuck to the aggregate. The water phase of the emulsion inherently contributes to the high water content in the even layer of asphalt concrete, and the next evaporation rate is influenced by ambient conditions. Thus, there is uncertainty as to both the speed and extent of drying in the curing stage of asphalt concrete laid from asphalt emulsions, with the accompanying perspective of changing important properties at any point in the curing process.

Asphalt emulsion used in the hot mixing process includes a class of anionic emulsions called high-liquid emulsions. The preparation of these emulsions has a long established procedure in which the emulsion is stabilized by in situ saponification of organic acids, usually present in the form of tall oil. Bitumen with improved residue properties is produced after the water has been removed by the hot mixing process.

For example, U.S. Patent No. 2,355,319 describes an emulsion in which tall oil is saponified with sodium hydroxide, giving tall soap that serves as an emulsifier, which gives improved emulsion residue properties in hardened asphalt concrete.

U.S. Patent No. 3,904,428 similarly describes an asphalt emulsion in which, for example, tall oil saponified with sodium hydroxide in the presence of a significant amount of water is ground with asphalt cement in a specified temperature range to form a gel coat

163 713 a mass containing higher than usual quantities of asphalt. It is said that a higher asphalt content reduces the asphalt's tendency to drain a wet aggregate and provides a more complete coating.

U.S. Patent No. 4,422,084 describes high flow emulsion processes in which tall oil is first mixed with asphalt pretreated with various modifiers that affect asphalt properties but do not affect the destruction of the emulsion. Also disclosed is a process in which an emulsifier containing for example tall oil reacted with a caustic solution in water is mixed with asphalt. The ratios of the emulsifier components can be varied to adapt to different asphalt compositions.

The publication of the Tall oil Products Division of the Pulp Chemicals Association, Tall Oil and Its Uses / FWDodge Company, 1965 / emphasizes the importance of surfactants in the emulsion to move water onto the aggregate and facilitate the bonding of asphalt cement. For this purpose, the use of tall oil fatty acids was described as an emulsifier in fluidized asphalt used for roads.

A general overview of hot and cold surface application processes can be found in Wright and Paquette Highway Engineering, 4th Edition / John Wiley and Sons, 1979 /. A more up-to-date overview of hot mixing methods was published in the Principles of Conatruotion of Hot-Mix Asphalt Pavementa, January 1983, to which reference has already been made. For an overview of cold mixing processes using asphalt emulsions, see A Basic Asphalt Emulsion Manual, Asphalt Institute, Manual Series No. 19 / Ms - 19 /, March, 1979.

The saponification reaction is used to solidify normally liquid hydrocarbons such as light gasoline, which facilitates their handling and use. For example, US Patent No. 2,385,817 discloses the solidification of normally liquid hydrocarbons by in situ formation of metallic soaps obtained from the saponification of a mixture of stearic acid and california with sodium hydroxide and a small amount of anhydrous methyl alcohol. Alcohol is said to speed up the reaction. Liquid hydrocarbons are light gasoline and other petroleum spirits, which are flammable and are intended for use as motor fuels. As such, they are much lighter in the refining of crude oil than the asphalt residue.

Similarly, lubricating soaps also based on lighter oil fractions have been described, for example, by Lockhart at American Lubricants / Chemical Publishing Company,

1927 / atr, 163 et seq. And in U.S. Patent No. 3,098,823. Surprisingly, water has been recognized as an undesirable ingredient in a lubricant. For example, U.S. Patent No. 2,394,907 lubricant is prepared by suspending sodium hydroxide in a liquid non-active medium, such as mineral oil, milling sodium hydroxide therein, and saponifying the fatty acid in the absence of water. Heating the mixture to the saponification temperature initiates the reaction to give undesirable water as a by-product which must be removed.

U.S. Patent No. 2,888,402 describes a similar reaction, but uses a metal hydroxide containing hydration water that is released on heating and which is likely to initiate a saponification reaction. Lithium hydroxide, especially mentioned as the source of water, initiates the first saponification stage, followed by other metal hydroxides in the second stage.

Despite the long history and extensive use of lubricants in which organic gels were created by saponification in situ, in the field of asphalt, grease has never been interlaced and the grease technology has not been adapted to achieve significant benefits from gel formation in asphalt materials. However, the use of asphalt on roads, roof constructions and special applications, until the present invention, remained a technological province in traditional asphalt cement processes and, to a lesser extent, with fluxed asphalt and emulsions.

Currently, asphalt cement for pavement must be selected so that asphalt concrete

163 713 did not unnecessarily soften at higher temperatures and did not crack at lower temperatures. The need for this selection leads to the use of softer asphalt in the north or in a colder climate and harder asphalt grades in the south or in a warmer climate. However, in many climates, pavements are exposed to both high and low extreme temperatures, leading to trade-offs in the selection of asphalt, with no particular grade being completely suitable for the entire climate range.

Thus, the most important is the temperature sensitivity of asphalt cement when used on asphalt concrete. Asphalt must maintain structural integrity at high temperatures without becoming too brittle and brittle at low temperatures. However, I also have to survive on asphalt surfaces for many cycles of temperature changes, freezing and thawing, and constantly changing loads. The lower the slope of the viscosity / temperature curve in the log-log viscosity system, the more favorable the temperature sensitivity characteristics of asphalt cement are.

