High-rut-resistance recycled asphalt pavement technology based on surface activated glass powder

Abstract

A glass powder surface gradient activation-asphalt interface bonding enhancement technology is created for the first time, and the industry bottleneck that the compatibility of waste glass and asphalt is poor is broken through. The core of the method comprises the following steps: 1, an original pretreatment process: carrying out three-stage crushing, wet magnetic separation (the magnetic field intensity is 1.2 T), plasma etching (the ratio of Ar to O2 is 4: 1, and the power is 800W) and controllable ball milling (zirconium oxide balls are used for ball milling) on waste glass; according to interface molecular engineering, a bifunctional silane coupling agent (KH-792: gamma-aminoethyl aminopropyl trimethoxy silane) and titanate (NDZ-201) are compounded with a modifying agent (the mass ratio is 3: 1), and a-Si-O-Ti-cross-linked network 3 is constructed on the surface of the glass powder through in-situ hydrolytic condensation. According to mixture collaborative design, mineral powder is replaced by 35-55% of activated glass powder, and the particle size ratio of the activated glass powder to the mineral powder is 1: 2, D90 is smaller than or equal to 20 [mu] m < 2 >, D90 is smaller than or equal to 20 [mu] m < 2 >, and D90 is smaller than or equal to 20 [mu] m < 2 >. The technical effect of forming a core-shell structure reinforced phase in the SBS modified asphalt is as follows: the dynamic stability reaches 5032 + / -210 times / mm (JTGE20-2011T0719), and compared with the traditional mixture, the water sensitivity (TSR) is improved by 79.7% from 81.3% to 96.5%.

Description

Summary of the Invention

[0001] 1. Deep processing technology for waste glass

[0002] Waste glass sorting -- three-stage jaw crushing to ≤3mm -- wet magnetic separation -- removal of Fe / Ni impurities -- plasma etching -- surface activation -- controllable ball milling -- inert atmosphere protection -- grading and sieving -- D100≤45μm.

[0003] Key parameters:

[0004] Ball milling media: anhydrous ethanol (solid-liquid ratio 1:5), milling speed 280 rpm, milling time 120 min

[0005] Particle size control: Online feedback adjustment using a laser particle size analyzer (target D50 = 8.5 ± 0.5 μm)

[0006] This process achieves surface activation and morphology control of glass powder through synergistic physical-chemical modification, and consists of four treatment stages:

[0007] 1.1 Raw material pretreatment

[0008] After manual sorting to remove foreign objects such as ceramics and metals, the waste glass enters the drum washing machine. It is then sprayed with a 60℃ hot alkaline solution (5wt% NaOH) for 30 minutes to dissolve any organic label residue. Subsequently, a high-pressure water jet (15MPa pressure) is used to peel off the surface silicate deposit.

[0009] After crushing and shaping, the cleaned glass fragments undergo two-stage jaw crushing:

[0010] Primary crushing (gap width 50mm) reduces material to a particle size ≤30mm.

[0011] Secondary crushing (10mm gap width) produces intermediate products with a particle size ≤5mm.

[0012] During the crushing process, liquid nitrogen is continuously sprayed to control the temperature (-20℃) to inhibit the propagation of microcracks.

[0013] 1.2 Component Purification

[0014] In wet magnetic separation, glass particles and deionized water are mixed at a mass ratio of 1:3 to form a slurry, which is then passed through a gradient magnetic field device. The slurry is held in a 1.2T strong magnetic field for 120 seconds, effectively removing magnetic impurities such as Fe2O3 and NiO (residual amount <0.03wt%).

[0015] Flotation separation was performed by adding dodecylamine collector (0.2 kg / t) to the slurry. Al2O3 impurities were preferentially removed by flotation in an acidic environment with pH 3.5, thereby increasing the purity of SiO2 to 99.1 ± 0.2%.

[0016] 1.3 Surface Nanostructuring

[0017] Plasma etching: Glass particles are placed in an RF plasma reaction chamber (frequency 13.56MHz), and an argon / oxygen mixture (volume ratio 4:1) is introduced. The etching process is performed at 800W for 40 minutes. After etching, a nano-pit structure (diameter 50-80nm, aspect ratio 0.6-0.8) is formed on the surface, with a silanol group density of 12 pits / μm. 2 Increased to 28 / μm 2 .

[0018] Ball milling refinement: A zirconia ball mill jar (35% filling rate) was used, with a media ball diameter ratio of Φ3mm:Φ5mm = 1:2. Grinding was carried out at 280 rpm for 120 minutes under anhydrous ethanol protection, and the process was monitored in real time using a laser particle size analyzer. When D... 50 The grinding process was terminated when the particle size reached 8.5 ± 0.5 μm.

[0019] Activation modification and coupling agent grafting were performed by dissolving KH-792 silane coupling agent and NDZ-201 titanate in an ethanol / water solution (9:1 volume ratio) at a mass ratio of 3:1, and adjusting the pH to 5.0±0.2. The solution was atomized and sprayed into glass powder preheated at 110℃, and reacted in a high-speed mixer (1200 rpm) for 15 minutes. After aging and stabilization, the modified glass powder was aged in an oven at 120℃ for 24 hours to promote the hydrolysis-condensation reaction of silane. Finally, the powder was deagglomerated by air jet milling (inlet pressure 0.7 MPa) to obtain activated glass powder with good flowability.

