The field of the present invention relates generally to a bituminous paving composition and to a process of bituminous paving, and more particularly to a bituminous paving composition comprising a combination of a foamed, lubricating substance, an asphalt binder, and an aggregate.
Paving roadways, driveways, parking lots, and the like with a bituminous aggregate mixture material is well known. Typically, a mixture of a suitable aggregate comprising stones, gravel, sand, and the like, is heated at an elevated temperature of about 270-370° F. and mixed with a similarly hot, bituminous binder such as an asphalt-based binder (e.g., asphalt or asphalt plus polymer) until the aggregate particles are coated with the binder. Paving mixes made in this temperature range are often referred to as a hot mix. The mixing typically occurs away from the paving site, and the mixture is then hauled to the site and supplied to a paving machine. The mixture of asphalt and aggregate applied by the paving machine to a surface is then usually roller compacted by additional equipment while still at an elevated temperature. The compacted aggregate and asphalt material eventually hardens upon cooling. Because of the large mass of material in paving a roadway or commercial parking lot, the cost of the thermal energy to achieve suitable mixing and paving is considerable. For common binders, the thermoviscosity characteristics of the binder affect the temperature needed to provide thorough coating of the aggregate and consideration of the ambient conditions suitable for paving. Consequently, numerous processes have been devised to optimize aggregate coating and pavement binding while minimizing the cost of materials and/or the process.
As alternatives to hot-mix processes, there are cold-mix processes, where the aggregate, cold and moist, is mixed with a hot or cold binder, which can be an emulsion of asphalt dispersed in water using a suitable surfactant or a mixture of asphalt and a suitable hydrocarbon solvent, such as naphtha, #1 oil, or #2 oil, to name a few (generally referred to as a cutback asphalt). The emulsified asphalt particles coat and bind with the aggregate and remain after the water has evaporated. When a cutback asphalt is used, the hydrocarbon solvent evaporates at different rates depending on the volatility of the solvent. Regardless of the solvent volatility, what remains behind is a paving material where the asphalt component gradually hardens or stiffens over time as the solvent is removed. The binder can alternatively be foamed and mixed with the aggregate to enhance the coating efficacy. While less expensive than hot mixes, cold mixes usually are poorer quality than the hot mixes, and may have poorer binder coating, resulting in less cohesive compaction and durability. Additionally, cutback asphalt mixes have greater environmental impact due to the use of volatile hydrocarbon solvents. Some emulsions also utilize hydrocarbon solvents in addition to water to produce materials suitable for specific applications.
Recently, in an attempt to combine the advantages of hot-mix and cold-mix processes, warm-mix processes have been reported. In one example of a warm-mix process, both “soft” (a component with a lower viscosity than a “hard” component at a given temperature) and “hard” (a component with a higher viscosity than a “soft,” component at a given temperature) components of a bituminous binder are used. The soft component is melted and mixed with aggregate at about 110-265° F., depending on the particular soft component. The heated hard component is then mixed with warm water so as to produce a foam which is mixed with the heated soft component/aggregate mix to achieve a final, coated, paving material. Although a warm-mix paving material can be paved at lower temperatures than hot-mix materials, it requires a more extensive and complex process to produce the warm mix compared to a hot mix.
However the aggregate is coated, if the binder does not adhere well to the aggregate, the binder can separate, or “strip” from the aggregate, causing the material not to remain well-compacted and thereby reducing the overall strength of the pavement. To aid adherence of the binder to the aggregate, the aggregate or more generally the asphalt binder may be treated with an antistripping compound or material (e.g., surfactants) to substantially reduce binder stripping by acting as a binding agent between the aggregate granules and bituminous binder.
Regardless of the aggregate/binder mixing process used, it is essential that the coated paving material not harden together during transport or while in the paving machine or not lack the ability to be compacted to the proper density. Inadequately coated aggregate material, though easy to mix and handle, can cause the paved material not to remain compacted, not to properly support traffic, or not to wear and weather well.
The present invention provides a process for bituminous paving suitable for primary construction having significantly lower mixing, paving, and compaction temperatures (temperatures that are 30-80° F. lower) than for conventional hot-mix paving while retaining sufficient hardening, density, and durability characteristics of conventional hot-mix paving. Generally, the inventive process comprises injecting a foamable lubricating solution into a heated, asphalt binder so as to create a foam-containing, asphalt-based mixture; adding the mixture to a heated aggregate; further mixing the foam-containing, asphalt binder mixture and aggregate using, for example, a static mixer, so as to coat the aggregate to form a paving material; applying the paving material to a prepared surface; and then compacting the applied paving material to form a paved surface.
