Dodecane Molecules Research Articles

Enhancing emulsion stability and adsorption of Pickering emulsions using alkylated cellulose nanofibers

Cellulose nanofibers (CNFs) extracted from plant cell walls form a three-dimensional network in water and stabilize the dispersion of droplets, which are used as emulsion stabilizers. In this study, four types of alkyl-grafted CNFs (ACNFs) with different lengths of dialkyl chains (diC4, diC6, diC8, and diC10) were synthesized by the surface modification of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized CNF (TOCNF) to improve the stability of oil-in-water Pickering emulsions (PEs). The ACNF-stabilized emulsions with a 20/80 ratio of oil/water were prepared using two different oils (olive oil and eucalyptus oil) and the ACNF 1.0 % dispersion, and the changes over time were investigated at approximately 25 °C. Compared to TOCNF, the ACNFs provided more stable olive oil-PE (o-PE) and eucalyptus oil-PE (e-PE) although the stabilization behaviors of o-PE and e-PE differed. Olive oil, which contained rich long-chain fatty acids, was more likely to interact with the ACNFs, thereby promoting the interfacial adsorption of oil droplets. On the other hand, eucalyptus oil is mainly composed of 1,8-cineole and does not have alkyl chains, so the interaction with the ACNFs was weak and therefore, sufficient interfacial adsorption could not be obtained. The results of the particle size distribution and viscosity measurements also showed that the ACNFs contributed significantly to the stabilization of o-PE. Based on the overall experimental results, it was determined that the diC6-ACNF gave the most significant stability improvement. Therefore, we designed an alkylated CNF that mimics diC6-ACNF for MD simulations. MD simulations showed that hydrophobic modification created a hydrophobic interaction between the alkyl chain and dodecane molecules as the oil, leading to the enhancing adsorption of ACNF at the oil droplet interfaces.

Effects of Sulfate Ions on Crude Oil Adsorption/Desorption on Carbonate Rocks: Experimental and Molecular Simulations.

In the background of the strong oil wettability and low production by water flooding in carbonate reservoirs, low-salinity water containing sulfate ions can significantly change the surface wettability of carbonate rocks and thus increase the sweeping area; however, the absorption and desorption mechanisms of the oil film in the carbonate rock surface remain unclear. This paper analyzed the wettability alternation of carbonate rocks' surface in pure water and sodium sulfate solution. At the same time, MD (Materials Studio) software was used to simulate the formation process of the oil film and the effect of sulfate ions on the desorption of the oil film on the surface of carbonate rocks. The experimental results showed that sodium sulfate solution could accelerate the rate from oil-wet to water-wet and the final contact angle (49°) was smaller than that in pure water. The simulation results showed that dodecane molecules moved to the surface of calcite to form a double layer of the oil film and that the oil film near the calcite surface had a high-density stable structure under the van der Waals and electrostatic action. The hydrating sulfate ions above the oil film broke through the double oil film to form a water channel mainly under the action of electrostatic force and a hydrogen bond and then adsorbed on the calcite surface. A large number of water molecules moved down the water channel based on a strong hydrogen bonding force and crowded out the oil molecules on the surface of the calcite, resulting in the oil film detachment. This work aims to explain the interaction of oil molecules, water molecules, and SO42- ions at the molecular scale and guide the practical application of low-salinity water flooding in carbonate reservoirs.

Effect of mixed collector on the LRC flotation: an experimental and molecular dynamics simulation study

ABSTRACT To investigate the mechanism underlying the effect of mixed collector (MC) composed of diesel and span-80 on LRC flotation, a combination of experimental and molecular simulation approaches was employed. The flotation results demonstrated that the use of MC yielded superior flotation performance compared to diesel alone. The ratio of diesel to span-80 emerged as a key factor influencing the performance of MC collection. Furthermore, molecular dynamics (MD) simulations were employed to investigate the adsorption processes of dodecane and MC molecules on the LRC surface in the LRC/dodecane/water and LRC/MC/water systems, respectively. The analysis encompassed microstructure, dynamic properties, interaction energy, and hydrogen bonding. The findings indicated that the presence of span-80 molecules facilitated the direct entry of dodecane molecules in MC into “microscopic cavities,” thereby enhancing the adsorption of MC on the LRC surface. The analysis of interaction energy revealed a stronger interaction between MC molecules and the coal surface, with van der Waals energy playing a major role in the adsorption process. Additionally, span-80 molecules induced hydrogen bonding adsorption on the LRC surface.

