CN114479485A - Ultrathin wearing layer asphalt material and preparation and application thereof - Google Patents

Ultrathin wearing layer asphalt material and preparation and application thereof Download PDF

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Publication number
CN114479485A
CN114479485A CN202011162922.4A CN202011162922A CN114479485A CN 114479485 A CN114479485 A CN 114479485A CN 202011162922 A CN202011162922 A CN 202011162922A CN 114479485 A CN114479485 A CN 114479485A
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asphalt
temperature
block copolymer
oil
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CN114479485B (en
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郭小圣
袁俊
张建峰
傅丽
刘树华
徐青柏
刘成
吴晓颖
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • EFIXED CONSTRUCTIONS
    • E01CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01CCONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00Coherent pavings made in situ
    • E01C7/08Coherent pavings made in situ made of road-metal and binders
    • E01C7/18Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders
    • E01C7/26Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders mixed with other materials, e.g. cement, rubber, leather, fibre
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses an ultrathin wearing layer asphalt material, which comprises the following components in parts by weight: matrix asphalt: 100 parts of (A); rich in aromatic oil: 3-10 parts of thermoplastic block copolymer and 2-8 parts of thermoplastic block copolymer; nano diamond powder: 1-7 parts; DOA: 1-5 parts; a stabilizer: 0.1-1 part. The invention greatly enhances the tensile toughness of the whole modified asphalt and improves the high-temperature rutting resistance of the asphalt material, the 60 ℃ viscosity of the obtained asphalt is far higher than the relevant specification requirements, and the asphalt material has strong adhesion to stone materials. The method can be widely applied to paving the ultrathin wearing layer in the maintenance of the asphalt pavement.

Description

Ultrathin wearing layer asphalt material and preparation and application thereof
Technical Field
The invention relates to the technical field of modified asphalt, in particular to a special asphalt material for an ultrathin wearing layer and a preparation method thereof.
Background
With the rapid development of high-grade roads in China, people put higher requirements on the aspects of safety, comfort, environmental protection and the like of the roads. After the asphalt pavement is used for a period of time after the vehicle is opened, the construction depth or roughness of the road surface is gradually reduced due to the increase of transport vehicles and the increasingly serious heavy load phenomenon, and the anti-skid performance is rapidly reduced, so that the driving safety and the comfort of the vehicle are directly influenced.
The ultra-thin wearing layer is an effective measure for prolonging the service life of the road surface, improving the running quality, improving the safety characteristics (including skid resistance and drainage), reducing noise and other road surface functions, and the thickness of the ultra-thin wearing layer is about 20mm generally. When the method is used for restoring the anti-skid performance of the road surface, preventive maintenance of a high-grade asphalt road surface or surface treatment of medium diseases, the service life of the road can be prolonged by 8-10 years, the friction coefficient of the road surface can be improved, noise is reduced, the driving safety of the road surface is ensured, the flatness of the road surface is improved, and good surface texture is achieved.
The quality of the asphalt is one of the main factors restricting the use quality of the asphalt pavement, and the ultra-thin wearing layer is directly influenced by the natural factors and the vehicle load effect because the ultra-thin wearing layer is positioned on the upper layer of the asphalt concrete pavement, so the requirement on the performance quality of the asphalt is higher. In the prior art, asphalt selected for the ultrathin wearing layer is mainly used for improving the anti-stripping performance of a cementing material by increasing the proportion of polymers such as SBS and the like or doping waste rubber powder, rock asphalt and the like, but the effect is limited, and because the long-term wear resistance of the current additive is limited, the wear resistance of a road surface can be better in a short period, but structural damage such as falling, flying and the like is easy to occur after long-term traffic is opened.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a modified asphalt material with ultrahigh abrasion resistance and a preparation method thereof. The modified asphalt material is mainly used for paving the road surface with an ultra-thin wearing layer. The invention aims to improve the strong wrapping property and the adhesiveness of the asphalt material to stone, and further improve the abrasion resistance and the stripping resistance of the pavement.
The invention provides an ultrathin wearing layer asphalt material, which comprises the following raw material components in parts by weight:
matrix asphalt: 100 parts of (A);
rich in aromatic oil: 3-10 parts; preferably 5-8 parts;
2-8 parts of thermoplastic block copolymer, preferably 3-7 parts;
nano diamond powder: 1-7 parts, preferably 2-6 parts;
DOA: 1-5 parts, preferably 2-4 parts;
a stabilizer: 0.1 to 1 part, preferably 0.2 to 0.7 part.