[0020] Key points of process control:

[0021] 1) Particle size distribution control

[0022] Particle size distribution was monitored using laser diffraction (ISO 13320). Requirements:

[0023] D 10 ≥2.8μm (to avoid agglomeration of excessively fine powder)

[0024] D 90 ≤20μm (to ensure filling effect)

[0025] Span factor (SPAN) = (D 90 -D 10 ) / D 50 <1.5

[0026] 2) Surface characteristic verification

[0027] Contact angle test: The modified water contact angle is ≥105° (unmodified glass powder is 28°).

[0028] Infrared spectroscopy analysis: at 1110 cm⁻¹-1 A characteristic Si-O-Ti peak appears at 1540 cm⁻¹. -1 -NH bending vibration peak appears at [location].

[0029] BET specific surface area: 4.2 ± 0.3 m² 2 / g (230% higher than untreated glass powder)

[0030] 3) Environmental control requirements. Oxygen content in the ball milling process <50ppm (nitrogen protection); humidity control parameter for the modification reaction RH <30%.

[0031] Comparison of process innovation

[0032]

[0033]

[0034] 1.4 Synergistic Mechanism of Coupling Agents

[0035] The diamine group (-NH-CH2-CH2-NH2) of KH-792 forms an amide bond with the carboxyl group of pitch, while the isopropoxy group (-OCH(CH3)2) of the titanate ester condenses with the glass surface after hydrolysis, forming a long-chain alkyl group (C 14 H 29 -) Oriented arrangement to form a hydrophobic layer.

[0036] Molecular configuration design principles

[0037] Functional group complementarity matching

[0038] γ-aminoethylaminopropyltrimethoxysilane (KH-792) and isopropyltris(dioctylpyrophosphoryloxy)titanate (NDZ-201) were selected and compounded at a mass ratio of 3:1 based on the following molecular characteristics:

[0039] KH-792 contains a diamine group (-NH-CH2-CH2-NH2), which can form an amide bond with the carboxyl group (-COOH) in asphalt (bond energy ≈ 350 kJ / mol).

[0040] NDZ-201 contains long-chain alkyl (C 14 H 29 -), its hydrophobicity is compatible with asphalt hydrocarbon components.

[0041] The pyrophosphate oxy group of titanate hydrolyzes to form Ti-OH, which then forms a Si-O-Ti covalent bond with silane (bond energy > 420 kJ / mol).

[0042] Spatial resistance control

[0043] Confirmed through molecular dynamics simulations (COMPASS force field):

[0044] KH-792 molecular chain length: 1.2 nm

[0045] NDZ-201 alkyl chain length: 2.3nm

[0046] After compounding, a gradient molecular layer is formed ( Figure 1 This effectively reduces the interfacial energy to 38.2 mN / m (compared to 52.7 mN / m for a single silane system).

[0047] Interfacial Reaction Kinetics

[0048] Hydrolysis was controlled by maintaining a pH of 5.0 ± 0.2 in an ethanol / water (9:1 V / V) mixed solvent to achieve selective hydrolysis.

[0049] Si(OR)3+H2O->{Slow}Si(OR)2OH+ROH

[0050] Ti(OR)4+2H2O->{fast}Ti(OH)4+4ROH

[0051] An acidic environment inhibits silane self-condensation, ensuring that >85% of the hydrolysis products are monomeric silanols.

[0052] The condensation reaction pathway involves a two-stage reaction of the modifier on the glass powder surface:

[0053] ①Silane-glass bonding:

[0054] Si(OR)2OH+HO-Si(glass)-Si-O-Si(glass)+H2O}

[0055] Activation energy of the reaction: 72.3 kJ / mol (determined by DSC)

[0056] ②Silane-titanium ester crosslinking:

[0057] Ti(OH)4+HO-Si-R-Ti-O-Si-R+2H2O}

[0058] The curing process was completed at 120℃, and the 1110 cm³ was measured by FTIR. -1 The intensity of the characteristic peak of Si-O-Ti was increased by 3.2 times.

[0059] Interface structure representation

[0060] Chemical bonding verification, X-ray photoelectron spectroscopy (XPS) analysis showed:

[0061] N1s binding energy 399.8 eV (-NH2→-NHC(O)- conversion)

[0062] The Ti2p3 / 2 peak shifts to 458.5 eV (Ti-O bond formation).

[0063] Microscopic morphology observation, transmission electron microscopy (TEM) reveals a three-layer gradient structure:

[0064] 1) Glass matrix (SiO2)

[0065] 2) Inorganic / organic hybrid layer (Si-O-Ti-OC, thickness 5-8nm)

[0066] 3) Alkyl chain oriented layer (thickness 12-15 nm)

[0067] This structure enables an interfacial shear strength of 18.7 MPa (compared to 11.1 MPa for a single silane system).

[0068] Thermodynamic stability mechanism, entropy increase stabilization effect, long-chain alkyl (C 14 H 29 -) The extension conformation in asphalt increases the entropy of the system (ΔS = +23.7 J / mol·K), which offsets the decrease in entropy due to interfacial reaction (ΔS = -18.2 J / mol·K), resulting in a positive net entropy.

[0069] Molecular motion inhibition. Dynamic thermomechanical analysis (DMA) showed that the glass transition temperature (Tg) increased to 64.3℃ (compared to 51.2℃ in the unmodified system), and the interfacial storage modulus (E') reached 2.8 GPa (an increase of 142%), indicating that the coupling agent network effectively inhibited the movement of asphalt molecular chain segments.

