A stress luminescence type chemical anchoring fog seal material with blackening and wear resistance functions and a construction method thereof

Abstract

The application discloses a stress luminescence type chemical anchoring fog seal layer material with blackening and wear resistance functions and a construction method thereof, and relates to the technical field of pavement engineering pre-maintenance. The fog seal layer material is prepared from near-neutral non-ionic emulsified asphalt as a stable reaction matrix, high-carbon black content activated latex slurry is introduced to realize blackening and network enhancement of the asphalt pavement, the interface bonding and mechanical-optical response triggered by traffic load are realized through core-shell structure stress luminescence particles, and the interface chemical anchoring reaction is triggered when the demulsification of the interface catalytic anti-skid aggregate. The components play a synergistic effect in the storage, construction and service stages, and finally form a reinforced seal layer with stress luminescence visual guidance, high blackness, high anti-skid and long-term durability functions on the pavement, and the application is especially suitable for improving the road traffic safety in dark environments such as tunnels and road sections without street lamps.

Description

Technical Field

[0001] This invention relates to the field of pavement pre-maintenance technology, and in particular to a stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions and its construction method. Background Technology

[0002] With the continuous growth of road traffic volume and the increasing demand for preventative maintenance, fog seal technology has been widely used due to its advantages such as convenient construction, low cost, and high efficiency. Traditional fog seal materials mainly focus on sealing micro-cracks, preventing water infiltration, and delaying asphalt aging, emphasizing the restoration and maintenance of pavement durability. Although they can restore the appearance of the pavement to a certain extent, their blackening effect is often not lasting, and their function is relatively limited. However, with the popularization of green safety and intelligent transportation concepts, single functions are no longer sufficient to meet the high-performance requirements of current pavement materials, especially in areas with poor visibility such as unlit road sections at night, tunnels, and sharp bends. There is an urgent need for a pavement material that can automatically emit light when vehicles or pedestrians pass by, providing early, dynamic warnings to drivers of vehicles behind or oncoming vehicles, thereby improving the level of active safety.

[0003] While existing functional fog seal technologies attempt to incorporate reflective or photoluminescent materials to enhance nighttime warning and aesthetic effects, significant shortcomings remain: First, reflective materials rely on external light sources, while photoluminescent materials depend on light energy reserves. Their performance deteriorates rapidly in tunnels, during rainy weather, or under continuous low light conditions, making it difficult to achieve continuous and reliable active warnings independent of external light energy. Second, functional components and base materials are mostly physically mixed, lacking synergistic enhancement effects, leading to decreased wear resistance, skid resistance, and durability. Furthermore, the materials struggle to maintain a significant blackening effect over the long term. Third, functional materials are susceptible to the strong acid and alkaline environment of emulsified asphalt, partially failing before storage or application, affecting long-term performance stability. In addition, traditional fog seals rely on physical adhesion to the road surface, making them prone to peeling under traffic and moisture erosion. Repairing them after failure is complex and costly.

[0004] Therefore, there is an urgent need to develop a new type of fog seal material that can trigger active luminescence warnings under traffic loads in low-light environments, while also taking into account multiple functions such as blackening and anti-skid properties as well as long-term durability. This will enable the synergistic effect between functional components, strengthen the chemical bond with the road surface, and build a comprehensive maintenance system that can be easily updated. Summary of the Invention

[0005] The purpose of this invention is to provide a stress-luminescent chemically anchored fog seal material with blackening and wear-resistant functions, and its construction method, to solve the problems existing in the prior art. The fog seal material of this invention uses near-neutral nonionic emulsified asphalt as a stable reactive matrix. It achieves asphalt pavement blackening and network reinforcement by introducing activated latex with high carbon black content. It achieves interfacial bonding and a mechanical-optical response triggered by traffic loads through core-shell structured stress-luminescent particles, and triggers an interfacial chemical anchoring reaction through interfacial catalytic anti-skid aggregates during demulsification. The components exert a synergistic effect during storage, construction, and service, ultimately forming a reinforced seal layer on the road surface with stress-luminescent visual guidance, high blackness, high anti-skid properties, and long-term durability. It is particularly suitable for improving road traffic safety in low-light environments such as tunnels and sections without streetlights.

[0006] To achieve the above objectives, the present invention provides the following solution:

[0007] One of the technical solutions of the present invention is a stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions. The raw materials include the following components by mass: 5-15 parts of high carbon black content activated latex, 5-10 parts of core-shell structure stress-luminescent particles, 15-30 parts of interface catalytic anti-skid aggregate, and 100 parts of near-neutral nonionic emulsified asphalt.

[0008] The high carbon black content activated adhesive latex is a stable latex formed by dispersing high carbon black content activated adhesive in an aqueous medium.

[0009] The core-shell structured stress-luminescent particles consist of a stress-luminescent particle core, an epoxy resin shell, and functional groups grafted onto the surface of the epoxy resin shell.

[0010] The interface-catalyzed anti-slip aggregate is a hard aggregate with a surface modified with a silane coupling agent and a catalyst.

[0011] The near-neutral nonionic emulsified asphalt is an asphalt emulsion with a pH value of 6.0-8.0, which is stable due to steric hindrance.

[0012] In the stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions of the present invention, near-neutral nonionic emulsified asphalt, high carbon black content activated latex, core-shell structured stress-luminescent particles, and interface-catalyzed anti-skid aggregate together constitute a functionally synergistic system. The near-neutral nonionic emulsified asphalt provides a chemically stable binder matrix, ensuring the stability of the outer functional groups of the core-shell structured stress-luminescent particles and the interface-catalyzed anti-skid aggregate during storage and their activity during construction. During the road surface demulsification process, the interface-catalyzed anti-skid aggregate creates an acidic microenvironment at the interface, synergistically promoting the hydrolysis and condensation of silanes on its surface, achieving chemical bonding with asphalt and aggregate. During the road surface forming stage, the interface-catalyzed anti-skid aggregate, high carbon black content activated latex, and core-shell structured stress-luminescent particles work synergistically to enable the fog seal material to simultaneously achieve the comprehensive functions of stress-luminescent visual guidance, high blackness color restoration, high anti-skid safety assurance, and long-lasting chemical anchoring durability.