In the technical scheme, the base asphalt is selected from residual oil and/or asphalt obtained by atmospheric or vacuum distillation, wherein the penetration (25 ℃, 100g, 5s, 1/10 mm) is 45-130, and is preferably AH-50, AH-70, AH-90 asphalt or base asphalt meeting the technical requirements of JTG F40-2004 on 50A, 70A and 90A road petroleum asphalt.
In the technical scheme, the aromatic-rich oil is a component rich in aromatic hydrocarbon and is derived from extract oil of lubricating oil base oil in the solvent refining process; the weight content of aromatic hydrocarbon in the aromatic-rich oil is 40% -80%; preferably at least one of furfural refined extract oil and phenol refined extract oil.
In the above technical solution, the thermoplastic block copolymer is styrene-butadiene block copolymer (SBS); the styrene-butadiene block copolymer (SBS) is a particle with a linear structure or a star-shaped structure, and the S/B ratio of the blocks is 20/80-40/60.
In the technical scheme, the particle size of the nano diamond powder is 5-15 nm. The nano diamond powder is produced by explosion method, i.e. the explosive containing graphite micropowder is exploded in a closed high-pressure container, and the graphite microparticles can be instantaneously transformed into diamond microparticles of several nanometers to tens of nanometers by the high pressure and high temperature generated during explosion.
In the technical scheme, the DOA is deoiled asphalt, the softening point of the DOA is not lower than 90 ℃, and the PI value is more than 3.0. The DOA can be derived from heavy components which are obtained by solvent deasphalting of residual oil and contain no solvent, namely, the heavy components are recovered by the solvent, and the solvent used in the dissolving and removing process is selected from one or more than one of propane, isobutane, n-butane or n-pentane.
Further, the stabilizer is a simple substance, a compound or a mixture of the simple substance and the compound containing the sulfur element.
The second aspect of the invention provides a preparation method of an ultrathin wearing layer asphalt material, which comprises the following steps:
(1) shearing and dispersing the thermoplastic block copolymer in aromatic-rich oil for swelling development;
(2) mixing the nano-diamond powder with the substance obtained in the step (1) and forming;
(3) and (3) mixing and shearing the hot matrix asphalt, the particles obtained in the step (2) and DOA uniformly, adding a stabilizer, uniformly mixing, and continuously performing thermal development to obtain the ultrathin wearing layer asphalt material.
In the above technical solution, the swelling development conditions in step (1) are as follows: the temperature is 80-120 ℃, and the preferred temperature is 90-110 ℃; the shearing speed is 3000-6000 rpm, preferably 4000-5000 rpm; the development time is 1-3 h, preferably 1.5-2.5 h.
In the technical scheme, the molding in the step (2) is to perform extrusion granulation by using a screw extruder, wherein the screw extruder is a single-screw extruder or a double-screw extruder, preferably a double-screw extruder, and the length-diameter ratio L/D is 30: 1-40: 1; controlling the temperature of the screw extruder to be 120-160 ℃, and controlling the screw rotating speed to be 30-150 r/min; preferably, eight temperature stages are used, wherein the operating conditions are as follows: the temperature of one section is 130-150 ℃; the second section is 135-155 ℃; the three sections are 140-160 ℃; the fourth section is 140-160 ℃; the fifth section is 150-160 ℃; the six sections are 150-160 ℃; the seven sections are 145-160 ℃; the eight sections are 150-160 ℃. This process allows the nanoparticles to be sufficiently absorbed or adsorbed by the polymer intermolecular gaps.
In the technical scheme, the temperature of the matrix asphalt in the step (3) is 140-170 ℃, DOA is added, the mixture is uniformly stirred, the temperature is increased to 180-190 ℃, the mixture is sheared and stirred until a uniform system is formed, and then the stabilizer is added, stirred and developed. The shearing rotating speed is 1000-5000 rpm, and the rotating speed for adding the stabilizer to stir and develop is 500-1000 rpm.
The invention provides an application of an ultrathin wearing layer asphalt material in maintenance of an asphalt pavement.
Compared with the prior art, the ultrathin wearing layer asphalt material and the preparation method thereof provided by the invention have the following advantages:
(1) the asphalt material of the invention fully utilizes the high specific surface area and the high strength of the nano diamond powder, effectively enhances the interaction force between the thermoplastic block copolymer and the asphalt molecules, enables the particle density of the additive to be similar to that of the asphalt, effectively prevents the segregation and delamination phenomena in the preparation process and the thermal storage and transportation process, and simultaneously greatly enhances the tensile toughness, the rutting resistance and the stone wrapping force of the whole modified asphalt.
