CROSS REFERENCE TO RELATED APPLICATIONS

|0001) This application claims the benefit of United States ProMsional Patent Application 60, 141.389. filed Decembei 30, 2008 and United States Prox isional Patent Application 61 /142.847. filed January 6. 2009. Both of these documents aie incorporated b> reference in their entireties

BACKGROUND OF THE INVENTION Field of the Im ention

[0002} This im ention generally relates to asphalt-rubber compositions and s\ stems and methods for preparing same Description of the Related Art

|0003| Asphalt paλ'ement suffers from oxidative hardening o\ er time This oxidatn e haidenmg causes cracking of the pavement, potholes, and loose gravel on the surface The addition of rubber, such as crumb rubber from recycled automobile tires, to an asphalt bmdei. substantial!) reduces the rate of oxidatne hardening of asphalt pax ement and increases the useful life of a road This asphalt -rubber mixture is typically reierred to as asphalt-rubber binder (ARB)

|0004] ARB and aggregates aie typically mixed together and spread onto road surfaces to form asphalt pavement Because prior art ARB is highh temperature sensiij\ e. it can be applied to roads onh under certain surface tempei atui e and weather conditions This in turn limits road paλ ing activities to only a few months of the year in most regions of the country Additionally, special heating/blending equipment are often required at job sites to keep the mixture free flowing and homogeneous In some cases, additn es are added to asphalt-rubber hot mix material to reduce segregation, crusting, or lumping of the crumb rubbei These additives, however, could ha\ e detrimental effects on other properties of the mixture I hus. there is a current need for an improx ed ARB system that is less sensitn e to em iionmental conditions and can be easih applied to surfaces without requiring expensive or complex equipment or additives to keep the mixture free flowing and homogeneous.

SUMMARY OF THE INVENTION

|0005] The chemical compositions, methods, processes, and systems of the invention each have several aspects, no single one of which is solely responsible for its desirable attributes. Without limiting the scope of this invention, its more prominent features will now be discussed briefly. After consideration of this discussion and particularly after reading the section entitled "Detailed Description ^" one will understand how the features of this invention provide advantages that include, for example, a waterborne asphalt-rubber composition that is less temperature sensitive and can be easily applied to road surfaces.

|0006) Generally, the disclosure herein relates to methods of preparing emulsions of an asphalt-rubber binder, and compositions related to these methods. Emulsilϊcation of asphalt-rubber binder for pavement preservation systems has been considered by many as not achievable because of the difficulties in emulsifying a mixture containing crumb rubber and asphalt. For example, asphalt-rubber binder normally may not readily be emulsified because the rubber particles disrupt the laminar How of the asphalt-rubber matrix during mixing in a colloidal mill. The present methods overcome these difficulties by pre-compounding the crumb rubber in a manner so as to facilitate dispersion in the final emulsion. In some embodiments, the pre-compounding may eliminate disruption of the laminar flow which may occur when emulsifying a binder by means of a colloidal mill. While not limiting any embodiment by theory, it is believed that during mixing, the pre-compounded crumb rubber moiety is substantially homogenized into the asphalt droplets of the asphalt emulsion, thus forming a smooth and uniform emulsion of asphalt-rubber binder.

|0007] In some embodiments, the present methods comprise immersing finely ground tire rubber in an asphalt to form a hot rubber adhesive. For example, some methods comprise immersing, under steady stirring, a finely ground tire rubber (crumb rubber), about 80-140 mesh, in a waterless, up to about 350 ⁰ F polymer modified asphalt, whereby the ground tire rubber swells and reacts thereby "coating ^" the individual crumb

-~>- iubber moietx to ioim a hoi iubber adhesn e The reacted hot rubber adhesive may then be compounded under high shear with an asphalt emulsion and can be formulated as a coating sealing and or adhesn e The resulting asphalt iubber emulsion will cure quickly to a non tracking w atei resistant asphalt rubber bindei or surfacing element with supeπor resistance to oxidatn e hardening weather or mechanical wear It may also be formulated to cure at non-traditional winter temperatures down to 4OF and at night time The resulting asphalt-rubber binder emulsion has improλ ed adhesion cohesion, early green stiength and water iesistance when employed m ambient cured, structural waterproofing and pax ement preserv ation systems

10008} Some of these methods comprise treating the crumb rubber with an asphalt composition to form an asphalt coated crumb rubber composition and then mixing the asphalt coated crumb rυbbei composition with an asphalt emulsion to form an emulsified asphalt-rubber bindei A variety ol asphalt emulsions may be used to provide emulsions ol asphalt-rubber bindei Foi example in some embodiments an asphalt emulsion ma\ be a pioduct oi mixing a first asphalt w ith water and a surfactant to foπn a first emulsion With iespect to the makeup of an asphalt emulsion an asphalt emulsion ma\ preierablv comprise a first asphalt a surfactant and water

10009] A Λ anetv of asphalt-coated crumb rubber compositions may be used to proxide emulsions of asphalt-rubber binder For example an asphalt-coated crumb iubber composition mav be a product of mixing a pluiahtv of crumb rubber particles with an effectn e amount ol a second asphalt to coat the particles wherein the second asphalt has caused the particles to sw ell While the makeup of the asphalt-coated crumb rubber composition \ aπes one example may include a plurality of crumb rubber particles and a second asphalt wherein the particles are substantially coated with the second asphalt and the pai tides ha\ e sw elled in the presence ol the second asphalt

|0010| Thus one method ior preparing an emulsion ol an asphalt-rubber bindei comprises mixing a Inst asphalt emulsion with an asphalt-coated crumb rubber composition to pro\ ide an emulsion ol an asphalt-rubber binder wherein the fust asphalt emulsion is a product of mixing a first asphalt with w ater and a surlactant to form a first asphalt emulsion and wherein the asphalt-coated crumb rubber composition is a product ol mixing a plurahtv ol crumb rubbei particles w ith an elfectn e amount of a second asphalt to coat the particles and wherein the second asphalt has caused the particles to swell

[0011 ] Another aspect relates to a method for preparing an emulsion of an asphalt-rubber binder comprising mixing a first asphalt emulsion with an asphalt-coated crumb rubber composition to pro\ide an emulsion of an asphalt-rubber binder, wherein the first asphalt emulsion comprises a first asphalt, a surfactant and water and wherein the asphalt-coated crumb rubber composition comprises a plurality of crumb rubber particles and an effective amount of a second asphalt to coat the particles, the particles are substantially coated with the second asphalt, and the particles have swelled in the presence of the second asphalt

|0012] Some methods foi preparing an emulsion oi an asphalt-rubber binder compiise mixing a first asphalt with water and a first sui fact ant to form a first emulsion, mixing a plurality ol crumb rubber particles with an effectn e amount of a second asphalt to coat the particles to prox uie an asphalt-coated crumb rubber composition and allowing the particles to swell and mixing the first asphalt emulsion with the asphalt-coated crumb rubber composition to pro\ ide an emulsion of an asphalt-rubber binder

|0013) Some embodiments proxide an emulsion of an asphalt-rubber binder prepared by a process described herein Another aspect i elates to an emulsion of an asphalt-rubber binder comprising an asphalt crumb rubber, representing about 30% to about 50% of the total weight oi all non-volatile components of the emulsion, which has swollen in the presence ol the asphalt, a cationic surfactant, and water, wherein the emulsion is stable at a pH below about 7

|0014) Also prox ided is an asphalt emulsion comprising an asphalt having a pen \ alue of from about 0 dmm to about 30 dmm. an amido amine surfactant, an ammonium salt thereof or a combination thereof and watei representing about 30% to about 50% of the weight ol the emulsion

|0015) Some embodiments piovide an asphalt-coated rubber composition comprising an asphalt, crumb rubber and an amount of a cationic surfactant which is effective to increase the hvdiopbilicity of the composition as compared to a composition which is identical except that it has no added cationic surfactant |00 J 6] In one embodiment, the invention piovides a process for piepaπng an asphalt-iubber composition that meets the definition for asphalt rubber binder set forth in ASTM D8-02 or de\ iations thereof which may be established by the specii\mg agenc\ from time to time In a preferred embodiment, this process provides an asphalt-rubber binder as an emulsion The process generally comprises obtaining asphalt of different penetration grades, combining the asphalt of each grade with preselected chemicals to form sepaiate piemixed components, blending the prermxed components together under predetermined conditions to form, upon curing, an asphalt-rubbei composition that meets certain physical lequirements for asphalt-rubber bindei . such as those set forth m ASTM D8-02. Advantageously, the resulting asphalt-rubber composition not only meets the physical requπements of ARB used in road paving but also has improved dispersion of the iubbei . such as dispersion of the rubber m an oil-m-w ater emulsion of an asphalt

|0017J These asphalt-rubber compositions may also be used as a binder, coating, sealant, adhesn e. oi a combination thereof, and may be adapted for ioad paving, roofing, and othei related applications For example, in certain embodiments, an asphalt- rubbei binder composition oi and asphalt-rubbei binder emulsion may be used as a HMA primer. SAM] punier. SAMl (stress absorbing membrane interlayer) chip binder, lejuvenatmg sealer, log seal, skid iesistant traffic lane sealant-surface binder, seal coat binder, ISSA (International Slurry Surfacing Association) Type 1. Type 11. or Type 111 Micro slurry binder, or cold mix adhesive inclusn e of RAP. Dl 227 Type Ul B roof membrane, submerged membrane hnei. flashing cement, steel or concrete pipe coating, waterproofing mastic(s). and the like, or a combination thereof

|0018] In a preferred implementation, asphalt of three different penetration grades are selected, which includes a hard asphalt, pjeferabh ha\ mg a pen value ol between about 0 dmm and about 50 dmm. or between about 0 dmm and about 90 dmm. a medium asphalt, prefeiably ha\ ing a pen value of between about 90 dmm and about 200 dmm oi betw een about 150 dmm and about 200 dmm. and a soft asphalt, preferably having a pen \ alue of betw een about 200 dmm and about 300 dmm The haid asphalt is prefei ably mixed with certain surfactants and w ater to form a hard pen asphalt emulsion The soft asphalt is preferably modified by a polymer and then mixed with certain surfactants and w atei to form a soft pen-polymei modified asphalt emulsion The

