Effect of copolymer structure on micellar behavior of acrylamide-octylphenylpoly (oxyethylene) acrylate surfactant

Acrylamide-octylphenylpoly (oxyethylene) acrylate copolymer (AM-C₈PhEO_nAc) surfactant is the copolymer of acrylamide (AM) and octylphenylpoly (oxyethylene) acrylate macromonomer (C₈PhEO_nAc). The effect of the copolymer structure on the micellar behavior in aqueous solution was studied using dynamic light scattering. It has been found that the length of ethylene oxide (EO) in the branch and the content of C₈PhEO_nAc in the copolymer surfactant have great effects on the size and distribution of the micelles. For AM-C₈PhEO₇Ac copolymer, at the concentration of 5 × 10⁻⁴ g/ml, the micellar size increases with the increase of C₈PhEO₇Ac content. However, for AM-C₈PhEO₁₀Ac copolymer, the result is the opposite; the micellar size decreases with the increase of C₈PhEO₁₀Ac content. Larger C₈PhEO_nAc content leads to narrower micellar distribution. For copolymer surfactants with equal C₈PhEO_nAc content, when the concentration of copolymer solution is the same, the copolymer with longer EO length forms smaller micelles. Received: 2 February 2000 Accepted: 6 October 2000     

Physical and chemical properties of zinc Cyanoferrates(II)

Neutral zinc cyanoferrate(II) Zn₂Fe(CN)₆ · 2.5H₂O and its hydrogen form HZn_1.5Fe(CN)₆ · 4.5H₂O were synthesized and studied. X-ray diffraction, vibrational spectroscopy, and ¹H NMR showed that Zn₂Fe(CN)₆ · 2.5H₂O in aqueous solutions undergoes reversible hydrolysis. The hydrogen form of zinc cyanoferrate(II) is stable up to ≈200°C. The conductivity of HZn_1.5Fe(CN)₆ · 4.5H₂O in the temperature range 90–120°C is σ = 10^?3.3 S/cm, which is about three orders of magnitude higher than the conductivity of the neutral salt.     

Viscometric study of the sodium hyaluronate-sodium chloride-alkyl-(n)-ammonium surfactant system

Viscosity and rheological properties of the system sodium hyaluronate (NaHA)-NaCl-alkyl-(n)-ammonium surfactant were studied. The system with monomeric (n=1) surfactant dodecyltrimethylammonium bromide DTAB separated into two phases below the 200 mM NaCl concentration. At high NaCl concentration (>0.3 M), the hyaluronate–surfactant interaction is screened. At low NaCl concentration (0.2 M), the hyaluronate–surfactant interaction appears at higher concentration of micelles. In the system with dimeric surfactant (n=2) alkanediyl-,ω-bis(dimethyldodecylammonium bromide) referred to as 12-s-12, the hyaluronate–surfactant interaction was observed at low surfactant concentration, opposite to the case of NaHA-NaCl-monomeric surfactant. In certain range of surfactant concentration, viscosity of the system can be fairly good described by the empirical Jones–Dole equation. However, the fit fails at high surfactant concentration. From the rheological measurements follows that NaHA aqueous solution shows non-Newtonian behaviour. When adding NaCl and shearing, viscosity increases as a result of affecting the ion atmosphere which surrounds micelles, by shearing. The same effect was observed in the system NaHA-NaCl-ammonium surfactant (both monomeric and dimeric). The hyaluronate–surfactant interaction is assumed at low shearing. The influence of surfactant structure on viscosity at the same NaCl concentration shows that the increasing value of the carbon number in spacer of dimeric surfactant increases viscosity and stretches the hyaluronate coils.     

Synergistic flame-retardant and smoke suppression effects of zinc borate in transparent intumescent fire-retardant coatings applied on wood substrates

Journal of Thermal Analysis and Calorimetry - A series of novel phosphorus, boron, and zinc-containing flame retardants (ZPEAs) were synthesized by the esterification of cyclic phosphate ester with...     

Effect of surfactant types on particle size and morphology of flame-retardant zinc borate powder

Zinc borate is a boron-containing chemical material that is used to increase the flame retardancy of polymeric materials, dyes, cables, fabrics, carpets, and the internal parts of automobiles and planes. Commercially used zinc borate, which has the formula of 2ZnO·3B ₂ O ₃ ·7H ₂ O, has a particle size between 10 and 20 μm. However, recent studies have shown that nanosized flame retardants have more superior flame retardancy and less negative effects on mechanical properties than microsized flame retardants. Nanosized flame retardants disperse more homogeneously and even low quantities are sufficient to provide high flame resistance. In this study, nano zinc borate powder was synthesized by a wet chemical method and the effects of nonionic, anionic, and cationic surfactants on the particle size and morphology of the zinc borate particles were investigated. Chemical purity and physical structures of the synthesized zinc borate powder were analyzed by XRD, FTIR, TG-DTA, TEM, and Zetasizer. The analysis results showed that the zinc borate powder had a chemical formula of 2ZnO·3B ₂ O ₃ ·7H ₂ O. TEM and Zetasizer results indicated that the nano zinc borate powder, which had nanoscale particle size distribution with needle- and flake-like structures, was synthesized using nonionic, anionic, and cationic surfactants.     

