Spontaneous formation of polymer nanoparticles by good-solvent evaporation as a nonequilibrium process

In recent years, polymer nanoparticles have been investigated with great interest due to their potential applications in the fields of electronics, photonics, and biotechnology. Here, we report the spontaneous formation of polymer nanoparticles from a clear solution containing a nonvolatile poor solvent by slow evaporation of a volatile good solvent. During evaporation of the good solvent, the solution gradually turns turbid. After evaporation, polymer nanoparticles of homogeneous shape and size are dispersed in the poor solvent. Homogeneous nucleation and successive growth of polymer particles takes place during the dynamic nonequilibrium process of solvent evaporation. The size of the particles, ranging from tens of nanometers to micrometer scale, depends on both polymer concentration and the solvent mixing ratio. Because of the physical generality of the particle formation mechanism, this procedure is applicable to a wide variety of polymers with suitable combinations of solvents. Here, we also show unique features, surface structures and surface properties of polymer nanoparticles prepared by this method.     

Ultrasonic-assisted de-agglomeration and power draw characterization of silica nanoparticles

Breakage of nanoparticle cluster require high-intensity devices for stable and uniform distribution of aggregates. The ultra-sonication process is a high energy-intensive technique that produces cavitation effect to break the aggregates. In the present study, ultra-sonication is used for the de-agglomeration of fumed silica nanoparticles in low to high viscosity liquids. Water- and glycerol-based dispersion has been investigated at different solid loadings (up to 10 wt% for water-based dispersion and 5 wt% in glycerol-based dispersion) and viscosity of continuous phase (1–100 mPa.s). Breakup mechanism and kinetics have been studied at optimized operating conditions and no significant effect is found at different solid loadings on breakup mechanism. Particle size measurements are reported and found that volume of fine generation increased with an increase in sonication time. Further, it is observed that the stability of dispersion in the liquid is very high even at high concentration of solid used. Larger agglomerates are found at high viscosity of continuous phase and a lag is also observed for 100 mPa.s glycerol solution even at low solid loading (1 wt%). From, rheological characterizations it is found that the behavior of dispersed solution changed with time, temperature and solid loading. Erosion is found to be the breakup mechanism and further, validated with scattering light characterization. Furthermore, power draw increased with an increase in the viscosity of continuous phase, however, no significant effect of solid loading is observed. It is also observed that process is more energy-efficient at higher solid loading as the volume of fine produced is more as compared to low solid loading. Therefore, it can be concluded that the stable and uniform dispersion of nanoparticles can be achieved using an ultra-sonication device at high solid loading in viscous liquids.     

A facile one-pot synthesis of highly luminescent CdS nanoparticles using thioglycerol as capping agent

Absence of emission concentration quenching accompanied by high emission efficiency in a solid state is highly challenging though very attractive, for example, for fabrication of solid state light emitters or fluorescent organic nanoparticles (FONs). Here, formation of FONs based on novel p-phenylenediacetonitrile derivatives by re-precipitation method in aqueous solutions is demonstrated. The exceptionality of the derivatives employed is manifested by nitrile groups-induced steric hindrance effects inhibiting concentration quenching of emission. Consisting of different size and polarity end-groups, phenyl groups in one compound and hexyl-carbazolyl in another, the derivatives were examined and compared in regard to nanoparticle formation morphology, size tunability, spectral signatures, and fluorescence turn-on efficiency. The variation of solvent/non-solvent ratio allowed to achieve tuning of the FON sizes from 55?nm up to 360?nm and resulted in maximal fluorescence on/off ratio of 38. Spectrally resolved confocal fluorescence microscopy revealed somewhat different molecule arrangement in different FONs suggesting dominant amorphous-like phase, which was confirmed by small angle X-ray scattering measurements. The FONs were verified to be stable against degradation or conglomeration into larger clusters at least over a couple of months thus implying their feasibility for practical applications. Finally, potential application of the fluorescent p-phenylenediacetonitrile nanoparticles for organic vapor sensing via fluorescence on/off switching was demonstrated.     