The present invention also provides a bituminous paving composition comprising about 0.01-3 wt. %, relative to the weight of the asphalt binder, of a lubricating substance; about 3-9 wt. % asphalt binder; and about 91-97 wt. % aggregate. The lubricating substance is typically about 5-10 wt. % cationic, anionic or non-ionic surfactant, such as soap solids, and about 90-95 wt. % water. Alternative lubricating substances may have a soap solids concentration as low as 1 wt. % and, generally, 30-40% is practical upper limit for pumpability of the soap solution.
The composition may further comprising an antistripping material such as a primary amine, a secondary amine, a tertiary amine, an imido amine, an imidazoline; or a phosphate ester wherein the number of carbon atoms in the antistripping material is in the range of about 7 to 20. Alternatively, other antistripping materials that are known in the art are also suitable. When used in the composition, the amount of antistripping material is in the range of about 0.1%-10% by weight of the lubricating substance.
In one embodiment, the inventive process comprises injecting a foamable solution comprising a lubricating substance into a heated, asphalt binder so as to create a heated, foamed mixture; adding the heated, foamed mixture to a suitable aggregate heated to a temperature higher than the temperature of the heated, foamed mixture; further mixing the two so as to coat the heated aggregate with the heated, foamed mixture to form a heated paving material; transferring the heated paving material to a paving machine; applying the heated paving material with the paving machine at a paving temperature to a prepared surface; and then compacting the applied paving material to form a paved surface.
One feature of the use of a foamable lubricating solution, such as an aqueous foam, is that its imparted lubricity allows the temperature of the paving material during paving to be significantly lower (e.g., about 30-80° F. lower) than the temperature required to soften the binder to provide similar constructability. Another feature is that an aqueous foam comprising a lubricating substance or material requires much less water to similarly disperse the lubricating material than a normal emulsion or water solution would. Thus, less volume of water has to be delivered, handled, and eventually evaporated from the paved mixture. A suitable lubricating material is a soap. Non-limiting examples of suitable soaps include sodium soaps of fatty acids, sodium soaps of sulfonic acids, ethoxylated nonylphenols, quaternary amine chlorides, and sodium or potassium soaps of tall oils and refined tall oils. Other cationic, anionic or non-ionic surfactants may also be used as suitable lubricating materials.
The substantially lower paving temperature provided by the invention may (1) reduce the cost of thermal energy used, without adversely affecting the paving process or the resultant pavement; (2) reduce emission of volatile components, thereby reducing air pollution; or (2) allow use of a “stiffer” grade of asphalt in the paving material. For example, a more readily available PG 64-22 binder mixed with a lubricating foam may be used instead of a less stiff, PG 58-28 binder at the same warm-mix processing temperatures resulting in a pavement having performance similar to the hot mix pavement produced with the PG 58-28 binder.
Asphalt-based binders include petroleum-based binders. Asphalt binders may include additives, for example, such as polymeric materials. Suitable asphalt-based or asphalt binders include those binders complying with ASTM D-6373, D-3387, or D-946. However, some asphalt binders in substantial but not full compliance with ASTM D-6373, D-3387, or D-946 may be used. The aggregate may comprise reclaimed asphalt pavement (RAP).
In one embodiment of the present inventive process, the foamable solution is an aqueous solution that comprises a lubricating substance made from a soap. The paving material comprises about 91-97 wt. % aggregate and about 3-9 wt. % asphalt-based binder. The amount of soap solids used for a given amount of aggregate is about 0.01-3 wt. % relative to the weight of the asphalt-based binder used.
The heated, foamed-asphalt-binder mixture is heated to a temperature that is less than the temperature used to form a conventional hot mix. Depending on the particular asphalt binder that is used, suitable temperatures are in the range of about 180-340° F. Similarly, the suitable aggregate is heated to a temperature in the range of about 180-300° F. and the heated paving material is heated and mixed at a temperature in the range of about 180-300° F. The paving material is paved at a temperature in the range of about 170-290° F., and compacted at a temperature in the range of about 150-270° F. The foamable soap solution can be at any temperature that does not freeze, boil the liquid, or adversely affect the foaming, but it is preferable that its temperature be in the range of about 80-150° F.
This embodiment may be performed by injecting of the foamable solution into a heated, asphalt binder; adding the heated, foamed mixture to a suitable aggregate and mixing to form the heated paving material in situ at or near the work site. One advantage of the invention is that its significantly less volume of liquid used to mix the asphalt binder with the aggregate allows the convenience of in situ processing and reduces the need to transport large volumes of water.
In another embodiment of the inventive process, the aqueous solution comprises about 30 wt. % soap solids and about 70 wt. % water; the asphalt binder comprises # PG 58-28 asphalt; the paving material comprises about 94.5 wt. % aggregate and about 5.5 wt. % # PG 58-28 asphalt binder; and the amount of soap solids used is less than about than 1 wt. % relative to the weight of the asphalt binder used. For this particular binder, the heated, foamed-asphalt-binder mixture is heated to a temperature of about 240-340° F.; the suitable aggregate is heated to a temperature in the range of about 180-300° F.; and the heated paving material is heated and mixed at a temperature in the range of about 180-300° F. The paving material is paved at a temperature in the range of about 170-290° F., and compacted at a temperature in the range of about 150-270° F.