Asphalt cements harden as a result of oxidation by prolonged exposure to the surroundings and increased traffic. Aging hardening is another property of asphalt concrete to which weight should be attached. The smaller the slope of the viscosity / time curve plotted in the log-log viscosity system, the more favorable the hardening characteristics with age.

In addition, it is important that asphalt cement applied as asphalt concrete exhibits favorable durability properties under the influence of normal weather changes and aging. Durability Is a measure of resistance to disintegration over time in prevailing weather conditions and heavy traffic. Factors affecting durability are repeated freezing and thawing as well as oxidation accompanying the aging process.

It is clear that asphalt cement would qualitatively move more towards the ideal if the lowest AC grades in line with low temperature considerations for brittleness and brittleness could combine more viscous higher AC grades without sacrificing their high temperature properties. Unfortunately, the mixing of AC grades in current hot mixing processes, although technically feasible, is not associated with a satisfactory compromise of ownership. For example, mixing certain asphalt grades does not result in the desired temperature-dependent viscosities in the mix for each grade, the mixed product has intermediate properties between the original values.

Similarly, when using asphalt cements for roofing, sensitivity to temperature and hardening due to aging is taken into account. Laminated asphalt roofing accounts for the majority of commercial and industrial roofing in the United States. The layering of roof coverings is associated with leveling the successively changed layers of asphalt and asphalt impregnated mats, with asphalt being used hot as asphalt cement.

For specialized asphalt applications, including joint and crack fillers, circulation agents, waterproofing and moisture resistance (ASTM D 449), sensitivity to temperature and hardening due to aging should also be taken into account when determining the final behavior of these products.

Therefore, the object of the present invention was to obtain gelatinized asphalt cement with improved properties over traditional cement, including reduced temperature sensitivity and lower hardening due to aging, and to obtain these results in a traditional hot mixing process in existing hot mixing devices , standard equipment for roofing and equipment for special applications. This was achieved thanks to the methods of the invention.

Thus, the method for producing gelled multi-grade asphalt cement involves a / liquefying substantially dry asphalt material, b / saponifying therein at least one fatty acid and at least one resin acid by reacting with at least a saponifying amount of a substantially dry alkali metal base and c / removing water

163 713 reaction to form gelled universal asphalt cement.

Simply put, the method involves saponification in liquid asphalt, substantially free of water, of at least one fatty acid and at least one resin acid using an alkali metal base or adding an already saponified product to the liquefied asphalt. The resulting gelled asphalt cement is used in traditional methods on roads, roofs and special applications. Further features and advantages of the invention will become apparent from the following description of preferred embodiments of the invention.

Traditional asphalt cement at elevated temperatures occurring in hot mixing processes has rheological properties of the liquid. Asphalt remains liquid, transferable in accordance with its special viscosity-temperature relationship, throughout its connection with agrgaatarn and leveling its layer in the form of asphalt concrete. In this physical state it is susceptible to runoff from the aggregate depending on such factors as temperature, nature and area of ​​the aggregate area as well as the size and configuration of free spaces.

It has now been discovered that asphalt can be gelled by a direct saponification reaction, requiring only trace amounts of ionizing liquid to form an ionizing zone in liquid asphalt where soap can begin. The water produced as the reaction progresses is sufficient to sustain the reaction because it passes through the entire asphalt and saponification mixture. Water removal is part of the method.

Due to the favorable quality change of the gelled universal asphalt prepared according to the method of the invention, an asphalt grade with a lower AC (lower viscosity) can be selected to obtain asphalt concrete with low temperature grade characteristics, while it exhibits high temperature characteristics of higher grades (i.e., higher viscosity).

As a result, such asphalt cements allow for a greater flattening of the viscosity / temperature curve than was obtained for any single species or mixture of species. Similarly, improved hardening properties due to aging and flattening of the viscosity / time curve are observed.

Accordingly, the term multi-species asphalt as used herein means new gelled asphalt cement with reduced temperature susceptibility and improved hardening properties due to aging compared to traditional asphalt cement. Multi-grade asphalt cement produced by the new method is substantially free of water, as indicated by its ability to store at 100 ° C or higher without foaming. It is suitable for mixing with the aggregate to produce asphalt concrete by the traditional hot mixing method, as well as it is suitable for roofing applied by the traditional method and in special applications.

By the method of the invention, the gelled, substantially water-free, multi-grade aafalt cement is preferably prepared by gelation of a liquid asphalt material, substantially free of water, by soapsing at least one fatty acid and at least one resin acid in reaction with an alkali metal base in fine crushed essentially dry fine-grained form and subsequent removal of the reaction water from the reaction mixture. Water normally bound to the reaction components is usually sufficient to initiate the saponification reaction without causing the reaction rate to accelerate so that unwanted foaming with the reaction water occurs as it evaporates from the reaction mixture.