Synthesis, characterization, and controlled aggregation of biotemplated polystyrene nanodisks

Cross-linked polystyrene nanodisks were prepared by controlled polymerization of styrene and divinylbenzene in the interior of bicelles, discoidal lipid aggregates. Aggregation behavior of polymer nanodisks was studied in water, organic solvents, and solid phase. Nanodisks form stable dispersions in aqueous solutions of surfactants, such as sodium dodecyl sulfate (SDS). Varying SDS/nanodisk ratio allowed us to control the size of nanodisk aggregates. Nanodisks are readily solubilized in nonpolar organic solvents, such as toluene and carbon tetrachloride, to yield stable monodisperse suspensions. These findings open opportunities for creating nanodisk-based nanocomposite materials. Stable nanodisk suspension in toluene enabled small angle neutron scattering (SANS) measurements. SANS data confirmed the nanodisk diameter and allowed accurate measurement of nanodisk thickness (19.5 ± 1.0 Å). In solid phase, nanodisks aggregate in sub-micron platelets.     

Preparation of luminescent ZnS:Cu nanoparticles for the functionalization of transparent acrylate polymers

Highly luminescent ZnS:Cu nanoparticles were synthesized in a coprecipitation route using aqueous salt solutions and thiopropionic acid as stabilizer. The method yields a stable, transparent particle dispersion in water and allows for a good control over particle size in the range of 3-10 nm as determined by dynamic light scattering, small angle X-ray scattering and transmission electron microscopy. Strong luminescence of the nanoparticles was observed under UV-excitation and emission colors could be adjusted in the range of blue to green by varying the Cu-doping concentration. The phase transfer of the ZnS:Cu nanoparticles into non-polar solvents using octylamine was used for a hydrophobic surface functionalization. The hydrophobic particles were used for the fabrication of transparent bulk nanocomposites via in situ-polymerization of dispersions in laurylacrylate. A high transparency of the composite materials, and the luminescence of the ZnS:Cu nanoparticles is retained during the phase transfer and the polymerization process allowing for the integration of a new luminescent functionality into the polymer material.     

Influence of synthesis parameters on iron nanoparticle size and zeta potential

Zero valent iron nanoparticles are of increasing interest in clean water treatment applications due to their reactivity toward organic contaminants and their potential to degrade a variety of compounds. This study focuses on the effect of organophosphate stabilizers on nanoparticle characteristics, including particle size distribution and zeta potential, when the stabilizer is present during nanoparticle synthesis. Particle size distributions from DLS were obtained as a function of stabilizer type and iron precursor (FeSO₄·7H₂O or FeCl₃), and nanoparticles from 2 to 200 nm were produced. Three different organophosphate stabilizer compounds were compared in their ability to control nanoparticle size, and the size distributions obtained for particle volume demonstrated differences caused by the three stabilizers. A range of stabilizer-to-iron (0.05–0.9) and borohydride-to-iron (0.5–8) molar ratios were tested to determine the effect of concentration on nanoparticle size distribution and zeta potential. The combination of ferrous sulfate and ATMP or DTPMP phosphonate stabilizer produced stabilized nanoparticle suspensions, and the stabilizers tested resulted in varying particle size distributions. In general, higher stabilizer concentrations resulted in smaller nanoparticles, and excess borohydride did not decrease nanoparticle size. Zeta potential measurements were largely consistent with particle size distribution data and indicated the stability of the suspensions. Probe sonication, as a nanoparticle resuspension method, was minimally successful in several different organic solvents.     

Rheological Behavior of Polyarylsulfone 1‐Butyl‐3‐Methylimidazolium Chloride Solutions

Polyarylsufone polymers are engineering thermoplastics that can only be dissolved in polar solvents. We found that polyarylsufone has good solubility in ionic liquid (IL) with IL being a new kind of green solvent; thus, ILs are potential substitutes for conventional molecular solvents. However, the thermodynamics in ionic liquids are different then those in conventional solvents, so ILs as solvents have attracted enormous attention recently. Rheological behavior is an important factor in polymer material processing. The rheological behavior of polyarylsulfone (PASF) in both N, N,‐dimethylacetamide (DMAc) and ionic liquid 1‐butyl‐3‐methylimidazolium chloride [(Bmim) Cl] were studied in this paper as a function of concentration for concentrated solutions. It is interesting that the rheological behavior of the PASF/(Bmim) Cl solution is very different from that of PASF/DMAc solutions. In DMAc, as concentration increases viscosity increases, while the rheological behavior of the PASF/(Bmim) Cl solution exhibits a maximum in the viscosity‐concentration plots.     