[0070] Quantitative verification of synergistic effect

[0071]

[0072]

[0073] Theoretical model construction

[0074] Relationship between interface enhancement factor (IEF) and coupling agent ratio:

[0075] IEF=1+k1·CSi+k2·CTi+k3·(CSi·CTi)

[0076] in:

[0077] CSi,CTi: Silane / Titanium Ester Concentration (wt%)

[0078] k1 = 0.62, k2 = 0.41, k3 = 0.85 (determined using the response surface methodology)

[0079] Model R 2 =0.96, predicted optimal ratio CSi / CTi = 2.8~3.2

[0080] Innovative scientific significance

[0081] 1) Design of double bonding sites

[0082] Breaking through the traditional single-action mode of coupling agents, a dual mechanism of "amine-carboxyl chemical bonding + alkyl chain physical entanglement" is established.

[0083] 2) Reaction kinetic regulation

[0084] By controlling pH, the hydrolysis rates of silanes and titanates are matched, avoiding self-polymerization side reactions.

[0085] 3) Entropy-driven stability

[0086] This study is the first to reveal the contribution of the entropy increase effect of long-chain alkyl groups to interfacial thermal stability.

[0087] 2. Interface molecular design (distinct from existing patents)

[0088]

[0089] Modification process: The modifier solution (concentration 1.8wt%) and glass powder (pre-dried at 110℃) react in a high-speed mixer (1200rpm) → mature at 120℃ → air jet milling to deagglomerate.

[0090] This technology overcomes the limitations of traditional single-component coupling agents by constructing a three-in-one interface structure of "dual functional group synergy - gradient bonding - entropy stability". Its core innovations are as follows:

[0091] 2.1 Molecular structure topology optimization

[0092] Functional group complementary design

[0093] Amine double bonding: The primary amine group (-NH2) at the end of the KH-792 molecule forms a double bonding site with the secondary amine group (-NH-). The primary amine group preferentially condenses with the carboxyl group in the asphalt to form an amide bond (-NHC(O)-), while the secondary amine group forms a weaker but reversible coordinate bond with the carbonyl group (bond energy ≈ 60 kJ / mol). This design enables the interface to reconfigure its bonding under fatigue loads.

[0094] Titanium-oxygen bridging network: The Ti-OH groups generated by the hydrolysis of NDZ-201 simultaneously condense with Si-OH groups on the glass surface and silanol groups on KH-792, forming a ≡Si-O-Ti-O-Si≡ three-dimensional cross-linked network. Molecular dynamics simulations show that this structure increases the interfacial fracture energy to 5.8 J / m. 2 (The single silane system has a strength of 2.3 J / m) 2 ).

[0095] Spatial configuration regulation, alkyl chain folding inhibition:

[0096] C of titanate 14 The alkyl chain interacts with the saturated molecules in asphalt through van der Waals forces. Its extended conformation length (2.3 nm) is greater than the average intermolecular distance of asphalt (1.7 nm), forcing the asphalt molecules to align in a specific orientation. Figure 3 Small-angle X-ray scattering (SAXS) confirmed the presence of a Bragg peak in the interface region. It corresponds to a 3.5nm periodic structure.

[0097] Molecular layer gradient transition: The interface region forms a four-layer structure of "glass-(Si-O-Ti) inorganic layer-(Si-R-NH) organic layer-asphalt", and the elastic modulus smoothly transitions from 73GPa (glass) to 1.2GPa (asphalt), eliminating the modulus abrupt change (>50GPa) of traditional interfaces.

[0098] 2.2 Bonding Dynamics

[0099] Competitive reaction inhibition, silane self-condensation inhibition:

[0100] In a weakly acidic environment with pH = 5.0, the hydrolysis rate constant kh of KH-792 is 0.18 min. -1 This is far below its neutral condition (kh = 0.42 min). -1 Meanwhile, titanate preferentially hydrolyzes to produce Ti-OH, which occupies the intermolecular condensation sites of silane molecules, resulting in a self-condensation product ratio of <7% (compared to >35% in traditional processes).

[0101] The directional condensation pathway involves a two-step reaction process:

[0102] Step 1: Rapid anchoring of titanate to glass surface (activation energy Ea = 45 kJ / mol)

[0103] Ti(OR)3OPO3H+HO-Si(glass)→Ti(OR)3OPO3-Si(glass)+H2O

[0104] Step 2: Co-condensation of silane and titanate (Ea = 68 kJ / mol)

[0105] Si(OR)2OH+HO-Ti-OPO3-Si(glass)→Si-O-Ti-OPO3-Si(glass)+ROH

[0106] The path is labeled with isotopes ( 18 The condensation efficiency reached 92±3% when verified by O-H2O combined with mass spectrometry.

[0107] 2.3 Mechanisms for resisting environmental erosion

[0108] A water molecule barrier layer is formed, in which long-chain alkyl groups (C14H29-) form a dense arrangement in the interface region, reducing the water molecule diffusion coefficient to 1.7 × 10⁻⁶. -14 m 2 / s (unmodified interface is 5.3×10) -13 m 2 / s). Molecular simulations show that water molecules need to overcome an energy barrier of 38 kJ / mol to penetrate the alkyl layer.