The asphalt material may be derived from any asphalt source, such as natural asphalt, rocky asphalt or preferably asphalt from petroleum obtained in the refining process. Asphalt can be selected from bitumens of the currently specified grade according to AASHTO and ASTM or it can be a mix of different bitumens that does not meet the definition of Some specific grade. This includes asphalt purged asphalt, vacuum distillation asphalt, steam distillation asphalt, fluxed asphalt and asphalt roofing asphalt. Additives such as anti-peeling agent or polymers can be added to the asphalt. The preferred multi-species asphalt of the invention uses soft grade asphalt, such as AC-5, when asphalt for pavement is desired. Alternatively, you can choose gilsonit

163 713 natural or synthetic, used alone or mixed with asphalt from petroleum. Synthetic asphalt mixtures suitable for use in the method of the invention are described, for example, in US Patent No. 4,437,896.

Liquid asphalt material containing saponification components is passed through a high shear mill to reduce the particle size of the alkali metal base and dispersed the base and organic acid components throughout the mass of liquid asphalt to facilitate the saponification reaction. Use a high shear mill of the type that reduces the particle size of the base to less than about 425 microns.

Alternatively, gelled asphalt can be produced by adding soap previously prepared to liquid asphalt. Since the previously prepared soap is essentially free of reaction water, it is relatively hard and preferably, before adding it to liquid asphalt, it must be ground or melted. Choice between saponification in situ and saponification on. the outside requires balancing several factors. Although in situ, undesirable water is formed in liquid asphalt, but it evaporates easily at predominant temperatures. The external reaction requires additional steps and additional equipment for carrying out the reaction, storage, milling (when the saponification reaction product is stored as solid soap) and transfer. Molten soap introduces a critical factor in controlling temperature and temperatures generally higher than liquid asphalt. Therefore, it is preferred to conduct the reaction in situ.

The asphalt material, preferably petroleum asphalt, is heated to obtain a free flowing liquid or to a slightly higher temperature to facilitate the evaporation of water from the saponification reaction. Temperatures of about 175 ° C to about 235 ° C, preferably about 205 ° C, may be used.

As the alkali metal base, alkali metal, alkali metal oxide, alkali metal hydroxide or alkali metal salt such as sodium metal, sodium oxide, sodium carbonate or preferably sodium hydroxide can be used, or the corresponding potassium or lithium compounds can be used. The preferred base when introduced should be substantially dry in finely divided form.

Refined organic acids (for the present purpose together with their ethers) can be used as one or more saturated and unsaturated straight or branched fatty acids containing from about 12 to about 24 carbon atoms. Examples are stearic, oleic, linoleic, linolenic and organic sulfonic acids. As resin acids, for example, abietic, neoabietic, dihydroxyabietic, palustr or isodextroplmaric acid, or mixtures thereof, can be used.

The organic acid is preferably and conveniently added in the form of tall oil. Tall oil is a liquid resinous material obtained in the production of paper from the digestion of wood pulp. Technical tall oil, generally, contains a complex of fatty acids, mainly acids with 18 carbon atoms, resin acids, non-saponifiable substances along with sterols, higher alcohols, waxes and hydrocarbons. The proportions of ingredients in tall oil will vary depending on many factors, including the geographical location of the trees supplying wood pulp. Preferably the content of non-saponifiable substances in the wood pulp is below about 30% (ASTM 0 803). The ratio of fatty acids to resin acids should be in the range of about 0.7 to about 2, preferably about 1: 1. Where crude tel. Oil is used, about 2% by weight of asphalt is preferred for reaction with at least a stoichiometric amount of an alkali metal base. If refined tall oils or individual fatty acids are selected from sources other than tall oil, or if the fatty acids are mixed with resin acids into synthetic tall oil, the amounts of acid components used should roughly match the composition of crude tall oil. It is generally preferred to fully neutralize the alkali metal base with tall oil, indicating approximately equimolar amounts of acid and base.

All that is needed to initiate the saponification reaction is a tiny amount of ionizing medium such as water. For example, the amount of water normally present in a moisture state on the surface of a hygroscopic base such as substantially dry sodium hydroxide used as reagent is sufficient. Similarly, the water normally present in technical tall oil is sufficient to start the reaction. When choosing a base that has one or more hydration water molecules associated with it, like hydrated lithium hydroxide, the heat of liquid asphalt will release enough water to initiate the reaction.

If the entire reaction system does not contain water or another ionizing medium / when, for example, a dry non-hygroscopic base and water-free refined tall oil have been used / the addition of a small amount of water to liquid asphalt will start the reaction. It is of course important that the addition is done at a point where the water would be introduced into the liquid asphalt before it evaporates. An injection at or near the mill inlet will usually be sufficient. For orientation, the amount of water below 0.001% by weight on asphalt will be appropriate. In practice, the saponification reaction proceeds with an amount of water that cannot be measured by standard techniques.

Irrespective of the source of the ionizing medium, thorough mixing achieved at the milling stage is usually sufficient to obtain the desired decomposition before evaporation. Of course, when the reaction water forms, there is an abundance of ionizing medium and it is desirable to produce substantially dry asphalt cement at this evaporation temperature.

Small amounts of alcohol such as methyl alcohol or other lower aliphatic alcohols can also be used as the ionizing medium. The alcoholate formed by the reaction with the alkali metal hydroxide in the same way facilitates the saponification reaction by forming water as the reaction progresses. U.S. Patent No. 2,385,817 describes the accelerating properties of alcoholates in the saponification of liquid hydrocarbons such as light gasoline. Generally, the use of alcohol is avoided as it is a complication in the process of requiring storage and handling of one more ingredient.