Grafting of PMMA brushes on titania nanoparticulate surface via surface-initiated conventional radical and “controlled” radical polymerization (ATRP)

Stable dispersion of titania nanoparticles in organic solvents are obtained by grafting poly(methyl methacrylate) layer on to the surface. Titania nanoparticles are synthesized through the hydrolysis of titanium (IV) isopropoxide. The average size of the titania particles is found to be 15 ± 2 nm. The polymer layer was introduced onto the surface by immobilizing the initiating moiety. Azo initiator moiety required for surface-initiated conventional free radical polymerization and a tertiary bromide initiator moiety required for ATRP are attached covalently to the titania nanoparticulate surface through the surface hydroxyl groups. The “encapsulation” of PMMA layer results in the steric stabilization of the titania nanoparticles. Another important finding is that it is possible to grow polymer layer in a controlled fashion.     

Surface-modification in situ of nano-SiO2 and its structure and tribological properties

The preparation of a series of dispersible nano-SiO₂ by surface-modification in situ was described in this paper. It is found that some silane coupling agents can be combined with nano-SiO₂ by covalent bonds, which change the nanoparticle's surface properties and make nano-SiO₂ disperse well and steadily in many organic mediums. The structure of nanoparticles was characterized by transmission electron microscopy (TEM), infrared spectrum (IR), X-ray photoelectron spectra (XPS) and thermogravimetric analysis (TG). The dispersivity of these nanoparticles in organic solvents was measured by light transmittance. Considering such superior dispersion in oily solvents and very small size, we primarily investigated their tribological behaviors as additive in lubricant on wear testers. The results show that they can evidently increase anti-wear ability and reduce the friction coefficient of lubricant.     

Quantification of the Particle Size and Stability of Graphene Oxide in a Variety of Solvents

The exceptional solution processing potential of graphene oxide (GO) is always one of its main advantages over graphene in terms of its industrial relevance in coatings, electronics, and energy storage. However, the presence of a variety of functional groups on the basal plane and edges of GO makes understanding suspension behavior in aqueous and organic solvents, a major challenge. Acoustic spectroscopy can also measure zeta potential to provide unique insight into flocculating, meta‐stable, and stable suspensions of GO in deionized water and a variety of organic solvents (including ethanol, ethylene glycol, and mineral oil). As expected, a match between solvent polarity and the polar functional groups on the GO surface favors stable colloidal suspensions accompanied by a smaller aggregate size tending toward disperse individual flakes of GO. This work is significant since it describes the characteristics of GO in solution and its ability to act as a precursor for graphene‐based materials.     

有机溶剂热生长技术制备纳米CdS及其与聚苯胺复合膜的光学性能

以溶剂热生长技术(solvothermal technique)制备了半导体CdS的纳米微粒,并采用XRD、TEM、ED对其结构进行表征。在ITO导电玻璃上,采用电化学方法合成聚苯胺薄膜,以提拉的方法将CdS的纳米颗粒涂布其上,自组装得纳米CdS／PANI膜,并以荧光光谱(PL)及非线性Z-扫描法研究其光学特性。实验结果显示：经CdS修饰后,CdS／PANI膜的荧光发射峰强度增强,位置较单一PANI膜移至420nm处,同时经修饰后的复合物膜的非线性光学特性也有显著的提高。     

Homogeneous dispersion of gadolinium oxide nanoparticles into a non-aqueous-based polymer by two surface treatments