(2) In the preparation method provided by the invention, in order to ensure that the nano-diamond powder is fully adsorbed and contacted with the thermoplastic block copolymer molecules, the gaps among the polymer molecules are opened by swelling, and then the heating high-pressure condition of a screw extrusion process is preferably utilized, so that the nano-diamond powder particles are fully and tightly attached to the polymer molecular chains, the cohesive force of the modified asphalt molecules is greatly enhanced, and the capacity of resisting the deformation of external shearing force is enhanced.
(3) The preparation method of the asphalt material provided by the invention is simple and easy to realize, the components in the asphalt material have good dispersibility in an asphalt phase, the DOA material with low cost can not only cooperate with the nano diamond powder to improve the high-temperature anti-rutting performance of the asphalt material, but also cooperate with the SBS polymer to improve the dynamic viscosity of the asphalt, the 60 ℃ viscosity of the obtained asphalt is far higher than the relevant standard requirements, and the asphalt material has strong adhesion to stone materials.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples.
Example 1
(1) Mixing 3 parts by weight of thermoplastic block copolymer (linear) and 5 parts by weight of furfural extract oil at 90 ℃ and 3000rpm, shearing and swelling for 1.5h to obtain a component A1; wherein the thermoplastic block copolymer is SBS particle with linear structure, and the block ratio S/B is 20/80.
(2) Component A1 was mixed with 2 parts by weight of nanodiamond powder (5 nm, specific surface area 400 m)2Adding the mixture into a screw extruder (the length-diameter ratio L/D is 35: 1), setting the screw rotation speed to be 50 r/min, uniformly mixing, blending, extruding and granulating by using a double-screw extruder to obtain a component B1. The extruder operating conditions were: the first section is 130 ℃; the second section is 135 ℃; the third section is 140 ℃; the fourth section is 140 ℃; the fifth section is 150 ℃; the six sections are 150 ℃; the seven sections are 145 ℃; the eight sections are 150 ℃.
(3) Adding the component B1 into 100 parts by weight of 150 ℃ petroleum-based asphalt, and mixing and shearing the two at the heating temperature of 180 ℃ for 0.5 h at the shearing speed of 1000 rpm; after shearing, 2 parts by weight of DOA and 0.2 part by weight of sulfur were slowly added, and stirred at 500 rpm for 2 hours to obtain asphalt material C1, the properties of which are shown in Table 1.
Example 2
(1) Mixing 5 parts by weight of SBS (linear) and 6 parts by weight of furfural extract oil at 100 ℃ and 4000rpm, shearing and swelling for 2 hours to obtain a component A2; wherein the thermoplastic block copolymer is SBS particle with linear structure, and the block ratio S/B is 30/70.
(2) Component A2 was mixed with 4 parts by weight of nanodiamond powder (10 nm, specific surface area 380 m)2Adding the mixture into a screw extruder (the length-diameter ratio L/D is 35: 1), setting the screw rotation speed to be 50 r/min, uniformly mixing, blending, extruding and granulating by using a double-screw extruder to obtain a component B2. The extruder operating conditions were: the first section is 130 ℃; the second section is 135 ℃; the third section is 140 ℃; the fourth section is 140 ℃; the fifth section is 150 ℃; the six sections are 150 ℃; the seven sections are 145 ℃; the eight sections are 150 ℃.
(3) Adding the component B2 into 100 parts by weight of petroleum-based asphalt at 155 ℃, mixing and shearing the two at the heating temperature of 180 ℃ for 0.5 h, wherein the shearing speed is 3000 rpm; after shearing, 3 parts by weight of DOA and 0.5 part by weight of sodium sulfide are slowly added, and the mixture is stirred for 2 hours at the rotating speed of 800 rpm, so that an asphalt material C2 is obtained, wherein the properties of the asphalt material are shown in Table 1.
Example 3
(1) Mixing 7 parts by weight of SBS (linear) and 8 parts by weight of furfural extract oil at 110 ℃ and 5000rpm, shearing and swelling for 2.5h to obtain a component A3; wherein the thermoplastic block copolymer is SBS particle with linear structure, and the block ratio S/B is 40/60.
(2) Component A3 was mixed with 6 parts by weight of nanodiamond powder (15 nm, specific surface area 360 m)2Adding the mixture into a screw extruder (the length-diameter ratio L/D is 35: 1), setting the screw rotation speed to be 50 r/min, uniformly mixing, blending, extruding and granulating by using a double-screw extruder to obtain a component B3. The extruder operating conditions were: the first section is 135 ℃; the second section is 140 ℃; the third section is 145 ℃; the four sections are 150 ℃; the fifth section is 155 ℃; the six sections are 155 ℃; the seven sections are 160 ℃; the eight sections are 160 ℃.