The following examples illustrate the practical application of the invention.

Example 1. To a 3.8-liter heated insulated vessel, with a conical bottom, 1500 g of AC-20 asphalt cement heated to 205 ° C was added. A valve was placed at the bottom of the cone to allow asphalt to pass through the high shear colloid mill and be returned to the top of the vessel. Asphalt was circulated through the mill and 3.7 g of sodium hydroxide in beads were added during this time. The beads were protected against moisture to avoid the introduction of unwanted water. Circulation of the mixture was continued for about 2 minutes until the taken sample passed through a 425 micron sieve. 30 g of crude tall oil were added to the circulating mixture. One mole of water was formed in the on-going reaction for every mole of organic acid in crude tall oil. The water disappeared as a foam with continued heating and stirring. As the reaction progressed, the viscosity increased. Stirring continued until foaming ceased, indicating completion of the reaction, approximately 15 minutes after the addition of tall oil. Samples were taken for determinations. The results of the various tests are given in Table 1 and Figs. 1-3 together with the results of the aefalt cement samples determination before being subjected to a multi-species treatment in the above procedure.

Example II The procedure was as in Example 1, but AC-5 asphalt cement was used instead of AC-20 asphalt cement. The physical properties of the cement asphalt obtained are given in Table 1 and Figs. 1-3 and compared with the properties of the same asphalt before being treated for the multi-species character of Example I.

Example III. The procedure was as in Example 1, but the AC-20 asphalt cement was replaced with the AC-10 asphalt cement. The physical properties of the asphalt cement obtained are given in Table 1 and Figs. 1-3, and compared with the properties obtained from testing the same asphalt cement before being subjected to a multi-species treatment according to Example 1.

Multi-species gelled asphalts for the descriptive purposes of Table 1 and Figs. 1-3 are specified by providing both a traditional asphalt grade and an equivalent grade based on viscosity at 60 ° C, to which grades have been transformed in a multi-species treatment. For example, MC-5-20 indicates multi-species asphalt wy10

163 713 ——— <= - 1. .-- J / MG-5-20 / J

AC-5

-----1 ’

AC-S asphalt having AC-20 asphalt properties at 60 ° C.

Table 1 «woia αα a» aa «» maia · * in m «« «« «a <o» o ββ »o,« · * η «« α «α · · α« «αβ> α <ow β · ββο «· α

Before processing After processing ', / MC-20-40 | / MC-10-30 / • AC-20! AC-10 ·

AC-40

AC-20

AC-10! AC-5

Penetration 3.9 ° C, 200 g, 60 sec, donated

Penetration 25 ° C, dnn Viscosity

3.9Cc, 0.1 sec-1 Pa.sx 106

Viscosity

25 ° C, sec -1,

Crimson

Viscosity

135 ° C, 10 sec -1 Pa.s

Softening point ° C

Index

Penetration / PI /

Number of Gloss / PVN /

Viscosity after 5 h TFOT

Aging Index

Viscosity after 15 n TFOT

Aging Index

Viscosity after rolling TFOT

350

0,47

57,2 *0,1

-3,09

640

6,2

182

0,37

111

2,2

1.83

2600 l

X.

L

172

I + I

AND

AND

AND

I t III

1.3 | !

AND

AND

8.0 J

395

5.4

298 ! 131

3.0

0.25! 0.22 j 1.9 J 1.4 iii

J 51.1 47.2 ♦ 0.3 | +0.4 and! ! -0.68

43,9 ♦0,1

380

-3.84 units

175

-0.47 J

AND

AND

115

J 2.01 J 1.93 j 2.17

And Ili

1670

677

390

1

AND

9.18 J 7.44 and 7.34 |

73,9 + 3,5 + 1.29

630

1.59

AND

AND

120 { 480

67,2 +5,8 + 1,58

420

1.41

7.43 years

II

890

439

210

111

<td>Index aging</td><td>f 1 1 1</td><td>and 1 2.54 units</td><td>1 2.41 and '1</td><td>1 1 2.31 J</td><td>1 1 2.09 J</td>

<td></td><td>.....__ L_.</td><td>....... L ...</td><td>... - -L_</td><td>. -___ L_.</td><td>___- "L__</td>

1.34

3.30 I 1.40 I

530 and 431 and

1 AND

J.

1,45

220

0,65

65,5 + 5,4 + 1,09

240

1,09

330

1,50

380

1,73

The results presented in Table 1 allow a direct comparison of various properties of the indicated asphalt cement grades before 1 after treatment giving the multi-species feature in traditional hot mixing of asphalt cement. The tests included two widely used procedures for determining asphalt susceptibility temperature.

The first procedure includes the penetration index / PI / developed by Pfeiffer and Van □ normal and described in the Journal of Insutute of Peutech of Technologism 12: 414/1936 /. In these proceedings, the value O is used for typical road bitumens. With values ​​above zero, temperature sensitivity is lower, with values ​​below zero, there is a higher temperature sensitivity than normal asphalt cements have. Table 1 shows that, for all grades of tested bitumen, PI has been significantly improved due to the treatment giving the multi-species feature.