Gadolinium oxide nanoparticles are more and more used. They can notably provide interesting fluorescence properties. Herein they are incorporated into a non-aqueous-based polymer, the poly(methyl methacrylate). Their dispersion within the polymer matrix is the key to improve the composite properties. As-received gadolinium oxide nanopowders cannot be homogeneously dispersed in such a polymer matrix. Two surface treatments are, therefore, detailed and compared to achieve a good stability of the nanoparticles in a non-aqueous solvent such as the 2-butanone. Then, once the liquid suspensions have been stabilized, they are used to prepare nanocomposites with homogeneous particles dispersion. The two approaches proposed are an hybrid approach based on the growth of a silica shell around the gadolinium oxide nanoparticles, and followed by a suitable silane functionalization; and a non-hybrid approach based on the use of surfactants. The surface treatments and formulations involved in both methods are detailed, adjusted and compared. Thanks to optical methods and in particular to the use of a ??home made?? confocal microscope, the dispersion homogeneity within the polymer can be assessed. Both methods provide promising and conclusive results.     

Influence of the Substitution Degree on the Dilute Solution Properties of Cellulose Acetate

Modification of intrinsic viscosity, coil size, and preferential adsorption coefficients of cellulose acetate with various substitution degrees in single and mixed solvents was investigated at different temperatures. Miscibility is attained by specific competitive interactions between the solvent-solvent and solvent-polymer systems, which induce modification in the composition of solvent mixtures both inside and outside the polymer coil. The conformational properties in solutions were correlated with the preferential adsorption coefficients, known as depending on the interaction parameters of the polymer/solvent/solvent systems. The intermolecular interactions observed in the cellulose acetate solutions assure the main properties necessary for obtaining membranes with different applications.     

The effect of solvent on the crystal structure and size distribution of cadmium sulfide nanocrystals

CdS nanocrystals with different structures were synthesized by the method of solution precipitation using thiourea and cadmium acetate as starting materials in different solvents: water, methanol and N,N-dimethylformamide (DMF). Our results show that the solvent has direct effect on the structure and size of the final nanoparticles. It was found that using DMF, as a solvent, results in producing smaller nanoparticles with the cubic structures, while using the other solvents gives rise to larger nanoparticles with the hexagonal structure. It was also found that using heat during washing the precipitate results in a more homogenous size distribution of CdS nanocrystals. On the basis of our experimental results we also suggest a critical structure transformation size.     

Polymer thermophoresis in solvents and solvent mixtures

The thermophoresis of homopolymer chains dissolved in a pure non-electrolyte solvent or solvent mixture is theoretically examined. Thermophoresis is related to the temperature-dependent pressure gradient in the solvent layer surrounding the monomer units (mers). The gradient is produced by small changes in the solvent or solvent mixture density due to the mer-solvent interaction. The London-van der Waals interaction was considered as the main reason of the excess pressure around mers. The resulting expression for the thermophoretic mobility (TM) contains the Hamaker constant for mer-solvent interaction, as well as solvent thermodynamic parameters, including the cubic thermal expansion coefficients of the solvents and the temperature coefficient of the solvent partition factor (for the solvent mixture). This expression is used to calculate the interaction constants for polystyrene and poly(methyl methacrylate) in several organic solvents and binary solvent mixtures using thermophoretic data obtained from thermal field-flow fractionation. The calculated constants are compared with values in the literature and found to follow the same order among the different solvents and to be of the same order of value although several times larger. Furthermore, the model explains weak polymer thermophoresis in water compared with less polar solvents, which correlates also with monomer size. The concentration dependence of polystyrene TM in solvent mixtures also provides a satisfactory explanation by the proposed theory using a concept of secondary diffusiophoresis due to secondary temperature-induced solvent concentration gradient. The method for the evaluation of the diffusiophoresis contribution is proposed.     

Synthesis and self-assembly of magnetic nanoparticles

We report the synthesis and self-assembly of different shapes and sizes of FePt nanoparticles. Our study shows that surfactants and solvent play an important role in the synthesis of different shapes and sizes of FePt nanoparticles. Higher boiling point solvents lead to the formation of spherical nanoparticles and low boiling point solvents form cubic nanoparticles. Our studies also indicate that self-assembly of FePt nanoparticles on substrates is a complex process that is sensitive to the concentration of excess surfactant in the nanoparticle solution.     