_ **)_ medium asphalt is piefcrably mixed and reacted with crumb rubber at about 350 ⁰ F to form an asphalt-rubber blend and then combined with a certain surfactant and optionally water to form a mastic The hard pen asphalt emulsion, soft pen-polymer modified asphalt emulsion and mastic are then subsequently blended at different ratios to lorm a vaπetv of w aterbome asphalt-rubber composition(s) In one implementation, the hard pen asphalt emulsion and soft pen-polymer modified asphalt emulsion are first mixed togethei to form an emulsion pre-blend, which is subsequently blended with the mastic to provide a substantially homogeneous, free flowing waterbome asphalt-rubber emulsion blend that can be applied to road surfaces at various temperatures The crumb rubber mastic may be dissolved or dispeised in any phase of the waterbome composition For example, the rubber mastic may be a separate solid phase dispersed in the one or more liquid phases oi the emulsion, the rubber mastic may be a separate liquid phase dispersed in one or more of the liquid phases of the emulsion, or the rubbei mastic may be dissoh ed into one or moi e oi the liquid phases of the emulsion In certain prelerred embodiments the cuied final compound conforms with the rubber/asphalt ratios prescribed b\ ASTM D61 14-97 to pro\ ide a suitable asphalt-rubber binder for asphalt pavement In another embodiment, this asphalt-rubbei emulsion blend is mixed w ith aggregate at about 32°F to about 100 ⁰ F or about 130 ⁰ F to provide an asphalt pax ement Some asphalt-rubbei bindei emulsions may be capable of curing during the winter or at night Foi example, some asphalt-rubber binder emulsions may fully cure at tempeiatures as low as about 40 ⁰ F or about 32°F

|0019J In another embodiment, the invention provides a waterbome asphalt- rubber binder composition This composition may be used as a binder, coating sealant, adhesn e or a combination thereof, and may be adapted for road paving roofing and other i elated applications For example, in certain embodiments, an asphalt-iubber bmdei composition or and asphalt-rubber binder emulsion may be used as a HMA primer SAMl pπmer. SAMl (stress absorbing membrane mterlayer) chip binder rejuvenating sealer tog seal skid resistant traffic lane sealant-suiface binder, seal coat binder ISSA (International Slurry Surfacing Association) Type 1. Type 11. or Type 111 Micro slum binder or cold mix adhesn e inclusiv e of RAP. Dl 227 Type 111 B ioof membrane, submerged membrane liner, flashing cement, steel or concrete pipe coating. w aterpi oofing mastic(s). and the like, or a combination thereof. In one implementation, the composition comprises asphalt; crumb rubbei : an epoxidized unsaturated triglyceride, a soh ent dispersed w ood rosm ester, a functional vegetable oil deπvatn e. or a combination thereof: a sui factant. and optionally water. In another implementation, the composition consists essentially of: asphalt: crumb rubber, an epoxidized unsaturated tnglycende. a solvent dispersed wood rosin ester, a functional vegetable oil dem atn e. or a combination thereof, an unsaturated fatty acid: one or more surfactants, an optionally substituted styrene butadiene styrene block copolymer, one or more cross linking agents; and optionally water. In another implementation, the composition consists essentially of: asphalt: crumb rubber: an epoxidized unsaturated triglyceride, a solvent dispersed w ood rosin ester, a functional vegetable oil derivative, or a combination thereof, an unsaturated fatty acid, one or more surfactants, an optionally substituted styrene butadiene styrene block copohmer. one or more cross linking agents: a glycol ether: and optionally water.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIGURE 1 is a flow chart depicting a process for preparing an emulsion of asphalt-rubber binder related to some embodiments

|002] J FIGURE 2 is a flow chart depicting a process for pi epaπng an asphalt- rubber binder emulsion blend related to some embodiments.

DETAILED DESCRIPTION

[0022] FIGURE 1 illustrates a process 10 for preparing an emulsion of asphalt-rubber binder. Generally, the process comprises selecting at least two different asphalts, or processing two separate quantities of the same asphalt or type of asphalt, emulsifying one asphalt and combining the other asphalt with crumb rubber, then recombining the compositions to provide the emulsion of asphalt-rubber binder.

|0023] With respect to FIGURE L one of the asphalts is generally referred to as the "first asphalt ^" 20. and the other asphalt is generally referred to as the "second asphalt ^" 30. purely for convenience to avoid confusion when describing these processes. Other nomenclature may be employed either for convenience, or to provide a description related to a property of the asphalts.

|0024] In the process for preparing an emulsion of asphalt-rubber binder 10 of FIGURE ] . a first asphalt 20 is combined with water and a surfactant, such as a premixed combination of surfactant and water 25. and optional additives 27. to provide a first asphalt emulsion 40. Preferably, the first asphalt 20 is about 50% (w/w) to about 70% (w \v). or about 60% (w/w) and the surfactant/water 25 is about 30% (w/w) to about 50% (\\ /w). or about 40% (w/w) of the first asphalt emulsion 40. The surfactant/water 25 is preferably separately prepared by blending water and the surfactant(s). In one implementation, the water is about 35% to about 40%, or about 37%, and the surfactant(s) are about 0.5% to about 4%. or about 2.2%. of the total weight of the first asphalt emulsion 40. In another implementation, the surfactant consists essentially of about ] . ] % Prime Plex ER 582 surfactant and about 1.1 % Indulin W-5 surfactant, based upon the weight of the emulsion.

(0025) The first asphalt 20 is preferably at a temperature between about 300 ⁰ F to about 350 ⁰ F at the time it is premixed with the surfactant/water 25. and the surfactant water 25 is at a temperature between about 70 ⁰ F and about 90 ⁰ F. In a preferred implementation, the mixing of the first asphalt 20 and the surfactant/ water 25 is carried out at a rate such that the resulting emulsion is about 190°F to about 21 O ⁰ F after the mixing. In some embodiments, the asphalt and the surfactant, water may be mixed by co-milling through a colloid mill. |0026] In a separate system or vessel, a second asphalt 30 is combined with crumb rubber 122. and optional components such as a surfactant 35 and/or additn es 37. to provide an asphalt-coated crumb rubber composition 50 The asphalt-coated crumb rubber composition 50 comprises a plurality of crumb rubber particles 122 which are coated with the second asphalt 30 In some embodiments, an anhydrous surfactant 35 is added prior to. during, or after mixing the second asphalt 30 with the crumb rubber 122 without the addition ol any w ater Howe\ er. the process may optionally be carried out without added water and without any added surfactant Other additives 37 which may be included eithei before, after, or during the mixing of the second asphalt 30 and the crumb rubber 122 include fatty acids such as stearic acid, oleic acid. etc.. rosms such as wood rosm;high flash point organic soh ents such as mineial spirits: additional surfactants, etc In some embodiments, at least a portion of the mixing of the crumb rubber particles 122 and the second asphalt 30 occurs in the presence of stearic acid or oleic acid, a fatty amine surfactant an ammonium salt of an amine surfactant, or a combination thereof For some exemplary methods, at least a portion of the mixing of the crumb rubber particles 122 and the second asphalt 30 occurs m the presence of wood rosin, mineral spirits, a second surfactant, a third surfactant comprising an amine functional group, an ammonium salt, oi a combination theieof.

|0027J The second asphalt 30 may in some instances be above ambient temperature when mixed with the crumb rubber 122 For example, the second asphalt 30 may be heated to from about 325°F to about 375 ⁰ F. or preferably about 350 ⁰ F. and the crumb rubber 122 max be added to the second asphalt 30

|0028) W hile theie aie a number of diffeient types of asphalt-coated crumb rubber compositions 50. tw o types of an asphalt-coated crumb rubber compositions include a mastic 128 and a hydrophihcized asphalt coated crumb rubber 52.

[0029] For a hydrophihcized asphalt-coated crumb rubber 52. the crumb rubber particles 122 be about 60% to about 90% of the total weight of all nonvolatile components of the composition Preferably, the second asphalt 30 is about 25% and the crumb rubber 122 is about 75% of the w eight of the hydrophihcized asphalt- coated crumb rubbei 52 Non-λ olatile components include those that do not significantly evaporate during the in-situ curing process of the final adhesive In some embodiments. the hydrophilicized asphali coaled crumb rubber 52 may be prepared by spraying hot second asphalt 30 onto the surface of crumb rubber 122, then stirring the coated rubber within a heated blending vessel until sufficient swelling of the crumb rubber occurs. A surfactant 35 or other additives 37 may be added to second asphalt 30 before it is sprayed onto the crumb rubber 122. or they may be added after the the asphalt 30 is added.