□ the second procedure involves the number of Pen-viscosity / PVN / developed by Mc Leod discussed in Pztceeeings of Asphalt Paving Technologiats 41: 422/1972 /. PVN uses high temperature asphalt viscosity and penetration by comparing with good and bad bitumen PVN index values. Again, values ​​above zero indicate that asphalt is less susceptible

163 713 for temperature than for values ​​below zero. Table 1 shows that all tested bitumens similarly have been substantially improved with respect to temperature sensitivity by machining providing a multi-species feature.

Fig »1 shows the relationship between penetration, which is a measure of viscosity and temperature. Multi-grade bitumens have a flatter slope, which indicates a lower sensitivity to temperature susceptibility ·

Similarly, Fig. 2 graphically shows a smaller slope of the viscosity / temperature curve for asphalt improved in the process giving it a multi-species feature. Again, all bitumen treated according to the invention has a flatter slope indicating lower temperature sensitivity than traditional untreated bitumen.

Table 1 also shows the effect of the process according to the invention on the hardening property of bitumens. The method according to ASTM 0 1754 Test Method for Effect of Heat and Air on Asphaltic Materials / TFOT / was used to characterize the rate of bitumen hardening due to aging. Also indicated is the hardening rate on the 9th effect of aging obtained by dividing the viscosity of asphalt after TFOT by the viscosity before TFOT. This ratio of the viscosity after keeping the thin layer in the oven to the viscosity before holding the thin layer in the oven is called the aging index. Table 1 indicates a significant improvement in asphalt during machining giving a multi-species feature both with respect to the TFOT index and the aging index.

The thin layer oven test was extended to show the long-term aging effect of the thin asphalt layer by increasing the aging time from 5 to 15 hours. Table 1 shows that the hardening rate due to aging has been substantially reduced by the treatment described in the examples.

Fig. 3 is a graph of viscosity changes as a function of curing time due to aging in a thin film oven test. It is clear that multi-species asphalt has a lower slope of the viscosity / TFOT curve indicating a slower hardening rate due to aging than traditional asphalt.

It should be noted that normal methods for measuring the viscosity of asphalt cements such as ASTM O 2170 and ASTM O 21 71 are not suitable for multi-species asphalt because asphalt is not a Newtonian liquid. Due to non-Newtonian properties, ASTM P-160/1984 / Viscosity of Asphalt Emulsion Residues and Non-Newtonian Bitumens are the preferred methods for determining viscosity using a capillary vacuum viscometer. The results of the various tests are given in Table 1 together with the results obtained from the asphalt samples before being treated to give the asphalt a multi-species feature according to the invention.

From the above comparative tests it can be seen that the machining giving the multi-species feature significantly and positively affects the quality of penetration, viscosity and viscosity indicators after 5 and 15 hours of aging TFOT. For example, the viscosity of AC-5 asphalt before treatment at 60 ° C was 53 Pa.s. After the multi-species treatment, the viscosity increased to 220 Pa.s meeting the viscosity requirements of asphalt AC-20 according to AASHTO M-226. Similarly, there is a better hardening effect due to aging for each bitumen improved with the use of multi-species treatment.

Example IV Following the procedure of Example 1, 1500 g of AC-10 cement asphalt was used instead of the asphalt used in this example, and 5.25 g of anhydrous potassium hydroxide was used instead of the sodium hydroxide of Example I. The test results are given in Table 2.

Example V · Following the method of Example IV, 2.24 g of anhydrous lithium hydroxide was used instead of the potassium hydroxide used in this example. The test results are given in Table 2.

Example VI. Following the method of process H, 5 g of anhydrous sodium carbonate was used instead of the potassium hydroxide used in this example. The results are shown in Table 2.

163 713

<td></td><td></td><td>Tb</td><td>and 1</td><td>and 2</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td>F J Example IV 1</td><td rowspan="2"> 1 1 1 1</td><td>Example V</td><td>S Example VI and</td><td></td><td>Attempt control</td><td></td>

<td></td><td></td><td>* KOH</td><td>L10h</td><td rowspan="2">and Na-CO,²³</td><td></td><td>AC-10</td><td></td>

<td></td><td></td><td>nul-</td><td> - 4 -</td><td></td><td></td><td></td><td></td>

<td></td><td>·· ”L _——</td><td>r ''</td><td></td><td></td><td>-r ~ "</td><td>'Γ</td><td></td><td></td>

<td></td><td>Penetration, dmm</td><td>l 75 1</td><td>and</td><td> 87</td><td>J 70</td><td></td><td> 90</td><td></td>

<td></td><td>Viscosity, 6O ° C, Pa.s</td><td> { 185</td><td>1 1 and</td><td> 134</td><td>J 230</td><td> 1</td><td> 115</td><td></td>

<td></td><td>Softening point, ° C</td><td>1 J 53.3</td><td>1 and and 1</td><td> 52,2</td><td>1 and {65</td><td></td><td> 50</td><td></td>

<td></td><td>Penetration Index / PI /</td><td>J * 0.8</td><td>1 and and</td><td> ♦0,6</td><td> ♦ &gt;2,9</td><td></td><td> ♦0,2</td><td></td>