Molecular dynamics of interfacial crystallization of dodecane on hydroxylated silica surface impacted by H2O and CO2.

The morphology of dodecane in a nanopore at temperatures typical in exploited or depleted oil reservoirs is investigated using molecular dynamics simulation. The dodecane morphology is found to be determined by interactions between interfacial crystallization and surface wetting of the simplified oil, while "evaporation" only plays a minor role. The morphology changes from an isolated, solidified dodecane droplet to a film with orderly lamellae structures remaining within, and finally to a film containing randomly distributed dodecane molecules, as the system temperature increases. In a nanoslit under the impact of water, since water wins against oil in surface wetting on the silica surface due to electrostatic interaction induced hydrogen bonding between water and the silanol group of silica, the spreading of dodecane molecules over the silica surface is impeded by this water confinement mechanism. Meanwhile, interfacial crystallization is enhanced, leading to always an isolated dodecane "droplet," with crystallization weakening as the temperature increases. Since dodecane is immiscible to water, there is no mechanism for dodecane to escape the silica surface, and the competition of surface wetting between water and oil determines the morphology of the crystallized dodecane droplet. For the CO2-dodecane system in a nanoslit, CO2 is an efficient solvent for dodecane at all temperatures. Therefore, interfacial crystallization rapidly disappears. The competition of surface adsorption between CO2 and dodecane is secondary for all cases. The dissolution mechanism is a clear clue for the fact that CO2 is more effective than water flooding in oil recovery for a depleted oil reservoir.

Energetic and Structural Characterizations of the PET–Water Interface as a Key Step in Understanding Its Depolymerization

We report molecular simulations of the interaction between poly(ethylene terephthalate) (PET) surfaces and water molecules with a short-term goal to better evaluate the different energy contributions governing the enzymatic degradation of amorphous PET. After checking that the glass transition temperature, density, entanglement mass, and mechanical properties of an amorphous PET are well reproduced by our molecular model, we extend the study to the extraction of a monomer from the bulk surface in different environments, i.e., water, vacuum, dodecane, and ethylene glycol. We complete this energetic characterization by the calculation of the work of adhesion of PET surfaces with water and dodecane molecules and by the determination of the contact angle of water droplets. These calculations are compared with experiments and should help us to better understand the enzymatic degradation of PET from both the thermodynamic and molecular viewpoints.

Emulsification mechanism of surfactants in different oil phases: A dissipative particle dynamics study

The type of oil component affects the emulsification behaviors of surfactants while the underlying mechanism remains vague. In this work, the dissipative particle dynamics (DPD) method is conducted to analyze the behaviors of polyoxyethylated alcohols non-ionic surfactant at different water/oil (W/O) interfaces. Towards this end, the benzene and dodecane molecules are chosen as representatives of aromatic and alkane, respectively. The density distribution of surfactants, the radial distribution functions between different pairs of components, and the diffusion coefficient of surfactants are investigated, along with the morphological analysis. The phenomenon of similarity and intermiscibility is observed at the nanoscale between the hydrophobic chain of the surfactant and the oil phase, and in addition, it is found that the diffusion constant of surfactant molecules in water/benzene systems is nearly three times larger than that in water/dodecane systems, and a local maximum value of diffusion coefficient appears near the critical micelle concentration. This work provides a theoretical guidance for the screening and use of surfactants under different external environments.

Molecular Resolution Imaging of Adsorption of Dodecane on a Lignite Surface by Frequency Modulation AFM