[0109] Self-repair function

[0110] The secondary amine group (-NH-) undergoes reversible breakage and recombination under humid and hot conditions:

[0111] >N-H+H2O<=>N:+H3O+

[0112] Dynamic mechanical analysis (DMA) showed that after 5 dry-wet cycles, the interfacial modulus of the compound system retained 91%, while that of the single silane system decreased to 67%.

[0113] 2.4 Thermodynamic stability mechanism

[0114] Due to the entropy compensation effect, the conformational entropy (Sconf) of the titanate alkyl chain in asphalt satisfies:

[0115] Sconf=kBlnΩ∝N0.6

[0116] Where N is the number of alkyl carbon atoms (N = 14), when the interface is formed, the entropy decreases by ΔSbond = -18.2 J / mol·K, but the entropy increases by ΔSchain = +26.4 J / mol·K when the alkyl chain is unbound, and the net entropy change ΔStotal > 0.

[0117] The interface can be minimized

[0118] The modified interfacial tension γSL satisfies the Young-Dupré equation:

[0119]

[0120] The surface energy γS of the glass decreased from 72 mN / m to 38 mN / m (measured by the Owens-Wendt method), which is close to the asphalt surface energy γL = 32 mN / m, making γSL < 2 mN / m.

[0121] Experimental verification data

[0122] 1) Molecular layer thickness (measured by ellipsometer)

[0123] Inorganic layer: 5.8±0.3nm

[0124] Organic layer: 13.2±0.7nm

[0125] 2) Bonding energy distribution (AFM force curve)

[0126] Bonded types Bond energy (pN) percentage covalent bond 320-380 62.3％ Coordinate key 120-150 28.5％ van der Waals 40-80 9.2％

[0127] 3) Long-term service performance, Hainan Ring Expressway physical project (36 months): interface peeling rate is only 3.8% (traditional modification > 15%), rut depth is 2.1mm (design limit 7mm).

[0128] Theoretical model innovation

[0129] Interface durability prediction equation:

[0130]

[0131] Parameter meaning:

[0132] tf: Interface expiration time (in years)

[0133] IEF: Interface Enhancement Factor (IEF = 2.35 for this technology)

[0134] Ea = 75 kJ / mol (Activation energy for damp-heat aging)

[0135] A = 2.6 × 10 -6 B = 0.18, C = 1.42 (regression coefficients)

[0136] The model has been validated in 12 climate zones, with a prediction error of <±8%.

[0137] 3. Asphalt Mixture Design System

[0138] AC-13 gradation optimization model:

[0139] Pglass = 0.42ln(ESAL) - 1.75

[0140] The condition for the formula is: ESAL 10^6.

[0141] Pglass: Glass powder replacement ratio (%)

[0142] ESAL: Design Equivalent Shaft

[0143] Characterization of the paste structure (TEM evidence):

[0144] An organic coating layer with a thickness of 15-20 nm is formed on the surface of the glass powder, creating a gradient transition interface with the asphalt.

[0145] This system breaks through the limitations of traditional empirical design and establishes a multi-scale collaborative optimization model of "surface energy-gradation-interface". Its core design hierarchy is as follows:

[0146] 3.1 Gradation Optimization Theory

[0147] Based on the principle of axial load-fatigue damage equivalence, an analytical expression for the glass powder substitution ratio Pg is established for the glass powder content model:

[0148]

[0149] In the formula:

[0150] Ne: Design Equivalent Axle Rank (ESAL)

[0151] N0 = 1.0 × 10^6 (reference axis number)

[0152] k = 0.42 (axle load sensitivity coefficient, calibrated through a three-point bending fatigue test)

[0153] b = -1.75 (Minimum Dosage Compensation Term)

[0154] ΔPT=0.0085×(Tmax-50) (Temperature correction term, where Tmax is the highest design temperature of the road surface)

[0155] Skeleton gap ratio control

[0156] Introducing the glass powder filler factor λ:

[0157]

[0158] Design principles:

[0159] λ = 1.05 sim 1.15 (forming a dense-skeleton structure)

[0160] Vvma: Mineral aggregate void fraction (%)

[0161] Vbe: Effective bitumen volume (%)

[0162] 3.2 Grout Structure Design

[0163] Three-phase interface construction

[0164] 1. Core layer: Activated glass powder (D 50 =8.5μm) as a rigid reinforcing phase

[0165] 2. Shell: An organic-inorganic hybrid layer constructed with coupling agents (15-20 nm thick)

[0166] 3. Continuous phase of asphalt: SBS modified asphalt forms a viscoelastic matrix.

[0167] Rheological property regulation

[0168] Verification of the mechanism for improving the composite modulus (G) of the adhesive paste using a dynamic shear rheometer (DSR):

[0169]

[0170] parameter:

[0171] Gm: Asphalt matrix modulus (MPa)

[0172] Gp: Glass powder modulus (73 GPa)

[0173] φp: Volume fraction of glass powder

[0174] ν = 0.35 (Poisson's ratio)

[0175] When φp=0.12, G increases by 248% at 60℃.

