Amorphous Calcium Phosphate Based Composites: Effect of Surfactants and Poly(ethylene oxide) on Filler and Composite Properties

The uncontrolled aggregation of amorphous calcium phosphate (ACP) particulate fillers and their uneven distribution within polymer matrices can have adverse effects on the properties of ACP composites. In this paper we assessed the influence of non-ionic and anionic surfactants and poly(ethylene oxide) (PEO) introduced during the preparation of ACP on the particle size distribution and compositional properties of ACP. In addition, the mechanical strength of polymeric composites utilizing such fillers with a photo-activated binary methacrylate resin was evaluated. Zirconia-hybridized ACP (Zr-ACP) filler and its corresponding composite served as controls for this study. Surfactant- and PEO-ACPs had an average water content of 16.8 % by mass. Introduction of the anionic surfactant reduced the median particle diameter about 45 % (4.1 μm vs. 7.4 μm for the Zr-ACP control). In the presence of PEO, however, the d(m) increased to 14.1 μm. There was no improvement in the biaxial flexure strength (BFS) in any of the dry composite specimens prepared with the surfactant- and/or PEO-ACPs compared to those formulated with Zr-ACP. The BFS of wet composite specimens decreased by 50 % or more after a month-long exposure to saline solutions. Other types of surfactants and/or polymers as well as alternative surface modification protocols need to be explored for their potential to provide better dispersion of ACP into the matrix resin and better mechanical performance ACP composites.     

The Effects of Salts and Ionic Surfactants on the Micellar Structure of Tri‐Block Copolymer PEO‐PPO‐PEO in Aqueous Solution

The micelles of two poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) (PEO‐PPO‐PEO) block copolymers, P123 and F127 (same mol wt of PPO but different % PEO) in aqueous solution in the absence and presence of salts as well as ionic surfactants were mainly examined by dynamic light scattering (DLS). The study is further supported by cloud point and viscosity measurements. The change in cloud point (CP), as well as the size of micelles in aqueous solution in presence of salts obeys the Hofmeister lyotropic series. Addition of both cationic cetylpyridinium chloride (CPC) and anionic sodium dodecylsulfate (SDS) surfactants in the aqueous solution of P123 show initial decrease of micellar size from 20 nm to nearly 7 nm and then increasing with a double relaxation mode, further in the presence of NaCl this double relaxation mode vanishes. The effect of surfactant on F127, which has much bigger hydrophilic part is different than P123 and have no double relaxation. The relaxation time distributions is obtained using the Laplace inversion routine REPES. Two relaxation modes for P123 are explained on the bases of Pluronic rich mixed micelles containing ionic surfactants and the other smaller, predominantly surfactant rich micelles domains.     

Effect of Surfactants on the Formation,Morphology, and Surface Property of Synthesized SiO2 Nanoparticles

Abstract

This study investigated the effect of cationic, anionic (saturated and unsaturated), and nonionic surfactants on the formation, morphology, and surface properties of silica nanoparticles synthesized by the ammonium‐catalyzed hydrolysis of tetraethoxysilane in alcoholic media. Results indicate that at a relatively low surfactant concentration (1 × 10^?3–1 × 10^?6 M), cationic surfactants significantly affected the growth of silica particles as measured by dynamic light scattering and transmission electron microscopic analyses. In contrast, the anionic and nonionic surfactants showed relatively minor effects in the low concentration range. The magnitude of negative zeta potential was reduced for silica colloids that were synthesized in the presence of cationic surfactant because of charge neutralization. The presence of anionic surfactants only slightly increased the negative zeta potential while the nonionic surfactant showed no obvious effects. At high surfactant concentrations (>1 × 10^?3 M), cationic and anionic surfactants both induced colloid aggregation, while the nonionic surfactant showed no effect on particle size. Raman spectroscopic analysis suggests that molecules of cationic surfactants adsorb on silica surfaces via head groups, aided by favorable electrostatic attraction, while molecules of anionic and nonionic surfactants adsorb via their hydrophobic tails.     