The consumption of dodecane, a critical flotation collector, in the flotation of low-rank coal is particularly high; however, the adsorption mechanism of dodecane on coal still remains unclear. To shed light on this issue, the molecular-scale adsorption structure of dodecane on a lignite surface was investigated in situ by frequency modulation atomic force microscopy (FM-AFM) for the first time. The adsorption structure of dodecane on highly oriented pyrolytic graphite (HOPG) and mica has been detected in advance. Meanwhile, molecular dynamics (MD) simulations are utilized to elucidate and illustrate the adsorption structure on HOPG, mica, and lignite. Experimental results from FM-AFM show that a layered structure of dodecane molecules is formed on HOPG, while there is no stable adsorption structure on mica. Meanwhile, a few local monolayer structures of dodecane molecules are observed on the surface of lignite, and their thickness is approximately 1 nm, which is less than the molecular chain length of dodecane. It is speculated that the dodecane molecules are adsorbed on lignite selectively, with the capacity to form a stable adsorption structure. As indicated by MD simulations, the interaction energy between dodecane and the mentioned surfaces is in the order HOPG > lignite > mica. And the MD simulation results show a desirable match with direct observation by FM-AFM. In accordance with the characterization of the lignite sample surface, large amounts of polar oxygen-containing functional groups may hinder dodecane adsorption behavior. Through in situ molecular resolution imaging of the interface structure between dodecane and a raw lignite surface, we provide a new perspective for exploring the interaction mechanism between nonpolar collectors and a lignite surface.

Effect of Hydration Layer on the Adsorption of Dodecane Collector on Low-Rank Coal: A Molecular Dynamics Simulation Study

The hydration layer has a significant effect on the adsorption behavior of reagents during the flotation process of low-rank coal. Understanding the effect of hydration layer on the adsorption of common collectors on low-rank coal is a prerequisite for proposing a new enhanced coal floatation method. In this study, a smooth low-rank coal surface model with a density of 1.2 g/cm3 was constructed and compared with the XPS results. Three different systems, coal-water, coal-collector, and coal-water-collector, were constructed. Molecular dynamics method was applied to study the adsorption behaviors of water and dodecane molecules. Simulation results revealed that a stable hydration layer with a thickness of about 5 Å was formed due to the strong attraction of coal surface. The negative value of interaction energy (IE) indicated that dodecane molecules could spontaneously adsorb on the coal surface. Dodecane molecules were successfully adsorbed on the coal surface when it was located inside the hydration layer. While the dodecane molecule was outside the hydration layer, it could not pass through the hydration layer on the surface of low-rank coal.

Role of dodecane on coal particle-bubble interaction in aqueous phase

Even if coal particles are hydrophobic, interaction between these particles and air bubbles can be enhanced by nonpolar oil in froth flotation. The role of a nonpolar liquid dodecane on coal particle-bubble interaction in aqueous phase was investigated and compared to that of a solid analogue, paraffin wax via a combined application of water contact angle and particle-bubble stability measurements, and molecular dynamics simulations. It was found both dodecane and paraffin wax can increase hydrophobicity of coal surface and attachment stability of coal particle-bubble aggregates when they covered the coal particles. Despite similar chemical structure and hydrophobicity, dodecane was more effective than paraffin wax. Molecular simulations confirmed that, comparing to the unmodified coal particle, both dodecane and paraffin wax models could increase the attachment strength of coal particle. However, different from immobile solid paraffin wax, we demonstrated that the liquid like properties of the dodecane layers present on the coal particle surfaces play an essential role in the particle-bubble interaction. When the coal particle covered by dodecane arrived at gas−water interface, the dodecane molecules will migrate and rearrange to form a new film at this interface. In addition to hydrophobic attraction of the gas bubble, the dodecane film will provide additional adhesion towards the coal particle due to oleophilicity of the coal particle, enhancing the stability of bubble-particle aggregate.

Surface tension at the interface between aqueous solution of surfactant and alkane. A comprehensive quantum chemical and thermodynamic approach

A thermodynamic model is used to analyse the adsorbed layers of CnDMPO (n = 12, 13), CnTAB (n = 10, 12, 14, 16) and SDS at the aqueous solution/hexane and aqueous solution/dodecane interfaces. The combined model assumes that the adsorption of alkane from the oil phase is governed by the Frumkin model, and the adsorption of the surfactant molecules from the solution obeys the reorientation model. We are able to show that at low surfactant concentrations a remarkable decrease of interfacial tension occurs due to a cooperative formation of a mixed adsorption layers by surfactant and alkane molecules. By a quantum chemical semi-empiric (PM3) simulation we analyse the orientation of oil and surfactant molecules in the interfacial layer, and calculate the relative amounts of adsorbed surfactant and alkane. The values obtained from the thermodynamic models agree well with those results calculated via the PM3 simulation. The results show, that at the interface the short-chain hexane molecules can form bi-layers with the long-chain surfactants, while the dodecane and surfactant molecules having commensurable chain lengths are mainly forming mixed monolayer.

