Asphalt Emulsifier Research Articles

Study on production of cation asphalt emulsifier for micro-surfacing by using sulfomethylated lignin

This paper describes the research achievement in manufacturing the cation asphalt emulsifier for micro-surfacing using an eco-friendly material which is rich in resources and low in production cost. This material is alkali lignin which used to be treated as wastes during the processing of wood and the cation asphalt emulsifier for micro-surfacing made from this is sulfomethylated lignin quaternary ammonium salt cation emulsifier. This emulsifier is synthesized through sulfomethylation and quaternary-ammonization of alkali lignin so as to allow the emulsifier molecule to contain two hydrophilic groups inside it. Newly developed cation emulsifier is widely used for micro-surfacing for its high emulsifying power and slowly-disintegrable and fast-setting ability.

Synthesis and Characterization of an Amphoteric Asphalt Emulsifier

Abstract A novel amphoteric asphalt emulsifier of octadecylbis(propanamide)-(3’-sodium phosphate-2’-hydroxypropyl)ammonium chloride was synthesised from the raw materials octadecylamine, acrylamide, epichlorohydrin and sodium dihydrogen phosphate. The tertiary amine octadecyl-bis(propanamide) was synthesised from octadecylamine and acrylamide (step 1). Sodium 3-chloro-2-hydroxypropyl phosphate (intermediate) was obtained from epichlorohydrin and sodium dihydrogen phosphate (step 2). The asphalt emulsifier was obtained from octadecyl-bis(propanamide)-tertiary amine and the intermediate by quaternisation reaction (step 3). The yield of the final product reached 94.90%. The structure was identified by FTIR, 1H-NMR and elemental analysis. The critical micelle concentration of the product is 1.46 × 10–5 mol L–1. The surface tension at CMC is 37.78 mN ν–1. The saturated adsorption amount of asphalt emulsifier is 2.72 × 10–3 mmol ν–2. The occupied area per asphalt emulsifier molecule at CMC is 0.611 nm2 mol–1. The surfactant is a fast-setting asphalt emulsifier.

Synthesis of imidazoline biosurfactants and application as an asphalt emulsifier

This study synthesized an imidazoline biosurfactant (IM-BioSurf) from biomass residue and tetraethylenepentamine in two steps. Its structure was characterized by Fourier transform infrared spectroscopy (FT-IR) and proton NMR spectra (1H-NMR). The critical micelle concentration (CMC) and surface tension (γCMC) of IM-BioSurf were measured, as well as the interfacial tension between the IM-BioSurf aqueous solution and asphalt. At 298 K, the CMC and γCMC of IM-BioSurf were 4.95 g/L and 38.27 mN·m−1, respectively. IM-BioSurf significantly reduced the oil-water interfacial tension, thus conferring excellent surface and interfacial activity. Emulsified asphalt prepared with the IM-BioSurf emulsifier had excellent storage stability and a uniform particle size distribution with an average size of 1.55 μm. In addition, the influence of IM-BioSurf on evaporation residue performance indicators was very small. Moreover, micro-surface tests showed that the emulsified asphalt acts as an excellent binder in asphalt mixtures. Most importantly, the biomass residue used to prepare IM-BioSurf can be readily obtained at low cost. As such, it is environmentally friendly, sustainable, and can greatly reduce the cost of emulsifier production. IM-BioSurf has broad application prospects as an asphalt emulsifier.

Synthesis and characterization of an amphiphilic lignin-based cationic surfactant

Based on the application of alkali lignin polymer modification, not only can the alkali lignin green treatment be realized, but also the dependence on petroleum-based materials can be effectively reduced, and the properties of the modified polymer can be enhanced. Therefore, in this study, α-cinnamon group as the lipophilic group and diethylenetriamine group as the hydrophilic group were successfully introduced into alkali lignin to construct a lignin-based amphiphilic cationic surfactant. The lipophilic group introduced through the amine methylation reaction causes the lignin derivative to form a regular arrangement of lipophilic groups at the oil phase interface, and diethylenetriamine is introduced into the lignin through amine methylation reaction and ketoamine condensation reaction. Effectively enhance the hydrophilicity of the lignin derivative. The characterization of this lignin derivative is accomplished by different methods, such as elemental analysis, Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1HNMR) and X-ray photoelectron spectroscopy (XPS). The physical and chemical properties of the lignin derivative are tested by testing its stability in acidic solution, Zeta potential, surface tension, critical micelle concentration (CMC) and hydrophilic-lipophilic balance (HLB). Studies have shown that this amphiphilic cationic surfactant obtained by modifying alkali lignin has good performance, which means that it can be used as a W/O emulsion as an asphalt emulsifier, wetting agent, etc.