[0013] Further, the preparation steps of the high carbon black content activated rubber latex include: heating and mixing waste tire rubber powder, softener and regeneration activator to obtain a mixture; heating and extruding the mixture to obtain an extruded material; pressing the extruded material to obtain a high carbon black content activated rubber; mixing the high carbon black content activated rubber with water, emulsifier and polymer stabilizer, and shearing and dispersing to obtain the high carbon black content activated rubber latex.

[0014] High carbon black content activated latex can not only utilize the high carbon black content in waste tire rubber powder to provide a high-contrast dark background for stress luminescence and enhance the visibility of luminescence, but the active functional groups generated after activation can also form a cross-linking network with the asphalt matrix to achieve interface strengthening.

[0015] Optionally, the waste tire rubber powder has a particle size of 40-80 mesh and a carbon black content of 25-40 wt%.

[0016] Optionally, the softener includes aromatic oils.

[0017] Optionally, the regeneration activator includes 420 regeneration activator.

[0018] Optionally, the mass ratio of the waste tire rubber powder, softener, and regeneration activator is 100:3-5:1.5-2.5.

[0019] Optionally, the heating and mixing temperature is 60-70°C, and the time is 5-10 minutes.

[0020] Optionally, the temperature of the heated extrusion is 180-205℃, and the extrusion rate is 2-4 kg / min; the heated extrusion is carried out in a twin-screw extruder.

[0021] Optionally, the pressing temperature is 65-70℃, and the number of pressing cycles is 5-7; the pressing is carried out through refining rollers, that is, the extruded material is repeatedly pressed through refining rollers at 65-70℃ 5-7 times.

[0022] Optionally, the emulsifier includes at least one of fatty alcohol polyoxyethylene ether and block polyether surfactants.

[0023] Optionally, the polymeric stabilizer includes at least one of hydroxyethyl cellulose and xanthan gum.

[0024] Optionally, the mass ratio of the high carbon black content activated adhesive to water, emulsifier, and polymeric stabilizer is 30-50:45-65:1-3:0.2-1.0.

[0025] Optionally, the shear dispersion rotation speed is 2000-5000 rpm, and the time is 20-40 min.

[0026] Optionally, the carbon black content in the high carbon black content activated adhesive is 25-40 wt%.

[0027] Optionally, the carbon black content in the high carbon black content activated latex is 10-20 wt%.

[0028] Further, the preparation steps of the core-shell structured stress-luminescent particles include: mixing stress-luminescent material particles, anhydrous ethanol, and KH-560 (a type of silane coupling agent), heating and refluxing to obtain surface-activated stress-luminescent particles; mixing the surface-activated stress-luminescent particles with epoxy resin, diluent, and curing agent, stirring and premixing to obtain a composite slurry; granulating the composite slurry by spray drying to obtain core-shell particles (with stress-luminescent material particles as the core and epoxy resin as the shell); dispersing the core-shell particles in toluene to obtain a suspension; mixing the suspension with a silane hydrolysate prepared from KH-550 (a type of silane coupling agent), heating and stirring to obtain the core-shell structured stress-luminescent particles (specifically, functionalized luminescent core-shell particles with silanol functional groups (-Si-OH) grafted onto their surface).

[0029] Furthermore, the core-shell structured stress-luminescent particles have a particle size of 20-150 μm and a Mohs hardness of not less than 6; their structure is as follows: a stress-luminescent material particle with a particle size of 10-100 μm serves as the core, and is surrounded by an epoxy resin shell with a thickness of 5-25 μm. The epoxy resin shell is covalently grafted with an aminopropylsilane molecular chain, the end of which is an active silanol group.

[0030] This core-shell structured stress-luminescent particle utilizes a three-layer "core-shell-functional group" design to achieve long-term stable luminescence performance while enhancing interfacial bonding. The luminescent core is surface-activated using the silane coupling agent KH-560, strengthening the bond between the core and the epoxy resin shell. The rigid epoxy resin shell effectively isolates the luminescent core from water and oxygen corrosion. The silane functional groups grafted onto the shell enable strong chemical bonding with the asphalt matrix and aggregates, significantly improving wear resistance and peel resistance. Its core function is that when vehicles or pedestrians pass, the mechanical stress applied to the road surface excites the particle to emit light, providing early, dynamic warnings to drivers of vehicles not yet in the area about the presence of road users in low-light conditions.

[0031] The reason for using different silane coupling agents when performing surface activation treatment on the luminescent material core and when grafting functional groups onto the core-shell particles is that the core and epoxy shell are rigidly covalently bonded, requiring the epoxy groups of KH-560 to achieve "homogeneous bonding" with the epoxy resin; while the outer shell of the particles and the asphalt are polar chemically bonded, requiring the amino groups of KH-550 to achieve "strong gripping" with the acidic components of the asphalt. Reversing the order or using a single silane will result in weak core coating (easily peeling off the outer shell) or weak bonding between the outer shell and the asphalt (easily detaching particles), neither of which can simultaneously meet the two progressively higher core requirements of "firm coating" and "tight adhesion".

[0032] Optionally, the stress-luminescent material particles comprise SrAl2O4:Eu 2+ Particles or SrAl2O4:Dy 3+ Particles.

[0033] Optionally, before mixing the stress-luminescent material particles, anhydrous ethanol, and KH-560, the process further includes a step of vacuum drying the stress-luminescent material particles at 50-70°C for 2-6 hours.