(3) Adding the component B3 into 100 parts by weight of petroleum-based asphalt at 160 ℃, mixing and shearing the two at the heating temperature of 180 ℃ for 0.5 h, wherein the shearing speed is 5000 rpm; after shearing, 4 parts by weight of DOA and 0.7 part by weight of sulfur are slowly added, and the mixture is stirred for 2 hours at the rotating speed of 1000 rpm to obtain an asphalt material C3, wherein the properties of the asphalt material are shown in Table 1.
Comparative example 1
The preparation method and the formula of the material are the same as those of the example 2, and the difference is that SBS and furfural extract oil are not subjected to the first-step shearing swelling treatment, the furfural extract oil, nano-diamond powder and SBS are directly mixed and added into an extruder to prepare the petroleum road asphalt material C4, and the properties of the petroleum road asphalt material are shown in the table 1.
Comparative example 2
The preparation method and the formula of the material are the same as those of the example 2, and the only difference is that no nano diamond powder material is added, so that the petroleum road asphalt material C5 is prepared.
Example 4 (test example)
The performance of the samples of the above examples and comparative examples was measured, and the results are shown in tables 2 and 3.
TABLE 1 composition of asphalt material for petroleum road (parts by weight)
Item Furfural extract oil Asphalt with petroleum base Nano diamond powder Stabilizer SBS DOA Bituminous material
Example 1 5 100 2 0.2 3 2 C1
Example 2 6 100 4 0.5 5 3 C2
Example 3 8 100 6 0.7 7 4 C3
Comparative example 1 6 100 4 0.5 5 3 C4
Comparative example 2 6 100 - 0.5 5 3 C5
TABLE 2 Main Properties of Petroleum road asphalt materials
Bituminous material Base asphalt C1 C2 C3 C4 C5
Penetration 25 deg.C/0.1 mm 51 54 56 59 57 65
Penetration index PI -0.8 1.2 1.5 1.4 0.6 -0.4
Softening point/. degree.C 49.1 84.5 87.8 87.2 80.3 69.5
Viscosity at 60 ℃ Pa.s 291.3 9632.4 9890.1 9543.3 8498.1 3846.3
Viscosity and toughness 6.6 37.3 39.1 38.2 28.2 15.3
Toughness of 4.1 26.4 27.2 26.7 22.1 10.4
Storage for 48h differential softening point/deg.C - 1.3 1.0 1.1 6.1 10.4
After TFOT penetration ratio (25 ℃)/% 65.8 78.2 83.5 76.1 67.2 61.9
TABLE 3 Rut factor | G |/sin δ (kPa) of asphalt material for petroleum road
Temperature/. degree.C Base asphalt C1 C2 C3 C4 C5
64 3.82 8.16 8.91 8.88 7.15 3.71
70 2.11 4.52 5.03 4.45 3.13 2.33
76 0.89 1.88 2.86 2.32 1.11 0.89
82 0.75 1.24 1.82 1.60 0.96 0.78
As can be seen from tables 2 and 3, the modified petroleum road asphalt material of the present invention has good comprehensive properties. The results of the property analysis of A1, A2 and A3 show that the softening point of the petroleum asphalt is higher than 80 ℃, the dynamic viscosity at 60 ℃ is high, and the high-temperature performance of the whole asphalt material is very excellent; the viscosity toughness and toughness of the asphalt are far higher than the index requirements of common modified asphalt and high-viscosity modified asphalt, which shows that the nano diamond powder, SBS and the like endow the asphalt material with super-strong tensile resistance and deformation resistance, and the high viscosity toughness shows that the asphalt material has very good wrapping property and binding power to stone, endows the pavement with good abrasion resistance, and can effectively prevent flying diseases of the pavement; the difference of the 48h segregation softening point of the modified asphalt material meets the requirement of the storage stability of the modified asphalt, because the effective permeation and crosslinking composite action are generated between the nano diamond powder and the SBS through the processes of swelling first and extruding later, the strength and the density of the SBS are increased, the SBS can be more stably existed in the asphalt without the layering phenomenon, and therefore, the two materials can be seen to generate a very good synergistic effect.
Comparing the properties of the C2 and C4 materials, it is clear that the modified asphalt material has poor stability and limited improvement of high temperature performance without first swelling treatment, because the nano diamond powder has nano size effect, is easy to agglomerate and precipitate, and cannot fully interact with substances such as SBS to exert synergistic effect. Comparing the properties of the C2 and C5 materials, it can be seen that the asphalt material has poor high-temperature performance when no nano diamond powder is added, single SBS can not effectively improve the high-temperature performance by one level, and the toughness are both low.