Influence of Emulsifier on Surface Mass Transfer Based on Molecular Dynamics Simulations

To explore the effect of emulsifier structure on mass transfer performance, and provide theoretical basis and ideas for the structure design of new asphalt emulsifier. The mass transfer process of the anionic surfactant sodium dodecyl benzene sulfonate (SDBS) and its four isomers on the solid surface of calcium carbonate, as well as the resulting main chemical component of its aggregates, were studied using molecular dynamics (MD) simulations. It was found that the SDBS and its isomers can be adsorbed on the calcium carbonate surface over a relatively short time and gradually form an aggregate structure during the mass transfer process. In this process, Na ions have no obvious aggregation behavior in the polar head of the emulsifier. The calculated interfacial interaction energy indicates that the adsorption performance and aggregation on the calcium carbonate surface are related to the degree of branching and steric hindrance of the emulsifier molecule. Both the lipophilic group and the hydrophilic group in the emulsifier promote its diffusion into the solution. The results show that molecular dynamics（MD） simulations can be used to supplement experiments to provide the necessary microscopic information and theoretical basis for further experimentation.

Preparation and stabilisation mechanism of asphalt-in-water Pickering emulsion stabilised by SiO2 nanoparticles

In order to improve the performance property of emulsified asphalt, a particle emulsifier is introduced in this study. It serves both as the stabiliser and modifier for the asphalt. A new type of emulsified asphalt, the Nano-SiO2 stabilised asphalt, is prepared successfully. In this paper, a comparison of the stabilisation mechanism between the Pickering and the common emulsion is made. Then, based on the scanning electron microscope results, settlement, and Zeta potential tests, the wettability of the surface-modified Nano-SiO2 with a polycondensate material is analysed. Afterwards, the stable Nano-SiO2 emulsified asphalt is prepared. The stability mechanism of the emulsion is examined through a microscopic approach. Finally, the engineering indexes are tested on the Nano-SiO2 emulsified asphalt. It is revealed that except for the slightly sacrificed ductility, the Nano-SiO2 emulsified asphalt can meet the Chinese emulsified asphalt specification, with improved stability, penetration, and softening point of the residual after evaporation. This study verifies the feasibility of using the Nano-SiO2 as an asphalt emulsifier for preparing Picking emulsions.

Synthesis and Properties of Bifunctional Asphalt Emulsifier

Cationic asphalt emulsifier needs to adjust the system to acidity during use, which will bring potential corrosion hazard to emulsified asphalt production equipment. In this paper, a bifunctional asphalt emulsifier with emulsification and corrosion inhibition was synthesized. The results show that the bifunctional cationic asphalt emulsifier has excellent surface activity, the critical micelle concentration is 56.23 μg/g, and the surface tension value is 25.79 mN/m, the prepared emulsified asphalt has good stability, and the stability of 1d and 5d are 0.28 % and 0.97 %, respectively. At the same time, the asphalt emulsifier has good corrosion inhibition performance for different material test pieces and different corrosive environments. The mechanism study shows that the emulsifier forms a dense adsorption protective film on the metal surface, so that the metal surface in the acid environment is protected from corrosion and the corrosion rate is lowered.

Modified Chitosan as a “Multi‐subtype” Macromolecular Emulsifier for Preparing Asphalt Emulsion