[0176] 3.3 Surface Energy Balance Design

[0177] Component surface energy parameters

[0178] Components <![CDATA[Dispersion component γd (mJ / m 2 )]]> <![CDATA[Polar component γp (mJ / m 2 )]]> Test methods Activated glass powder 38.2 1.5 Steam adsorption method SBS modified asphalt 28.7 3.3 Contact Angle Method Basalt aggregate 41.9 12.6 Columnar peeling method

[0179] Adhesion work optimization

[0180] Calculation of aggregate-asphalt adhesion work (W_{AB}):

[0181]

[0182] Traditional system: WAB = 106.3 mJ / m 2

[0183] In this design system: WAB = 132.7 mJ / m 2 (Increase of 24.8%)

[0184] 3.4 Volumetric Parameter Design

[0185] Key volume indicators

[0186] parameter Design value Control basis Design porosity VV 3.8-4.2％ Balancing high-temperature stability and low-temperature crack resistance VMA (Volume Amount) ≥15.2％ Ensure sufficient space for adhesive filling Asphalt saturation VFA 68-72％ Avoid asphalt leakage or drying

[0187] Effect of glass powder content

[0188] Establish a regression model between porosity (VV) and P_g:

[0189] VV=4.87-0.063Pg+0.0012Pg2(R2=0.94)

[0190] When Pg = 40%, VV reaches its minimum value of 4.05%.

[0191] 3.5 Innovation in mixing process

[0192] Staged mixing control

[0193] Aggregate preheating stage: Basalt aggregate is dried and mixed at 185±5℃ for 30 seconds to evaporate surface moisture. Dry mixing stage: Activated glass powder is added and mixed for 45 seconds to ensure the powder evenly coats the aggregate. Wet mixing stage: 165℃ SBS modified asphalt is sprayed in and mixed continuously for 90 seconds.

[0194] Temperature field control is achieved through real-time monitoring using infrared thermal imaging.

[0195] Dry mixing end temperature: 172±3℃

[0196] Discharge temperature: 158±2℃

[0197] Temperature gradient < 15℃ / m 3 (To avoid localized aging)

[0198] 3.6 Multi-indicator collaborative verification

[0199] High temperature performance

[0200] Hamburg rutting test (50℃): Deformation rate 0.021 mm / 1000 cycles (specification requirement ≤0.05)

[0201] MSCR test: Irreversible compliance J_{nr}=0.78kPa -1 (62% lower than traditional mixtures)

[0202] Durability

[0203] Test Project This system Standard requirements Freeze-thaw splitting strength ratio (TSR) 96.5％ ≥80％ stiffness modulus after long-term aging 8,924 MPa ≤12,000MPa

[0204] Fatigue life

[0205] Four-point bending fatigue equation:

[0206] logNf=14.23-3.56logε(R2=0.97)

[0207] At a strain level of 200 με, the fatigue life reaches 153,842 cycles.

[0208] Physical engineering verification

[0209]

[0210]

[0211] Innovative summary:

[0212] 1. A pioneering ternary coupled design model of "axle load-temperature-material" was developed to achieve precise control of glass powder doping.

[0213] 2. Establish surface energy balance design criteria to solve the interfacial compatibility problem of solid waste packing materials.

[0214] 3. A three-phase reinforcement theory for the adhesive is proposed to explain the mechanism of improved rutting resistance from a microscopic perspective.

[0215] 4. Develop gradient mixing process to ensure the complete formation of nanoscale interface structures.

[0216] Data source: Certified by the Highway Research Institute of the Ministry of Transport (Report No.: RIOH-2025-GL-028), and meets the requirements of the "Technical Specification for Recycling Asphalt Pavement of Highway" (JTG / T 5521-2023).

[0217] Originality

[0218] This patented technology is significantly innovative in terms of material design, process optimization, and performance improvement, mainly in the following aspects:

[0219] 1. Efficient activation and interface enhancement of waste glass powder (material innovation)

[0220] Pioneering plasma etching + silane / titanium ester composite modification technology

[0221] Unlike traditional single silane coupling agent treatments (such as US 9,840,679), this technology uses argon-oxygen plasma etching to construct nanoscale pits (50-80 nm deep) on the surface of glass powder, increasing the silanol group density by 133% (12 → 28 pits / μm). 2 ), and combined with KH-792 / NDZ-201 two-component coupling agent, to form an interface structure synergistically enhanced by covalent bonds (Si-O-Ti) and coordination bonds (-NH…O=C).

[0222] Comparative data: The interfacial shear strength reaches 18.7 MPa (compared to only 11.1 MPa for traditional silane modification).

[0223] Precise control of glass powder gradation

[0224] A coupled model of "axial load-temperature-dosage" is proposed to achieve the optimal replacement ratio (35-55%) under different working conditions, and solve the problem of porosity imbalance caused by blind mixing in existing technologies.

[0225] 2. Multi-scale collaborative design of asphalt mixtures (methodological innovation)

[0226] Three-phase adhesive structure design

[0227] TEM confirmed that a 15-20 nm organic-inorganic hybrid layer was formed on the surface of the glass powder, forming a gradient transition interface with the asphalt (the modulus smoothly decreased from 73 GPa to 1.2 GPa), while traditional techniques are prone to stress concentration due to abrupt interface changes.

[0228] Application of surface energy balance theory

[0229] For the first time, a surface energy matching equation for the three components of aggregate-asphalt-glass powder was established, resulting in a 24.8% increase in adhesion work to 132.7 mJ / m. 2 It is significantly superior to existing technologies that focus solely on the aggregate-asphalt interface.

[0230] 3. Extreme Environment Adaptability Processes (Application Innovation)

[0231] Gradient mixing process in frozen soil areas

[0232] By using separate heating of coarse and fine aggregates (165℃ / 155℃) and stepwise feeding of glass powder, the problem of segregation of the mixture caused by freeze-thaw cycles is solved (the porosity changes by only 0.3% after 300 freeze-thaw cycles).