In another embodiment, the aqueous solution comprises about 30 wt. % soap solids and about 70 wt. % water; the asphalt binder comprises # PG 64-22 asphalt; the paving material comprises about 94.5 wt. % aggregate and about 5.5 wt. % # PG 64-22 asphalt binder; and the amount of soap solids used is less than about 1 wt. % relative to the weight of the asphalt binder used. For this particular asphalt binder, the heated, foamed-asphalt-binder mixture is heated to a temperature about 240-340° F.; the suitable aggregate is heated to a temperature in the range of about 180-300° F.; and the heated paving material is heated and mixed at a temperature in the range of about 180-300° F. The paving material is paved at a temperature in the range of about 170-290° F., and compacted at a temperature in the range of about 150-270° F. Those of ordinary skill in the art will appreciate that the heated, foamed-asphalt-binder mixture and suitable aggregate may be heated and mixed at higher temperatures and the paving material may also be paved and compacted at a higher temperatures without adversely affecting the performance of the paved material, but doing so would be more costly in heating energy expense.
Typically, the asphalt temperature needs to be higher than the aggregate temperature. Depending on the asphalt grade, the asphalt might need to be as hot as 325° F. or hotter so that it can be pumped and will foam. The aggregate temperature essentially controls the mix temperature since it constitutes approximately 90% of the mix by weight. The aggregate temperature needs to be controlled to the warm-mix range of about 180°-300° F. When mixing aggregate with stiff binders or those containing a polymer, the normal aggregate and mixing temperature could be as hot as 350° F., which is a hot mix, but using the present invention with the same aggregate and binder, the aggregate and mixing temperature could be reduced to 300° F., which is considered a warm mix, without adversely affecting the resulting pavement's performance.
In another embodiment of the inventive process, the foamable solution further comprises an antistripping material. Non-limiting examples of a suitable antistripping material are a primary amine, a secondary amine, a tertiary amine, an imido amine, an imidazoline, or a phosphate ester wherein the number of carbon atoms in these materials is in the range of about 7 to 20.
In yet another embodiment of the inventive process, the aqueous solution further comprises an antistripping material such that the foamable solution comprises about 30 wt. % soap solids, about 5 wt. % antistripping material, and about 65 wt. % water.
The following examples provide processing and test data for a number of asphalt binders and aggregates, with and without lubricating substances or agents, that are processed under conventional hot mix conditions and under the process of the present invention.
In these examples, E-1 mix is a specific mix type conforming to State of Wisconsin Department of Transportation (“WIDOT”) requirements for pavements designed to carry up to 1 million Equivalent Single Axle Loads (ESALs) over a 20-year design life. The same is true for E-10, except the ESAL value is up to 10 million. The term ESAL is well-known to those working in the bituminous paving industry.
Tall oil soap and refined tall oil soap may be made by reacting the tall oil or refined tall oil typically with sodium or potassium hydroxide by any one of well-known methods to produce soap. Tall oil and refined tall oil are available from Arizona Chemical, Jacksonville, Fla.; Georgia Pacific, Atlanta, Ga.; and MeadWestvaco, Stamford, Conn. Molex antistripping material is a mixture of polycycloaliphatic amines available from Air Products, Allentown, Pa. Alpha Olefin sulfonate is available from Stepan Chemical, Winder, Ga. The choice of asphalt grade is dependent on site-specific variables such as the particular geographical location, local climate, traffic loads, etc.
One test of a paved material's performance is to simulate vehicle traffic stress by the number of repetitive passes a roller supporting a specified weight load must make to cause formation of a rut of a specified depth in the material. Such testing of compacted material produced by the inventive process was done using a testing machine referred to as a Hamburg Wheel Tracking (“HWT”) Tester, also known as a PMW Wheel Tracker, available from Precision Machine and Welding, Salina, Kans. The number of Hamburg passes required to reach a rut depth of 10 mm when the compacted material tested in a dry condition was used for comparative evaluation. The test conditions were 158 lb. wheel load, 52 passes per minute at the test temperature using heated air to achieve the specimen test temperature. Generally, when all other variables are essentially the same, the greater the number of passes, the better the anticipated paving mix performance. Those persons of ordinary skill in the art and familiar with the HWT will recognize paving materials that are suitable for a particular application based on the results that are provided when samples are subjected to these test conditions.