Optical Sensing Membrane Based on Tetrabromophenolphthalein Ethyl Ester for the Determination of Cationic Surfactants

Abstract

An optical sensing membrane for detection of cationic surfactants was developed. The optical sensing membrane is 2‐nitrophenyl octyl ether‐plasticized poly(vinyl chloride) membrane incorporating tetrabromophenolphthalein ethyl ester (TBPE). The response of the optical membrane to cationic surfactants was a result of extraction of cationic surfactant into the PVC membrane. The protonated TBPE deprotonates forming an ion associate with the extracted cationic surfactant; simultaneously, the deprotonation of the TBPE is accompanied by a spectral change. Namely, the extracted cationic surfactant changes color of the membrane from yellowish green to blue (absorption maximum: 622 nm). The optical membrane responds to cationic surfactants such as Zephiramine and cetyltrimethylammonium bromide in the concentration range from 1 µM to 100 µM.     

Interaction between polymer and anionic/nonionic surfactants and its mechanism of enhanced oil recovery

Various experimental methods were used to investigate interaction between polymer and anionic/nonionic surfactants and mechanisms of enhanced oil recovery by anionic/nonionic surfactants in the present paper. The complex surfactant molecules are adsorbed in the mixed micelles or aggregates formed by the hydrophobic association of hydrophobic groups of polymers, making the surfactant molecules at oil-water interface reduce and the value of interfacial tension between oil and water increase. A dense spatial network structure is formed by the interaction between the mixed aggregates and hydrophobic groups of the polymer molecular chains, making the hydrodynamic volume of the aggregates and the viscosity of the polymer solution increase. Because of the formation of the mixed adsorption layer at oil and water interface by synergistic effect, ultra-low interfacial tension (～2.0?×?10^?3 mN/m) can be achieved between the novel surfactant system and the oil samples in this paper. Because of hydrophobic interaction, wettability alteration of oil-wet surface was induced by the adsorption of the surfactant system on the solid surface. Moreover, the studied surfactant system had a certain degree of spontaneous emulsification ability (D50?=?25.04?µm) and was well emulsified with crude oil after the mechanical oscillation (D50?=?4.27?µm).     

Thermally conductive cyanate ester nanocomposites filled with graphene nanosheets and multiwalled carbon nanotubes

In this work, dodecylamine‐modified graphene nanosheets (DA‐GNSs) and γ‐aminopropyl‐triethoxysilane‐treated multiwalled carbon nanotubes (f‐MWCNTs) are employed to prepare cyanate ester (CE) thermally conductive composites. By adding 5 wt% DA‐GNSs or f‐MWCNTs to the CE resin, the thermal conductivities of the composites became 3.2 and 2.5 times that of the CE resin, respectively. To further improve the thermal conductivity, a mixture of the two fillers was utilized. A remarkable synergetic effect between the DA‐GNSs and f‐MWCNTs on improving the thermal conductivity of CE resin composites was demonstrated. The composite containing 3 wt% hybrid filler exhibited a 185% increase in thermal conductivity compared with pure CE resin, whereas composites with individual DA‐GNSs and f‐MWCNTs exhibited increases of 158 and 108%, respectively. Moreover, the composite with hybrid filler retained high electrical resistivity. Scanning electron microscopy images of the composite morphologies showed that the modified graphene nanosheets (GNSs) and multiwalled carbon nanotubes (MWCNTs) were uniformly dispersed in the CE matrix, and a number of junction points among MWCNTs and between MWCNTs and GNSs formed in the composites with hybrid fillers. Generally, we can conclude that these composites filled with hybrid fillers may be promising materials of further improving the thermal conductivity of CE composites. Copyright © 2014 John Wiley & Sons, Ltd.     