[0030] For the mastic ]28. the second asphalt 30 may be about 60% to about 80%. and the crumb rubber particles 122 may be about 20% to about 40% of the total weight of all non-volatile components of the composition. Preferably, the second asphalt 30 is about 60% and the crumb rubber 122 is about 30%. or the asphalt is about 75% and the crumb rubber is about 25%. of the weight of the mastic 128. In another implementation, the crumb rubber particles 122 have a diameter from about 650 microns (μm) to about 75 μm.

|0031) In some embodiments, the mastic 128 comprises about 60.5% (w 'w) second asphalt 30. about 30% (w/w) crumb rubber 122. about 4% (w/w) epoxidized soy oil. about 4% (w'w) water, and about 1 .5% surfactant. In other embodiments the mastic 128 consists essentially of about 60.5% (w/w) second asphalt 30, about 30% (w/w) crumb rubber 122. about 4% (WΛV) epoxidized soy oil. about 4% (w/w) water, and about 1 .5% surfactant. In another embodiment the mastic 128 consists essentially of about 60.5% (w/w) second asphalt 30. about 30% (w/w) crumb rubber 122. about 4% (WΛV) epoxidized soy oil. about 4% (WΛV) water and/or glycol ether, and about 1.5% surfactant. In still another embodiment, the mastic 128 consists essentially of about 55% (w'w) medium asphalt, about 30% (w'w) crumb rubber 122. about ] 1 % (w/w) high flash point solvent dissolved wood rosin ester, about 2.5% (w/w) water, and about 1.5% (ww) surfactant. In some embodiments, addition of volatile components to the mastic are sequential. For example, the initial asphalt crumb rubber reaction may occur at a high temperature (325-375 ^c F). After the high temperature reaction, the mixture may then be allowed to cool to below ^; Hash point of subsequent additives so that additives can be blended into the mixture. [0032] The first asphalt emulsion 40 may be combined with the asphalt- coated crumb rubber composition 50, such as a mastic 128 or a hydrophilicized asphalt- coated crumb rubber 52. to provide an emulsion of asphalt -rubber binder 60 In some embodiments, asphalt emulsion 40 may be combined with the asphalt-coated crumb rubber composition 50 under high speed shear until the mixture is fully homogeneous

[0033] Some of these processes may further comprise mixing a third asphalt, with a polymer to provide a polymer modified asphalt: mixing the polymer modified asphalt with water and a fourth surfactant to pro\ide a second asphalt emulsion: and mixing the second asphalt emulsion with at least one of the first asphalt emulsion, the asphalt-coated crumb rubber composition, and the emulsion of the asphalt-rubber binder. In some embodiments, the third asphalt may be softer than the first asphalt

|0034] FIGURE 2 illustrates a process 100 for preparing an asphalt-rubber binder system which follow s the basic process of the process outlined m FIGURE L but includes additional steps This process also utilizes a third asphalt which has a different hardness than the first asphalt and the second asphalt. For example, in these processes the fiist asphalt is referred to as "hard asphalt. ^" the second asphalt is referred to as "medium asphalt. ^" and a third asphalt is referred to as "soft asphalt ^" The process 100 generally comprises selecting asphalt of different penetration grades, mixing each grade of asphalt separately with chemicals to form a plurality of premixed feedstock configured w ith different properties, and then combining the premixed feedstock to foπn an asphalt- rubber composition that upon curing, would exhibit physical properties equivalent to the asphalt-rubber binder(s) prepared pursuant to ASTM D61 14-97 (2002) or deviations thereof which may be established by the specifying agency from time to time

|0035) In processes depicted in FIGURE 2. the process begins by providing a hard asphalt 102. preferably having a pen \alue of between about 0 dmm and about 50 dmm. or betw een about 0 dmm and about 90 dmm. a soft asphalt 104. preferably having a pen \ alue of between about 90 dmm and about 300 dmm. or about 200 dmm and about 300 dmm. a medium asphalt 106. ha\ ing a pen \ alue of betw een about 150 dmm and about 200 dmm

|0036] In one embodiment, the process 100 comprises premixing the hard asphalt 102 with a surfactant'water 108 or a soap system, to form emulsion H 110. Preferably, the hard asphalt 102 is about 61 % (wΛv) and the surfactant/water 108 is about 39% (w/w) of emulsion H 110. The surfactant/water 108 is preferably separately- prepared by blending water and the surfactant(s). In one implementation, the water is about 37% and the surfactant(s) are about 2.2% of the total weight of emulsion H 110. In another implementation, the surfactant consists essentially of about 1.1 % Prime Plex ER 582 surfactant and about 1 .1 % lndulin W-5 surfactant.

|0037) The hard asphalt 102 is preferably at a temperature between about 300 ⁰ F to about 350 ⁰ F at the time it is premixed with the surfactant/water 108. and the surfactant/water 108 is at a temperature between about 70 ⁰ F and about 90 ^c F. In a preferred implementation, the mixing of the hard asphalt 102 and the surfactant/water 108 is earned out at a rate such that the resulting emulsion is about 190 ⁰ F to about 210 ⁰ F after the mixing. The asphalt and the surfactant/water are mixed by co-milling through a colloid mill.

[0038] In one embodiment, the process 100 further comprises premixing the soft asphalt 104 with a surfactant water 116 or soap system, to form emulsion H 118. Alternatively, in another embodiment, the soft asphalt 104 is first blended, preferably at about 350 ⁰ F. with an optionally substituted styrene butadiene styrene block copolymer (SBS) elastomer 112 to form a polymer modified asphalt 114. This polymer modified asphalt 1 14 is then blended with the surfactant/water 116 through a colloid mill to form emulsion S 118.

J0039) In one implementation, the soft asphalt 104 or the polymer modified asphalt 114 is about 61 %. and the surfactant water 116 is about 39%. of the total weight of emulsion S 118. The surfactant water may comprise about 37% water and about 2% surfactant with respect to the total weight of emulsion S 118. In one embodiment, the surfactant consists essentially of about 1 .1 % (Ww of 118) Prime Plex ER 582 surfactant and about 1 .1 % (WAY of 118) lndulin W-5 surfactant.

[0040] The soft asphalt or the polymer modified asphalt may comprise an ammendment such as an unsaturated fatty acid, including an olefin from the stearol family. In one embodiment, the polymer modified asphalt consists essentially of 58% (w/w of 118) soft asphalt. 1 .22% (w/\λ of 1 18) ammendment. and 2% (w/w of 1 18) SBS elastomer. In another embodiment, the asphalt and the ammendment are blended at

- 1 7- 325 ⁰ F, and the SBS is added and the mixture is i un through high shear until the SBS is dissoh ed

|0041] In one implementation, the soft asphalt 104 or polymer modified asphalt 114 is at a temperature between about 300 ⁰ F to about 35O ⁰ F at the time it is premixed with the surfactant/water 108 which is at a temperature between about 70 ⁰ F and about 90 ⁰ F In another implementation, the mixing of the soft asphalt 104 and the surfactant water 116 is earned out at a rate such that the resulting emulsion is about 190 ⁰ F to about 210 ⁰ F after the mixing In another implementation, after the initial combination of the soft asphalt 104 and the surfactant water 116 are initially combined, additional mixing occurs o\ er a period of from 1 houi to about 4 hours In another implementation the asphalt and the suifactant w ater are co-milled through a colloid mill After the soft asphalt emulsion is formed m the colloid mill, it may be stirred while it dissipates energy to a temperatυi e of 175°F or low er during storage

|0042] In another embodiment, the process 100 furthei comprises premixing the medium asphalt 106 with the crumb rubber 122 to form an asphalt-rubber blend 124 In some embodiments the asphalt-rubbei blend is combined with surfactant/water 126. or a soap system to provide a mastic 128 Alternatn ely a surfactant is added prior to during, or after the mixing the medium asphalt 106 with the crumb rubber 122 without adding any water er. in some embodiments neither water nor surfactant is added In one implementation the medium asphalt 106 is heated to from about 325 ⁰ F to about 375°F. and the crumb rubber 122 is added to the asphalt In another implementation, the medium asphalt 106 is heated to about 350 ⁰ F and the crumb rubber 122 is added to the asphalt In anothei implementation, once the crumb rubber 122 is added, the medium asphalt 106 and the crumb rubber 122 are mixed lor about 15 minutes until the piopei viscosity is achie\ ed as requned by D61 14 Table 1 to pioude the asphalt-rubber blend 124 Preferably the uscosity is from about 900 to about 1500 cps In one implementation the asphalt is about 60% and the crumb rubber is about 30% or the asphalt is about 75% and the crumb rubber is about 25% of the weight of the mastic 128 In another implementation the crumb rubber particles ha\ e a diameter from about 650 microns (μm) to about 7^ μm |0043] In some embodiments, the surfactant/ w atei 126. or soap system, JS separately prepaied by mixing the water and surfactant(s) In one embodiment, the water is about 4°o and the surfactant(s) aie about 1 5% ol the w eight of the mastic 128 In another embodiment, the asphalt-rubber blend 124 is then cooled to a temperature of from about 18O ⁰ F to about 210 ⁰ F. and the ammendment and the surfactant/water are thoroughly blended in to pro\ide a heavy mastic body consistency

|0044] In some embodiments, the mastic 128 comprises about 60 5% (w/w) medium asphalt 106. about 30% (w/w) crumb rubber 122. about 4% (w/w) epoxidized soy oil. about 4% (w/w) w ater, and about ] 5% surfactant In other embodiments the mastic 128 consists essentially of about 60.5% (w/w ) medium asphalt 106. about 30% (w/w) crumb rubbei 122. about 4% (w/w) epoxidized soy oil. about 4% (w/w) water, and about 1 5% surfactant In another embodiment the mastic 128 consists essentially of about 60 5% (w w) medium asphalt 106. about 30% (ww) crumb rubber 122. about 4% (w/w) epoxidized soy oil. about 4% (w/w) water and'or glvcol ether, and about 1 5% surfactant In still another embodiment, the mastic 128 consists essentially of about 55% (w/w) medium asphalt about 30% (w/w) crumb rubber 122. about 1 1 % (w/w) high flash point solvent dissoh ed w ood rosm ester, about 2 5% (w /w ) w ater, and about 1 5% (w'w) surfactant