[0034] Optionally, the mass of KH-560 is 1-3% of the mass of the stress-luminescent material particles.

[0035] Optionally, the temperature of the heating reflux reaction is 50-80℃, and the time is 2-6h.

[0036] Optionally, the epoxy resin includes bisphenol A type epoxy resin E-51.

[0037] Optionally, the diluent includes phenyl glycidyl ether.

[0038] Optionally, the curing agent includes methyltetrahydrophthalic anhydride.

[0039] Optionally, the mass ratio of the surface-activated stress-luminescent particles to epoxy resin, diluent, and curing agent is 100:80-120:10-20:60-80.

[0040] Optionally, the stirring and premixing speed is 1000-2500 rpm and the time is 20-40 min.

[0041] Optionally, the inlet temperature of the spray drying molding is 60-80℃, and the outlet temperature is 40-60℃.

[0042] Optionally, the mass concentration of core-shell particles in the suspension is 15-25%.

[0043] Optionally, the preparation steps of the silane hydrolysate include: mixing KH-550, water and anhydrous ethanol at a mass ratio of 1:1:10-12, adjusting the pH to 4-5 with acetic acid, and pre-hydrolyzing at 20-40℃ for 30-60 min to obtain the silane hydrolysate.

[0044] Optionally, the mass ratio of the core-shell particles in the suspension to the KH-550 in the silane hydrolysate is 10-15:1.

[0045] Optionally, mixing the suspension with the silane hydrolysate prepared from KH-550 includes adding the silane hydrolysate dropwise to the suspension.

[0046] Optionally, the heating and stirring reaction is carried out at a temperature of 50-70°C for 2-3 hours.

[0047] Optionally, after the heating and stirring are completed, the process further includes the steps of filtration, washing, and drying; the drying temperature is 60-80℃ and the time is 5-6 hours.

[0048] Furthermore, the preparation steps of the interface-catalyzed anti-slip aggregate include: mixing a silane coupling agent, an organometallic catalyst, and a solvent to obtain a composite treatment liquid; applying the composite treatment liquid to the surface of the hard aggregate by spraying; then heating and curing the mixture; and finally cooling to obtain the interface-catalyzed anti-slip aggregate.

[0049] This interfacial catalytic antiskid aggregate surface anchoring organic metal catalyst and silane coupling agent can provide durable antiskid resistance through its hard surface during the road demulsification process. It can also release the activity of the organic metal catalyst, drive the silane on the aggregate surface to hydrolyze and condense with the old pavement, form a strong chemical anchor, solve the problem of weak interlayer adhesion, and at the same time catalyze the cross-linking reaction of other components in the system, enhance the overall cohesion of the material.

[0050] Optionally, the silane coupling agent includes at least one of KH-550 and Si-69.

[0051] Optionally, the organometallic catalyst includes at least one of zinc acetylacetonate and tin acetylacetonate.

[0052] Optionally, the solvent includes at least one of anhydrous ethanol and isopropanol.

[0053] Optionally, the mass ratio of the silane coupling agent, organometallic catalyst, and solvent is 1-5:0.1-1:20-50.

[0054] Optionally, the hard aggregate includes fine sand with a particle size of 0.1-0.5 mm.

[0055] Optionally, the mass ratio of the hard aggregate to the composite treatment liquid is 100:5-10.

[0056] Optionally, the heating and stirring temperature is 80-100℃, and the time is 20-40 minutes.

[0057] Optionally, the heating curing temperature is 80-100℃ and the time is 1-2 hours.

[0058] Optionally, applying the composite treatment liquid to the surface of hard aggregate by spraying includes: applying the composite treatment liquid uniformly to the surface of hard aggregate by spraying within 10-15 minutes under continuous stirring and heating at 100°C, and continuing stirring and heating to make the total treatment time reach 30 minutes.

[0059] Furthermore, the preparation steps of the near-neutral nonionic emulsified asphalt include: mixing water, nonionic emulsifier and stabilizer, heating and stirring to obtain an aqueous phase; mixing the molten asphalt phase with the aqueous phase and emulsifying to obtain the near-neutral nonionic emulsified asphalt.

[0060] Near-neutral nonionic emulsified asphalt is the chemically stable cornerstone of the entire system. Its near-neutral (pH=6.0-8.0) properties provide a mild storage environment for acid- and alkali-sensitive stress luminescent materials and silane coupling agents, preventing premature failure of functional components. At the same time, its nonionic emulsifier forms a solvated polymer chain protective layer on the surface of asphalt droplets, which, through steric hindrance, ensures excellent compatibility and storage stability with each functional component.

[0061] Optionally, the nonionic emulsifier includes at least one of block polyether surfactants and sorbitan ester surfactants.

[0062] Optionally, the block polyether surfactant includes polyether-modified polysiloxane.

[0063] Optionally, the stabilizer includes at least one of hydroxyethyl cellulose and calcium chloride.

[0064] Optionally, the mass ratio of water, nonionic emulsifier and stabilizer is 97.5-94:2-4:0.5-2.

[0065] Optionally, the heating and stirring temperature is 55-65°C.

[0066] Optionally, the mass ratio of the molten bitumen phase to the aqueous phase is 50-70:40.

[0067] Optionally, the emulsification is carried out by a colloid mill, the outlet temperature of which is 85-98°C.

[0068] The second technical solution of the present invention: A method for preparing the above-mentioned stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions, comprising the following steps: mixing high carbon black content activated latex with near-neutral nonionic emulsified asphalt under low-speed shearing, then adding core-shell structured stress-luminescent particles, and continuing to mix under low-speed shearing to obtain a base liquid; mixing the base liquid with the interface catalytic anti-skid aggregate at low speed (this step is carried out on-site before construction spraying) to obtain the stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions.