Adsorption behavior of mixed dodecane/n-valeric acid collectors on low-rank coal surface: Experimental and molecular dynamics simulation study

In this investigation, a mixed collector (MC) of dodecane and n-valeric acid was used to improve low rank coal flotation. Fourier transformation infrared spectroscopy (FTIR) measurements and contact angle measurements were conducted to explain flotation responses. Furthermore, using a molecular dynamics (MD) simulation, the changes of water/collector (dodecane or MC)/coal systems were studied before and after adsorption to indicate the absorption behavior and mechanism. The results showed that a better flotation performance of low-rank coal was obtained using the MC compared to a conventional collector of dodecane. The hydroxyl (OH) or carbonyl (CO) or carboxyl (COOH) migration of the coal with the MC was stronger than that with dodecane as a solo collector, and the MC can enhance the hydrophobicity and lipophilicity of the coal surface. MD simulation results revealed the adsorption behavior of the MC on low-rank coal surfaces. Dodecane was mainly adsorbed on the hydrophobic surface of coal, and n-valeric acid was more inclined to act on the oxygen-containing functional group of coal, i.e., a hydrophilic surface. The mobility of = dodecane molecules on the coal surface was reduced owing to the presence of n-valeric acid, which increased the lipophilicity and hydrophobicity of the low-rank coal surface, thus attracting dodecane molecules of the MC and restricting their movement, and accelerating the departure of water molecules from the low-rank coal surfaces. There was also a higher interaction energy between the MC and low-rank coal. The simulation results are in good agreement with the measured results; this effectively explains the flotation results.

Improving the adsorption of oily collector on the surface of low-rank coal during flotation using a cationic surfactant: An experimental and molecular dynamics simulation study

The effect of a cationic surfactant, dodecyltrimethylammonium bromide (DTAB), on low-rank coal flotation using an oily collector (dodecane) was investigated by a combination of experimental tests and molecular dynamics simulations. Flotation results showed that the addition of DTAB during pulp conditioning increased the clean coal yield, while a high concentration of DTAB exerted a negative influence. To explain the flotation behavior and analyze the interaction between low-rank coal, DTAB and dodecane, a series of experimental tests were conducted and the results indicated that a relatively lower concentration of DTAB is beneficial for the adsorption of dodecane on low-rank coal surface. In addition, by measuring the induction time, it was found that low-rank coal particles were easily adhered to bubbles in the presence of suitable concentration of DTAB. However, a high concentration of DTAB brings about an adverse effect. Later, molecular dynamics (MD) simulations were carried out to illustrate the positive effect of DTAB on the adsorption reaction between low-rank coal and dodecane. The results showed that the abundant number of oxygen-containing groups in low-rank coal are responsible for the limited adsorption of nonpolar dodecane molecules on its surface, while the pre-adsorption of DTAB on the surface of low-rank coal enhances dodecane adsorption. This can be ascribed to the exposed hydrophobic structure of the coal-DTAB complex. As a result, dodecane molecules were more easily adsorbed on the surface of low-rank coal and the attraction of low-rank coal to dodecane in the presence of DTAB resulted in a lower mobility of dodecane molecules, and a larger interaction energy between dodecane and low-rank coal. The simulation results are in good agreement with experimental results.

Molecular dynamics simulations of the graphene sheet aggregation in dodecane

Molecular dynamics simulations are used to investigate the aggregation and behavior of two parallel graphene sheets (22.0–64.0 A in length) in dodecane. The dodecane layer formed on the graphene surface leads to an energy barrier which slows the rate of the graphene aggregation process when the two sheets are totally separated by dodecane molecules. The graphene sheets aggregate in dodecane only when portions of one graphene sheet are in contact with another sheet. The aggregation rate depends on the combined structures of the two graphene sheets. The aggregation rate for two parallel graphene sheets in half contact with one another is constant since the relative sheet geometry and spacing are nearly constant in the transition region between sheets where dodecane molecules are being displaced during aggregation. The aggregation rate for partially overlapped graphene sheets becomes progressively slower as aggregation continues since the area not overlapped decreases as the aggregation proceeds.