[0045] In some embodiments. Emusion H 110 and Emulsion S 118 are then blended to pro\ide the Emulsion Pre-Blend 120 The mastic 128 is then blended in under high speed shear until the mixture is fully homogeneous to provide the asphalt-rubber emulsion blend 130 In another embodiment, a crosslinkei is added during the blending of Emulsion H I lO and Emulsion S 118 to pro\ ide an asphalt adhesive or pavement with a crosshnked asphalt-rubber binder In another embodiment a crosslinker is added during the blending oi the Emusion pre-blend 120 and the mastic 128 to prov ide an adhesive or asphalt paλ ement with a ciosslinked asphalt-rubber binder

[0046] In some embodiments the asphalt pavement prepared using the compositions and methods described herein comprises asphalt-rubber binder which upon curing, will be equiv alent to the physical properties of asphalt-rubber bmdei prepared pursuant to ASTM D61 14-97 specifications |0047) As used herein, the term "asphalt ^" is a broad teim and shall have its ordmarλ meaning and shall include, but not be limited to. a dark brown to black cementitious material in which the predominating constituents are bitumens w hich occur m nature or are obtained in petroleum processing

|0048) Bitumen is a class of black or dark-colored (solid semisolid, or viscous) cementitious substances, natural or manufactured, composed principally of high molecular w eight hydrocarbons

10049] As used herein, the term "surfactant ^" is a broad term and shall have its ordinary meaning and shall include, but not be limited to. a compound or mixture of compounds ha\ ing both one or more hydiophobic or lipophilic moieties and one or more hydrophilic moieties in a single molecule A surfactant may be nonionic, anionic, cationic. oi amphoteric Depending on iactoi s such as pH. a given surfactant ma\ belong to more than one of these classes

|0050) Nonionic surf actants e no formal charge on the molecules Non- hmiting examples of nonionic surfactants include alkylphenol ethoxylates. such as nonylphcnol ethoxylates or octylphenol ethoxylates comprising 30 to 100 ethylene oxide units. C\ i s cthox\lated alcohols, including ethoxylated linear or branched alcohols such as ethowlated fatty alcohols, etc compi ising from 1 to about 10, to about 20. to about 30 or to about 50 ethylene oxide units. Cs i\ ethoxylated carbox\lic acids, including ethoxylated linear or branched carboxyhc acids such as ethoxylated fatty acids, comprising from 1 to about 10. to about 20. to about 30 or to about 50 ethylene oxide units. Cs i s ethoxylated carboxyhc acid alkyl esters, including ethoxylated linear or branched carboxyhc acid alkyl esters, e g ethoxylated fatty acid alkyl esters such as ethoxylated fatty acid methyl esters, compiising lrom 1 to about 10. to about 20. to about 30 or to about 50 ethylene oxide units, ethylene oxide based copolymers and block copolymers such as ethylene oxide piopy lene oxide copolymers, ethylene oxide propylene oxide block copolymers and the like, having an aveiage moleculai weight m the range ol about 1.000 to about 10.000 ethoxylated amines, including ethoxylated fatty amines such as tallow amines, containing about 5 to about 10. to about 20. to about 30. or to about 50 ethylene oxide units, ethoxylated diamines, including ethoxylated fatty diamines such as tallow diamines, containing about 5 to about 10. to about 20. to about 30. or to about 50 ethylene oxide units, and combinations thereol

[0051] An amine surfactant is anv sui factant containing an amine moiety or functional group. An amine moiety has two forms oi subsets In the first subset, or the neutral form, a nitrogen atom is directly attached to 3 independent atoms selected from carbon and hydrogen In the ammonium or ammonium salt form, or ammonium functional group, a nitrogen atom is direct 1\ attached to 4 independent atoms selected from carbon and hydrogen and carries a positn e formal charge If the ammonium includes nitrogen attached to a hydrogen, it is readily converted to the neutral form if the pH is sufficiently high

|0052] Fatty amines are nonionic suilactants if the pH is sufficiently high (i e basic) to keep the nitrogen atoms deprotonated so that \hey are in the neutral form A fatty amine is nitrogen attached to three moieties independently selected fiom H or a hydrocarbon In some embodiments, the nitrogen is attached to H or Cs ₂₂ hydrocarbon that is either unsaturated (i.e alky]) or has I . 2. 3. 4. 5. 6. 7. or 8 double bonds Examples include, but are not limited to tallow amine, tallow diamine soy diamine, tall oil diamine, tallow tiiarmne. tallow tetramme olev] diamine coco diamine, linear Cs jg petroleum-derived diamine, branched Cs ^ petroleum-derived diamine, linear C) _{2 18} alkylether diamine, branched C) ₂ is alkylether diamine, combinations thereof, and the like

[0053] Other nitrogen containing surfactants such as amidoamines, imidazolines, lmidoammes. lmines. amidoamines. amides, imadazoles. imidazolene. and the like, also have neutral and cationic forms analogous to amines These nitrogen containing surfactants are nonionic surfactants prox ided that the pH is sufficiently high (1 e basic)

|0054] Anionic surfactants ha\ e one or more negatn e foπnal charges on the molecules Examples include C _f1 ™ carbow hc acids, including but not limited to. linear and branched carboxyhc acids, which include fatty acids such as arachidic acid, arachidonic acid, behemc acid, eicosapentaenoic acid, lmoleic acid, α-lmolemc acid, γ- linolenic acid, myπstic acid, lauric acid, oleic acid, palmitic acid, palmitoleic acid, stearic acid, and the like. C _{6 30} carboxyhc acid sulfonates, including but not limited to. sulfonates of any of the caiboxvlic acids listed above. C _{6 30} alkyl suliates. C _t , _M ) alkylben7ene sulfonates, alkylphenol ethoxylate sulfonates, etc

[0055] Cationic surfactants have one or more positn e formal charges on the molecules Fatt> amines such as those described abo\ e are cationic if they are in the ammonium form due to sufficiently low pH (1 e acidic conditions) or the fact that the nitrogen is attached to 4 carbon atoms Nitrogen compounds such as amines or ammonium salts, amidoamines. imidazolines, imidoamines immes. amidoamines. amides, imadazoles. imidazolene. and the like, are also cationic sui factants provided that the pH is sufficiently low. or the nitrogen is quaternary , meaning that it is attached to 4 non-hydrogen atoms

|0056] Amphotei ic surfactants have either a positn e or a negative formal charge depending on the pH of the composition Sulfobetaines are an example

10057] In other embodiments, the surfactant is combined with lignin Lignm is a polymeric substance containing a hydroxy phenyl piopane backbone It is found m plant and vegetable tissue associated with cellulose or othei plant constituents In the pulp and paper industi y. hgnm-containing material such as \λ ood sti aw corn stalks bagasse and other suitable plant tissue may be processed to recox er the cellulose and pulp The residual pulping liquors are the mam sources of technical hgnins In some embodiments useful examples of hgnms include kraft soft wood lignin. kraft hardwood hgnm. bagasse lignin. organosol lignin desullonated hgnosulfonate. and combinations thereof In some embodiments, the sui factant comprises a nitrogen containing surfactant or an amine and hgnm

|0058] As used herein, the term "ammendment is a broad term and shall have its ordinary meaning and shall include, plant dem ed resinous substances which beneficially augment the adhesive, cohesive, and solubihtx parameters of asphalt Examples include functional \ egetable oil derivatives and unsaturated carboxyhc acids Emulsion of Asphalt-Rubber Binder

|0059] Mixing the first asphalt emulsion w ith the asphalt-coated crumb rubber composition provides an emulsion of an asphalt rubbei -binder While these compositions may vary considerablv the emulsion of an asphalt-rubber bmdei may comprise an asphalt, crumb rubber w hich has swollen in the presence of asphalt, a surfactant such as a cationic surfactant, and water. Preferably, the crumb rubber is about 1 5°Ό to about 45%. or about 30% to about 45-% of the total weight of all non-volatile components of the emulsion. In some embodiments, the pH should be below about 7. or about 2 to about 6.

|0060] One type of emulsion of asphalt-rubber binder is obtained from three separate asphalt compositions: an asphalt-rubber composition, a hard asphalt emulsion, and a soft asphalt emulsion, which may be combined into a single composition to provide an asphalt-rubber emulsion blend. While each of these separate asphalt compositions may vary considerably, the asphalt-coated crumb rubber composition may comprise medium hardness asphalt, crumb rubber, a surfactant, and water: the hard asphalt emulsion may comprise hard asphalt, a surfactant, and water: and the soft asphalt emulsion may comprise soft asphalt, a surfactant: and water. Each of these three compositions is described in more detail in later sections of this disclosure.