Photoluminescence of a soluble polypyrrole based on N-vinylpyrrole

Photoluminescence of a novel polypyrrole based on N-vinylpyrrole was systematically observed in organic solutions. The polymer, which has a unique molecular structure, exhibited good photoluminescence in organic solutions. The emission peak of the polymer exhibited one strong green emission band at around 510 nm in common organic solutions. The maximum fluorescence quantum yield of the polymer was found to be 0.16 in NMP solution with fluorescein as standard. At the same concentration, the photoluminescence intensity increased in the order of CHCl₃, THF, DMSO, CH₂Cl₂ and NMP. The photoluminescence spectrum had a slight red shift as the polarity of the solvents increased. The photoluminescence intensity also increased with the polarity of the solvent, except DMSO. This is because of its hygroscopicity in air and its viscosity. In THF solutions, the photoluminescence intensity increased until the concentration reached a certain weight percent (3.0×10⁻² wt.%) and then decreased with higher concentrations. This was most likely due to quenching in the aggregate phase. Furthermore, iron ion was a quencher in the DMSO solution. In a mixed solvent system of DMSO and water, water showed a typical quenching effect.     

Thermodynamics of polystyrene solutions. I. Interaction parameters and polymer order

The Maron theory was used to deduce from mostly osmotic pressure and light-scattering data the interaction parameters as a function of concentration, temperature, and polymer molecular weight for solutions of polystyrene in seven different solvents. These interaction parameters were then utilized to calculate the activity coefficients of the solvent in more concentrated solutions for comparison with experimental values deduced from vapor pressure measurements. When order was absent in the polymers (all cases but two), the agreement between calculated and observed activity coefficients was found to be very good. In the two cases where order was present, the activity coefficients observed in the concentrated solutions were higher than those calculated. These deviations were employed to find the degree of polymer order both in solution and in the original polymers.     

Optical properties of nanocomposites based on polymers and metal nanoparticles

The optical properties of nanocomposites of metal nanoparticles and polymers of two types have been studied. Gold and silver nanoparticles were obtained by laser ablation of corresponding metal targets in acetone and chloroform. The thus formed colloidal solutions were used to prepare nanocomposites of these nanoparticles in polymer matrices of polymethylmethacrylate (PMMA) and fluorine-containing polymer LF-32. The polymer matrix is found to promote aggregation of the metal nanoparticles under study into elongated chains. In turn, metal nanoparticles affect the polymer matrix. In the case of PMMA, suppression of the vibrational peaks of polymer in the low-frequency region of its Raman spectrum occurs. In the case of LF-32, gold and silver nanoparticles amplify the Raman signal of the polymer matrix. In addition, the Raman spectra of nanocomposites indicate aggregation of disordered carbon around the nanoparticles obtained by laser ablation in organic solvents. The possibilities of studying the ultrafast (about 1 ps) optical response of the nanocomposites obtained in order to use it in photonics elements are discussed.     

Dielectric Dispersion Study of Poly(vinyl Pyrrolidone)–Polar Solvent Solutions in the Frequency Range 20 Hz–1 MHz

Influence of polar solvents environment and polymer concentrations on the electrical properties (complex dielectric constant, ac electrical conductivity, complex electric modulus and complex impedance) of the solutions of poly(vinyl pyrrolidone) (PVP) in polar solvents, namely water, ethyl alcohol, ethylene glycol, diethylene glycol, poly(ethylene glycol), glycerol, dimethyl sulfoxide and dimethyl formamide, have been investigated in the frequency range 20 Hz–1 MHz at 25°C. Comparative analysis of the dielectric dispersion curves confirms that the solvent molecular size and number of its hydroxyl groups, and the solutions viscosity, are the major factors which governs the PVP chain segmental motion. The ionic conduction and electrode polarization phenomena has a dominant influence on the large increase of complex dielectric constant values of the solutions of PVP‐polar solvent in the lower frequency region. The values of relaxation times corresponding to these phenomena are also reported.