Oriented array of polyethylene-block-poly(ethylene oxide) nanoplatelets in unsaturated polyesters cross-linked coatings

Transparent coatings of cross-linked unsaturated polyester (UP) containing staggered platelets of polyethylene-block-poly(ethylene oxide) with their normal perpendicular to the substrate have been readily prepared by a solvent assisted spin-coating method. For this purpose, homogeneous liquid dispersions of block copolymer platelets in liquid UP resin have been prepared using a selective solvent, deposited onto flat substrates by spin-coating and converted into a transparent solid layer by photochemical cross-linking. Although such stratified morphology has been already reported for inorganic nanoplatelets (typically clay particles), we report for the fist time the formation of such stratified morphology in fully organic system. The shear-induced origin of this organization has been confirmed by the rheological properties of the uncured systems where a pronounced non-Newtonian behavior has been observed.     

Binding of a surfactant counterion to low-charge-density poly(acrylic acid) and poly(methacrylic acid)

The binding of a cationic surfactant, dodecylpyridinium (C12Py) chloride, with a low-charge-density poly (methacrylic acid) (PMA) was investigated in buffer solutions under the condition of constant pH. The binding isotherms with PMA consisted of two and three steps at a pH lower and higher than 3.2, respectively. Bindings in the first step were independent of pH and this step was considered to correspond to the solubilization of the hydrocarbon chains of C12Py into the nonpolar region of the compact form of PMA. This is the indication of the compact form from the binding isotherm. At pH higher than 3.2, the second step was discriminated and it depended on the pH. In the third step, a sharp rise in the degree of binding (β) was observed accompanying the solubilization of the precipitates of the PMA–C12Py complex. The binding with poly(acrylic acid) (PAA) and PMA in conventional unbuffered NaCl solutions was also examined and the pH profile of the solution during the binding process was determined. In the case of unbuffered NaCl solutions, the binding with PAA took place cooperatively at the critical association concentration (cac). The binding isotherm consisted of two steps and the pH decreased with the increase in β. The binding isotherm of PMA, on the other hand, consisted of three steps: the pH decreased slightly in the first step and considerably in the second step with the increase in β but it increased with β in the third step, exhibiting a pH minimum around 3.2. The binding in the first step coincided with that obtained in the buffered solutions. Linear relationships between β and the pH were found for both polymers. In the case of PMA, no cac was observed in both buffered and unbuffered NaCl solutions. Received: 24 January 2001 Accepted: 23 May 2001     

Water pH and surfactant addition effects on the stability of an Algerian crude oil emulsion

In many oil production sites water injection is used as a piston to push the crude out of the well. As the age of the field progresses, the ratio of water to oil produced increases. Agitation of a water and crude oil mixture may give stable water-in-oil emulsion in which the water remains dispersed for a long period of time. These emulsions can cause severe problems in production and transport processes since they normally possess high stability and viscosity. The most important water properties which may contribute to the emulsion stability include pH and additive content. In this study, we report on the effect of both, water pH and the presence of surfactant molecules (anionic, cationic or non-ionic) on the stability of an Algerian crude oil (Haoudh el Hamra well) aqueous emulsion prepared by a mechanical agitation procedure. The stability was followed by the test-bottle method to measure the resolved water separated from the emulsion, and optical microscopy to visualize the dispersed water droplets in the oil phase. The results of the effects of varying the aqueous-phase pH suggest that the neutral medium is more efficient than acidic or basic environment for stabilizing the emulsions. The addition of non-ionic surfactants has a better potential to improve crude oil emulsion stability with respect to both cationic and anionic surfactants which do not show any improvement in the oil/water phase compatibility.     