[0061 J The amounts of the different asphalt compositions in the emulsion blend may vary depending upon the circumstances. For example, while not intending to be limiting, the amount of the asphalt-rubber composition may be from about 25% (w w) to about 50% (w/w) or preferably from about 30% (w/w) to about 40% (w-w): the amount of hard asphalt emulsion may be from about 30% (\\ 'w) to about 60% (w/w) or preferably from about 40% (\v w) to about 50% (w/w): and the amount of soft asphalt emulsion may be from about to about 10% (w/w) to about 30% (w'w) or preferably from about 15% (w/w) to about 25% (w w).

(0062) The manner of blending the three emulsions may vary. In one non- limiting example, the emulsion blend may be prepared by thoroughly blending a hard asphalt emulsion and a soft asphalt emulsion, followed by blending in an asphalt-coated crumb rubber composition. In some embodiments, the asphalt-coated crumb rubber composition is blended in under high shear until the mixture is fully homogeneous. Each of: the hard asphalt emulsion, the soft asphalt emulsion, and the asphalt-coated crumb rubber composition used in the emulsion blend may be prepared by any of the methods described herein.

|0063) In a preferred embodiment, the emulsion of asphalt-rubber binder comprises: asphalt, crumb rubber, an epoxidized unsaturated triglyceride, a surfactant. and water; wherein the composition conforms to ASTM International Standard Specification for Asphalt -Rubber binder.

|0064] A crosshnker may be present in an emulsion of asphalt rubber binder. The crosslinker may be present because it was part of an asphalt emulsion, an asphalt- coated rubber composition, or another optional component incorporated into the final emulsion. For example, the crosslinker could be part of a soft asphalt emulsion described in FIGURE 2. which is incorporated into the blend. Alternatively, the emulsion of asphalt-rubber binder may further comprise a crosslinker which is not present in any of the asphalt components combined to form the final emulsion. Or one of the asphalt components combined to prepare the emulsion, such as the soft asphalt emulsion, may contain a crosslinker, and an additional amount of a crosslinker may be added to the final emulsion. The crosslinker may be added at any point during the blending of the asphalt compositions; and it may be useful in providing an asphalt pavement with a crosslinked asphalt-rubber binder.

|0065] The crosslinker may be any of the many crosslinkers known in the art. including those that work by an anionic, cationic. or free radical mechanism. In some embodiments, the crosslinker is sulfur or a sulfur compound, such as a thiol, thioether. disulfide, or the like. Preferably, the crosslinker comprises from 0 to 1000 carbon atoms and from 1 to 1000 sulfur atoms. In one embodiment, the crosslinker is an anionic crosslinker. Some non-limiting examples of useful anionic crosslinkers in are those comprising one or more functional groups independently selected from -CR ₂ -O ^" . -CR?- S ^" . -CR ₂ -CR ₂ ^" . and -CR ₂ -NR ^" . wherein each R is independently H. a hydrocarbon, or an additional bond which forms =C.

(0066] While not intending to be limiting, the emulsion of asphalt-rubber binder may be used to prepare an asphalt pavement at ambient temperatures by a process comprising mixing the emulsion blend with aggregate and allowing the mixture to dry. In one embodiment, the dry asphalt-rubber binder in the asphalt pavement comprises from about 15% (w/w) to about 50% (w/w). about 4% to about 12%. about 12% (w/w) to about 22% (w/w), or about 15% (w/w) to about 22% (w/w) of crumb rubber. (0067] In some embodiments, the emulsion blend may be cationic or anionic For some cationic emulsions, the pH may be from about 2 5 to about 4 5 For some anionic emulsions, the pH may be from about 8 to about 10

|0068] The compositions and methods described herein ma\ prox ide improvement m a variety of asphalt emulsion chai act eristics For example, some compositions or methods may proude improved adhesion, cohesion, early green strength, and/or water resistance when employed in a \ aπety of asphalt systems such as ambient cured, structural waterproofing and pa\ ement preservation s\stems These emulsions may also provide, inter aha. impro\ ed performance for asphalt ρa\ ement and other applications, such as resistance to oxidative hardening or oxidatn e embπttlement. resistance to weather or mechanical wear. impro\ ement in pa\ ement hie impro\ ed load distribution betw een aggregate and binder. impro\ ed skid resistance and the like

|0069] Another use of some of the emulsions described herein ma\ be as a street or highw ay seal For example the seal may stabilize and/or repair ra\ cling and micro-fissure(s) interrupt progressn e oxidative embπttlement. i ev erse diminished surface friction, or reduce tire noise

[0070] Some emulsions described hei em may also be used as a parking lot seal, for the maintenance of pa\ ement in parking areas and. w ith appropriate aggregate, low speed traffic surfaces For example, the seal may restore pavement suriace profile, interrupt progressive oxidative embπttlement. create a fuel resistant barrier, eliminate tracking, extend the repaving cycle, reduce tire noise, or re-establish diminished surface friction Asphalt-coated crumb rubber compositions

|0071] The asphalt-coated crumb rubber compositions ma\ compπse a second asphalt, and crumb rubber, and optionalh a surfactant For some asphalt-coated crumb rubber compositions such as hydiophihcized asphalt-coated crumb rubbei the crumb rubber may about 60% to about 80% of the w eight of all non-x olatile components of the asphalt-coated rubber composition For other asphalt-coated crumb rubber compositions, such as mastics the crumb rubber ma\ be about 20% to about 40% of the weight of all nonv olatile components of the asphalt-coated rubber composition The asphalt-coated crumb rubber compositions may compnse asphalt (such as medium hardness asphalt). crumb rubber, a surfactant and optionally λ\ater In some embodiments the asphalt- coated crumb rubber compositions mav comprise asphalt (such as medium hardness asphalt), crumb rubber, a surfactant and no added water, or alternatively less than about 2% ) water, about 1 % (w /vv) water, about 0 5% (w/w) water, about 0 1 % (w/w) water or about 0 01 % (\\/\\) water While not intending to be limiting, the asphalt-coated crumb rubber compositions may further comprise an ammendment such as a functional vegetable oil derivative

|0072] The amount of the second asphalt may v ary depending upon the circumstances In some embodiments, the medium hardness asphalt is from about 40% (w/w) to about 80% (w/w). from about 50% (wA\) to about 70% (w/w ). or about 60% (w/w) of the asphalt-coated crumb rubber composition

10073] In some embodiments, the second asphalt may be softei than the first asphalt For example, the second asphalt mav be a medium asphalt Medium hardness asphalt refers to asphalt having a haidness which ma\ be suitable lor use on an asphalt pavement road In a pieferred embodiment the medium haidness asphalt has a penetration value according to ASTM D5 of from about 50 dmm. about 100 dram or from about 150 dmm to about 200 dmm Altemativ elv. the medium hardness asphalt has a ring and ball softening point according to ASTM D36 of from about 85°F to about 100 ⁰ F With regaid to chemical composition the medium hardness asphalt may comprise Cs ₂ 4 hydrocarbons Foi example while not intending to be limiting, the hydrocarbon portion of the medium hardness asphalt may consist essentially of C _{8 24} hydrocarbons

|0074) Crumb rubber can be ground tire rubber including ground recv cled tire rubber For example the crumb rubber ma\ be ground recvcled tire rubbei which contains no visible nonfenous metal particle Alternativ ely the crumb rubber contains no more than about 0 01 % feπous metal particles bv weight T he particles of the crumb rubber may be any size suitable for dispersing in the asphalt-coated crumb rubber composition In some embodiments the particles of crumb rubber have a mean diameter from about 75 μm to about 650 μm Alternativ ely the crumb rubber may be from about 80 mesh to about 600 mesh from about 100 to about 600 mesh from about 20 to about 200 mesh, about ] 40 mesh (e g about 75μm to about 100 μm) or about 150 mesh In one non-limiting example, the crumb rubber is from about 100 mesh to about 600 mesh dern ed from MICRO-VULK GTR. a\ ailable from PπmePlex. LLC. The amount of the crumb rubber may van' depending upon the circumstances. For example, the crumb rubber may be at least about 15% (\\ w ). such as from about 15% (w w) to about 30% (w/w) from about 20% (w'w ) to about 40% (w/w). or from about 25% (w w) to about 35% (w/w) of all non-volatile components of the emulsion of an emulsion of an asphalt- rubber binder

|0075] A functional vegetable oil derivativ e is a derivative of a vegetable oil or other fatty substance, or a substance having a similar composition regardless of the on gin of the substance. In some embodiments, the functional vegetable oil derivative is epoxidized unsaturated tnglyceπde Epoxidized unsaturated tπglyceiide is a tn-ester of glycenne The glycenne bonds to three linear or branched carboxyhc acids, wherein at least one of the carboxyhc acids comprises an epoxide moiet\ For example, the epoxidized unsaturated triglyceride may be a denvatn e of an unsaturated iatty acid tπglycende such as a \ egetable or animal fat or oil. wherein at least one of the C=C moieties of the parent unsatuiated fatty acid triglyceride is replaced with an epoxide moiety (i.e. a three-membered ring containing an oxygen) If the parent unsatui ated fatty acid tnglycende has more than one C=C moiety, one. part, or all of the C=C moieties may be replaced by epoxide moieties Examples of \ egetable or animal fats or oils include coconut oil. corn oil. cottonseed oil. olive oil. palm oil. peanut oil. rapeseed oil. canola oil. safflower oil. sesame oil. soybean oil. sunflower oil. castor oil. tallow oil. and the like In one embodiment, the v egetable oil is soybean oil