AbstractThe “Multi‐subtype” macromolecular cationic asphalt emulsifier was synthesized based on chitosan (abbreviated as MCTS) via the ring‐opening reaction and quaternization. Then the structure of the emulsifier was characterized by FTIR and 1H‐NMR spectra. Moreover, the surface tension and critical micelle concentration (CMC) of the MCTS were determined from 298 to 313 K. The CMC and γcmc were 0.064 g L−1 and 38.85 mN m−1 at 298 K, respectively, and the lowest surface tension of the solution reached to 26.09 mN m−1 at 313 K. The tested Hydrophile‐Lipophile Balance (HLB) value of MCTS was 10, which can meet the requirement of asphalt emulsifier. Through emulsification experiments, the emulsifying ability of the MCTS was measured, and the results indicated that the emulsifier exhibited excellent application for asphalt. It may be caused by that the MCTS containing polar bundle groups could enhance the interaction between polar asphaltene and the emulsifier solution. Moreover, the prepared asphalt emulsion was more stable compared to the emulsion prepared by Gemini emulsifier. The demulsification experiments were also correspondingly done for emulsified asphalt. All the results showed that the MCTS has potential applications in the preparation of asphalt emulsion.

Synthesis and characterization of quaternary ammonium salt tertiary amide type sodium hydroxypropyl phosphate asphalt emulsifier

A novel asphalt emulsifier of octadecyl-bis(1-(N,N-dimethyl)propanamide)-(3′-sodium phosphate-2′-hydroxypropyl) ammonium chloride was synthesized in three steps by using octadecylamine, N,N-dimethyl acrylamide, epichlorohydrin, sodium dihydrogen phosphate, and reaction solvent of isopropanol as raw materials. In the first step, octadecyl-bis(1-(N,N-dimethyl)propanamide) tertiary amine was synthesized by the reaction of octadecylamine with N,N-dimethyl acrylamide. The second step is the reaction of epichlorohydrin with sodium dihydrogen phosphate to obtain sodium 3-chloro-2-hydroxypropyl phosphate (intermediate). The third step is the reaction of the first-step product with the intermediates to obtain the asphalt emulsifier product by quaternization reaction. The optimum conditions for the third step were as follows: reaction temperature at 70 °C, reaction time for 5 h, the feedstock mole ratio of epichlorohydrin to octadecylamine at 1.40. Under these conditions, the yield of asphalt emulsifier reaches 95.65%. The structure of asphalt emulsifier was characterized by FTIR, 1H-NMR and elemental analysis. The results show that the structure of asphalt emulsifier is the same as that of the target product. The critical micelle concentration (CMC) of the asphalt emulsifier at the temperature of 298 K is 1.15 × 10−6 mol L−1. The surface tension of aqueous solution at critical micelle concentration (γCMC) is 27.72 mN m−1. The saturated adsorption amount (ГCMC) of surfactant aqueous solution is 1.98 × 10−3 mmol m−2. The occupied area per surfactant molecule at the CMC (ACMC) of surfactant molecules is 0.837 nm2 mol−1. The performance test by emulsification with AH-70 asphalt and mixing with aggregate shows that the asphalt emulsifier has good emulsification property, and the prepared asphalt emulsion has good storage stability. The asphalt emulsifier is a rapid-set asphalt emulsifier.

The Synthesis and Characterization of a Novel Cationic Asphalt Emulsifier

A new cationic asphalt emulsifier of N,N-dimethyl-N-(3-(N',N'-dimethyl amido)-2-hydroxy propyl)- coconut oil amide propyl-1-ammonium chloride was synthesized by two steps reaction of coconut oil acyl propyl dimethyl tertiary amine (PKO), epoxy chloropropane and dimethylamine. The chemical structure of the key intermediate of N,N-dimethyl-N-(ethylene oxide-2-methylene)-coconut oil amide propyl-1-ammonium chloride was confirmed by FTIR, 1H NMR and elemental analysis. The optimum reaction condition of first step was obtained by single factor analysis: reaction time 5 h, reaction temperature 50 °C, feedstock mole ratio of epoxy chloropropane to PKO 1.05. The reaction yield is 82.15% and the epoxy value is 40.39% at the optimum conditions. The critical micelle concentration (CMC) of the asphalt emulsifier is 7.80×10-2 mol/L. The surface tension at CMC is 24.57 mN/m. The emulsifier showed excellent emulsification effect for the asphalt. The prepared bituminous emulsion had higher storage stability. The emulsifier belongs to medium-set asphalt emulsifier.