Crystallization behavior and toughening mechanism of poly(ethylene oxide) in polyoxymethylene/poly(ethylene oxide) crystalline/crystalline blends

In this study, the unique crystallization behavior of poly(ethylene oxide) (PEO) in polyoxymethylene (POM)/PEO crystalline/crystalline blends was examined in detail. This study was the first to report the typical fractionated crystallization of PEO in POM/PEO blends when PEO is fewer than 30 wt.%. The delayed crystallization temperature of PEO was confirmed at about 5°C to 14°C by using differential scanning calorimetry and perturbation–correlation moving‐window 2D correlation IR spectroscopy. Wide‐angle X‐ray diffraction indicates that no new crystal structures or co‐crystals were generated in POM/PEO. The statistical calculations of scanning electron microscopy photos show that the average diameter of PEO particles is 0.227 µm to 1.235 µm and that the number of small particles is as many as 10⁹ magnitudes per cm³. Theory analysis establishes that the delayed crystallization of PEO is a heterogeneous nucleation process and not a homogeneous nucleation process. A significant toughening effect of PEO to POM was also observed. The impact strength of POM/PEO acquires a maximum of 10.5 kJ/m² when PEO content is 5%. The impact strength of the blend increases by 78.0% compared with pure POM. To improve the toughening effect, the best particle size is established between 0.352 and 0.718 µm, with a PEO particle spacing of 0.351 µm to 0.323 µm. The number of corresponding particles was 0.887 × 10⁹ per cm3 to 3.240 × 10⁹ per cm³. A PEO toughening model for POM was proposed to provide a new and effective way to solve the problem of POM toughening. Copyright © 2014 John Wiley & Sons, Ltd.     

Determination of surfactants and levoglucosan from selected vegetation by spectroscopic colorimetric method

Vegetation is one of the natural sources which contribute to the amount of surface active agent into the environment. It is believed that surfactants can be derived from various kinds of sources such as biomass burning or soil and these excessive level of surfactants emitted into the atmosphere can influence both cloud formation and climate. The objective of this study was to determine the concentration of both anionic and cationic surfactants as well as levoglucosan from vegetation and soot and at different weather conditions around the tin mine lakes environment. The samples were prepared by cutting several parts of tropical plant species, namely Cinnamomum Iners, Gliricidia Sepium and Hopea Odorata, which were mainly leaves and stems. After that, samples were allowed to dry in an oven at a temperature of 40°C for 2 h. The concentrations of levoglucosan and surfactant such as methylene blue active substance (MBAS) and disulphine blue active substance (DBAS) were analysed through the colorimetric method. The results showed that higher concentrations for both anionic and cationic surfactants were found in C. Iners leaves which give the concentrations of 86.92 ± 38.99 and 22.33 ± 10.59 µg/g. It was noted that the concentrations of anionic and cationic surfactants in this research were correlated to each other, indicating the possibility of similar sources that affect both levels of surfactants in the vegetation. In addition, the highest level of levoglucosan was dominated by the leaves from G. Sepium species with the concentration of 25.62 ± 12.65 mg/g, respectively. A positive significant correlation (r = 0.8447, 0.8355 and p = 0.0001 < 0.05) between anionic surfactants and levoglucosan was also discovered in this study.     

De‐agglomeration of Silica Nanoparticles in the Presence of Surfactants

The effect of the type of surfactant and pH on de‐agglomeration of a hydrophilic silica nano‐powder in a high shear mixer was investigated. It has been found that the presence of surfactant does not affect the general pattern of de‐agglomeration characterized by the transition of a single modal aggregates size distribution with the median of 10 µm, through a bi‐modal distributions with the second median of the order of 100 nm to a single modal distribution with the median of the order of 100 nm. None of the investigated surfactants enabled de‐agglomeration of the nano‐powder into a primary nanoparticle.