Behavior of protruding lateral plane graphene sheets in liquid dodecane: molecular dynamics simulations

Molecular dynamics simulations are used to investigate the behavior of two parallel graphene sheets fixed on one edge (lateral plane) in liquid dodecane. The interactions of these sheets and dodecane molecules are studied with different starting inter-sheet distances. The structure of the dodecane solvent is also analyzed. The results show that when the distance between the two graphene sheets is short (less than 6.8 A), the sheets will expel the dodecane molecules between them and stack together. However, when the distance between two sheets is large (greater than 10.2 A), the two sheets do not come together, and the dodecane molecules will form ordered layers in the interlayer spacing. The equilibrium distance between the graphene sheets can only take on specific discrete values (3.4, 7.8, and 12.1 A), because only an integer number of dodecane layers forms between the two sheets. Once the graphene sheets are in contact, they remain in contact; the sheets do not separate to allow dodecane into the interlayer spacing.

Effect of Dodecane on the Surface Structure and the Electronic Properties of Pentacene on Modified Si (001)

The structural and the electronic properties of pentacene on modified Si (001) were investigated using scanning tunneling microscopy (STM), atomic force microscopy (AFM) and ultraviolet photoelectron spectroscopy (UPS). Dodecane was used to modify Si (001) substrates and then pentacene was deposited on dodecane/Si (001). Our STM results show a uniform distribution of aggregated dodecane molecules all over the clean Si (001). The surface structure of pentacene on dodecaene/Si (001) examined by AFM is analogous to that of pentacene on SiO2. The UPS data showed that the work function of pentacene on clean Si (001) and pentacene on modified Si (001) with dodecane was 6.41 and 5.57 eV, respectively. Our results prove that dodecane results in the work function difference between pentacene on clean Si (001) and pentacene on dodecane/Si (001).

Effects of the surroundings and conformerisation of n-dodecane molecules on evaporation/condensation processes.

The evaporation/condensation coefficient (β) and the evaporation rate (γ) for n-dodecane vs. temperature, gas pressure, gas and liquid density, and solvation effects at a droplet surface are analysed using quantum chemical density functional theory calculations of several ensembles of conformers of n-dodecane molecules in the gas phase (hybrid functional ωB97X-D with the cc-pVTZ and cc-pVDZ basis sets) and in liquid phase (solvation method: SMD/ωB97X-D). It is shown that β depends more strongly on a number of neighbouring molecules interacting with an evaporating molecule at a droplet surface (this number is estimated through changes in the surface Gibbs free energy of solvation) than on pressure in the gas phase or conformerisation and cross-conformerisation of molecules in both phases. Thus, temperature and the surrounding effects at droplet surfaces are the dominant factors affecting the values of β for n-dodecane molecules. These values are shown to be similar (at reduced temperatures T/Tc < 0.8) or slightly larger (at T/Tc > 0.8) than the values of β calculated by the molecular dynamics force fields (MD FF) methods. This endorses the reliability of the previously developed classical approach to estimation of β by the MD FF methods, except at temperatures close to the critical temperature.

GPU-Based Implementations of the Noniterative Regularized-CCSD(T) Corrections: Applications to Strongly Correlated Systems

The details of the graphical processing unit (GPU) implementation of the most computationally intensive (T)-part of the recently introduced regularized CCSD(T) (Reg-CCSD(T)) method [ Kowalski , K. ; Valiev , M. J. Chem. Phys. 2009 , 131 , 234107 ] for calculating electronic energies of strongly correlated systems are discussed. Parallel tests performed for several molecular systems show very good scalability of the triples part of the Reg-CCSD(T) approach. We also discuss the performance of the Reg-CCSD(T) GPU implementation as a function of the parameters defining the partitioning of the spinorbital domain (tiling structure). The accuracy of the Reg-CCSD(T) method is illustrated on three examples: the methyfluoride molecule, dissociation of dodecane, and open-shell Spiro cation (5,5'(4H,4H')-spirobi[cyclopenta[c]pyrrole] 2,2',6,6'-tetrahydro cation), which is a frequently used model to study electron transfer processes. It is demonstrated that a simple regularization of the cluster amplitudes used in the noniterative corrections accounting for the effect of triply excited configurations significantly improves the accuracies of ground-state energies in the presence of strong quasidegeneracy effects. For methylfluoride, we compare the Reg-CCSD(T) results with the CR-CC(2,3) and CCSDT energies, whereas for Spiro cation we compare Reg-CCSD(T) results with the energies obtained with completely renormalized CCSD(T) method. Performance tests for the Spiro, dodecane, and uracil molecules are also discussed.