[0069] Optionally, the rotational speed of the low-speed shearing is 1000-1500 rpm.

[0070] Optionally, the speed of the medium-low speed mixing is 300-500 rpm, and the time is 2-5 min.

[0071] The third technical solution of the present invention: a construction method for the above-mentioned stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions, comprising the following steps: pre-treating the road surface to be constructed; uniformly spraying the stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions onto the pre-treated road surface to be constructed; and curing under natural conditions after spraying.

[0072] Preferably, the construction method includes the following more specific steps:

[0073] S1. Road surface pretreatment: Clean and dry the road surface to be constructed to ensure that the road surface is free of dust, oil and moisture.

[0074] S2. Material preparation: Prepare the fog sealing material on-site according to the above preparation method;

[0075] S3. Material Spraying: Using specialized spraying equipment, evenly spray the fog seal material prepared in step S2 onto the pretreated road surface to be constructed, controlling the spraying rate to be 0.8-1.5 kg / m². 2 ;

[0076] S4. Curing and Shaping: After spraying, cure under natural conditions for 2-5 hours (the specific time depends on the environmental conditions such as temperature and humidity on site). After the emulsion breaks down, the water evaporates, the film turns black and the surface dries, traffic can be opened.

[0077] When the fog seal layer fails due to long-term use, steps S2-S4 can be repeated directly on the old layer surface to spray new fog seal material, thereby achieving rapid restoration and renewal of function.

[0078] The fog seal layer of the present invention adopts a construction process of first preparing the base liquid, adding aggregates on site, spraying and then curing to form the shape, and supports direct repaving of the old layer.

[0079] This invention provides a stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions, composed of four components: near-neutral nonionic emulsified asphalt, high-carbon-black-content activated latex, core-shell structured stress-luminescent particles, and interfacial catalytic anti-skid aggregate. The near-neutral nonionic emulsified asphalt forms a chemically stable binder matrix, providing a stable storage environment for the silanol functional groups on the surface of the acid- and alkali-sensitive core-shell structured stress-luminescent particles and the silane coupling agent on the surface of the interfacial catalytic anti-skid aggregate, preventing premature hydrolysis and failure. During the demulsification process, the interfacial catalytic anti-skid aggregate releases an organometallic catalyst, creating an acidic microenvironment at the interface. This microenvironment simultaneously activates three synergistic reaction pathways: activating the hydrolysis and condensation of silanes on the aggregate's own surface, achieving chemical anchoring of the fog seal to the existing pavement; catalyzing the high-carbon-black-content activated latex... The active functional groups in the latex crosslink with the asphalt matrix, enhancing the material's cohesion; and activate the silanol functional groups on the surface of the core-shell structure stress-luminescent particles, causing them to co-condense with the silanes on the asphalt matrix and aggregate surface, firmly fixing the luminescent particles; at the same time, the high carbon black content activated latex forms a reinforcing network in the system, which not only enhances the pavement's blackness and aesthetics, but also provides a high-contrast dark background for the core-shell structure stress-luminescent particles to enhance their luminescence visibility. Its active functional groups also participate in the crosslinking reaction, jointly improving the material's toughness and wear resistance; through the synergistic effect of the four components in ensuring storage stability, activating the reaction during construction, and realizing the functions in the molding stage, the fog seal material ultimately achieves the comprehensive functions of stress-luminescent visual guidance, high blackness color restoration, high anti-skid safety assurance, and long-term durability of chemical anchoring on the road surface.

[0080] The stress-luminescent chemical anchoring fog seal material of the present invention with blackening and wear-resistant functions is suitable for tunnels, road sections without external lighting, curves or pedestrian crossings; when vehicles or pedestrians pass by, the mechanical stress applied by it can excite the core-shell structure stress-luminescent particles to emit light, thereby providing drivers of distant vehicles that have not entered the area with an early dynamic warning of the presence of traffic participants ahead.

[0081] The present invention discloses the following technical effects:

[0082] (1) This invention achieves strong interlayer bonding and long-term functional stability through chemical anchoring and internal cross-linking mechanisms. Specifically, this invention enhances the interfacial bonding and internal strength of the material through chemical reactions. At the interlayer interface, the interfacial catalytic anti-skid aggregate can catalyze the chemical bonding between the silane coupling agent and the old pavement during the demulsification process, forming a strong chemical anchor and effectively preventing interlayer delamination. Inside the fog seal material, this process simultaneously promotes the formation of a stable three-dimensional cross-linked network between the latex, stress-emitting particles, and asphalt matrix, greatly improving the cohesive strength and integrity of the material, firmly fixing the functional components, thereby significantly improving erosion and wear resistance, and ensuring the long-term effectiveness of various functions.

[0083] (2) This invention comprehensively improves road performance and safety through the efficient synergy of multifunctional components. The high-carbon-black content activated latex provides a high-contrast dark background for the core-shell structure stress-luminescent particles, significantly enhancing their nighttime luminescence visibility. Simultaneously, its self-formed reinforcing network synergistically enhances the overall wear resistance and durability of the material with the asphalt matrix. The core-shell structure stress-luminescent particles participate in cross-linking through surface functional groups, maintaining luminescence performance while strengthening interfacial bonding. In low-light environments, they provide early warning to drivers through stress-induced luminescence. Meanwhile, the interfacial catalytic anti-skid aggregate, while providing durable anti-skid performance, synergistically enhances the long-term stability and firmness of the entire fog seal layer through its triggered interfacial chemical anchoring effect and internal cross-linking network. The components mutually promote and complement each other, forming a highly efficient, stable, and multi-layered safety-assured synergistic system.