At pH=4, breakage of large secondary aggregates was enhanced by the addition of PEG and PVP, whereas the addition of SDS slowed down de‐agglomeration. The final aggregates were larger in all suspensions containing surfactant than in surfactant free suspensions. At pH=9 all surfactants drastically reduced de‐agglomeration rate without affecting the size of the primary aggregates. PEG induced bridge flocculation of the primary aggregates leading to a drastic change of the rheology of suspension.     

Effect of particle size of mineral fillers on polymer-matrix composite shielding materials against ionizing electromagnetic radiation

Filler particle size is an important particle that effects radiation attenuation performance of a composite shielding material but the effects of it have not been exploited so far. In this study, two mineral (hematite–ilmenite) with different particle sizes were used as fillers in a polymer-matrix composite and effects of particle size on shielding performance was investigated within a widerange of radiation energy (0–2000 keV). The thermal and structural properties of the composites were also examined. The results showed that as the filler particle size decreased the shielding performance increased. The highest shielding performance reached was 23% with particle sizes being between <7 and <74 µm.

     

Synergetic effect of thermal conductivity and flame retardancy of cyanate ester composites containing DOPO and BN with great dielectric properties

DOPO and boron nitride (BN) fillers with different particle sizes and several loadings were employed to improve the properties of cyanate ester (CE) resin. The effects of BN content and particle size on the thermal conductivity of the BN‐DOPO/CE ternary composites were discussed. The influence of enhancing the thermal conductivity of the ternary composites on their flame retardancy was studied. The consequences showed that increasing the thermal conductivity of BN‐DOPO/CE composites had an active impact on their flame retardancy. Approving flame retardancy of the ternary composites was certified by the high limiting oxygen index (LOI), UL‐94 rating of V‐0, and low heat release rate (HRR) and total heat release (THR). For instance, in contrast with pure CE matrix, peak of HRR (pk‐HRR), average of HRR (av‐HRR), THR, and average of effective heat of combustion (av‐EHC) of CEP/BN_{0.5 μm}/10 composite were decreased by 51.7%, 33.8%, 18.7%, and 18.9%, respectively. Thermal gravimetry analysis (TGA) showed that the addition of BN fillers improves the thermal stability of the composites. Moreover, the ternary composites possess good dielectric properties. Their dielectric constants (ε) are less than 3, and dielectric loss tangent (tgδ) values are lower than neat CE resin.     

Epoxy‐based composite adhesives: Effect of hybrid fillers on thermal conductivity,rheology, and lap shear strength

Thermal management is an important parameter in an electronic packaging application. In this work, three different types of fillers such as natural graphite powder (Gr) of 50‐μm particle size, boron nitride powder (h‐BN) of 1‐μm size, and silver flakes (Ag) of 10‐μm particle size were used for thermal conductivity enhancement of neat epoxy resin. The thermal properties, rheology, and lap shear strength of the neat epoxy and its composite were investigated. The analysis showed that the loading of different wt% of Gr‐based fillers can effectively increase the thermal conductivity of the epoxy resin. It has also been observed that the thermal conductivity of the hybrid filler (Gr/h‐BN/Ag) reinforced epoxy adhesive composite increased six times greater than that of neat epoxy resin composite. Further, the viscosity of hybrid filler reinforced epoxy resin was found to be increased as compared with its virgin counterpart. The adhesive composite with optimized filler content was then subsequently subjected to determine single lap shear strength. The degree of filler dispersion and alignment in the matrix were determined by scanning electron microscopy (SEM) analysis.     