Characterization of Emulsified Asphalt Emulsifier for Cold Recycling Asphalt Mixture

Characterization of Emulsified Asphalt Emulsifier for Cold Recycling Asphalt Mixture

Improved Synthesis and Properties of N-(3-octadecylamino-2-hydroxyl) Propyl Trimethyl Ammonium Chloride

AbstractThe cationic surfactant, N-(3-octadecylamino-2-hydroxyl) propyl trimethyl ammonium chloride was synthesized by an improved synthesis method and the structure was confirmed by Mass Spectrometry and 1H NMR Spectrometry. The physiochemical properties of the product were investigated systematically by surface tension and conductivity measurements. Various physiochemical parameters were calculated to evaluate the surface activities of the surfactant. The results show that both the critical micelle concentration and the degree of counterion dissociation increased with increasing temperature, but the surface tension at CMC decreased, which is opposite to that obtained on the previous condition with increasing NaCl concentration. The thermodynamic parameters obtained from conductivity measurement show that the micelle formation of the surfactant is entropy-driven in the investigated temperature range. While used as an asphalt emulsifier, N-(3-octadecylamino-2-hydroxyl) propyl trimethyl ammonium chloride exhibited an excellent emulsifying ability and it was a medium-set asphalt emulsifier.

Synthesis and Properties of a Cationic Gemini Asphalt Emulsifier

AbstractA cationic Gemini surfactant with a benzene ring (abbreviated as C14‐CGB) was synthesized in 2 steps with aniline, epichlorohydrin, and N,N‐dimethyltetradecylamine as starting materials. This product was characterized using mass spectroscopy and nuclear magnetic resonance (1H NMR). The critical micelle concentration (CMC) and surface tension (γcmc) of C14‐CGB were measured from 298 to 313 K and thermodynamic parameters of micellization were calculated. The results showed that the CMC and γcmc were 1.269 × 10−3 mol L−1 and 38.33 mN m−1 at 298 K, respectively. Moreover, upon increasing the temperature, the CMC increases, γcmc decreases, the maximum surface adsorption capacity (Γmax) decreases, and the minimum molecular area (Amin) increases. The emulsified asphalt test showed that C14‐CGB is a slow‐breaking asphalt emulsifier exhibiting excellent emulsifying ability.

A novel cationic emulsifier used for preparing slow-cracking and rapid-setting asphalt: Synthesis, surface activity, and emulsification ability

ABSTRACTA novel cationic emulsifier including nonionic fatty alcohol polyoxyethylene ether was synthesized in two steps from epichlorohydrin, octadecyl dimethyl amine, and fatty alcohol polyoxyethylene ether, and the intermediate product could also be used as an emulsifier. Their structures were characterized by FTIR, and the surface activities were investigated by surface tension, electrical conductivity, and HLB. The obtained results indicated that the critical micelle concentration (CMC) of the final product was low, 0.442 mmol/L, and the surface tension at the CMC was 41.02 mN/m. The hydrophile-lipophile balance (HLB) value was 12, which meet the requirements of asphalt emulsifiers. A series of experiments of the emulsified asphalt prepared by the emulsifiers were performed. The results showed that the emulsified asphalt could be stably stored for more than 5 days when the emulsifier was 2 wt% and the pH value was between 3 and 4. The result of demulsification experiments showed that the emulsifier is a slow-cracking and rapid-setting asphalt emulsifier.

Synthesis and Properties of a Novel Gemini Surfactant with Bis-piperidinium

Abstract A novel cationic Gemini surfactant with bis-piperidinium and benzene ring (C10-CGP) was synthesized by aniline, epichlorohydrin and 1-bromodecane in three steps. The structure of C10-CGP was characterized by mass spectroscopy (MS) and nuclear magnetic resonance (1H NMR). The critical micelle concentration (CMC) and the corresponding surface tension (γ CMC) of C10-CGP were measured from 298 K to 313 K and the thermodynamic parameters of the micellization were calculated. The results showed that the critical micelle concentration (CMC) and γCMC were 0.976 × 10−3 mol · L−1 and 28.93 mN · m−1 at 298 K, respectively. With the temperature increase, the CMC increased, the maximum surface adsorption capacity (Γ max) decreased, the γ CMC decreased and the minimum molecule area (A min) increased. The free energy of the system during the micelle formation was negative. When the Gemini surfactant was used as an asphalt emulsifier, C10-CGP exhibited good a emulsifying ability. C10-CGP is a slow-set asphalt emulsifier.