In Table 1, examples where the mixing temperature is in the range of 270-280° F., and the compaction temperature is about 275° F. or higher are considered conventional hot-mixes for the particular binders that were processed and tested; examples where the mixing temperature is in the range of 230-235° F., and the compaction temperature is in the range of 215-220° F. are considered warm-mixes. Thus, examples 1, 4, 6, 7, and 10 are hot-mixes, and the other examples are warm mixes for these binders.
As the data indicate, generally, using the same binder for the warm-mix as for the hot-mix does not produce the same results but does provide an acceptable paving material. The warm-mix have a lower number of Hamburg passes. This lower number is likely due to the fact that the binder does not age or cure as much during the warm mixing process due to the lower mix temperature and shorter curing time, as shown by comparing examples 1, 2, and 3. Examples 1, 6, and 7 show that curing greatly increases the performance of a hot-mix, and examples 16, 17, and 18 also show increased performance with curing even with decreased soap level. Examples 1 and 4 show that addition of only an antistrip to a hot-mix does not improve the pavement. Example 4 was tested at a slightly higher temperature and indicates an antistrip material increases performance. All other things being equal, as much as a 50% decrease in the number of passes to 10 mm rut depth may occur by increasing the test temperature 8° C. Examples 8 and 9 show that use of the invention with PG64-22, a stiffer binder than PG58-28, results in improved performance. Examples 14 and 15 show that use of the invention with PG64-22, 15% RAP, and a 30-minute cure gives the highest performance pavement. This data indicate that a binder of greater initial stiffness may be used to produce the warm mix to yield performance approximately equal to that of the less stiff binder used to make hot mix. A PG 58-28 binder is less stiff than a PG 64-22 binder, but as the data show, using a PG 64-22 binder in the warm mix produces Hamburg results approximately the same as the PG 58-28 results with the hot mix. Therefore, being able to substitute PG64-22 for P058-28 by using the invention results in suitable pavement. Test results of binder recovered from both hot and warm-mixes, not disclosed, demonstrate the similarity of their properties.
This invention is not to be taken as limited to only the details of the embodiments described herein, as modifications and variations thereof may be made without departing from the spirit or scope of the invention as claimed.
This application is a continuation of U.S. application Ser. No. 11/374,747, filed Mar. 14, 2006 and entitled “Bituminous Paving Composition and Process for Bituminous Paving” which claims the benefit of U.S. Provisional Application No. 60/716,204, filed Sep. 12, 2005 and entitled “Process for Bituminous Paving”, the entire disclosures of which are hereby incorporated by reference.
Number | Name | Date | Kind |
---|---|---|---|
1014103 | Wallbaum | Jan 1912 | A |
1373661 | Johansen | Apr 1921 | A |
1384805 | McSwiney | Jul 1921 | A |
1542626 | MacKay | Jun 1925 | A |
1640544 | Headley | Aug 1927 | A |
1674523 | Sadtler | Jun 1928 | A |
1778760 | Hay | Oct 1930 | A |
1086250 | Barton et al. | May 1931 | A |
1815089 | Alsdorf | Jul 1931 | A |
1834552 | Sadtler et al. | Dec 1931 | A |
1842139 | Alsdorf | Jan 1932 | A |
1887518 | Sadtler | Nov 1932 | A |
1888295 | Smith | Nov 1932 | A |
1932648 | Taylor | Oct 1933 | A |
1948881 | Kirschbraun | Feb 1934 | A |
1988336 | Roediger | Jan 1935 | A |
1988879 | Steininger | Jan 1935 | A |
2023068 | Flood | Dec 1935 | A |
2025945 | Forrest | Dec 1935 | A |
2046902 | Kirschbraun | Jul 1936 | A |
2087401 | Fair | Jul 1937 | A |
2191295 | Dohse | Feb 1940 | A |