[0076] A soh ent dispersed wood rosin ester may be used in addition to. oi as an alternative to the functional vegetable oil derivative or epoxidized unsatui ated tnglycende Common solv ents foi dispersing the wood rosin ester include organic soh ents such as hydiocarbons. including mineral spirits, toluene. xv lene. and naptha soh ent (e.g. VM&P)

(0077] The amount of the ammendment. such as an epoxidized saturated tnglycende. may vary depending upon the circumstances For example, an ammendment. such as an epoxidized unsaturated tnglycende. may be from about ] % (w 'w) to about 10% (wΛv). from about 2% (w/w) to about 6% (w/w). or about 4 ⁰ O (w w) of the asphalt-coated crumb rubber composition.

|0078] The surfactant of the asphalt-coated crumb rubber composition may be any surfactant, including any of the possibilities descπbed above In some embodiments, the surfactant comprises a cationic or a nonionic surfactant. In other embodiments, the surfactant comprises a nitrogen-containing surfactant such as a fatty amine or a mtrogen- contaming cationic surfactant such as an amine surfactant in the ammonium salt form

|0079] The amount of the surfactant may vary depending upon the circumstances. For example, the surfactant may be from about 0.1 % ) to about 10% (\λ/w). from about 1 % (w/w). to about 4% (w/w). or from about 1 5% (w'w ) to about 3% (w w) of the asphalt-coated crumb rubber composition.

|0080] The amount of water in the asphalt-coated crumb rubbei composition may λ ary depending upon the circumstances For example, the water ma\ be about from about ] % (\\/w) to about 10% (\\ w). from about 2% (w/w), to about 6% (w w). or about 4% (w w) of the asphalt-coated crumb rubber composition For some applications, such as those which involve the laying of asphalt pavement at ambient temperatures, a reduced amount of w ater may be desirable For examples, in some asphalt-coated crumb rubber compositions, essentially no water is added, or alternatively, the w atei content ol the composition is about 2% (wΛv) or less, such as about 0.00001 % (w/w ) to about 2% (w'w). about 0 00001 % (w/w) to about 1 % (w/w). or about 0 00001 % (w'w ) to about 0.5% (w/w) Preferably, the asphalt-coated crumb rubber composition is prepared by heating crumb rubber and asphalt together until the crumb rubber sw ells or reacts The temperature of the heating may be any com enient temperature, such as from about 25O ⁰ F to about 450 ⁰ F. from about 300 ⁰ F to about 400 ⁰ F. or about 350 ^c F The heating may occur for any amount of time depending upon the circumstances In some embodiments, the heating is earned out from about 5 minutes to about 90 minutes, liom about 10 minutes to about 60 minutes, or about 15 minutes The heating may result m J range of Mscosities for the asphalt-crumb rubber combination Preferabh. the viscosiU is from about 500 cps to about 3000 cps. from about 700 cps to about 2000 cps. or from about 900 cps to about 1500 cps. |0081] While not intending to be limiting, the epoxidized unsatυiated tnglyceride ma) be added and mixed into the asphalt-crumb rubber combination alter the crumb rubber swells The mixing may occui at am temperature For example the mixture may be thoroughly blended at a temperature of from about 100 ⁰ F to about 300 ⁰ F. from about 150 ⁰ F to about 250 ⁰ F. or about 200°F

|0082] In some embodiments, the watei and the surfactants are mixed separately from the asphalt-crumb rubber blend until the surfactant is dissoh ed The surfactant solution is then mixed into the asphalt-crumb rubber blend prepared above In some preferred embodiments, the surfactants aie added directly to the asphalt-crumb rubber blend without being dissolved m water

[0083] In some embodiments, a lowei or no water content in the asphalt- coated crumb rubber composition may iesult m an asphalt pavement which ma\ cure more i apidly Foi example, a road made from the asphalt pavement mav be opened to traffic sooner after the asphalt pavement is laid It should be noted. ho\\ e\ ei that lor preferred embodiments, once the asphalt-coated crumb rubber composition is prepared for example, after the crumb rubber has swelled or reacted m the presence of the asphalt, the asphalt-coated crumb rubber composition may be mixed with waterbome compounds, such as watei m any emulsion composition described herein without substantially slowing the curing time as compared to that of the original emulsion First Asphalt Emulsion

(0084] The first asphalt compositions ma\ comprise a first asphalt a suifactant and water In some embodiments, the first asphalt may be hardei than the second asphalt For example, the first asphalt may ha\ e a pen \ alue in the range of about 0 dmm to about 100 dmm If a first asphalt composition is a hard asphalt emulsion such as Emulsion H 110 in FIGURE 2. the asphalt may be a hard asphalt Hard asphalt is asphalt which is substantially harder than that normallv used in roads For example the hard asphalt may have a penetration value ol fiom about 0 dmm to about SO dmm. or alteratnely. about 0 dmm to about 10 dmm In other embodiments, the haul asphalt has a πng and ball softening point of from about 155°F to about 165°F In terms ol chemical composition the hard asphalt may comprise hydrocarbons having at least 24 carbon atoms. For example, the hydrocarbon portion of the hard asphalt may consist essentially of C ₂ 4-5oo hydrocarbons.

(0085J The amount of the first asphalt may vary depending upon the circumstances. In some embodiments, the first asphalt is from about 40% (w/w) to about 80% (w/w); from about 50% (w/w) to about 70% (w/w): or about 60% (w/w): of first hard asphalt emulsion.

[0086] The first surfactant, or the surfactant of the first asphalt emulsion, may be any surfactant, including any of the possibilities described above. In some embodiments, the first surfactant comprises a cationic or a nonionic surfactant. For example, the surfactant may comprise one or more of: a nitrogen-containing surfactant such as a fatty amine; a nitrogen-containing cationic surfactant such as an amine surfactant in the ammonium salt fonn: an amido amine surfactant, an ammonium salt thereof, or a combination thereof; and a lignin amine surfactant, i.e. lignin combined with an amine. In some embodiments, the first surfactant comprises an amine or an ammonium functional group.

|0087) The amount of the surfactant may vary depending upon the circumstances. In some embodiments, the surfactant is from about 0.1 % (w/w) to about 10% (w/w), from about 1 % (w/w) to about 5% (w/w). or about 2% (w/w) of the first asphalt emulsion.

[0088] The amount of water in the first asphalt emulsion may vary depending upon the circumstances. For example, the water may be from about 25% (w/w) to about 80% (w/w), from about 30% (w/w) to about 50% (w/w). or from about 30% (w/w) to about 40% (w/w) of the first asphalt emulsion.

|0089] In some embodiments, the first asphalt emulsion is prepared by heating the hard asphalt in a separate vessel before mixing with the other components of the first asphalt emulsion. The heating may be at any temperature sufficient to soften the asphalt for mixing such as: from about 300 ⁰ F to about 400 ⁰ F. or about 325°F.

[0090] The water and the surfactants may be mixed separately until the surfactant is dissolved to form a soap solution. The soap solution may then be combined with the heated first asphalt and run through a colloid mill. Examples of suitable high shear colloid mills include, but are not limited to. Dahhvortb Superton. or Charlotte high shear colloid mills

|0091] The combination of the hot asphalt and cold soap may result in a mixing temperature below the boiling point of water, such as from about 180 ⁰ F to about 210 ⁰ F. or from about 190 ⁰ F to about 200 ⁰ F Continued mixing m the high shear colloid mill may produce an emulsion m which the oil droplets are suspended in water Soft asphalt emulsion

|0092) If a method relates to a soft asphalt emulsion, the soft asphalt emulsion may compose soft asphalt, a surfactant, and w ater In other embodiments, the soft asphalt emulsion further compπses an ammendment such as an unsaturated carboxyhc acid such as an olefin from the stearol famil)

[0093] Soft asphalt is asphalt which substantially softer than that normally used in roads For example, the soft asphalt may have a penetration \ alue greater than about 200 dmm The soft asphalt may also be characterized as having a ring and ball softening point of from about 60 ⁰ F to about 85°F With regard to chemical composition, the soft asphalt may comprise C _? s hydiocarbons For example, the hydrocarbon portion of the asphalt may consist essentially ol C: {, hydrocarbons