The Synthesis and Characterization of Novel Bis-cationic Asphalt Emulsifier

Three novel bis-cationic asphalt emulsifiers were synthesized by two steps reaction of N-tallow-1,3-diaminopropane, methyl acrylate, sodium hydroxide and chloroacetic acid. The structure of the product was confirmed by FTIR, 1 H NMR and elemental analysis. The emulsifier exhibits satisfactory emulsification. The prepared bituminous emulsion showed higher storage stability. The emulsifier belongs to medium-set and slow-set asphalt emulsifier. It can be designed to perform in a wide variety of applications including tack coat, fog seal, chip seal and slurry seal in asphalt pavement construction.

A novel betaine type asphalt emulsifier synthesized and investigated by online FTIR spectrophotometric method

A novel betaine type asphalt emulsifier 3-(N,N,N-dimethyl acetoxy ammonium chloride)-2-hydroxypropyl laurate was synthesized after three steps by the reaction of lauric acid, epichlorohydrin, dimethylamine and sodium chloroacetate. The optimum reaction conditions were obtained for the synthesis of the first step of 3-chloro-2-hydroxypropyl laurate. The esterification yield reaches 97.1% at the optimum conditions of reaction temperature 80?C, reaction time 6 h, feedstock mole ratio of epichlorohydrin to lauric acid 1.5, mass ratio of catalyst to lauric acid 2%. The chemical structure of the product was characterized by FTIR and 1H NMR. The first synthesis step of 3-chloro-2-hydroxypropyl laurate was monitored by online FTIR technique. The by-product was detected by the online FTIR analysis. Based upon the experimental data, a plausible reaction mechanism was proposed for the reaction. The CMC of the objective product has a lower value of 7.4?10-4 mol/L. The surface tension at CMC is 30.85 mN/m. The emulsifier is a rapid-set asphalt emulsifier.

Synthesis and Characterization of a Novel Cationic Type Asphalt Emulsifier

A novel cationic type asphalt emulsifier of 2-triethylenetetramine methylene-4-nonylphenol was synthesized by the reaction of nonyl phenol, triethylenetetramine and formaldehyde. The optimum reaction condition was obtained. The yield reaches 49.21% at the optimum reaction condition of the feedstock mole ratio of formaldehyde to nonyl phenol 2.8, feedstock mole ratio of triethylenetetramine to nonyl phenol 1.0, reaction temperature 95°C, and reaction time 5 h. The structure of the emulsifier was identified by FTIR. The emulsifier exhibits satisfactory emulsification. The emulsifier belongs to the class of rapid-set asphalt emulsifiers.

Synthesis of Novel Cationic Asphalt Emulsifier and its Investigation by Online FTIR Spectrophotometry

A novel cationic asphalt emulsifier of N-(3-polyoxyethylene nonyl phenyl ether (10)-2-hydroxyl) propyl-N,N,N-triethyl ammonium chloride was synthesized by nonylphenol polyoxyethylene ether (NP-10), epichlorohydrin and triethylamine. The optimum reaction condition was obtained. The yield reaches 48.72% at the optimum conditions of the feedstock mole ratio of NaOH to NP-10 1.0, the mole ratio of epichlorohydrin to NP-10 1.2, the mole ratio of triethylamine to NP-10 1.2, reaction temperature 70°C, and reaction time 8 h. The structure of the emulsifier was identified by FTIR. The synthesis process was monitored by online FTIR technique and the intermediate was detected. Based upon the experimental data, a plausible reaction mechanism was proposed for the reaction. The emulsifier belongs to slow-set asphalt emulsifier.

Synthesis of Lignin Amine Asphalt Emulsifier and its Investigation by Online FTIR Spectrophotometry

A novel cationic asphalt emulsifier of tetraethylenepentamine/formaldehyde modified lignin amine was synthesized by alkali lignin, tetraethylenepentamine and formaldehyde. The optimum reaction condition was obtained. The structure of the emulsifier was identified by FTIR. The synthesis process was monitored by online FTIR technique. Based upon the experimental data, a plausible reaction mechanism was proposed for the reaction. The target product has good surface activity and satisfactory emulsification effect. The prepared bituminous emulsion showed higher storage stability. The emulsifier belongs to slow-set asphalt emulsifier.