Poly(N-isopropylacrylamide) Microgels at the Oil−Water Interface: Interfacial Properties as a Function of Temperature

Highly monodisperse poly(N-isopropylacrylamide), PNiPAM, microgels were prepared by the conventional radical polymerization of NiPAM in the presence of dimethylamino ethyl methacrylate (DMAEMA) monomers at various concentrations. The effect of DMAEMA on the polymerization of PNiPAM microgels was examined at constant initiator (V50) and cross-linker (MBA) concentrations. The presence of DMAEMA in the synthesis batch allows for the preparation of PNiPAM microgels with controlled size and a narrow size distribution. The oil(dodecane)/water interfacial properties of the model PNiPAM microgels were then investigated. The pendant drop technique was used to measure the interfacial tensions as a function of temperature. Over the whole range of temperature (20-45 degrees C), the interfacial tension remains low (on the order of 17 mN/m) and goes through a minimum (12 mN/m) at a temperature of about 34 degrees C, which well matches the volume phase transition temperature (VPTT) of PNiPAM microgels. Below the VPTT, the decrease in the interfacial tension with temperature is likely to be due to the adsorption of dense layers because of the decrease of the excluded volume interactions. Above the VPTT, we suggest that the increase in the interfacial tension with temperature comes from the adsorption of loosely packed PNiPAM microgels. We also studied the effect of temperature on the stability of emulsions. Dodecane in water emulsions, which form at ambient temperature, are destabilized as the temperature exceeds the VPTT. In light of the interfacial tension results, we suggest that emulsion destabilization arises from the adsorption of aggregates above the VPTT and not from an important desorption of microgels. Aggregate adsorption would bring a sufficiently high number of dodecane molecules into contact with water to induce coalescence without changing the interfacial tension very much.

Molecular simulation of the transition from liquidlike to solidlike behavior in complex fluids confined to nanoscale gaps

We report molecular dynamics simulations at ambient temperature and pressure of dodecane films of thickness between three and eight molecular layers confined between mica surfaces. We use an accurate united-atom model for dodecane and an effective interaction between the dodecane and the confining mica surfaces that is consistent with the surface energy of a mica surface. At ambient normal pressure, the strong surface–fluid interaction leads to increased dodecane density as the wall spacing is narrowed, crossing into a density region corresponding to bulk solid when the confined film becomes narrower than six molecular layers. Correspondingly, we observed a dramatic transition from a liquidlike to an ordered, solidlike structure when the confined dodecane film is reduced from seven to six molecular layers, consistent with experimental observation of many orders of magnitude increase in viscosity at the same film thickness. The solidlike structure is characterized by the layering as well as the in-plane orientational order of the dodecane molecules. At an extreme confinement of three molecular layers, the solidlike confined film is able to sustain a nonzero shear stress. These results with realistic models provide an improved understanding of the solidlike behavior observed in surface force apparatus experiments.

Molecular dynamics simulation of boundary lubricated interfaces

A molecular dynamics simulation study of friction in boundary lubrication was conducted in order to investigate the atomic-scale behavior of lubricant molecules during sliding motion. The simulated system consisted of two silicon (001) semi-infinite substrates lubricated by a three-layer film of dodecane. Silicon was modeled using the Stillinger-Weber potential, and the dodecane with the Consistent Force Field function; a novel scheme was used to generate the silicon-dodecane interaction potentials. The simulations show that dodecane molecules strongly prefer to adsorb into the ledges on the silicon surface. The orientation of the adsorbed molecules depends, however, on the concentration of the lubricant at the surface, showing a tendency to stand up at high lubricant concentrations. In sliding, the dodecane layers adsorbed on the surfaces behave as a solid, whereas the middle layer exhibits liquid-like characteristics. The friction coefficient of this well-lubricated case was calculated to be 0.08.