[0094J The amount ol the soft asphalt may \ ary depending upon the ciicumstances For example, the soft asphalt may be from about 40% (w/w) to about 80% (w/w). from about 50% (w/w) to about 70% (w/w). or about 60% (w/w) of the soft asphalt emulsion

|0095) Any unsaturated carboxvhc acid may be used in the soft asphalt emulsion In some embodiments, the unsaturated carbox\hc acid compπses a C _< , -, ₍ > carboxyhc acid, including but not limited to linear and branched carboxyhc acids, which include fatty acids or olefins from the stearol family such as arachidonic acid, eicosapentaenoic acid, hnoleic acid, α-hnolemc acid, γ-linolemc acid, oleic acid, palmitoleic acid, and combinations thereof

|0096) The amount ol the unsaturated carboxyhc acid may vaiy depending upon the circumstances For example, the unsaturated carboxyhc acid may be from about 0 1 % (W'w) to about 5% (w/w). from about 0 5% (w/w) to about 2% (w/w ). or from about ] % (w/w) to about 1 5%(w/w) of the soft asphalt emulsion |0097] The surfactant of the soft asphalt emulsion may be any surfactant including any of the possibilities described abo\ e In some embodiments, the surfactant comprises a cationic or a nonionic surfactant For example, the surfactant may comprise one or more of a nitrogen-containing surfactant, such as a surfactant comprising an amine or an ammonium functional group, such as a fatty amine, a nitrogen-contaming cationic surfactant such as an amine surfactant in the ammonium salt form, an amido amine surfactant and a lignin amine surfactant, i e ligmn combined with an amine

[0098] The amount of the surfactant may vary depending upon the circumstances In some embodiments, the surfactant is from about 0 1 % (w/w) to about 10% (w/w), lrom about ] % (w/w) to about 5% (w w). or about 2% (w/w ) of the soil asphalt emulsion

|0099] The amount of water in the soft asphalt emulsion may vary depending upon the circumstances For example, the water may be horn about 10% (w w) to about 80% (w/w) lrom about 20% (w/w) to about 50% (w/w). or fiom about 30% (w/w ) to about 40% (w w ) of the soft asphalt emulsion

[0100] The soft asphalt emulsion ma\ further comprise an optionalh substituted styrene butadiene styrene block copolymer (SBS) SBS is a block copohmer comprising an optionally alkyl substituted polybutadiene chain which is attached to two distinct, independent optionally substituted polystyrene chains, one on each end ol the polybutadiene An optionally substituted polybutadiene chain is a polymeric chain formed lrom a butadiene which may be υnsubstituted. or all or wherein part of the monomers used to form the chain comprise one or more C| •, alkyl groups corresponding to anv position on the monomer An optionally substituted polystyrene is a polymeric chain formed from a styrene which ma\ be unsubstituted. or wherein all or part of the monomeis used to lorm the chain comprise one or more C ₁ •, alkyl groups corresponding to am position on the monomer

[OJ 01 ] In other embodiments, one or more of the polystyrene chains and the polybutadiene chain may have guest monomeric units up to about 5% about 10%. or about 50% of the total monomeric content A guest monomeπc unit is a monomer that is not an optionally substituted styrene which is incorporated into one or both ol the optionally substituted polystyrene chains, or a monomer that is not an optionally substituted butadiene which is incorporated into the polybutadiene chain or is incorporated into a branching or a radially branching group. Examples of guest monomers include optionally substituted ethylenes, optionally substituted aery] at es. and the like. In some embodiments, the SBS may be branched In other embodiments, the SBS may be radially branched.

|0102] The amount of SBS m the soft asphalt emulsion may vary depending upon the circumstances. In some embodiments, the SBS is from about 0.1 % (\v/w) to about 10% (Ww). from about 1 % (w/w) to about 5% (w/w). or about 2% (w/w) of the soft asphalt emulsion.

10103] In other embodiments, the SBS is crosslink ed. Crosslinking may be earned out using any of the many crosshnkers known in the art. as described above The amount of crosslinker in the soft asphalt emulsion may vary depending upon the circumstances In some embodiments, the crosslmker is from about 0.0001 % (w/w) to about 1 % (w w). from about 0.005% (w/w) to about 0 2% (w/w). or about 0.08% (w/w ) of the soft asphalt emulsion

|0J 04] The soft asphalt emulsion may be prepaied by a number of different methods For example, the soft asphalt may be mixed with the unsaturated fatty acid at an elevated temperature to form a soft asphalt-fatty acid composition The mixing may occur at an> e)e\ ated temperature useful to provide adequate mixing In some embodiments, the mixing temperature is from about 200 ⁰ F to about 450 ⁰ F. from about 300 ⁰ F to about 400 ⁰ F. or about 325°F. In a preferred embodiment, a combination of water and one or more surfactants are thoroughly mixed, and this surfactant liquid is then combined with the soft asphalt-fatty acid combination to pro\ ide a soft asphalt emulsion.

|0J05] The mixing of the water and surfactant may be done at any temperature that allow s such mixing In some embodiments, the mixing is done at from about 32°F to about 150 ⁰ F. about 70 ⁰ F to about 90°F. oi about 80 ⁰ F

J0J06] The mixing of the surfactant liquid with the soft asphalt-fatty acid combination may be done at any temperature that allows adequate mixing. In some embodiments, the mixing is done with the soft asphalt-fatty acid combination having a temperature of from about 200 ⁰ F to about 450 ⁰ F. or from about 280 ⁰ F to about 35O°F. preferably about 300 ⁰ F. and the water/surfactant combination, or soap system, having a temperature of from about 32 ⁰ F to about ] 50°F. or about 70 ^c F to about ] 10 ^c F. preferably about 80 ⁰ F. Once the heat is transferred from the warmer materials to the cooler materials, the temperature may be about 1 80 ⁰ F to about 210 ^c F as mixing continues.

|0107] The optionally substituted SBS is preferably added to the asphalt or the asphalt-fatty acid composition and mixed until the SBS is dissolved to provide a polymer modified soft asphalt. The polymer modified soft asphalt may be combined with the surfactant liquid in the same manner as the asphalt-fatty acid composition to provide other embodiments of the soft asphalt emulsion.

[0108] In other embodiments, a crosslink er is added to the polymer modified soft asphalt emulsion and mixed to provide, upon condensation, a crosshnked polymer modified soft asphalt. The crosslinker may be mixed under suitable conditions which will allow the crosshnker to be properly dispersed. Example 1 Composition A-Crumb rubber concentrate Table 1

Crumb Rubber Concentrate (Component #] ) tlemeni Weight (lbs) Solids Comments

1 ) Asphalt 60jf 60 5 Typically AC5 (90-200 pen. R&B =- S5-I0Q F)

Raise #] to 350 F then add 32 and mix for ~] 5 minutes

2) Crumb Rubber 30 0 30.0 Vulcanized ground scrap tire 650-75 micion range N aπes

Sub-total 9θT 90 5

3) Ammendment 4.0 4 0 Epoxidized SON oil or other functional \ egetable oil deme.

Cool blend of # l+#2+#3 to -200F. then thoroughly blend

Separately pre-blend #4 and *5. then add blend of #1-3 to achie\e heaN y mastic body consistency 4) 4819 1.5 1.2

5) H _: 0/sohent 4 00 0 May contain small quantity of glycol ether or other solvent

Total 100 00 95 ^~ 7

|0109] Table 1 summarizes one embodiment of the preparation of the crumb rubber concentrate. Asphalt (about 60.5 lbs. about 90-200 pen. ring and ball (R&B) softening temperature = about 85-100 ⁰ F) is heated to about 35O ⁰ F. Crumb rubber (about 30 lbs. vulcanized ground scrap tire, about 650-75 micron range) is then added and the combination is mixed for about 15 minutes whereupon the crumb rubber swells and reacts in the asphalt medium to a viscosity range of about 900-1500 cps. Epoxidized soy oil is then added as ammendment (about 4 lbs), and the mixture is thoroughly blended at about 200 ⁰ F. j OJ 10] Water (about 4 lbs) and a fatty amine surfactant (Azko Nobel Readicote 4819. about 1 5 lbs) arc mixed separately until the surfactant is dissolved This surfactant solution is then mixed into the asphalt-crumb rubber blend prepared abo\ e until a heavy mastic body consistency is achieved Composition B-Hard Pen Asphalt Emulsion Table 2

Hard Pen Asphalt Emulsion (Component #2)

Element Weight (lbs) Solids Comments

] ) H20 36 50 0- PotabJe

2) ER 582 ] 10 0 8^ P2 (Prime Ple\) Surfactant - other options commerciaIK available

3 A\ -S 1 IO CH4 Surfactant Lignin Amine Meade \Ves\aco C hemical

Sub Total 38 7 I 29

Pre-heat asphalt to 325 ^C F then co-mill with pre-blended soap' s\ sτem (H] -*2-£3 @ 80 ^c F) through colloid mil)

4) Asphalt 61 30 61 30 PDA or \ TB or 'blown' (_zero 10 pen _. R&B = ] -^-] 6s ^c F)

Sub Total 100 00 62 ^9

|OJ 11] Table 2 summarizes one embodiment of the prepaiation of the hard pen asphalt emulsion Asphalt (about 61 3 Ib. about 0-10 pen. R&B = about 155-165°F) is heated to about 325°F in a separate \ essel The soap is sepaiateh prepaied by dissolving or dispersing an amido amine surfactant (ER 582 surfactant, about 1 1 lbs. available from PπmePlex) and W-5 surfactant (about 1 ] lbs. lignin amine Meade Wesvaco Chemical) in water (about 36 5 lbs)

|0112) The asphalt and soap are pumped into a mixing chamber of a high shear colloid mill The combination of the hot asphalt and cold soap results in a mixing temperature below 200 ⁰ F Continued mixing in the high shear colloid mill produces an emulsion in which the oil dioplets are suspended m water Composition C-Polymer Modified Asphalt Emulsion Table 3 Soft Pen-Polymer Modified Asphalt Emulsion