As can be seen from table 3, from the characterization result of the rutting factor | G |/sin δ, the nano-diamond powder composite material effectively improves the high-temperature rutting resistance of the material, mainly because the dispersibility and the aging resistance of the nanoparticles are better exerted by the processes of swelling first and extruding second.
The invention has good modification effect, simultaneously utilizes renewable resources, and is an environment-friendly petroleum road asphalt material used for pavements.

Claims (13)

1. The ultrathin wearing layer asphalt material is characterized by comprising the following raw material components in parts by weight:
matrix asphalt: 100 parts of (A);
rich in aromatic oil: 3-10 parts; preferably 5-8 parts;
2-8 parts of thermoplastic block copolymer, preferably 3-7 parts;
nano diamond powder: 1-7 parts, preferably 2-6 parts;
DOA: 1-5 parts, preferably 2-4 parts;
a stabilizer: 0.1 to 1 part, preferably 0.2 to 0.7 part.
2. The bituminous material according to claim 1, wherein said aromatic-rich oil is an aromatic-rich component derived from a raffinate oil of a lubricant base oil during solvent refining; the weight content of aromatic hydrocarbon in the aromatic-rich oil is 40-80%; preferably at least one of furfural refined extract oil and phenol refined extract oil.
3. The bituminous material of claim 1, wherein said thermoplastic block copolymer is a styrene-butadiene block copolymer; the styrene-butadiene block copolymer is a particle with a linear structure or a star-shaped structure, and the S/B ratio of the block is 20/80-40/60.
4. The asphalt material according to claim 1, wherein the nano-diamond powder has a particle size of 5 to 15 nm.
5. The bituminous material according to claim 1, wherein said DOA is a deoiled bitumen having a softening point of not less than 90 ℃ and a PI value of > 3.0.
6. The bituminous material according to claim 1, wherein said stabilizer is an element, compound or mixture thereof containing elemental sulphur.
7. A process for the preparation of a bituminous material according to any one of claims 1 to 6, characterized in that it comprises the following steps:
(1) shearing and dispersing the thermoplastic block copolymer in aromatic-rich oil for swelling development;
(2) mixing the nano-diamond powder with the substance obtained in the step (1) and forming;
(3) and (3) mixing and shearing the hot matrix asphalt, the particles obtained in the step (2) and DOA uniformly, adding a stabilizer, uniformly mixing, and continuously performing thermal development to obtain the ultrathin wearing layer asphalt material.
8. The method according to claim 7, wherein the conditions for the swelling development in step (1) are: the temperature is 80-120 ℃, and the preferred temperature is 90-110 ℃; the shearing speed is 3000-6000 rpm, preferably 4000-5000 rpm; the development time is 1-3 h, preferably 1.5-2.5 h.
9. The preparation method according to claim 7, wherein the forming in the step (2) is extrusion granulation by using a screw extruder, the screw extruder is a single screw extruder or a double screw extruder, preferably a double screw extruder, and the length-diameter ratio L/D is 30: 1-40: 1; the temperature of the screw extruder is controlled to be 120-160 ℃, and the rotating speed of the screw is 30-150 r/min.
10. The method according to claim 7, wherein the forming in step (2) is performed in eight temperature stages under the following conditions: the temperature of one section is 130-150 ℃; the second section is 135-155 ℃; the three sections are 140-160 ℃; the fourth section is 140-160 ℃; the fifth section is 150-160 ℃; the six sections are 150-160 ℃; the seven sections are 145-160 ℃; the eight sections are 150-160 ℃.
11. The preparation method according to claim 7, wherein the temperature of the base asphalt in the step (3) is 140-170 ℃, DOA is added, the mixture is uniformly stirred, the temperature is increased to 180-190 ℃, the mixture is sheared and stirred until a uniform system is formed, and then the stabilizer is added, stirred and developed.
12. The preparation method according to claim 11, wherein the shearing rotation speed is 1000 to 5000rpm, and the rotation speed for adding the stabilizer and stirring development is 500 to 1000 rpm.
13. Use of a bituminous material according to any one of claims 1 to 6 or prepared according to the method of claims 8 to 12, for the laying of ultra-thin wearing courses in the maintenance of bituminous pavements.
CN202011162922.4A 2020-10-27 2020-10-27 Ultrathin wearing layer asphalt material and preparation and application thereof Active CN114479485B (en)

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