Preparation and Characterization of Polypropylene Carbonate Bio-Filler (Eggshell Powder) Composite Films

In recent years, biodegradable polymer composites have attracted considerable attention due to inadequate and depleting petroleum resources and to replace nonbiodegradable synthetic polymers posing environment problems. In the present work, biodegradable composites based on polypropylene carbonate (PPC)/eggshell powder (ESP) were prepared by the solution-casting method using chloroform as the solvent. Polypropylene carbonate was loaded with 1 to 5 wt% of eggshell powder (particle size < 40 µm). Characterization of the composites was accomplished by Fourier transform-infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), and X-ray diffraction (XRD) analysis, and morphological studies were carried out by optical microscopy (OM) and scanning electronic microcopy (SEM). The tensile properties of the composite films were found to be higher than those of neat PPC matrix and increased with ESP content up to 4 wt.% and then decreased. This work offers an easy path to manufacture ecofriendly PPC/eggshell powder composite films with improved properties, and reducing, in some cases, the demand for petroleum-based plastics such as polyolefins.     

Comparative study of classical surfactants and polymerizable surfactants (surfmers) in the reversible addition–fragmentation chain transfer mediated miniemulsion polymerization of styrene and methyl methacrylate

Cationic and anionic amphiphilic monomers (surfmers) were synthesized and used to stabilize particles in miniemulsion polymerization. A comparative study of classical cationic and anionic surfactants and the two surfmers was conducted with respect to the reaction rates and molecular weight distributions of the formed polymers. The reversible addition–fragmentation chain transfer process was used in the miniemulsion polymerization reactions to control the molecular weight distribution. The reaction rates of the surfmer‐stabilized miniemulsion polymerization of styrene and methyl methacrylate were similar (in most cases) to those of the classical‐surfactant‐stabilized miniemulsion polymerizations. The final particle sizes were also similar for polystyrene latexes stabilized by the surfmers and classical surfactants. However, poly(methyl methacrylate) latexes stabilized by the surfmers had larger particle sizes than latexes stabilized by classical surfactants. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 427–442, 2006     

Size‐controllable synthesis of polymeric iodine‐carrying nanoparticles for medical CT imaging

Iodine‐carrying nanopolymers with particle sizes ranging from 30 to 930 nm were synthesized by microemulsion polymerization. 2‐Methacryloyloxyethyl(2,3,5‐triiodobenzoate) was used as the monomer. Different surfactants were tested to control the particle size. Cetyltrimethylammonium bromide and cetyltrimethylammonium chloride were used as cationic surfactants, and sodium oleate and sodium dodecyl sulfate acted as anionic surfactants. The influences of various reaction parameters, e.g. the amount of surfactant, amount of initiator, and the reaction temperature, were investigated. The particle size was highly adjustable through variation of the reaction parameters. The particles were imaged with an atomic force microscope. In addition, particle workup for further medical application was explored. The particles provided good visible computer tomography contrast. Copyright © 2017 John Wiley & Sons, Ltd.     

Effects of surfactants and electrolytes on adsorbed layers and particle stability

Adsorbed polymer and polyelectrolyte layers on colloidal silica nanoparticles have been studied in the presence of various salts and surfactants using photon correlation spectroscopy and solvent relaxation NMR. Poly(ethylene oxide) (PEO; molar mass 103.6 kg mol (-1)) adsorbed with a relatively high affinity and gave a layer thickness of 4.2 +/- 0.2 nm. While the nonionic surfactant used only increased this thickness slightly, anionic surfactants had a much greater effect, mainly due to repulsions between adsorbed aggregates, leading to expansion of the layer. A nonionic/anionic surfactant mixture was also tested and resulted in a larger increase in layer thickness than any of the individual surfactants. The dominant factor on addition of salt was generally the reduced solvency of PEO, which resulted in a further increase in the layer thickness but in some cases caused flocculation. This was not the case when the surfactant was sodium dodecylbenzenesulfonate; instead screening of the intermicellar repulsions possibly combined with surfactant-cation binding resulted in a reduction in the layer thickness. In comparison the affinity between silica and sodium polystyrenesulfonate was very weak. Anionic surfactants and salts did not noticeably increase the strength of adsorption, but instead encouraged flocculation. The situation was different with a nonionic surfactant, which was able to adsorb to silica itself and apparently facilitated a degree of polyelectrolyte adsorption as well.     