[0233] Integrated flame retardant and noise reduction system for tunnels

[0234] By using microporous masterbatch and Helmholtz resonant cavity design, an oxygen index of ≥28% (GB 8624) and a noise reduction coefficient of NRC = 0.48 are achieved simultaneously, overcoming the technical contradiction of poor noise reduction performance of traditional flame-retardant pavement.

[0235] Beneficial effects (Advantages)

[0236] This patented technology exhibits the following significant advantages in practical applications:

[0237] 1. Performance Improvement

[0238]

[0239]

[0240] 2. Economic and environmental benefits

[0241] Cost savings:

[0242] Glass powder can reduce filler costs by 40% compared to mineral powder (¥210 / ton vs. ¥320 / ton).

[0243] The total life-cycle cost of roads in permafrost regions decreased by 19% (¥3.12 million / km vs ¥3.85 million / km).

[0244] Resource recycling:

[0245] Each kilometer consumes 112 tons of waste glass, reducing CO2 emissions by 18.7 tons.

[0246] Waste glass utilization rate ≥ 95% (traditional recycling rate < 30%)

[0247] 3. Construction adaptability

[0248] Rapid Repair: Airport Repair Implementation Example 3.5 Hours to Reopen Traffic (Civil Aviation Standard ≤ 4 hours)

[0249] Process compatibility: It can directly replace mineral powder without modifying existing mixing equipment.

[0250] Environmentally friendly: No hydrogen fluoride emissions (compared to hydrofluoric acid etching process)

[0251] This patent solves the three core problems of waste glass application in asphalt pavement through molecular-level interface design, multi-scale performance control and extreme working condition adaptability innovation. These problems are weak interface, rapid performance degradation and poor environmental adaptability. It has the triple advantages of high performance, low cost and greenness. The technology has reached the engineering promotion stage (cumulative application > 1 million m²). Attached Figure Description Figure 1 Waste glass processing flow chart Figure 2 Schematic diagram of asphalt mixture structure and gradation Figure 2-1 : A schematic diagram of a dense-skeleton structure formed by glass powder filling the gaps between aggregates. It may also include a three-phase interface structure of the mortar, i.e., a core layer active layer. Structural representation of tempered glass powder, organic-inorganic hybrid shell layer, and continuous bitumen phase. Figure 3 Construction process flow chart Figure 4 Deep processing technology for waste glass

[0252] Detailed Implementation (Industrial-Grade Example)

[0253] Example 1: Port heavy-duty road (design axle load BZZ-150)

[0254] (1) Raw material formula

[0255] Components Specification Dosage SBS modified asphalt PG76-22 4.8％ Activated glass powder D50 = 9.2 μm 2.6％ Basalt aggregate Continuous gradation AC-16 92.6％ Anti-stripping agent Amides 0.3％

[0256] Glass powder replacement rate: 52% (2.6% of the total mineral powder content of 5.0%).

[0257] (2) Production process flow

[0258] Aggregate heating (185±5℃) -> dry mixing: add activated glass powder and mix for 45 seconds

[0259] Dry mixing --> Wet mixing: Spray asphalt and mix for 90 seconds

[0260] Wet mixing --> Discharge: Temperature control 158±3℃

[0261] (3) Performance verification (third-party testing)

[0262]

[0263] Example 2: Highways in high-temperature and rainy areas (Innovation: Synergistic modification of glass powder / rubber powder)

[0264] Formula innovation: A composite of activated glass powder (2.2%) and 40-mesh adhesive powder (0.8%) to replace mineral powder.

[0265] Performance advantages: Low-temperature bending strain: 3821 με (24.7% higher than the pure glass powder system)

[0266] Noise reduction effect: Road noise reduced by 3.2 dB(A)

[0267] Original technical features (distinguishing them from existing patents)

[0268] 1) Interface Dual-Phase Enhancement Mechanism

[0269] Chemical bonding layer: long-chain alkyl groups of titanate are compatible with saturated phases in asphalt.

[0270] Mechanically interlocked layer: Nanoscale pits (depth 50-80nm) are formed by plasma etching.

[0271] 2) Anti-rutting multi-action model

[0272] mechanism Contribution rate Verification method Silicon-oxygen network enhancement 52.3％ Rheological time-temperature superposition Ball effect drag reduction 28.7％ Discrete Element Simulation (EDEM) Viscoelastic interface energy dissipation 19.0％ DMA phase angle analysis

[0273] 3) Environmental breakthrough

[0274] Heavy metal leaching test (EPA 1311):

[0275] Pb leaching concentration: 0.08 mg / L (< standard limit 5 mg / L)

[0276] Cr 6+ Not detected

[0277] The following three new detailed implementation examples cover special working conditions, extreme environments, and innovative application scenarios. Each example includes complete formula design, customized processes, and third-party verification data, and is scientifically explained using a four-level digital coding system:

[0278] Example 3: Roads in permafrost regions (G109 section of the Qinghai-Tibet Plateau)

[0279] 3.1 Technical Challenges

[0280] To address the issues of frost heave and cracking caused by freeze-thaw cycles (over 120 cycles per year), the mixture must possess both low-temperature crack resistance and water stability.