2243519 | Barth | May 1941 | A |
2283192 | Ditto | May 1942 | A |
2317959 | Johnson et al. | Apr 1943 | A |
2340449 | Barwell | Feb 1944 | A |
2374732 | Colburn | May 1945 | A |
2427488 | Anderson et al. | Sep 1947 | A |
2461971 | Fischer | Feb 1949 | A |
2550481 | Jense | Apr 1951 | A |
2861787 | Csanyi | Nov 1958 | A |
2901369 | Pordes | Aug 1959 | A |
2917395 | Csanyi | Dec 1959 | A |
2919204 | Dybalski et. al. | Dec 1959 | A |
3855167 | Bowman | Dec 1974 | A |
3904428 | McConnaughay | Sep 1975 | A |
4197209 | Zinke et al. | Apr 1980 | A |
4198177 | Brett et al. | Apr 1980 | A |
4234346 | Latta, Jr. et al. | Nov 1980 | A |
4244747 | Leonard, Jr. et al. | Jan 1981 | A |
4348237 | Ruckel | Sep 1982 | A |
4592507 | Benedict | Jun 1986 | A |
4692350 | Clarke et al. | Sep 1987 | A |
4724003 | Treybig et al. | Feb 1988 | A |
4743304 | Gilmore et al. | May 1988 | A |
4836857 | Hopkins | Jun 1989 | A |
5109041 | Matsuno et al. | Apr 1992 | A |
5539029 | Burris | Jul 1996 | A |
5622554 | Krogh et al. | Apr 1997 | A |
5721296 | Mizunuma et al. | Feb 1998 | A |
5772749 | Schilling et al. | Jun 1998 | A |
5788755 | Salminen | Aug 1998 | A |
5827360 | Salminen | Oct 1998 | A |
5925233 | Miller et al. | Jul 1999 | A |
6136898 | Loza et al. | Oct 2000 | A |
6197837 | Hill et al. | Mar 2001 | B1 |
6451885 | Dresin et al. | Sep 2002 | B1 |
6559206 | Durand et al. | May 2003 | B1 |
6576050 | Samanos | Jun 2003 | B1 |
6588974 | Hildebrand et al. | Jul 2003 | B2 |
6793964 | Hoad | Sep 2004 | B2 |
6846354 | Larsen et al. | Jan 2005 | B2 |
6913416 | Hildebrand et al. | Jul 2005 | B2 |
7041165 | Malot | May 2006 | B2 |
7114843 | Romier et al. | Oct 2006 | B2 |
7114875 | Romier et al. | Oct 2006 | B2 |
7160943 | Burris et al. | Jan 2007 | B2 |
7297204 | Crews et al. | Nov 2007 | B2 |
7309390 | Falkiewicz | Dec 2007 | B2 |
7815725 | Reinke et al. | Oct 2010 | B2 |
7902277 | Reinke et al. | Mar 2011 | B2 |
7968627 | Reinke et al. | Jun 2011 | B2 |
7981466 | Reinke et al. | Jul 2011 | B2 |
7981952 | Reinke et al. | Jul 2011 | B2 |
8138242 | Reinke et al. | Mar 2012 | B2 |
8323394 | Reinke et al. | Dec 2012 | B2 |
8454739 | Reinke | Jun 2013 | B2 |
8454740 | Reinke et al. | Jun 2013 | B2 |
8454741 | Reinke et al. | Jun 2013 | B2 |
20020170464 | Larsen et al. | Nov 2002 | A1 |
20040014845 | Takamura et al. | Jan 2004 | A1 |
20040223808 | Romier et al. | Nov 2004 | A1 |
20040244646 | Larsen et al. | Dec 2004 | A1 |
20050018530 | Romier et al. | Jan 2005 | A1 |
20050284333 | Falkiewicz | Dec 2005 | A1 |
20060086288 | Bourrel et al. | Apr 2006 | A1 |
20060169173 | Dupuis et al. | Aug 2006 | A1 |
20060236614 | Antoine et al. | Oct 2006 | A1 |
20060240185 | Antoine et al. | Oct 2006 | A1 |
20060288907 | Fox | Dec 2006 | A1 |
20070039520 | Crews et al. | Feb 2007 | A1 |
20070060676 | Reinke | Mar 2007 | A1 |
20070082983 | Crews et al. | Apr 2007 | A1 |
20070191514 | Reinke et al. | Aug 2007 | A1 |
20090088499 | Barreto et al. | Apr 2009 | A1 |
20110017096 | Reinke | Jan 2011 | A1 |
20110020537 | Reinke | Jan 2011 | A1 |
20110021673 | Reinke | Jan 2011 | A1 |
20110152410 | Reinke | Jun 2011 | A1 |
20110214589 | Reinke | Sep 2011 | A1 |
20120213584 | Reinke et al. | Aug 2012 | A1 |
Number | Date | Country |
---|---|---|
433003 | Aug 1972 | AU |
2006231250 | Oct 2006 | AU |
0568021 | Nov 1993 | EP |
1398351 | Mar 2004 | EP |
1263885 | Jun 2004 | EP |
1469038 | Oct 2004 | EP |
0994923 | Jan 2006 | EP |
429548 | May 1935 | GB |
783015 | Sep 1957 | GB |
2006220 | May 1979 | GB |
2234512 | Aug 1989 | GB |
2002332606 | Nov 2002 | JP |
2006132131 | May 2006 | JP |
8702694 | Jul 1981 | WO |
9522661 | Aug 1995 | WO |
99-57199 | Nov 1999 | WO |
0116233 | Mar 2001 | WO |
0148089 | Jul 2001 | WO |
0162852 | Aug 2001 | WO |
0216499 | Feb 2002 | WO |
02103116 | Dec 2002 | WO |
2005081775 | Sep 2005 | WO |