<td></td><td>Viscosity after / TFOT / 5 hours. Crimson</td><td>1 J 274.3</td><td>and and and and</td><td> 286</td><td>and and 418.9</td><td></td><td> 305,0</td><td></td>

<td></td><td>Aging Index</td><td>and 1.49</td><td>and 1</td><td> 2.13</td><td> ! 1,82</td><td></td><td> 2,65</td><td></td>

<td></td><td>Viscosity after / TFOT /</td><td> 1 1</td><td>1 and</td><td></td><td>1 and</td><td></td><td></td><td></td>

<td></td><td>15 hours, by Pa</td><td>J 560</td><td>1 and</td><td> 817,4</td><td> ! 641,7</td><td></td><td> 1140</td><td></td>

<td></td><td>Aging Index</td><td>J 3.03 1</td><td>and 1 1</td><td> 6.1</td><td>and 2.79 and</td><td>.-L-</td><td> 9,91</td><td></td>

Table 2 shows that all asphalt cements were substantially improved with respect to the compliance temperature based on the penetration index and the long-term aging index compared to the results obtained for AC-10 as the basic asphalt in the control.

Example VII. By using the method of Example 4, 2.2 g of sodium metal was used instead of potassium hydroxide. Less foam was observed. The results are given in Table 3 *

Example VIII. Following the procedure of Example 4, crude tall oil was first added to the cement asphalt, then mixed and sodium hydroxide beads were added to the high shear colloid mill * The results are shown in Table 3.

This example illustrates that the reverse order of addition of chemical components does not significantly affect the properties of treated asphalt giving the multi-species feature ·

Example IX. To the vessel of Example 1, 500 g crude tall oil heated to 148.9 ° C was added with thorough stirring, followed by 62.5 g of sodium hydroxide beads. 33.75 g was withdrawn from the resulting mixture and 1500 g of asphalt AC-10 kept at 205 ° C were added. The resulting mixture was passed through a high shear colloid mill. The multi-species product was tested as before and the results of the tests are presented in Table 3.

<td colspan="2"></td><td>T ab β</td><td> 1</td><td colspan="4">and 3</td>

<td></td><td></td><td> Example VII</td><td> 1</td><td>Example VIIIj</td><td>Example IX</td><td>ξ Try</td><td> 1 |</td>

<td></td><td></td><td>j metallic</td><td> 1</td><td>first oil and</td><td>added together</td><td>and agricultural accounts</td><td>and</td>

<td></td><td></td><td>J sodium and</td><td>and 1 1</td><td>tall J 1</td><td>tall oil and caustic soda</td><td>{AC-10 and</td><td rowspan="2">and 1 1</td>

<td>L</td><td></td><td>L - ... - ...</td><td> 1</td><td> 1</td><td>tangent</td><td> 1</td>

<td></td><td></td><td></td><td> •</td><td></td><td></td><td></td><td></td>

<td></td><td>Penetration</td><td> • 68</td><td> 1</td><td> 67 }</td><td> 72</td><td>J 90</td><td>and</td>

<td></td><td>Viscosity, 60 ° C, Pa.s</td><td> ! 310,5</td><td></td><td>327.5 'and</td><td> 240</td><td>and 115</td><td> 1 1</td>

<td></td><td>Temperature</td><td> 1</td><td> 1</td><td> 1</td><td></td><td>and</td><td>and 1</td>

<td></td><td>softening, ° C</td><td>ΐ 70.6</td><td> 1</td><td>65.6 and</td><td> 62,8</td><td>J 50</td><td>and and</td>

<td></td><td>Penetration index / PI / Lepkuje / ATFOT /</td><td>j + 3.8 1 and</td><td> 1 1 1</td><td>+ 2.9 J and and</td><td> + 2,5</td><td> 5 +0,2 1 1</td><td>1 j</td>

<td></td><td>5 hours</td><td>J 565</td><td>1 and</td><td>590 J.</td><td> 562</td><td> 305</td><td>and</td>

<td></td><td>Indake aging</td><td> ' 1,82</td><td> 1 1</td><td>1.80 ί</td><td> 2,34</td><td>'and 2.65</td><td> !</td>

<td></td><td>Viscosity / ATFOT / 15 hours</td><td> [ 480,5</td><td> 1 1</td><td>827.5 J</td><td> 812,5</td><td>J 1140</td><td> 1 1</td>

<td></td><td>Aging Index</td><td> ! 2,71</td><td>and AND</td><td> 2,53 !</td><td> 3,39</td><td>and¹ 9,91</td><td>L</td>

<td></td><td></td><td> .1--------</td><td>.at</td><td></td><td></td><td>, _L _____________</td><td></td>

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The above results show the physical properties of multi-species asphalt products from examples VII - IX. The results show a significant improvement in temperature sensitivity and hardening due to aging of multi-grade asphalt cement compared to the control AC-10 regardless of the order in which the ingredients are added.

