Stabilization of water-in-oil emulsions with continuous phase crystals

The role of continuous phase paraffin wax crystals on water-in-mineral oil emulsion ( = 0.2) aggregation, coalescence and sedimentation behavior was studied. Paraffin wax crystal properties were controlled by using two crystallization regimes. In regime 1, pre-crystallized wax was added prior to emulsification. In regime 2 (post-crystallization), molten wax was emulsified and quench-crystallized in situ following emulsification. Based on d_0,0 values, all emulsions containing quench-crystallized wax were more stable than their pre-crystallized equivalents (p < 0.05). Sedimentation analyses indicated that, over a 10-day period, regime 2 emulsions with 0.5% (w/w) or more wax in the continuous phase did not phase separate. Only regime 1 emulsions that contained 2% (w/w) added wax did the same. Brightfield and polarized light microscopy revealed the presence of aggregated wax crystal networks in both post-crystallized and pre-crystallized systems. However, the crystals forming the network were much smaller in the former. Atomic force microscopy and X-ray diffraction indicated that the presence of the emulsifier used to aid in emulsion formation also affected wax morphology and polymorphic behavior. In conclusion, due to the presence of a well-defined network structure, emulsions consisting of wax-crystallized in situ were more stable than emulsions with crystals added prior to emulsification.     

Synthesis of Some Additives and Study Effect of Gas Oil Composition on Flow Properties

Nine additives were prepared by esterification of dibasic acid (succinic, adipic, sebacic acid) and polyethylene glycol (Mol.wt.=600, 1000, 4000). These additives were characterized by infrared spectral analysis, average molecular weight and polydispersity index. Their influence on the depression of pour point for two type of paraffin gas oils (G1 and G2) were investigated, blends of paraffin gas oils G1 and G2 by different ratio, when their untreated and treated by additives were evaluated as pour point depressant in comparison with the original paraffin gas oils G1 and G2.

The effect of additive type and gas oil composition on wax crystal modification were studied using the photo micrographic analysis. Diethoxylate (eo=182) sebacate with blend gas oil No. 3 has achieved the best performance as pour point depressant. The photo micrographic analysis showed that, the wax morphology was greatly modified to fine dispersed crystals of compact size. A correlation between the pour point depression and the extent of wax modification was detected.     

Choice of paraffin inhibitors for crude oils by principal component analysis

Accumulation of paraffin wax in the equipment for petroleum production causes large financial losses. The most effective and most economic means of avoiding deposition is often to add chemical additives to the crude oil, but it is not easy to find the most suitable additive for a particular situation because the phenomena involved are too complex for traditional approaches. Principal component analysis is used for data reduction of parameters to represent chemical additives and crude oils. On the basis of physicochemical properties (including spectral parameters) and the activity of additives on the crystallisation temperature of the paraffin wax, crude oils are classified into two families and chemical inhibitors into three families. A model for predicting the activity of additives is discussed.     

Isomorphic interactions of ethylenic polymers and paraffin wax

The high degree of flexibility of blends containing minor amounts of partly crystalline copolymers of ethylene and vinyl acetate in paraffin wax seems to be a manifestation of some type of interaction. Low-angle x-ray diffraction of such blends showed a new long spacing intermediate in length between the polymer long spacing and the c axis length of the wax unit cell. This new long spacing appears to be a consequence of isomorphism involving cocrystallization of polymeric ethylene sequences and wax molecules. A lesser type of isomorphic interaction, epitaxy, occurs in polyethylene–wax blends: wax overgrows crystals of already crystallized polyethylene in the same orientation without a change in its c axial dimension.     

倍半硅氧烷/改性乙烯-乙酸乙烯酯共聚物复配降凝剂对蜡油倾点的影响

乙烯-乙酸乙烯酯共聚物(EVA)是原油常用的降凝剂(PPDs),但其分子结构相对比较单一,对部分油品降凝效果不佳。 为了提高EVA的降凝效果,使用硬脂酰氯与羟基化的EVA直接反应的方法制备烷基长链接枝改性EVA,并与带有烷基长链的倍半硅氧烷(SS)纳米粒子进行复配。 研究了改性EVA和SS复配降凝剂对蜡油的降凝效果和降凝机理。 结果表明:复配降凝剂为蜡提供晶核,使蜡晶变小并降低蜡的沉淀量,导致蜡油中形成的蜡晶难以搭接在一起,形成了松散的结构,当复配质量比m(EVA-g)∶m(SS-L)=1∶2时,在蜡油中的质量分数为0.1%时,蜡油倾点降低了25 ℃。     