[0281] 3.2 Formulation Design

[0282] Components Specification Dosage Functional Innovation Rubber-modified asphalt Elongation ≥40cm at -35℃ 5.5％ Rubber powder provides elasticity recovery Activated glass powder <![CDATA[D 90 ≤15μm]]> 2.3％ Replace 45% of mineral powder Basalt aggregate Continuous gradation AC-13 92.2％ Adding 30% freeze-thaw diabase Antifreeze-thaw additives Organosilanes 0.4％ Lower the freezing point to -32°C

[0283] 3.3 Process Innovation

[0284] Gradient mixing process

[0285] 1) Aggregate preheating:

[0286] The aggregate is heated in two stages:

[0287] Coarse aggregate (>4.75mm): 165℃, fine aggregate (≤4.75mm): 155℃

[0288] (Reduce temperature segregation)

[0289] 2) Step-by-step feeding:

[0290] Step 1: Mix coarse aggregate with 50% glass powder for 40 seconds.

[0291] Step 2: Mix the fine aggregate and remaining glass powder for 35 seconds.

[0292] Step 3: Inject asphalt and mix for 85 seconds.

[0293] Compaction control

[0294] Initial compaction temperature: ≥145℃ (2 passes with vibratory roller)

[0295] Re-compaction temperature: 125-135℃ (6 passes with a tire roller)

[0296] Final compaction temperature: >95℃ (for steel wheel rollers to eliminate wheel tracks)

[0297] 3.4 Performance Verification

[0298] Test Project result Standard requirements Compared with traditional materials Freeze-thaw splitting strength ratio 98.2％ ≥80％ +16.5％ Low-temperature bending strain (-30℃) 3512με ≥2500με +40.5％ Porosity after 300 freeze-thaw cycles 4.1％ ΔVV≤1.5% The change was only 0.3%.

[0299] Physical engineering: During 36 months of observation in the Nagqu section (altitude 4580m), the crack rate was only 0.82 linear meters / thousand square meters (compared to 4.37 linear meters / thousand square meters in the control section).

[0300] Example 4: Flame-retardant and noise-reducing pavement for tunnels (Qinling Zhongnanshan Tunnel)

[0301] 4.1 Technical Challenges

[0302] This addresses multiple issues within the tunnel, including high-temperature smoke (>200℃), noise reflection (reverberation time >4s), and visibility.

[0303] 4.2 Formulation Design

[0304]

[0305] 4.3 Innovation in the construction process of flame-retardant layer

[0306] Surface microporous structure: Asphalt / glass powder / flame retardant are premixed into masterbatch (particle size 2-3mm) using a twin-screw extruder and added last during mixing to retain surface micropores.

[0307] Heat reflective layer construction: Immediately after final pressing, spray nano TiO2 / SiO2 sol (30% solid content) to form a 0.2mm reflective layer.

[0308] Noise reduction mechanism: Helmholtz resonant cavity: glass powder fills the gaps between aggregates to form microcavities (0.5-1.2mm in diameter), with a peak resonant frequency of 1000-1600Hz (the main frequency of tire noise).

[0309] 4.4 Performance Verification

[0310] Test Project result Standard requirements Combustion toxicity index 0.82 ≤1.0 (GB8624) Noise Reduction Coefficient (NRC) 0.48 ≥0.35 Smoke transmittance (5 min) 89.7％ ≥80％ Coefficient of friction (BPN) 78 ≥55

[0311] Actual measurement data: Noise level inside the tunnel was reduced to 78 dB(A) (compared to 92 dB(A) for conventional road surfaces), and the smoke generation rate was reduced by 62% during fire tests.

[0312] Example 5: Rapid runway repair at Pudong Airport

[0313] 5.1 Technical Challenges

[0314] It meets the requirement of 4-hour open traffic, is resistant to fuel corrosion (JetA-1), and can withstand landing gear impact loads (ground pressure > 1.5MPa).

[0315] 5.2 Formulation Design

[0316] Components Specification Dosage Functional Innovation Epoxy modified asphalt gelation time 25 min 6.0％ Toughening with nano-alumina Activated glass powder <![CDATA[D 50 =5.5μm]]> 3.5％ Replace 60% of mineral powder Corundum aggregate Mohs hardness 9.0 89.5％ Add 40% sintered bauxite carbon fiber Length 6mm 0.5％ Improve bending toughness

[0317] 5.3 Process Innovation

[0318] Ultra-fast construction process

[0319] Microwave preheating substrate:

[0320] The repair area was preheated to 80°C using a 24kW microwave cart (2.45GHz) to remove moisture.

[0321] Segmented mixing and pouring:

[0322] Component A: Epoxy resin + glass powder (premixed at 120℃)

[0323] Component B: Curing agent + aggregate (135℃)

[0324] Spread immediately after on-site double-helix mixing for 60 seconds.

[0325] Intensity Development Control

[0326] Early strength: 2-hour Marshall stability > 25kN (meets emergency takeoff and landing requirements)

[0327] Final strength: 28-day compressive strength > 45 MPa

[0328] 5.4 Performance Verification

[0329] Test Project result Civil aviation standards Mass loss due to fuel erosion (48h) 0.18％ ≤0.5% (FAAP-401) Drop hammer impact toughness (25℃) <![CDATA[8.7kJ / m 2 ]]> <![CDATA[≥5.0kJ / m 2 ]]> Coefficient of friction (wet state) 0.82 ≥0.70 Opening hours 3h45min ≤4h

[0330] Engineering Applications: Completed 37 emergency repairs, with an average runway occupancy time of 3.2 hours; the repair area has accumulated over 1800 takeoffs and landings without damage.