Example X. Tests were carried out to show the sensitivity of asphalt emulsion residues containing a highly liquid residue to the residual moisture in the mixture. Washed limestone ASTM No. 8 was coated with 4% by weight of multi-grade asphalt cement made from asphalt AC-5 / to obtain asphalt cement MC-6-20 / and compared with similarly prepared traditional asphalt AC-20 / ASSHTO M-226 /. The HPMS-2h / ASSHTO M-140 / asphalt emulsion was also mixed with the aggregate by adding 5.7% by weight of the emulsion to obtain a 4% by weight residue of the asphalt mixture. Each batch of asphalt cement was mixed for 90 seconds with the aggregate at 150 ° C. The HFMS-2H asphalt emulsion aggregate was heated to a temperature approximately 55 ° C higher to remove water. The final temperature of the mixture in all cases was 135 ° C.

About 300 g of each mixture was placed in an oven at 150 ° C for 1 hour on a No. 4 sieve, 203.2 mm in diameter. A bowl was placed under each sieve to catch dripping asphalt. The following results were obtained

MG 5-20 AC-20 HFMS-2h

We play asphalt in a bowl 0 9.9 1.3

These tests illustrate the resistance of multi-species asphalt to migration from an aggregate compared to AC-20 asphalt cement and a highly fluid, medium solidifying residue of asphalt emulsion. It has been reported that the special properties of high-flow residues have reduced asphalt migration in mixtures. This test confirms this claim with respect to AC-20, but multi-species asphalt definitely outperforms the remaining HPMS emulsion in this respect.

Example XI. The properties of the mixtures of Example X were measured over a wide range of temperatures. The purpose of these tests was to determine whether improving test results for multi-grade asphalt cement would improve the properties of the asphalt / aggregate mixture (main material end use).

The same asphalt used in the drainage tests of Example 1 was used in the testing of the asphalt-aggregate mixture in this example. ASTM No. 5 aggregate and No. 8 aggregate and fine-grained sand were mixed to obtain 19.05 mm thick mixture (ASTM 0-3515). The aggregate and asphalt were heated to 150 ° C before mixing, except for HPMS-2h, which was mixed with the aggregate at 205 ° and HFMS-2h at 1S ° C for 90 seconds. Each combined mixture contained 4.5% by weight of asphalt. Each mixture was beaten with 75 blows of a Marshall compactor in accordance with ASTM 0-1559. Four mixtures of each asphalt were made and tested at four temperatures: 60 ° C, 37.8 ° C, 15 ° C and 4.5 ° C. This temperature range represents the wide range of pavement temperatures currently present. Stiffness was measured in Marshall and Hweem apparatuses according to ASTM 0-1559 and ASTM 0-1560. The results are shown in Table 4.

Table 4

<td colspan="2">j Test / temperature ° C</td><td>----- γ- and</td><td>MG 5-20</td><td>-r- AND _ _ |</td><td>AC-20</td><td> 1 1</td><td colspan="2">- - - | HFMS-2h emulsion J</td>

<td>J Hveem</td><td>60 ° C</td><td>and 1</td><td> 56</td><td>and 1</td><td> 55</td><td>L</td><td> 20</td><td>and and</td>

<td></td><td> 37,8</td><td> 1 1</td><td> 55</td><td> 1 1 1</td><td> 63</td><td> 1 1 1</td><td> 27</td><td>1 AND</td>

<td></td><td> 15</td><td> |</td><td> 55</td><td>1 AND</td><td> 66</td><td>1 AND</td><td> 33</td><td> 1 1</td>

<td></td><td> 4.5</td><td rowspan="2"> 1 1 1 1 |</td><td> 79</td><td> 1 1</td><td> 87</td><td> 1 1</td><td> 56</td><td>and 1</td>

<td> Marshall</td><td>60 ° C</td><td> 2450</td><td> 1 |</td><td> 2550</td><td> 1 |</td><td> 900</td><td> 1 1 |</td>

<td></td><td> 37.8</td><td> 1 1</td><td> 2850</td><td> 1 1</td><td> 4150</td><td>and 1</td><td> 1250</td><td> 1 1</td>

<td></td><td> 15</td><td> 1</td><td> 3100</td><td> 1</td><td> 4750</td><td>and 1</td><td> 1850</td><td>1 and</td>

<td></td><td> 4,5</td><td> !</td><td> 10000</td><td> 1 1</td><td> 17500</td><td> 1 1</td><td> 2900</td><td>and 1</td>

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These results indicate that the stiffness (i.e. durability) of an asphalt bar made of multi-grade asphalt cement does not increase as much as traditional asphalt cement.

These results also indicate that the mixture with emulsion (HFMS-2h) has an excessively low stability at high temperatures, which can be attributed to incomplete curing (i.e., the presence of residual moisture).

In Examples XII-XIV, trials were conducted to show that a minimum amount of water is needed to initiate the saponification reaction in the production of multi-grade asphalt cement.

Example XII. 1500 g of asphalt AC-10 was heated to 205 ° C and added to the same vessel that was used in Example 1. Sodium hydroxide, 3.75 g, was also preheated to dry molten state, added to asphalt and milled for 1 minute. Tall oil was heated for 2 hours at 135 ° C to dry completely. 30 g dry tall oil was added to the mixture of asphalt and caustic soda and milled for 15 minutes. The test results are shown in Table 5.