[0084] (3) This invention effectively improves the inherent disadvantages of waste tire rubber powder, such as surface inertness, poor compatibility with asphalt, and easy agglomeration, by activating the waste tire rubber powder. The resulting activated latex with high carbon black content not only retains the blackening and anti-aging advantages of carbon black in the rubber powder, but also can chemically crosslink with the asphalt matrix due to the introduction of active functional groups on its surface. Thus, it transforms from an inert filler material into an active reinforcing component, significantly improving the toughness, wear resistance, and durability of the material, and realizing the high-value-added resource utilization of waste tire rubber powder. In addition, based on the system design of this chemical activity, a firm bond is achieved between the fog seal layer and the old pavement through a similar interface anchoring and crosslinking mechanism. Therefore, after the functional layer fails, it can be directly repaved in situ without milling, realizing rapid functional restoration and long-term maintenance. Attached Figure Description

[0085] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0086] Figure 1 This is a schematic diagram of the preparation process of the stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions in this invention.

[0087] Figure 2 This is a schematic diagram of the core-shell structured stress-luminescent particles in this invention. Detailed Implementation

[0088] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0089] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0090] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0091] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0092] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0093] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0094] In the following embodiments and comparative examples of the present invention, room temperature refers specifically to 20-30°C.

[0095] The following embodiments of the present invention illustrate the preparation process of a stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions. Figure 1 As shown.

[0096] All raw materials used in the following examples and comparative examples of this invention are commercially available products. Waste tire rubber powder was purchased from Shandong Xinmingsheng Materials Technology Co., Ltd.; aromatic oil and 420 regeneration activator were purchased from Shanghai Huayi Group Huayuan Chemical Co., Ltd.; lauryl alcohol polyoxyethylene ether was purchased from Jiangsu Haian Petrochemical Plant; hydroxyethyl cellulose was purchased from Renqiu Shuangcheng Chemical Products Factory; silane coupling agent KH-560 and silane coupling agent KH-550 (γ-aminopropyltriethoxysilane) were purchased from Guangzhou Yihuisheng Chemical Co., Ltd.; bisphenol A epoxy resin E-51 was purchased from Shandong Suihua Biotechnology Co., Ltd.; phenyl glycidyl ether was purchased from Maclean's Co., Ltd.; methyltetrahydrophthalic anhydride was purchased from Shandong Moore Chemical Co., Ltd.; zinc acetylacetone was purchased from Shanghai Mairui Biochemical Technology Co., Ltd.; BE-3X asphalt emulsifier was purchased from Xi'an Huaze Road Materials Co., Ltd.; and polyether-modified polysiloxane (model 87) was purchased from Shanghai Koraman Reagent Co., Ltd.

[0097] Example 1

[0098] The preparation steps for activated latex with high carbon black content are as follows:

[0099] S1. Preparation of high carbon black content activated rubber: 100 parts by weight of 40 mesh dry waste tire rubber powder with a carbon black content of 32 wt%, 4 parts of aromatic oil softener and 2 parts of 420 regeneration activator are mixed at 60℃ for 10 min; then the mixture is reacted (i.e. extruded) at 200℃ through a twin-screw extruder at an extrusion rate of 3 kg / min; finally, the extruded material is cooled and screened through a crusher and granulator with a screen plate diameter of 8-10 mm (to separate incompletely reacted, hard rubber powder lumps or scorched rubber particles due to excessive temperature through the screen), and then repeatedly pressed 6 times through a refining roller at 70℃. After sheeting and cooling, a high carbon black content activated rubber with a carbon black content of 30.2 wt% is obtained.

[0100] S2. Preparation of latex paste: High carbon black content activated adhesive, water, emulsifier lauryl alcohol polyoxyethylene ether and polymer stabilizer hydroxyethyl cellulose are mixed at a mass ratio of 40:50:2:0.5 and sheared and dispersed at 3000 rpm for 30 min to obtain a high carbon black content activated latex paste with a solid content of 43.2%, of which carbon black accounts for 13.1% of the total mass of the latex paste.

[0101] Example 2

[0102] The preparation steps of core-shell structured stress-luminescent particles are as follows:

[0103] S1. Core pretreatment: Stress-luminescent material particles aluminate phosphor (SrAl2O4:Eu) are pretreated with aluminate phosphors. 2+ The average particle size (80 nm) was vacuum dried at 60 °C for 4 h, and then dispersed in anhydrous ethanol at a mass ratio of 1:6. Silane coupling agent KH-560, accounting for 2% of the mass of the stress luminescent material, was added, and the mixture was refluxed and stirred at 70 °C for 2 h. After centrifugation, washing and drying, surface-activated stress luminescent particles were obtained.

[0104] S2. Epoxy Resin Coating: Surface-activated stress-luminescent particles, bisphenol A type epoxy resin E-51, diluent phenyl glycidyl ether, and curing agent methyltetrahydrophthalic anhydride are mixed at a mass ratio of 100:80:10:60 and premixed in a high-speed disperser at a rate of 2000 rpm for 30 minutes to form a uniform composite slurry. Subsequently, the composite slurry is spray-dried and shaped using a spray granulation device at an inlet temperature of 80℃ and an outlet temperature of 50℃ to obtain core-shell particles with stress-luminescent material as the core and epoxy resin as the shell.

[0105] S3. Surface Functionalization of Particles: Core-shell particles were dispersed in toluene solvent to prepare a suspension with a mass concentration of 20%. Separately, silane coupling agent KH-550, deionized water, and anhydrous ethanol were mixed at a mass ratio of 1:1:10, and the pH was adjusted to 4.5 with acetic acid. The mixture was pre-hydrolyzed at 30°C for 40 min to obtain a silane hydrolysate. The silane hydrolysate was added dropwise to the suspension, with the mass ratio of core-shell particles to silane coupling agent KH-550 being 10:1. The mixture was mechanically stirred at 65°C for 2 h. After the reaction, the particles were filtered, washed three times with anhydrous ethanol, and vacuum dried at 70°C for 6 h to finally obtain functionalized luminescent epoxy particles with silanol functional groups grafted onto their surface, i.e., core-shell structured stress-luminescent particles (structural schematic diagram shown). Figure 2 As shown, its average particle size is 95 μm, the thickness of the epoxy resin shell is 15 μm, and its Mohs hardness is 7.2.