[0331] Comparison of innovative implementation examples

[0332]

[0333] Scientific value and engineering verification

[0334] 1. Adaptability to extreme environments

[0335] The example from the permafrost region underwent accelerated aging testing at a temperature difference of -45℃ to +35℃ (equivalent to 10 years of service).

[0336] The flame-retardant pavement underwent a full-scale tunnel fire test (HC hydrocarbon curve, peak temperature 1200℃).

[0337] 2. Rapid Repair Technology

[0338] Airport repair implementation examples: Development of dedicated rapid inspection equipment:

[0339] Infrared thermal imager monitors the curing process

[0340] Laser deflectometer (0.001mm accuracy) for assessing load-bearing capacity recovery

[0341] 3. Total life cycle cost

[0342] Project Type Traditional solution cost This technology cost Lifespan extension roads in permafrost areas ￥3.85 million / km ￥3.12 million / km +7.3 years Tunnel paving ￥6.2 million / km ￥5.5 million / km +9.1 years Airport repair <![CDATA[￥180,000 / m 2 > <![CDATA[￥140,000 / m 2 > Repair interval ×3

Claims

1. A recycled asphalt pavement material made from quartz powder, characterized in that, Includes the following components and their mass percentages: Asphalt binder: 4.5%–6.0%; Activated glass powder: 2.0%–3.5%, obtained from waste glass through plasma etching and modification with a complex coupling agent, D 50 ≤10μm, silanol group density ≥25 / μm 2 ; Aggregate: 90.5%–93.5%, using continuously graded basalt or diabase; Anti-stripping agent: 0.2%–0.5%.

2. The quartz powder recycled asphalt pavement material according to claim 1, characterized in that: The activated glass powder is modified by compounding KH-792 silane coupling agent and NDZ-201 titanate in a mass ratio of 3:1, and the total amount of modifier is 1.0% to 1.5% of the mass of the glass powder. The surface of the glass powder is etched by argon-oxygen plasma to form a nano-pit structure with a depth of 50-80 nm.

3. The quartz powder recycled asphalt pavement material according to claim 1 or 2, characterized in that: The asphalt binder is SBS modified asphalt or rubber composite modified asphalt, with a dynamic viscosity at 60℃ ≥20000 Pa·s. The proportion of glass powder replacing mineral powder is 30% to 55%, and the following relationship is satisfied: Where, N e To design the Equivalent Shaft Allocation (ESAL), T max The maximum design temperature of the road surface (°C).

4. A method for preparing recycled asphalt pavement material of quartz powder according to any one of claims 1 to 3, characterized in that, Includes the following steps: 1) Waste glass pretreatment: Waste glass is purified to a SiO2 content of ≥99% through crushing, magnetic separation (magnetic field strength ≥1.2T), and flotation (pH=3.5~4.0); Plasma etching: Processed for 30–50 minutes in an Ar / O2 mixed gas (4:1 volume ratio) at 800W power; Ball milling refinement: Using zirconia ball milling media, grinding was carried out to D level under anhydrous ethanol protection. 90 ≤20μm; 2) Activation of glass powder: Dissolve KH-792 and NDZ-201 in an ethanol / water solution (9:1 volume ratio) and adjust the pH to 5.0 ± 0.2; Spray coating the surface of preheated glass powder (110℃) and cure at 120℃ for 24 hours; 3) Mixing the mixture: After heating the aggregate to 180-185℃, add activated glass powder and dry mix for 45-60 seconds; Inject asphalt at 155-165℃ and wet mix for 90-120 seconds, then control the discharge temperature to 155-160℃.

5. The preparation method according to claim 4, characterized in that: The ball milling process uses a gradient ball diameter ratio (Φ3mm:Φ5mm=1:2), a rotation speed of 280±10rpm, and a grinding time of 100~150 minutes; During the mixing stage, the temperature field is monitored in real time using infrared thermal imaging to ensure that the temperature difference between aggregate and asphalt is ≤10℃.

6. A construction method for the quartz powder recycled asphalt pavement material according to any one of claims 1 to 3, characterized in that: The paving temperature is ≥150℃, the initial compaction temperature is ≥140℃, and the final compaction temperature is ≥90℃. For applications in permafrost regions, a gradient compaction process is adopted: Initial compaction: Vibratory roller (frequency 35Hz, amplitude 0.8mm) 2 passes; Secondary compaction: 6 passes with a tire roller (pressure 0.5MPa); Final compaction: Steel wheel roller (static compaction) eliminates wheel tracks.

7. The construction method according to claim 6, characterized in that: In the construction of flame-retardant pavement in tunnels, nano-TiO2 / SiO2 sol (30% solid content) is sprayed immediately after final compaction to form a 0.1-0.3mm heat-reflective layer; in the rapid repair of airports, microwave preheating of the substrate (80-100℃) and epoxy segmented mixing are used (components A and B are heated to 120℃ / 135℃ respectively).

8. An application of recycled asphalt pavement made from quartz powder, characterized in that... Applicable to the following scenarios: Heavy-duty traffic roads: Dynamic stability ≥ 4500 cycles / mm; Roads in permafrost regions: freeze-thaw splitting strength ratio ≥95%; Flame-retardant and noise-reducing pavement for tunnels: oxygen index ≥28%, noise reduction coefficient NRC ≥0.45; Airport rapid repair: reopens to traffic within 4 hours, with a compressive strength of ≥45MPa after 28 days.

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