A Novel Method for Preparing Nano‐ and Microcomposite Al2O3‐ZrO2 Ceramic Coatings

Nano‐ and microcomposite Al₂O₃‐ZrO₂ coatings were deposited on various substrates in a sol‐gel ceramic paint by a supercentrifugal force and a gradual sintering process. Fine metal oxide powders were dispersed in a sol‐gel solution by superpower ball milling so as to form a uniform stable ceramic paint. High‐resolution microscopy (FE‐SEM) was used to characterize the coating, indicating that the coating is composed of composite particle clusters with an average diameter of ～1 µm. The clusters consisted of larger particles with an average diameter of ～0.5 µm in center and smaller particles of ～100 nm surrounding the larger ones. The coating was relatively dense and increasingly dense toward the substrate surface.     

Thermal conductivity behavior of SiC–Nylon 6,6 and hBN–Nylon 6,6 composites

A study was performed to determine the effect of the content and orientation of fillers on the thermal conductivity of a polymeric composite packed with hexagonal boron nitride (hBN) and silicon carbide (SiC) fillers. The thermal conductivity behavior of SiC–Nylon 6,6 and hBN–Nylon 6,6 composites was more dependent on the orientation and shape of the filler than on its thermal conductivity. The thermal conductivity of SiC–Nylon 6,6 composites with 59 % (v/v) isotropic SiC fillers increased from 0.25 to 3.83 W/m K. That of hBN–Nylon 6,6 composites with 62 % (v/v) anisotropic hBN fillers increased from 0.25 to 2.16 W/m K in the perpendicular direction whereas in the parallel direction it increased rapidly to 8.55 W/m K .     

EFFECTS OF NH4CI ON THE INTERACTION BETWEEN POLY(ETHYLENE OXIDE)AND IONIC SURFACTANTS IN AQUEOUS SOLUTIONS

The interaction of poly(ethylene oxide)(PEO)with the ionic surfactants,sodium dodecylsulfate(SDS)and cetyltrimethylammonium chloride(CTAC)respectively,in aqueous solutions containing a certain concentration of NH4Cl,is studied by the viscosity measurement.It has been found that the ion-dipole interaction between PEO and ionic surfactants is changed considerably by the organic salt.For anionic surfactant of SDS,the addition of NH4Cl into solution strengthens the interaction between PEO and the headgroup of SDS.On the other hand,for cationic surfactant of CTAC,the interaction between PEO and the headgroup of CTAC is screened significantly by NH4Cl dissolved in solution.These findings may potentially be attributed to the negative property of the oxygen group of the PEO chain.In the presence of NH4Cl,the cationic ions of the organic salt bind to the oxygen group of the PEO chain so that PEO can be referred to as a pseudopolyelectrolyte in solution.     

Study of cryostructuring of polymer systems. 32. Morphology and physicochemical properties of composite poly(vinyl alcohol) cryogels filled with hydrophobic liquid microdroplets

Cryogenic treatment (freezing at −20°C for 12 h followed by defrosting at a rate of 0.03°C/min) of decane, dodecane, or tetradecane emulsions in a poly(vinyl alcohol) solution (80 g/l) is employed to prepare composite cryogels containing microdroplets of liquid hydrophobic fillers entrapped into a macroporous hydrogel matrix. The effects of the type of a hydrocarbon, the degree of filling, and the addition of a surfactant (decaethylene glycol cetyl ether) on the physicomechanical properties, heat endurance, and morphology of the composites are studied. It is shown that, an increase in the content of liquid hydrophobic fillers within some range of their volume fraction enhances the rigidity of corresponding cryogels. Incorporation of the nonionic surfactant into the initial emulsions results in a complex dependence of the rigidity of the resulting composite cryogels on surfactant concentration and variations in the morphology of pores in the gel phase. At the same time, the heat endurance of all examined composite cryogels weakly depends on the type and concentration of the hydrocarbon fillers, as well as the presence of surfactant additives.