[0106] Example 3

[0107] The preparation steps of interfacial catalytic anti-skid aggregate are as follows:

[0108] A composite treatment solution was prepared by uniformly mixing silane coupling agent KH-550, organometallic catalyst zinc acetylacetonate, and anhydrous ethanol at a mass ratio of 2:0.2:30. The composite treatment solution was then applied uniformly to the surface of dry fine sand (particle size 0.1-0.5 mm, with a gradation of >0.3 mm particles accounting for 55 wt% and <0.15 mm particles accounting for 8 wt%) at a mass ratio of 100:10 to the composite treatment solution via spraying, under continuous stirring and heating at 100°C, within 10-15 minutes. Stirring and heating continued until the total treatment time reached 30 minutes. The treated fine sand (i.e., the mixture) was then cured at 90°C for 2 hours and subsequently cooled to room temperature to obtain interfacial catalytic functionalized anti-slip fine sand, which is the interfacial catalytic type anti-slip aggregate.

[0109] Example 4

[0110] The preparation steps for near-neutral nonionic emulsified asphalt are as follows:

[0111] S1. Preparation of aqueous phase: Water, polyether-modified polysiloxane and ethyl cellulose are mixed in a mass ratio of 97.5:1.5:1 and heated and stirred at 60°C until completely dissolved to obtain a homogeneous aqueous phase;

[0112] S2. Emulsification: Heat No. 70 base asphalt to a molten state at 150℃, and then emulsify it together with the freshly prepared hot water phase at a mass ratio of 60:40 through a colloid mill, controlling the outlet temperature of the colloid mill to 90℃.

[0113] S3. Cooling and conditioning: Cool the emulsified product to room temperature to obtain near-neutral nonionic emulsified asphalt (pH=7.2).

[0114] Example 5

[0115] The preparation steps for a stress-luminescent chemically anchored fog sealant material with blackening and wear-resistant properties are as follows:

[0116] S1. Preparation of base liquid: By mass, 10 parts of high carbon black content activated latex (prepared in Example 1) and 100 parts of near neutral nonionic emulsified asphalt (prepared in Example 4) were mixed under low-speed shear (speed of rotation of 1000 rpm) for 5 min, and then 5 parts of core-shell structure stress luminescent particles (prepared in Example 2) were added, and the mixture was continued to be mixed under low-speed shear for 5 min to obtain multifunctional emulsified asphalt base liquid;

[0117] S2. On-site compounding: Before construction spraying, mix 15 parts of interface catalytic anti-skid aggregate (prepared in Example 3) with the multifunctional emulsified asphalt base liquid obtained in step S1 at low speed (700 rpm) for 3 minutes in a mixing equipment to obtain stress luminescent chemical anchoring fog seal material with blackening and wear resistance functions.

[0118] Comparative Example 1

[0119] Same as Example 5, except that the high carbon black content activated latex is replaced with unactivated high carbon black content latex. The preparation steps of the unactivated high carbon black content latex are as follows: dry waste tire rubber powder with 40 mesh and carbon black content of 32wt%, water, emulsifier lauryl alcohol polyoxyethylene ether and polymer stabilizer hydroxyethyl cellulose are mixed in a mass ratio of 40:50:2:0.5 and sheared and dispersed at 3000rpm for 30min to obtain high carbon black content latex.

[0120] Comparative Example 2

[0121] Same as Example 5, except that the core-shell structured stress-emitting particles are replaced with stress-emitting material particles (aluminate phosphors based on SrAl2O4:Eu) by mass. 2+ ).

[0122] Comparative Example 3

[0123] Same as Example 5, except that the near-neutral nonionic emulsified asphalt obtained in Example 4 is replaced by an emulsified asphalt prepared with commercially available BE-3X asphalt emulsifier. The preparation method of this emulsified asphalt is the same as in Example 4, except that the block polyether surfactant is replaced by an BE-3X asphalt emulsifier.

[0124] Comparative Example 4

[0125] Same as Example 5, except that the interface catalytic anti-slip aggregate is replaced with hard aggregate fine sand.

[0126] Comparative Example 5

[0127] Same as Example 5, except that the core-shell structured stress-luminescent particles obtained in Example 2 are replaced with the unfunctionalized core-shell particles obtained in step S2 of Example 2.

[0128] Comparative Example 6

[0129] Same as Example 5, except that the core-shell structured stress-luminescent particles prepared in Example 2 are replaced with core-shell structured stress-luminescent particles with different stages of silane coupling agent application. The preparation method of the core-shell structured stress-luminescent particles is the same as in Example 2, except that the silane coupling agent KH-560 used in step S1 is replaced with the silane coupling agent KH-550 used in step S3. That is, the KH-560 used in step S1 is replaced with KH550 by an equal mass, and the KH-550 used in step S3 is replaced with KH-560 by an equal mass.

[0130] Comparative Example 7

[0131] Same as Example 5, except that the same mass of the interfacial catalytic anti-slip aggregate prepared in Example 3 is replaced with an anti-slip aggregate without organometallic catalyst. The preparation method of the anti-slip aggregate is the same as in Example 3, except that the same mass of the organometallic catalyst zinc acetylacetone is replaced with silane coupling agent KH-550 in the preparation process. That is, silane coupling agent KH-550 and anhydrous ethanol are uniformly mixed at a mass ratio of 2.2:30 to obtain a composite treatment solution.