Recycled PP/EPDM/talc reinforced with bamboo fiber: Assessment of fiber and compatibilizer content on properties using factorial design

Thermoplastic composites reinforced with natural fibers have attracted the attention of many researchers, not only for environmental concerns, but also for economic reasons, recyclability, ease of processing, etc. One promising application is in the automotive industry due to their low cost and weight. This industry is increasingly pressured to produce vehicles that consume less fuel and are less polluting. Therefore, plastics reinforced with fibers are required to produce lighter parts to replace the much more abrasive glass fiber and mineral filled composites. One of the most widely used polymers in the automotive sector for manufacturing interior and exterior vehicle components is talc filled EPDM (ethylene-propylene-diene monomer) toughened polypropylene (PP). In this context, the aim of this study was to assess mechanical and thermal properties of bamboo fiber reinforced recycled talc filled PP/EPDM composites compatibilized with maleic anhydride grafted polypropylene (PP-g-MAH). Composites were prepared, according to a 2² factorial design with center point, in a Haake twin screw extruder with subsequent injection molding. Injected specimens were subjected to tensile, flexural, impact and fatigue testing. Morphological analyses were performed by scanning electron microscopy (SEM), and thermal analyses by thermogravimetry (TGA) and differential scanning calorimetry (DSC). Addition of bamboo fiber significantly increased tensile and bending strength, modulus and fatigue life, and decreased elongation at break and impact strength. On the other hand, addition of the compatibilizer had a positive effect only on tensile and flexural strength, and fatigue life whereas the effect was negative on elongation at break and impact strength. The addition of fiber and compatibilizer did not appreciably affect the matrix melting temperature, but slightly increased crystallization temperature and in some cases the degree of crystallinity.     

Adsorption of hexyl-alpha,omega-bis(dodecyldimethylammonium bromide) gemini surfactant on silica and its effect on wettability

The adsorption of hexyl-alpha,omega-bis(dodecyldimethylammonium bromide) (C(12)C(6)C(12)Br(2)) gemini surfactant on silica and its effect on wettability have been studied. The structure of the adsorbed aggregates experiences an evolving course with the increase of C(12)C(6)C(12)Br(2) concentration. It is from no aggregates to circular islands, then to semicontinuous islands, and at last to the two-bilayer structure. No matter what kind of aggregates are in existence, their thickness values are to be the same 3.3+/-0.3 nm. The fraction of silica surface covered by the surfactant aggregates also varies from nearly zero at 0.05 mM to approximately 0.92 at 5.0 mM. The variation of contact angle against C(12)C(6)C(12)Br(2) concentration shows two distinct regions. The upward shift indicates that the surfactant molecules are adsorbed with their hydrophobic tails facing air upon increasing concentration, while the downward shift reveals that the surfactant aggregates are in existence with the hydrophilic headgroups facing air. IR spectra suggest that two different courses are involved with the increase of the surfactant concentration. One possible course is that the surfactant tails pack more closely and orderly, and the other may be that the spacer changes from stretched profile to bended conformation upon increasing the surfactant concentration.     

Thermogravimetry of heteroleptic zinc tri-tert-butoxysilanethiolates: synthesis and crystal structure of bis(tri-tert-butoxysilanethiolato)(pyridine) zinc(II)

Thermal behaviour of three silanethiolate zinc complexes i.e., bis(tri-tert-butoxysilanethiolato)bis(pyridine) zinc(II), bis(tri-tert-butoxysilanethiolato)bis(N-methylimidazole) zinc(II) and bis(tri-tert-butoxysilanethiolato) (2-methylpyridine) zinc(II) was studied. In order to determine the steps involved in thermal decay, decomposition intermediates were identified by means of IR spectroscopy and solid residues were analysed. Enthalpies of undergoing processes were estimated on the basis of DTA curves. The results of the study were applied to the synthesis of a new complex - bis(tri-tert-butoxysilanethiolato)(pyridine) zinc(II). NMR and IR spectra of this complex were measured and crystal and molecular structures were determined.     

Effects and structures of the O/Cu surfactant layer in O-mediated film growth of Cu on Ru(0 0 0 1)

The O-mediated Cu-film growth on O-precovered Ru(0 0 0 1) is investigated by means of scanning tunneling microscopy for growth temperatures between 300 and 600 K. Cu-films on clean Ru(0 0 0 1) grow in a multilayer mode. For O precoverages (Θ) between 0.2 ML (monolayer) and the saturation coverage (Θ=0.5 ML), a layer-by-layer growth is observed at growth temperatures between 350 and 450 K. On Cu-islands, an O/Cu surfactant layer is formed, which floats on-top of the growing film and induces the layerwise Cu-film growth. The surface coverage of the O/Cu surfactant layer linearly rises with the O precoverage up to Θ≈0.4 ML, where it completely covers the surface. Two different types of the surfactant layer are identified, inducing different surfactant mechanisms. For Θ=0.1–0.4 ML, the O/Cu surfactant structure (A-type) displays some local order and induces inhomogeneous nucleation at the misfit-induced relaxation structure of the Cu-film. The layer-wise growth is explained by the concept of two mobilities, implying a large attempt frequency for adatom jumps over the interlayer diffusion barrier at the steps. For Θ = 0.4–0.5 ML, a disordered O/Cu surfactant layer is established (B-type), inducing homogeneous nucleation. The layer-wise Cu-film growth is attributed to a reduction of the effective interlayer diffusion barrier. Cu-film growth at 400 K on the ordered (3×2√3)O/Cu structure formed at temperatures around 520 K yields the conclusion that the O/Cu surfactant structures are composed of randomly arranged O–Cu–O strings and disrupted “Cu₂O(1 1 1)” fragments.     