Example XIII. Following the method of Example 12, 2.2 g of sodium metal was used in place of sodium hydroxide. The test results are shown in Table 5.

Example XIV. By following the method of Example 13, 0.015 g of water was added to tall oil and mixed before being added to asphalt.

Table 5

<td rowspan="2">} [vol</td><td rowspan="2">Example XII / dry /</td><td colspan="2">J Example XIII i</td><td rowspan="2">Example XV / water /</td><td rowspan="2">-T 1 1 1 AND</td>

<td>¹ /dry/</td><td>1 1 _ x ..</td>

<td>Penetration, 3.9 ° C, U 200 g, 60 seconds, dmm and</td><td> 31</td><td>ί 3!</td><td> 1 1 1 1</td><td> 31</td><td> 1 1 1 1</td>

<td>Penetration 25 ° C, · 100 g, S sec, dmm {</td><td> 83</td><td>and 111 1</td><td>1 t 1 1</td><td> 35</td><td> 1 1 1 1</td>

<td>Viscosity, 60 ° C, sec- on and Pa.s J</td><td> 307,5</td><td> 1 1 ! 92,0</td><td>1 1 and and and</td><td> 275,0</td><td> 1 1 1 1</td>

<td>Softening point, j °_C j</td><td> 70</td><td>J 47.2 1 t</td><td>1 1 1 t</td><td> 65</td><td> 1 1 1 1</td>

<td>Penetration Index / PI / J</td><td> + 4,3</td><td> ! +0,7 1</td><td> 1 1 1</td><td> + 3,8</td><td>9 AND</td>

<td>Viscosity after 5 hours TFOT, Pa.sj</td><td> 425</td><td>1 J 178.5</td><td> 1 1 1 1</td><td> 401</td><td> 1 1 1 |</td>

<td>Aging Index and</td><td> 1,38</td><td>j 1.92</td><td>AND 1</td><td> 1,45</td><td> 1 1</td>

<td>Viscosity after 15 hours TFOT, Pa.s'</td><td> 197,5</td><td>1 1 J 682.0</td><td> 1 1 1 1 1</td><td> 679,6</td><td> 1 1 1</td>

<td>Aging Index *</td><td> 1,62</td><td>J 7.41</td><td> 1 1</td><td> 2,47</td><td> 1 1</td>

<td></td><td></td><td> 1</td><td> 1</td><td></td><td>-J</td>

These results indicate that the saponification reaction occurred in Examples XII and XIV in which comparable properties were observed in asphalt cement. The reaction appeared in Example 12 where all reagents were specially dried. Nevertheless, there was enough moisture (below the laboratory measuring capacity) in the system to start the reaction.

In Example 13 there was no reaction despite the same procedure for drying tall oil. Here, metallic sodium replaced dry molten sodium hydroxide of Example XII.

Again, using metallic sodium and dry tall oil, but also by adding a small amount of water (0.001% by weight to asphalt) to the mixture, the saponification reaction occurred, as shown in Example 14.

Example XV Proceeding as in Example 1, instead of AC-20, roof asphalt Type I / ASTM 0 312 / was used. In table 6, the test results were compared with base cement under typical roof tests.

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Table 6

<td></td><td colspan="2">.and..·.....-......- 1 1 1 1 1 1</td><td>Before processing Type I</td><td> 1 1 1 1 1 1</td><td>After treatment / MG-Typ-I-II / Type i</td><td>L 1 1 1 1</td><td>Type II spacification ASTM 0 312</td>

<td></td><td>Softening temperature, ° C</td><td> 1 1</td><td> 63,3</td><td> 1 1 1 1 1</td><td> 77,2</td><td> 1 1 1 1 1</td><td>70 to 60</td>

<td></td><td>Penetration, O ° C, 200 g, 60 sak., Dmn</td><td>f |</td><td> 14</td><td> 1 1 1 1 1</td><td> 14</td><td> 1 1 1 1</td><td> 6+</td>

<td>and</td><td>Penetration, 25 ° C, 100 g 5 sak ·, dmm</td><td> 1 1 1 1 |</td><td> 40</td><td>1 1 t 1 l</td><td> 34</td><td> 1 1 « 1 1</td><td>16 to 40</td>

<td></td><td>Penetration, 46.1 ° C, 50 g 5 sak., Dmm</td><td> 1 • | 1</td><td> 102</td><td> 1 1 1 |</td><td> 70</td><td> 1 1</td><td> 100</td>

<td></td><td>Penetration Index / PI /</td><td> 1 1 1</td><td> -2,2</td><td> 1 1 1</td><td> 0</td><td></td><td></td>

These tests indicate that the treated asphalt has low temperature properties of type I asphalt for roofing, and high temperature properties of asphalt type II for roofing ·

PI is also significantly lower in the treated asphalt, indicating a lower temperature sensitivity.

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Viscosity, 10 Pa-_s

<img file="PL163713B1_D0001.tif" />

1,5J .....................

-17,8 «,4 26,7 40,9 71,1 93,3 115,6 137,8

Temperature, ° C

Fig. 2

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<img file="PL163713B1_D0002.tif" />

Figure 3

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<img file="PL163713B1_D0003.tif" />

Temperature, ° C

Fig.1

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