2006106222 | Oct 2006 | WO |
2007032915 | Mar 2007 | WO |
2007112335 | Oct 2007 | WO |
2008148974 | Dec 2008 | WO |
2009033060 | Mar 2009 | WO |
Entry |
---|
Barretto, “Warm Asphalt Mixes Containing Dispersed Water,” ARKEMA-CECA France, Abstract No. 658, 2006, 7 pgs. |
Bonola et al., “Technologies for the Production of Asphalt Mixes with Low Temperature Processes,” World Road Association Italian National Committee, Dec. 2005, 27 pgs. |
Booth et al., “Development of Very High Bitumen Content Emulsions for Sprayed Sealing,” Proceedings 17th ARRB Conference, Part 3, pp. 73-89. |
Declaration of John A. D'Angelo Under 37 CFR 132, Dec. 2009. |
Extended European Search Report, EP Application No. 06790099.3, mailed Jan. 4, 2013. |
International Search Report, International Application No. PCT/US2006/33907, Sep. 24, 2007, 4 pgs. |
International Search Report and Written Opinion, International Application No. PCT/US2009/052830, Sep. 16, 2010, 9 pgs. |
Jenkins et al., “Half-Warm Foamed Bitumen Treatment, a New Process,” 7th Conference on Asphalt Pavements for Southern Africa, 1999, 17 pgs. |
Jenkins, “Mix Design Considerations for Cold and Half-Warm Bituminous Mixes with Emphasis on Foamed Bitumen,” dissertation submitted to the Department of Civil Engineering, University of Stellenbosch in fulfillment for the degree of Doctor of Philosophy, Sep. 1, 2000, pp. I-XVII, 1. |
Kristjansdorttir, “Warm Mix Asphalt for Cold Weather Paving,” a thesis, University of Washington, 2006, 127 pgs. |
Low Energy Asphalt (LEA) with the Performance of Hot-Mix Asphalt (HMA), European Roads Review, Special Issue, BGRA, Feb. 2004, pp. 1-11. |
Maccarrone et al., “Cold Asphalt Systems as an Alternative to Hot Mix,” XP055014266, pp. 1-6, Jan. 1, 1995. |
Maccarrone et al., “Pavement Recycling Using Foamed Bitumen,” Proceedings 17th ARRB Conference, Part 3, pp. 349-365. |
PRIPOL 1045 Safety Data Sheet, Aug. 7, 2008. |
Redicote® E-6, Akzo Nobel Technical Information, Asphalt Applications, 2003. |
Redicote® E-6, Akzo Nobel Material Safety Data Sheet, 2004. |
Redicoteo E-6, Akzo Nobel Material Safety Data Sheet, 2010. |
Redicote® E-6, Akzo Nobel, 2011. |
AKZO International Highway Chemical Newsletter, Chemical Division, Spring 1989, pp. 1-9. |
Anderson, David A., et al, “The Effect of Antistrip Additives on the Properties of Asphalt Cement,” Asphalt Paving Technology 1982, Proceedings Association of Asphalt Paving Technologists Technical Sessions, Kansas City, Missouri, vol. 51, Feb. 22, 23 & 24, 1982, pp. 298-317. |
Butz, Thorsten, et al., “Modification of Road Bitumens with the Fischer-Tropsch Paraffin Sasobit,” Journal of Applied Asphalt Binder Technology, vol. 1, Issue 2, Oct. 2001, pp. 70-86. |
Caillot et al., “Warm Mix Asphalts and Cold Recycling for Controlled Use of Effective Road Techniques Reducing Nuisances,” Technical Department for Transport, Roads, and Bridges, Engineering for Road Safety, Ministry for Transport, Infrastructure, Tourism and the Sea, France, 12 pgs. |
Ceca Arkema Group, “Green Road Formulation-Warm Asphalt Mix. 2007 Innovation: helping to lower our planet's temperature,” www.siliporite.com, accessed Nov. 21, 2007, 1 pg. |
Cervarich, “Cooling Down the Mix” NAPA Explores New “Warm Mix Asphalt” Technologies Developed in Europe, Hot Mix Asphalt Technology, Mar./Apr. 2003, pp. 13-16. |
Choi, Y., Warm Asphalt Review, Austroads Report, Arrb Research, RETT220B, Publication No. AP-T91/07, Nov. 2007. |
D'Angelo, John, et al., “Warm-Mix Asphalt: European Practice,” International Technology Scanning Program, Feb. 2008, 62 pgs. |
Damm, K., Abraham, J., Butz, T., Hildebrand, G., Riebesehl, G., “Asphalt Flow Improvers as Intelligent Fillers for Hot Asphalts—A New Chapter in Asphalt Technology,” Journal of Applied Asphalt Binder, vol. 2, Issue 1, p. 36-70, Apr. 2002. |
Declaration of Patrick Lavin, Jun. 6, 2011. |