磁流变液组分对其沉降性影响的研究进展

磁流变液是一种形态和性能受外加磁场控制的新型智能材料。在汽车、建筑、医疗、航空航天多种领域具有重要的应用价值,但磁流变液沉降性问题一直是影响其广泛应用的难题。因此,首先从载液、磁性颗粒和添加剂三方面出发,简要回顾了近几年在磁流变液沉降性方面的研究,指出了影响磁流变液沉降性的因素主要有：载液的粘度、磁性颗粒的形状和尺寸、磁性颗粒与载液之间的密度差、添加剂的种类与添加量等。并给出了有效提高磁流变液沉降性的可行策略,最后从磁流变液的沉降现象与应用方面对沉降性研究进行了展望。     

Total internal reflection Raman spectroscopy of barley leaf epicuticular waxes in vivo

The use of total internal reflection (TIR)-Raman spectroscopy to examine cuticular wax layers in vivo at the surface of barley leaves (Hordeum vulgare L. cultivar Pastoral) is demonstrated. The limited penetration depth (40 nm) of the evanescent wave compared to the thickness of the wax layer eliminates problems arising from fluorescence from underlying pigments. Epicuticular wax crystals are observed to be more crystalline than the amorphous wax layer, which is analysed after removal of the wax crystals by cellulose acetate stripping. Carotenoids are detected as trace species in the cuticular waxes.     

Control of the water permeability of polyelectrolyte multilayers by deposition of charged paraffin particles

We present a new way to protect polyelectrolyte multilayers from water, consisting in the adsorption and subsequent fusing of charged wax particles atop a multilayer. The formation of the wax layer is demonstrated by different techniques such as ellipsometry, contact angle measurements, and atomic force microscopy. The diffusion of water in protected and unprotected multilayers is studied by in situ neutron reflectometry. Whereas a top layer of wax crystals already allows substantial reduction of the diffusion, the fusion of this top layer leads to the dominating exclusion of water from the multilayers when dipped in water. This method opens up new interesting avenues for polyelectrolyte multilayers in practical applications where permeability of water, ions, or hydrophilic drugs is an issue.     

Rheological Properties of Model and Crude Oil Systems when Wax Precipitate under Quiescent and Flowing Conditions

Wax precipitation and deposition is a recurring challenge in transportation of crude oil, and increased knowledge about the behavior of such systems is necessary. Microscopy and differential scanning calorimetry were used to follow the crystallisation of wax for two model systems. The amount of solid was also determined by the latter method as well. The flow and viscoelastic behavior were investigated around the wax precipitation temperature, and the yield stress was determined both after dynamic and static cooling. Interpretation of the results was carried out in view of crystal growth and microstructure of the wax crystals. The variables that were studied were wax composition, amount of wax and thermal and shear history.     

聚苯乙烯胶晶的组装

采用自然沉降法、离心法和垂直沉积法组装了聚苯乙烯胶晶。实验结果表明,所得胶晶都具有面心立方结构,结构有序性相当高。自然沉降法和离心法适用于块体胶晶的组装,自然沉降法适用于胶晶膜的组装。     

Measuring free-energy difference between crystal polymorphs through eutectic melting

We describe a method to measure the free-energy difference, DeltaG, between crystal polymorphs from their calorimetric data of eutectic melting with a common additive. The use of different additives yields DeltaG as a function of temperature. The method is suitable for crystals that chemically decompose or physically transform before melting. It applies to not only true polymorphs but also pairs of racemate and conglomerate of resolvable enantiomers. We illustrate the method with the polymorphs of glycine, d-mannitol, and tazofelone and report a new value (123 degrees C) for the enantiotropic transition temperature of alpha and gamma glycine. We show how different additives (including a liquid additive, water) can be used for different compounds. The DeltaG data thus obtained are important for structure-stability studies and controlling crystallization in polymorphic systems.     