Element Weight (lbs) Solids (lbs) Comments

1 ) Asphalt 58 00 58 00 VTB ΛC5 or blend (pen 20- R&B -

60 85°F)

2) Ammendment 1 22 I 22 Olefin from stearol famiK e g oleic acid amount Pre blend # 1 -* ^■ -2 at 325 ^C F then add ≠3 and run through high shear until dissoKed

3) SBS Elastomer 2 00 2 00 Radiallv branched w ith crosslink functionality bv sulfur compound

SubTotal 61 22 61 22 4) H2O 36 58 0 Potable

5) ER582 ] 10 0 8S #4 7 are pre blended soap sv^em

6) W 5 1 10 0 44

Subtotal 38 78 1 29

Total 100 0 62 59

|0113] Table 3 summarizes one embodiment of the preparation of the polymer modified asphalt emulsion Asphalt (about 58 lbs. about 200+ pen. R&B = about 60- 85°F) is combined with an unsaturated fatty acid ammendment (about 1 2 lbs) at about 325 ⁰ F and mixed until the composition is uniform throughout Radially branched styrene butadiene styrene block copolymer (Kraton 1 1 18. about 2 lbs), is then added, and the mixture is run through a high shear mixer until the polymer is dissolved and the composition is mixed for at least about 8 hours at about 300 ⁰ F

|0114] A combination oi watei (about 36 5 Ib) ER 582 (about ] 1 Ib) and W -5 (about 1 1 Ib) are tboroughh mixed at about 80 ⁰ F This is then co-milled with the cioss- hnked polymer modified asphalt at about 300 ⁰ F Composition D-Asphalt Emulsion Table 4

Element W eight Solids (Jbs) Comments (lbs)

Composition B 28 1 ^" VS OO Stir Composition B and Composition C then add Mastic Composition A until JuIh homogeneous

Composition C 19 00 1 1 89

Composition A 35 00 34 45

Crosslmker 1 00 0 ^O SL4005 Resin from PπmePlex

Total 100 00 75 01

(0115) Table 4 summarizes one embodiment of the pieparation oi an asphalt- rubber binder emulsion which provides a minimum of about 15% crumb iubber based upon the total 'neat binder w eight per ASTM Standard D8-02

Composition B (about 45 wt° o) and composition C (about 19 wt%) are thoroughh blended, and composition A (about 35 \\t%) is added undei high speed shear until the mixture is tully homogeneous Example 2

|0116] The procedure of Example 1 is earned out except that the preparation of Composition A-Crumb rubber concentrate, is modified as follows Composition A-Crυmb rubber concentrate Table 5

Crumb Rubber C oncentrate (Component τ l )

Element Weight (lbs) Solids Comments

1) Asphalt 60 5 60 5 Tvpicalh AC5 (90-200 pen R&B - 85 100 F)

Raise #1 to 350 F then add * 2 and mix ior -15 minutes

2) Crumb Rubber 30 0 30 0

Sub-total 90 5 90 5

3) Ammendment 4 0 4 0 Epoxidrzed soy oil or other functional \egetable oil derπ e

Cool blend of #]4if2+#3 to - -200F then tboroushlv blend #4 to achieve heaw mastic bod\ consistencv

4) 4819 1 5 1 2

Total 96 95 7

|0117) Table 5 summanzes one embodiment of the preparation of the crumb rubber concentrate Asphalt (about 60 5 lbs. about 90-200 pen. ring and ball (R&B) softening temperature = about 85-100 ⁰ F) is heated to about 350 ⁰ F Crumb rubber (about 30 lbs. vulcanized ground scrap tire, about 650-75 micron range) is then added and the combination is mixed for about 15 minutes whereupon the crumb rubber swells and reacts m the asphalt medium to a Mscosity range of about 900-1500 cps Epoxidized soy oil is then added as ammendment (about 4 lbs), and the mixture is thorough!) blended at about 200 ⁰ F A fatty amine surfactant (Azko Nobel Readicote 4819 about 1 5 lbs) is then mixed mto the asphalt-crumb rubber blend until a heavy mastic body consistent is achieved Example 3

|0118) Composition B (about 45 wt%) and composition C (about 20 v%t%) are thoroughly blended, composition A (about 35 wt%) is then added under high speed shear until the mixture is fully homogeneous Finally, a crosslink er is added ( 1 0% SL4005 resin, as described in the product data sheet, available from PπmePlex. LLC) Example 4 Street and Higrm ay Safety Seal

|0U9] A crumb rubber concentrate is prepared as described in Example 2 The crumb rubber employed is a finely ground tire (80-140 mesh) A cationic emulsion is then prepared having a pH oi about 2 5 to about 4 5 using the crumb rubber concent] ate as descπbed in Example 1 or Example 2 The emulsion is formulated to ha\e about 50% to about 55% solids by distillation, about 15% to about 22% ground tire rubber, and have an viscosit} of less than about 100 seconds |0120] The emulsion thus prepared is diluted by about 50% and sprayed on street or highway asphalt pavement at spread rates of about 0 1 OgaLsq >d

|0121] The skid coefficient (per ASTM E274-06) and the wet surface locked wheel stopping distance of a treated road is compared to the skid coefficient of an untreated road for smooth round stone aged pa\ ement. angular aged pavement, and new pavement In every case, the skid coefficient and the stopping distance was significantly better for the treated pavement Example 5 Street and Highway Safety Seal

|0122) The procedure of Example 3 is carried out except that a range of crushed aggregates were added to the emulsion Up to 5 lbs/gal (of concentrated binder) aie used This will further improλ e skid coefficient, stopping distance, and othei indicators of road perfoimance Example 6 Parking Lot Seal

[0123] A crumb rubber concentrate is prepared as described in Example 2 The crumb rubber employed is a finelv ground tire (80-140 mesh) A cationic emulsion is then prepared having a pH of about 2 5 to about 4 5 using the crumb rubber concentrate as described in Example 1 or Example 2 The emulsion is formulated to have about 50% to about 65% sohds by distillation, about 4% to about 12% ground tire rubber, and have an viscosity of less than about 100 seconds

|0124] The emulsion thus prepared is diluted by about 25% to about 40% and sprayed or spread on parking lot asphalt pa\ ement at spread rates of about 0 15 gal/yd ^" to about 0 30 gal yd" Example 7 Base asphalt emulsion formula

|0125] Asphalt (about 1 18 Ib. about 0-10 pen. R&B = about ] 55-165°F) is heated to about 325°F in a separate \ essel A soap is separately prepared b\ dissolving or dispersing an amido amine surfactant (ER 582 surfactant, about 2 lbs. available from PnmePlex) in water (about 80 lbs) The asphalt and soap are pumped into a mixing chamber of a high shear colloid mill The combination of the hot asphalt and cold soap results m a mixing temperature below 200 ^c F. Continued mixing in the high shear colloid mill produces an emulsion m which the oil droplets are suspended in w ater Hydrochloric acid (about 0.6 lbs) is then mixed into the composition to bring the pH to about 2 Example 8 Hvdrophilicized asphalt-coated crumb rubber

|0126] Asphalt (about 30 lbs. about 90-200 pen, ring and ball (R&B) softening temperature = about 85-100 ⁰ F) is heated to about 350 ⁰ F and mixed with a carboxyfunctional blend of stearic acid, oleic acid, and palmitic acid (10/60/30 w/w/w: about 20 lbs), and a fatty amine surfactant (about 0.6 lbs RediCoat 4819, from Akzo Chemical). Part of this mixture (about 25 lbs) is then sprayed onto the surface of the crumb rubber (about 75 lbs) by means of a Thermal Turbo Integrator, as supplied by PrimePlex. LLC.

[0127] The base asphalt emulsion formula (about 4 parts by weight) is then blended with the hydrophihcized asphalt-coated rubber (about 1 part by weight) to provide an emulsion of asphalt rubber binder wherein the crumb rubber is about 22 percent of the weight of the non-volatile components of the emulsion. Example 8 Mastic

[0128] A mixture of wood rosin (3 5 lbs), mineral spirits (3.5 lbs), and a surfactant (1.4 lbs RediCoat E-7000 av ailable from Akzo Chemical) are mixed with asphalt (about 60.9 lbs. about 150-200 pen. ring and ball (R&B) softening temperatuie = about 85-10O ⁰ F) at about 350 ^c F. A fatty amine surfactant (about 0.7 lbs RediCoat 4819. from Akzo Chemical) and ground tire rubber (about 30 lbs. 80 mesh) are blended into the mixture under high shear to provide a mastic having 87% non-volatile components and about 30 % ground tire rubber by weight

[0129J The mastic (25 lbs) is combined with the base asphalt emulsion formula (15 lbs) and water (2 5 lbs) under high shear to provide an emulsion of asphalt rubber binder having about 16% ground tire rubber based upon the weight of the nonvolatile components of the emulsion

[0130] While the abo\ e detail description has shown, described, and pointed out novel features of the invention as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details oi the systems, methods, processes, or compositions illustrated may be made b\ those skilled in the art without departing from the spirit of the invention As w ill be recognized, the present im ention may be embodied w ithin a form that does not provide all of the features and benefits set forth herein, as some features may be used or practiced separated from others