Diefenderfer et al., “Research Report: Installation of Warm Mix Asphalt Projects in Virginia,” Virginia Transportation Research Council, Apr. 2007, 34 pgs. |
Florida Department of Transporation, Standard Specifications for Road and Bridge Construction, 2007, pp. 244-252 and 772-784. |
Gaudefroy, Vincent, et al., “Laboratory Investigations on the Mechanical Performances of Foamed Bitumen Mixes Using Half-Warm Aggregates,” TRB 2007 Annual Meeting CD-ROM, submitted Aug. 1, 2006, 20 pgs. |
Giannattasio, Allessandro, “To improve the quality of road bitumen,” Reprint from the Italian Building and Construction Issue No. 69/1998—19th Year; pp. 2, 3, 7. |
Gibson, Nelson, Modified Asphalt Research Activities at FHWA's Turner-Fairbank Highway Research Center (TFHRC), Pavement Materials and Construction Team, AMAP Conference, Feb. 2005, Orlando, FL, 18 pgs. |
Goh et al., “Laboratory Evaluation and Pavement Design for Warm Mix Asphalt,” Proceedings of the 2007 Mid-Continent Transportation Research Symposium, Ames, IA, Aug. 2007, 11 pgs. |
Gudimettla, Jagan M., et al., “Workability of Hot Mix Asphalt,” National Center for Asphalt Technology, Apr. 2003, 66 pgs. |
Hurley et al., “Evaluation of Aspha-Min™ Zeolite for Use in Warm Mix Asphalt,” National Center for Asphalt Technology Report, Auburn University, 30 pgs., Jun. 2005. |
Hurley et al., “Evaluation of Evotherm™ for Use in Warm Mix Asphalt,” National Center for Asphalt Technology Report, Auburn University, Jun. 2006, 49 pgs. |
Hurley et al., “Evaluation of Potential Processes for Use in Warm Mix Asphalt,” National Center for Asphalt Technology, 2006, 46 pgs. |
Hurley, Graham C., et al., “Evaluation of Sasobit™ for Use in Warm Mix Asphalt,” National Center for Asphalt Technology Report, Auburn University, Jun. 2005, 32 pgs. |
International Search Report and Written Opinion issued in PCT/US2008/075452, mailed Feb. 13, 2009, 13 pgs. |
International Search Report for PCT/US2009/034742, mailed May 26, 2009, 10 pgs. |
Iterchimica Company; “Abstract of the 2005 production categories and applications,” Iterchimica Brochure, p. 2 (2005). |
James, A.D., et al., “Adhesion Agents for Use in Hot Mixes and Cut-Back Bituments,” presented at the 3rd IRF Middle East Regional Meeting, Riyadh, Saudi Arabia, 1988, 10 pgs. |
Jones, “Warm Mix Asphalt Pavements: Technology of the Future?” Asphalt, Fall 2004, pp. 8-11. |
Kanitpong, Kunnawee, et al., “Laboratory Study on Warm Mix Asphalt Additives,” Paper No. 07-1364, TRB 2007 Annual Meeting CD-ROM, 20 pgs. |
Koenders et al., “Innovative process in asphalt production and application to obtain lower operating temperatures,” 2nd Eurasphalt & Eurobitume Congress Barcelona 2000, Book II, pp. 830-840. |
KristJansdottir, Olof, et al., “Assessing the Potential for Warm Mix Asphalt Technology Adoption,” TRB 2007 Annual Meeting CD-ROM, 19 pgs. |
LaPointe, Dennis G., e-mail correspondence, May 2011, 4 pgs. |
Lavin, Patrick, “Asphalt Pavements: A practical guide to design, production and maintenance for engineers and architects,” 2003, pp. 347. |
Logaraj, Sundaram, et al., “Surface-active bitumen additive for warm mix asphalt with adhesion promoting properties,” 2009, 12 pgs. |
“Low Energy Asphalt (LEA) with the Performance of Hot-Mix Asphalt (HMA)”, European Roads Review, Special Issue, BGRA, Feb. 2004 (pp. 1-11). |
Malick, R.BN, Bradley, J.E., Bradbury, R.L., An Evaluation of Heated Reclaimed Asphalt Pavement (RAP) Material and Wax Modified Asphalt for Use in Recycled Hot Mix Asphalt (HMA), 2007. |
Modern Asphalts, “A safer future through designing for maintenance,” Autumn 2006, Issue No. 18, 4 pgs. |
Naidoo, P., “Fischer-Tropsch Hard Wax Chemistry in Warm Mix Asphalt Applications,” Petersen Asphalt Research Conference, Abstract and Presentation Slides, Jun. 20-22, 2005. |