Noncovalent polymerization of mesogens crystallizes lysozyme: correlation between nonamphiphilic lyotropic liquid crystal phase and protein crystal formation

Crystallization of proteins is important for fundamental studies and biopharmaceutical development but remains largely an empirical science. Here, we report the use of organic salts that can form a class of unusual nonamphiphilic lyotropic liquid crystals to crystallize the protein lysozyme. Certain nonamphiphilic organic molecules with fused aromatic rings and two charges can assemble into stable thread-like noncovalent polymers that may further form liquid crystal phases in water, traditionally termed chromonic liquid crystals. Using five of these mesogenic molecules as additives to induce protein crystallization, we discover that molecules that can form liquid crystal phases in water are highly effective at inducing the crystal formation of lysozyme, even at concentrations significantly lower than that required for forming liquid crystal phases. This result reveals an example of inducing protein crystallization by the molecular assembly of the additives, and is consistent with a new mechanism by which the strong hydration of an assembly process provides a gradual means to compete for the water molecules to enable solvated proteins to form crystals.     

Effect of modified nano-silica/EVA on flow behavior and wax crystallization of model oils with different wax contents

The nano-hybrid pour-point depressant (PPD) was prepared with organically modified nano-silica covering in EVA. The effects of modified nano-silica/EVA on the flow behavior and wax crystallization of model oils with different wax contents were evaluated. Compared with pure EVA and nano-silica/EVA, modified nano-silica/EVA exhibited a better effect, when doped with 500?ppm, the pour point of the model oil containing 20?wt% wax was reduced from 33°C to 0°C. However, it is noteworthy that pour point cannot accurately reflect the effect of YSiO2/EVA as cold flow improver for a high wax content. The crystal morphology and crystallization behavior of the model oils at low temperature were also observed using polarizing optical microscopy (POM). The results indicated that modified nano-silica/EVA can reduce the size of the wax crystals and disperse the wax crystals by heterogeneous nucleation.     

Synthesis and Evaluation of Some Novel Polymeric Surfactants Based on Aromatic Amines Used as Wax Dispersant for Waxy Gas Oil

Dicarboxy methyl ethoxylated aniline and 1,3‐dicarboxy methoxy benzene were synthesized as intermediate monomers to prepare six polyester surfactants. The first three of them were obtained by polyesterification of dicarboxy methoxy ethoxylated (EO=10) aniline with polyethylene glycol (M. wt.; 400, 600, 1000). The product named as An E₁₀ 400, An E₁₀ 600, and An E₁₀ 1000. The later three was obtained by polyesterification of 1, 3 dicarboxymethoxy benzene with the same PEG at different molecular weights. The product named as; R 400, R 600, and R 1000. These polyesters were characterized by FT.ir, and GPC. These polyesters were evaluated as pour point depressants of a mixed blend of Egyptian Western desert gas oil, (PP=18^oC). The obtained data showed that, the maximum reduction of pour point was obtained with An E₁₀ 1000 (ΔPP=15°C) and R 1000 (ΔPP=18°C) regarding to the two groups of polyesters respectively. Blends from these compounds were done. From the results, it was found that, the blend IV exhibit the maximum depression of pour point, (ΔPP=24°C). The photomicrographic investigation for the change of wax crystals morphology and size as the results of using the pour point dispersants was carried out after the treatment by the blends. The photomicrographic pictures showed a great modification of wax crystals was obtained as a result of dispersion of wax by the additives. The results were compared with a commercial additive at 1000 ppm. It was found that, its ΔPP=18°C. This work was extended to study the surface active properties of these polyesters at liquid/air interface. The obtained data were used to explain the discrepancy of these polyesters toward pour point depression.     

Lipidic Matrixes Containing Clove Essential Oil: Biological Activity,Microstructural and Textural Studies

Clove essential oil (CEO) is known for having excellent antioxidant and antimicrobial properties, but the poor stability of its components to light and temperature compromise this activity. The aim of this study is to evaluate the textural, antioxidant, antimicrobial and microstructural properties of matrixes produced with representative natural waxes and CEO. Thus, waxy emulsifiers, such as beeswax, candelilla wax, carnauba wax, and ozokerite wax, were employed to create such matrixes. The thermal, microstructural, textural, wetting, antioxidant, antimicrobial and infrared characteristics of the matrixes were then studied. The diverse chemical composition (long-chain wax esters in carnauba wax and short-chain fatty acids and hydrocarbons in beeswax and ozokerite wax, respectively) explained the differences in wetting, texture, melting, and crystallization characteristics. Crystal forms of these matrix systems varied from grainy, oval, to needle-like shape, but keeping an orthorhombic allomorph. The alignment and reorganization of beeswax and ozokerite wax into needle-like crystals increased the matrix strength and adhesion force compared to those of carnauba and candelilla matrixes, which showed weak strength and grainy morphology. The former two waxes and their matrixes also showed the largest plasticity. These lipidic matrixes show potential use for topical applications having acceptable antioxidant and textural properties.     