[0132] Test Example 1

[0133] To verify the actual effect of the fog seal material, a series of performance tests were conducted on the fog seal materials prepared in Example 5 and Comparative Examples 1-7. Specimen preparation fully simulated actual construction and maintenance conditions: First, AC-13 asphalt mixture base course specimens (300mm × 300mm) were formed using a standard rutting slab mold to simulate real asphalt pavement. After cleaning and drying the base course specimens, the fog seal material prepared in the examples or comparative examples was evenly sprayed onto the base course surface using a small laboratory-grade spraying device. The material dosage was strictly controlled to be 1.0 kg / m² using a precise weighing method. 2After spraying, the specimens were horizontally cured at room temperature (25℃) for 4 hours until they demulsified and formed, and then directly used for subsequent performance tests. Based on the specimens prepared above, the performance tests were conducted according to the following scheme: First, the apparent blackness of the samples was measured using a spectrophotometer to evaluate its blackening effect on restoring the appearance of asphalt pavement; then, in a darkroom environment, a pressure testing machine was used to apply a fixed pressure (10kN) to the specimens, and a luminance meter was used to simultaneously measure the initial luminance L0 of the pressure area. Next, a wet abrasion tester was used to perform quantitative abrasion treatment on the specimens (using a standard abrasion head, applying a total load of 4.5kg, and acting for 5min) to simulate wear under actual traffic loads. After abrasion, the remaining luminance L1 of the worn area of ​​the specimens was measured again in a darkroom under the same pressure conditions. The protective effect of the core-shell structure on stress-luminescent material particles was quantitatively evaluated by comparing the brightness retention rate before and after wear. The brightness retention rate was calculated as: Brightness retention rate = (L1 / L0) × 100%. Simultaneously, according to the standard "Pendulum Friction Coefficient Tester" (JT / T 763-2017), the pendulum value of the specimens in the wear area was measured to evaluate the anti-skid performance of the fog seal layer. Finally, destructive mechanical property tests were conducted. According to the "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering," the wear value of another set of parallel specimens was measured through a wet wheel abrasion test to quantitatively evaluate its wear resistance. Furthermore, the adhesion between the fog seal layer and the base layer was evaluated through a pull-out test (25℃). A pull-out head was bonded to the surface of the fog seal layer using high-strength epoxy resin and stretched vertically at a constant rate of 1 mm / min until failure. The pull-out strength was recorded. The test results are shown in Table 1.

[0134] Table 1 Comparison of Fog Sealing Material Performance

[0135]

[0136] Test results show that the fog seal material prepared by this invention (Example 5) exhibits significant advantages in key indicators such as apparent blackness, brightness retention, anti-skid performance, wear resistance, and pull-out strength. Specifically, comparing Example 5 with Comparative Example 1, it can be found that the activated latex, through surface-active treatment, uniformly disperses nano-carbon black and forms a stable nano-carbon black network in asphalt, increasing the blackness of asphalt pavement by 10.1% and improving friction resistance by 20.1%. Comparing Example 5, Comparative Example 2, Comparative Example 5, and Comparative Example 6, it can be found that the core-shell structured stress-luminescent particles, through the synergistic effect of epoxy resin coating and KH-560 surface silane modification, form a strong covalent anchoring layer on the surface of the luminescent core, thereby effectively blocking water vapor erosion. At the same time, the core-shell structured stress-luminescent particles grafted onto the KH-550 surface have a strong covalent anchoring layer on the surface of the asphalt matrix. The interfacial bonding was significantly enhanced, and the combined effect of the two factors effectively improved the brightness retention and wear resistance. Comparing Example 5, Comparative Example 3, and Comparative Example 4, it was found that the near-neutral emulsified asphalt provided a stable chemical environment for the functional components. Combined with the interfacial catalytic anti-skid aggregate, chemical anchoring was formed through catalytic silane crosslinking, resulting in an increase in anti-skid performance of 18.5% (compared to Comparative Example 3) and 10.3% (compared to Comparative Example 4), and an increase in friction resistance of 35.0% (compared to Comparative Example 4) and 15.3% (compared to Comparative Example 3), respectively. Pull-out strength test data showed that the interlayer bond strength of Example 5 reached 8.2 MPa, significantly higher than Comparative Example 4 and Comparative Example 7. This directly confirms the chemical anchoring effect induced by the interfacial catalytic anti-skid aggregate from a mechanical property perspective, successfully transforming traditional physical adsorption into a strong chemical bond. These results fully verify that the components, through activation treatment, core-shell structure, neutral environment compatibility, and interfacial catalysis, jointly achieved a comprehensive improvement in the overall performance of the fog seal material.

[0137] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A stress-luminescent chemical anchoring fog sealant material with blackening and wear-resistant properties, characterized in that, By mass fraction, the raw materials include the following components: 5-15 parts of high carbon black content activated latex, 5-10 parts of core-shell structured stress luminescent particles, 15-30 parts of interface catalytic anti-skid aggregate, and 100 parts of near-neutral nonionic emulsified asphalt. The high carbon black content activated adhesive latex is a stable latex formed by dispersing high carbon black content activated adhesive in an aqueous medium. The core-shell structured stress-luminescent particles consist of a stress-luminescent particle core, an epoxy resin shell, and functional groups grafted onto the surface of the epoxy resin shell. The interface-catalyzed anti-slip aggregate is a hard aggregate with a surface modified with a silane coupling agent and a catalyst; the catalyst is an organometallic catalyst, including at least one of zinc acetylacetonate and tin acetylacetonate; The near-neutral nonionic emulsified asphalt is an asphalt emulsion with a pH value of 6.0-8.0; The preparation steps of the high carbon black content activated rubber latex include: heating and mixing waste tire rubber powder, softener and regeneration activator to obtain a mixture; heating and extruding the mixture to obtain an extruded material; pressing the extruded material to obtain a high carbon black content activated rubber; mixing the high carbon black content activated rubber with water, emulsifier and polymer stabilizer, and shearing and dispersing to obtain the high carbon black content activated rubber latex. The preparation steps of the core-shell structured stress-luminescent particles include: mixing stress-luminescent material particles, anhydrous ethanol, and KH-560, heating and refluxing to obtain surface-activated stress-luminescent particles; mixing the surface-activated stress-luminescent particles with epoxy resin, diluent, and curing agent, stirring and premixing to obtain a composite slurry; granulating the composite slurry by spray drying to obtain core-shell particles; dispersing the core-shell particles in toluene to obtain a suspension; mixing the suspension with a silane hydrolysate prepared from KH-550, heating and stirring to obtain the core-shell structured stress-luminescent particles.