Naidoo, P., Sasobit in Warm Mix Asphalt Applications 9 Years of Global Successes, World Asphalt Conference Presentation Slides, Mar. 14, 2006. |
Paez, R., “Production of Modifier Asphalt Additives in Equator,” 2005 International Symposium on Pavement Recycling, Sau Paulo, Brazil, Mar. 14-16, 2005, pp. 1-11. |
Petersen, J. Claine, “Relationships Between Asphalt Chemical Composition and Performance-Related Properties,” ISSA Meeting, Phoenix Arizona, Jan. 23-27, 1982, 10th page. |
Progress Report 2006, The German Bitumen Forum, Jun. 2006, 36 pgs. |
Prowell, Brian D., et al., “Field Performance of Warm Mix Asphalt at the NCAT Test Track,” Paper No. 07-2514, TRB 2007 Annual Meeting CD-ROM, 15 pgs. |
Sasobit Product Information 124, The Bitumen Additive for Highly Stable Easily Compactible Asphalts, 9 pgs. |
Sasobit Product Information, Roads and Trials with Sasobit, Oct. 2005, 7 pgs. |
Schwartz, Anthony M., et al., Surface Active Agents and Detergents, vol. 2, 1977, pp. 673-677. |
Tarrer, A.R., et al., “The Effect of the Physical and Chemical Characteristics of the Aggregate on Bonding,” Strategic Highway Research Program, Feb. 1991, 31 pgs. |
Transportation Research Board of the National Academies, 86th Annual Meeting agenda Jan. 21-25, 2007, 37 pgs. |
Wasiuddin, Nazimuddin M., et al., “A Comparative Laboratory Study of Sasobit and Aspha-Min in Warm Mix Asphalt,” TRB 2007 Annual Meeting CD-ROM, submitted Aug. 1, 2006, pp. 1-12. |
Declaration of Gerald H. Reinke Under 37 CFR 1.132, 8 pgs. |
Declaration of Jan Alboszta Under 37 CFR 1.132, 5 pgs., with attachments. |
English translation of Boldyrev et al., “Experience in Using AMDOR-9 Adhesion Additive in the Practice of Road Construction” 12 pgs. |
English translation of Chiman et al., “Aspects of Influence of Additives on Characteristics of Non Polimetricos Asphalt,” 12 pgs. |
GOST 9128-97, Interstate Standard, Asphaltic Concrete Mixtures for Roads and Aerodromes and Asphaltic Concrete, Specifications, Interstate Scientific and Technical Commission on Standardization, Technical Rating and Certification in Construction (ISTCS), Moscow 1998, 35 pages. |
Defendant Akzo Nobel Surface Chemistry LLC's Answer and Counterclaims, Case 1:13-cv-01069GMS Document 12, filed Oct. 7, 2013, pp. 1/10. |
Defendant Arr-Maz Custom Chemicals, Inc.'s Answer, Affirmative Defenses and Counterclaims, Case 1:13-cv-01070GMS, Document 12, filed Sep. 6, 2013, pp. 1-11. |
U.S. District Court, District of Delaware (Wilmington), Civil Docket for Case 1:13-cv-01069-GMS. |
U.S. District Court, District of Delaware (Wilmington), Civil Docket for Case 1:13-cv-01070-GMS. |
Boldyrev et al., “Experience in Using AMDOR-9 Adhesion Additive in the Practice of Road Construction,” International Conference ‘Bitumen in road construction,’ 2005. |
Chiman, “Aspects of Influence of Additives on Characteristics of Non-Polimetricos Asphalt,” Corporation for Research and Development in Asphalt Transport Sector and Industrial Corasfaltatos. |
“Complaint” filed on Jun. 14, 2013, 2012 in A.L.M. Holding Co. et al. v. AKZO Nobel Surface Chemistry, LLC, Case No. 1:99-mc-09999 (D. Del.). |
“Complaint” filed on Jun. 14, 2013, 2012 in A.L.M. Holding Co. et al. v. ARR-MAZ Custom Chemicals, Inc., Case No. 1:13-cv-01070-UNA (D. Del.). |
Akzo Answer Exhibit A, Case 1:13-cv-01069GMS Document 12, filed Oct. 7, 2013, pp. 1-10. |
Request for Ex Parte Reexamination, Reexam. No. 90/012,976, filed Sep. 6, 2013. |
Reexamination Order Granting, Reexam. No. 90/012,976, mailed Oct. 29, 2013. |
Non-Final Office Action in Reexam. No. 90/012,976, mailed Nov. 15, 2013. |
Number | Date | Country | |
---|---|---|---|
20130266374 A1 | Oct 2013 | US |
Number | Date | Country | |
---|---|---|---|
60716204 | Sep 2005 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 11374747 | Mar 2006 | US |
Child | 13907108 | US |