Wax inhibition by comb-like polymers: support of the incorporation-perturbation mechanism from molecular dynamics simulations

Deposition of wax on a cold surface is a serious problem in oil production. Progress in developing more effective wax inhibitors has been impeded by the lack of an established mechanism connecting the molecular structure to inhibitor efficiency. Some comb-like polymers having long alkyl side chains are known to decrease the rate of wax formation. Among several possible mechanisms, we investigate here the incorporation-perturbation mechanism. According to this mechanism, the inhibitor molecules in oil are preferentially partitioned (incorporation) toward the wax-rich (amorphous) wax deposits (soft wax), which then serves as a perturbation to slow down the ordering transition of soft amorphous wax into more stable but problematic hard wax crystals. Indeed, molecular dynamics simulations on an effective inhibitor molecule in both the oil phase and in the amorphous wax phase support the idea that the oil-to-wax partition of the inhibitor is energetically favorable. With the inhibitor molecule embedded, the structure of wax crystal is disturbed, significantly decreasing the order and significantly lowering the cohesive energy density relative to that of the pure wax crystal, supporting the slower transition from soft wax to hard wax. Thus, in the presence of an effective wax inhibitor, crystallization (formation of hard wax) is slowed dramatically, so that there is time to flush out the soft wax with a high-pressure flow inside the pipeline. This suggests design principles for developing improved wax inhibitors.     

Theoretical study of the prohibited mechanism for ethylene/vinyl acetate co-polymers to the wax crystal growth

To understand the effect of pour point depressants (PPD) on the wax growth is important for designing PPD additives for use with different oils with high efficiency and good economics. In our current study, molecular mechanics, molecular dynamics, and quantum mechanics calculations were performed to investigate the prohibited mechanism of ethylene/vinyl acetate (EVA) additives on the paraffin deposition in oils. On the wax surface, a single C18 molecule and clusters were preferably deposited on the wax surface (010) in a parallel conformation, which resulted in the formation of large blocks of wax crystal. MD simulation indicated that the linear conformation of EVA was more favorable to be adsorbed onto the carbon backbone of the wax surface (010) with the polar fragments of vinyl acetate staying upside of the surface. Furthermore, four EVA molecules can efficiently optimize the inhibition effect for the deposition of the solute C18 molecules over 10x8 size wax surface (010). According to the simulation results, a simplified rational model was established to estimate the minimum dosage of EVA-type PPD for fuels with different paraffin contents. In a certain degree, this simplified model has provided an effective route to correlate microstructures and the properties of polymer-involving systems, which will shed light on the application of theoretical studies in industries.     

用X射线衍射图研究柴油低温流动改进剂的作用

通常,柴油中含有15%～30%的正构烷烃。在低温下,柴油中大分子量的蜡以晶体形式析出,可堵塞导管和滤清器,导致了柴油机供油的困难[1]。柴油在低温下的流动性能不仅关系到柴油机燃料供油系统在低温下能否正常供油,而且与柴油在低温下的储存和运输等作业能否进行有密切的关系。加入低温流动改进剂改善柴油的低温流动性能,以其成本低,操作简便而成为解决柴油低温流动性能的首选方法,并在工业上得到广泛应用[2]。柴油在低温下蜡的析出直至影响其流动性能的过程是一个蜡结晶的过程,由于蜡的组成复杂,其结晶过程也很复杂[3]。用X射线衍射法分…     

Thermal characteristics of crude oils treated with rheology modifiers

Thermal characteristics of eight crude oils and their treatment with additives were studied by differential scanning calorimetry (DSC), thermomicroscopy, viscometer and pour point tester. Different additives were found as more effective for different type of crude oils depending on the wax content. Crude oils showed a reduced pour point after treatment with additives. Effects of different additives were also discussed by analysing the DSC curves and thermomicroscopy result.     

液晶润滑的研究进展*

综述了近10多年来国内外液晶润滑及液晶添加剂的研究进展。概括了溶致液晶和热致液晶的润滑性能的理论研究及实验结果, 比较了不同类型液晶的润滑机理及在不同实验条件下的抗减摩性能, 以及它们作为普通润滑剂、合成油脂等的添加剂时的润滑效果。