2. The stress-luminescent chemical anchoring fog sealant material with blackening and wear-resistant functions as described in claim 1, characterized in that, The softener includes aromatic oils; And / or, the regeneration activator includes 420 regeneration activator; And / or, the mass ratio of the waste tire rubber powder, softener, and regeneration activator is 100:3-5:1.5-2.5; And / or, the heating and mixing temperature is 60-70°C, and the time is 5-10 min; And / or, the temperature of the heated extrusion is 180-205℃, and the extrusion rate is 2-4 kg / min; And / or, the pressing temperature is 65-70°C, and the number of pressing cycles is 5-7; And / or, the emulsifier includes at least one of fatty alcohol polyoxyethylene ether and block polyether surfactant; And / or, the polymeric stabilizer includes at least one of hydroxyethyl cellulose and xanthan gum; And / or, the mass ratio of the high carbon black content activated adhesive to water, emulsifier and polymeric stabilizer is 30-50:45-65:1-3:0.2-1.0; And / or, the shear dispersion is performed at a rotation speed of 2000-5000 rpm for a time of 20-40 min.

3. The stress-luminescent chemical anchoring fog sealant material with blackening and wear-resistant functions as described in claim 1, characterized in that, The stress-luminescent material particles include SrAl2O4:Eu 2+ Particles or SrAl2O4:Dy 3+ Particles; And / or, the mass of the KH-560 is 1-3% of the mass of the stress-luminescent material particles; And / or, the temperature of the heating reflux reaction is 50-80°C, and the time is 2-6 hours; And / or, the epoxy resin includes bisphenol A type epoxy resin E-51; And / or, the diluent includes phenyl glycidyl ether; And / or, the curing agent includes methyltetrahydrophthalic anhydride; And / or, the mass ratio of the surface-activated stress-luminescent particles to epoxy resin, diluent, and curing agent is 100:80-120:10-20:60-80; And / or, the mass concentration of core-shell particles in the suspension is 15-25%; And / or, the preparation steps of the silane hydrolysate include: mixing KH-550, water and anhydrous ethanol at a mass ratio of 1:1:10-12, adjusting the pH to 4-5 with acetic acid, and pre-hydrolyzing at 20-40℃ for 30-60 min to obtain the silane hydrolysate; And / or, the mass ratio of the core-shell particles contained in the suspension to the KH-550 contained in the silane hydrolysate is 10-15:

1.

4. The stress-luminescent chemical anchoring fog sealant material with blackening and wear-resistant functions as described in claim 1, characterized in that, The preparation steps of the interface-catalyzed anti-slip aggregate include: mixing a silane coupling agent, an organometallic catalyst, and a solvent to obtain a composite treatment liquid; applying the composite treatment liquid to the surface of a hard aggregate by spraying; then heating and curing the mixture; and finally cooling to obtain the interface-catalyzed anti-slip aggregate.

5. The stress-luminescent chemical anchoring fog sealant material with blackening and wear-resistant functions as described in claim 4, characterized in that, The silane coupling agent includes at least one of KH-550 and Si-69; And / or, the solvent includes at least one of anhydrous ethanol and isopropanol; And / or, the mass ratio of the silane coupling agent, organometallic catalyst and solvent is 1-5:0.1-1:20-50; And / or, the hard aggregate comprises fine sand with a particle size of 0.1-0.5 mm; And / or, the mass ratio of the hard aggregate to the composite treatment liquid is 100:5-10; And / or, the temperature for heat curing is 80-100℃, and the time is 1-2 hours.

6. The stress-luminescent chemical anchoring fog sealant material with blackening and wear-resistant functions as described in claim 1, characterized in that, The preparation steps of the near-neutral nonionic emulsified asphalt include: mixing water, nonionic emulsifier and stabilizer, heating and stirring to obtain an aqueous phase; mixing the molten asphalt phase with the aqueous phase and emulsifying to obtain the near-neutral nonionic emulsified asphalt.

7. A method for preparing a stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions as described in any one of claims 1-6, characterized in that, Includes the following steps: High carbon black content activated latex and near-neutral nonionic emulsified asphalt are mixed evenly under low-speed shearing, and then core-shell structured stress-luminescent particles are added and mixed evenly under low-speed shearing to obtain a base liquid; the base liquid is mixed with the interface catalytic anti-skid aggregate at low speed to obtain the stress-luminescent chemical anchoring fog seal material with blackening and wear resistance functions.

8. A construction method for a stress-luminescent chemical anchoring fog seal material with blackening and abrasion resistance functions as described in any one of claims 1-6, characterized in that, Includes the following steps: The road surface to be constructed is pretreated; the stress-luminescent chemical anchoring fog seal material with blackening and wear-resistant functions is evenly sprayed onto the pretreated road surface to be constructed, and after spraying, it is cured under natural conditions.

Images