Synergistic effects of organo‐sepiolite and zinc borate on the fire retardancy of polypropylene

Polypropylene (PP)/sepiolite/zinc borate (BZn) composites were prepared by melt extrusion after pre‐modification of sepiolite with cetyltrimethylammonium bromide. The synergistic effects of organo‐sepiolite (OSEP) and BZn on the fire retardancy of PP were studied. X‐ray diffraction and transmission electron microscopy were used to characterize the morphology of the composite. Thermogravimetric analysis, cone calorimetric analysis, limiting oxygen index, and the UL‐94 protocol (Demaisheng technology Co. Ltd.,Shenzhen,China) were used to assess the thermal stability and fire retardancy of the composites. The fire retardancy of PP was greatly improved by introducing OSEP and BZn. The reduction in peak heat release rate for PP/BZn composites at 10% BZn loading is 62% compared with pristine PP, but increased to 78% for PP/10%BZn/10%OSEP composite. Other fire retardant parameters were also improved. The fire performance index of PP/10%BZn/10%OSEP composite was 0.045 sm²/kW compared with 0.014 sm²/kW of pristine PP. The average mass loss rate was 12.1 g/sec/m² for the composite with both additives compared with 30.1 g/sec/m² for pristine PP; the smoke production rate decreased by 37% from 0.117 m²/s of pristine PP to 0.074 m²/s of PP/OSEP/BZn. The char residue of composite increased from 0.6% in pristine PP to 12.19% in the composite. The limiting oxygen index increased from 17.1 in pristine PP to 20.8 in the composite: all the samples could obtain a UL‐94 horizontal burn rating. Copyright © 2013 John Wiley & Sons, Ltd.     

Copper(I) complexes with fluorinated hydrotris(pyrazolyl)borate: Influence of electronic effects on their structure,physicochemical properties,and reactivity

Copper(I) coordination complexes of the anionic fluorinated ligand, hydrotris(3-trifluoromethyl-5-methyl-1-pyrazolyl)borate (L0f⁻), i.e. the copper(I) carbonyl complex, [Cu^I(L0f)(CO)] (1), the copper(I) triphenylphosphine complex, [Cu^I(L0f)(PPh₃)] (2), the copper(I) acetonitrile complex, [Cu^I(L0f)(NCMe)] (3), and the corresponding copper(I) triphenylphosphine complex with hydrotris(3,5-diisopropyl-1-pyrazolyl)-borate anion (L1⁻), i.e. [Cu^I(L1)(PPh₃)] (4), were synthesized in order to investigate the influence of the electron-withdrawing groups on the pyrazolyl rings. The structures of complexes 1, 2, and 4 were determined by X-ray crystallography. While X-ray crystallography did not show definitive trends in terms of copper(I) atom geometry, the clear influence of the electronic structure of the pyrazolyl rings is observed by spectroscopic techniques, namely, IR and multinuclear NMR spectroscopy. Finally, the relative stability of the copper(I) complexes is discussed.     

The effects of a silane coupling agent on curing characteristics and mechanical properties of bamboo fibre filled natural rubber composites

The effects of a silane coupling agent on curing characteristics and mechanical properties of bamboo fibre filled natural rubber composites were studied. Scorch time, t₂ and cure time, t₉₀ of the composites decrease with increasing filler loading and with the presence of a silane coupling agent, Si69. Mooney viscosity also increases with increasing filler loading but at a similar filler loading shows lower value with the presence of Si69. The mechanical properties of composites viz tensile strength, tear strength, hardness and tensile modulus were also improved with the addition of Si69.     

Metal-organotetraphosphonate inorganic-organic hybrids: crystal structure and anticorrosion effects of zinc hexamethylenediaminetetrakis(methylenephosphonate) on carbon steels

The synthesis and structural characterization of the first polymeric M-HDTMP organic-inorganic hybrids are described [M = Zn2+, Ca2+; HDTMP = hexamethylenediaminetetrakis(methylenephosphonate)]. The 3D crystal structure of the Zn2+ analogue [Zn(HDTMP) x H2O] is described. The Zn center is found in a distorted octahedral environment of phosphonate oxygens. There is a long Zn...O interaction (2.622 A) originating from a protonated -P-OH group. Synergistic combinations of Zn2+ and the tetraphosphonate are found to form films that protect against the corrosion of carbon steels.     

The effect of selected surfactants on the structure of a bicellar system (DMPC/DHPC) studied by SAXS

The stabilizing or disturbing effect of different surfactants on the bicellar phase of phospholipids significantly depends on their type. The effect of different surfactants on the bicellar structure made of a mixture of phospholipids 1,2-dimyristoyl-sn-glycero-3-phosphocholine and 1,2-dihexanoyl-sn-glycero-3-phospho-choline (DMPC/DHPC) has been studied by the small angle scattering of synchrotron radiation. The study has been performed for three surfactants: dodecyldimethyl-(hexyloxymethyl)ammonium chloride, n-undecylammonium chloride and t-octylphenoxypolyethoxyethanol (Triton X-100) introduced into a bicellar solution of DMPC/DHPC (2.8:1). The bicellar phase has been disturbed in the shortest time in the presence of dodecyldimethyl-(hexyloxymethyl)ammonium chloride in this system a transition from the bicellar to lamellar structure has been directly visible. The changes have been less pronounced in the presence of undecylammonium chloride and practically not noted in the presence of Triton X-100.     

Effect of surfactant on porosity and swelling behaviors of guar gum-g-poly(sodium acrylate-co-styrene)/attapulgite superabsorbent hydrogels

Novel fast-swelling porous guar gum-g-poly(sodium acrylate-co-styrene)/attapulgite (GG-g-P(NaA-co-St)/APT) superabsorbent hydrogels were prepared by simultaneous free-radical graft copolymerization reaction of guar gum (GG), partially neutralized AA (NaA), styrene (St) and attapulgite (APT) using N,N'-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator in aqueous solution and the surfactant self-assembling templating pore-forming technique. Fourier transform infrared (FTIR) spectroscopy confirmed that the surfactant could be removed from the final hydrogel product by methanol/water (8:1, v/v) washing process and the surfactant only act as micelle template to form pores. The effect of surfactant type on the porous microstructure of the hydrogel was assessed by field emission scanning electron microscope (FESEM). It was shown that incorporation of proper amount of anionic surfactant sodium n-dodecyl sulfate (SDS) in the gelling process of the hydrogel can obviously enhance the swelling capacity and initial swelling rate. The salt-sensitivity of the SDS-added hydrogel in distilled water and 15 mmol/L NaCl, CaCl(2) solution or 15 mmol/L NaCl and CaCl(2) solution was investigated, and it was found that the swelling-deswelling capability is quite reversible. A similar reproducible on-off switching behavior was observed in the 1 mmol/L solution of phosphate buffer at pH 2.1 and 7.4.     

Sequential injection spectrophotometric determination of zinc(II) in pharmaceuticals based on zinc(II)–PAN in non-ionic surfactant medium

A sequential injection analysis (SIA) spectrophotometric method for the determination of trace amounts of zinc(II) with 1-(2-pyridylazo)-2-naphthol (PAN) is described. The method is based on the measurement of absorbance of the zinc(II)–PAN chelate solubilized with a non-ionic surfactant, Triton X-100, no extraction procedure is required in the proposed method, yielding a pink colored complex at pH 9.5 with absorption maximum at 553 nm. The SIA parameters that affect the signal response have been optimized in order to get the better sensitivity and minimum reagent consumption. A linear relationship between the relative peak height and concentration was obtained in the concentration range of 0.1–1.0 μg ml⁻¹. The limit of detection (LOD, defined as 3σ) and limit of quantification (LOQ, defined as 10σ) were 0.02 and 0.06 μg ml⁻¹, respectively. The sample throughput about 40 samples/h was obtained. The repeatability were 1.32 and 1.24% (n = 10) for 0.1 and 0.5 μg ml⁻¹, respectively. The proposed method was successfully applied to the assay of zinc(II) in three samples of multivitamin tablets. The results were found to be in good agreement with those obtained by flame atomic absorption spectrophotometric method and with the claimed values by the manufactures. The t-test showed no significant difference at 95% confidence level.     

Effects of a heavy metal (zinc) on organic adsorption capacity and organic removal in activated sludge

Applied Biochemistry and Biotechnology - Effects of a common heavy metal (zinc) on activated sludge were studied with a sequencing batch reactor (SBR). Organic removal in activated sludge was...