Formation and stability of string phase in polyamide 6/polystyrene blends in confined flow: Effects of nanoparticles and blend ratio

Influences of silica nanoparticles on the microstructural evolution of polyamide 6 (PA6)/polystyrene (PS) blends with varying blend ratios were investigated in confined shear flow. Hydrophilic silica nanoparticles were found to promote the formation of PA6 strings with excellent shape stability during shearing. It was ascribed to the promoted coalescence of PA6 droplets induced both by the significantly increased droplet viscoelasticity and confinement, and the reduced interfacial tension by adding silica nanoparticles. Additionally, the width and aspect ratio of droplets obtained by experiments were compared with the predictions of Maffettone–Minale, Minale, Shapira‐Haber, MMSH, and modified M models. Good agreements were found in the droplet width in blends with low nanoparticle concentrations, whereas the experimental aspect ratio showed a negative deviation to model predictions, which was attributed to the enhanced droplet viscoelasticity and the omitted droplet orientation angle in these models. © 2015 American Institute of Chemical Engineers AIChE J, 62: 564–573, 2016     

Improving mechanical and thermal properties of short carbon fiber/polyamide 6 composites through a polydopamine/nano-silica interface layer

Carbon fiber (CF) reinforced matrix composites have been applied widely, however, the interfacial adhesion of composites is weak due to smooth and chemically inert of CF surface. To solve this problem, A polydopamine/nano-silica (PDA-SiO₂) interfacial layer on carbon fiber surface was constructed via polydopamine and nano- SiO₂ (CF-PDA-SiO₂) by a facile and effective method to reinforce polyamide 6 composites (CFs/PA6). The effects of PDA-SiO₂ interfacial layer on crystallization structure and behavior, thermal properties, and mechanical properties of CFs/PA6 composites were investigated. Furthermore, interfacial reinforcement mechanism of composites has been discussed. This interfacial layer greatly increased the number of active groups of CF surface and its wettability obviously. The tensile strength of CF-PDA-SiO₂/PA6 composites increased by 28.09%, 19.37%, and 26.22% compared to untreated-CF/PA6, CF-PDA/PA6, and CF-SiO₂/PA6 composites, respectively, which might be caused by the increased interfacial adhesion between CF and PA6 matrix. The thermal stability, crystallization temperature, crystallinity, and glass transition temperature (T_g) of CF-PDA-SiO₂/PA6 composites improved correspondingly, attributing to the heterogeneous nucleation of nano-SiO₂ in the crystalline area and hydrogen bonds with molecular chains of PA6 in the amorphous area. This work provides a novel strategy for the construction of interfaces suitable for advanced CF composites with different structures.     

Effect of compatibilizer on the dispersion of untreated silica in a polypropylene matrix

BACKGROUND: A new processing method for polypropylene–untreated precipitated silica (PP/SiO₂) composites based on the incorporation of a second polymer phase of polyamide 6 (PA6) is presented and compared with a more classic one making use of compatibilizers: glycerol monostearate (GMS), ethylene acrylic acid ionomer (IAAZE) and maleic anhydride grafted polypropylene (MA‐graft‐PP). The effects of processing methods and conditions on the microstructure and properties of PP/SiO₂ composites prepared by melt compounding are investigated with a view to reduce the size of aggregates of silica from the micrometre to the nanometre scale and to improve the link between filler and matrix. RESULTS: On the one hand, the presence of GMS and IAAZE compatibilizers significantly improves the dispersion of the silica particles. On the other hand, when using a PA6 second phase, the SiO₂ particles are dispersed in PA6 nodules. Within these nodules, SiO₂ appears dispersed at the nanoscale but with larger particles (‘aggregates’) of about 200 nm. Significant improvements in tensile strength and modulus are obtained using MA‐graft‐PP compatibilizer. An increase in impact strength is observed in the case of GMS compatibilizer. Thermal parameters indicate also that silica plays the role of nucleation agent for PP matrix. All improvements (tensile strength, modulus and impact strength) increase with the addition of compatibilized PA6 second phase. CONCLUSION: By the incorporation of masterbatch of silica in PA6 as a second polymer polar phase, a successful new production method for PP/SiO₂ nanocomposites has been developed. Interestingly, this method does not require any (expensive) pre‐treatment of the silica. Copyright © 2007 Society of Chemical Industry     

Online study of the formation of PA6 droplets in PP matrix under shear flow

Breakup process of polyamide 6 (PA6) in polypropylene (PP) matrix under shear flow was online studied by using a Linkam CSS 450 stage equipped with optical microscopy. Both tip streaming and fracture breakup modes of PA6 droplets were observed in this study. It was reported that the droplet would break up by tip streaming model when the radio of the droplet phase viscosity to the matrix phase viscosity (η_r = η_d/η_m) is smaller than 0.1 (Taylor, Proc R Soc London A 1934, 146, 501; Grace, Chem Eng Commun 1982, 14, 225; Bartok and Mason, J Colloid Sci 1959, 14, 13; Rumscheidt and Mason, J Colloid Sci 1961, 16, 238; de Bruijn, Chem Eng Sci 1993, 48, 277). However, the tip streaming model was observed even when the viscosity ratio was much greater than 0.1 (η_r = 1.9). In this study for the tip streaming mode, small droplets were ruptured from the tip of the mother droplet. On the other hand, the mother droplet was broken into two or more daughter droplets with one or several satellite droplets between them for the fracture mode. It was found that PA6 droplet was much elongated at first, and then broke up via tip streaming or fracture to form daughter droplets or small satellite droplets with the shape of fiber or ellipse. Stopping shearing, those elongated droplets began to shrink, and finally became spheres. Moreover, it was found that the average domain size of those PA6 spheres considerably decreased with increasing shear time. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2690–2695, 2007     

Preparation and properties of nylon 6/carboxylic silica nanocomposites via in situ polymerization

Nylon 6/carboxylic acid‐functionalized silica nanoparticles (SiO₂‐COOH) nanocomposites were prepared by in situ polymerization of caprolactam in the presence of SiO₂‐COOH. The aim of this work was to study the effect of carboxylic silica on the properties of the nylon 6 through the interfacial interactions between the SiO₂‐COOH nanoparticles and the nylon 6 matrix. For comparison, pure nylon 6, nylon 6/SiO₂ (unmodified) and nylon 6/amino‐functionalized SiO₂ (SiO₂‐NH₂) were also prepared via the same method. Fourier transform infrared spectrometer (FTIR) spectroscopy was used to evaluate the structure of SiO₂‐COOH and nylon 6/SiO₂‐COOH. The results from thermal gravimetric analysis (TGA) indicated that decomposition temperatures of nylon 6/SiO₂‐COOH nanocomposites at the 5 wt % of the total weight loss were higher than the pure nylon 6. Differential scanning calorimeter (DSC) studies showed that the melting point (T_m) and degree of crystallinity (X_c) of nylon 6/SiO₂‐COOH were lower than the pure nylon 6. Mechanical properties results of the nanocomposites showed that nylon 6 with incorporation of SiO₂‐COOH had better mechanical properties than that of pure nylon 6, nylon 6/SiO₂, and nylon 6/SiO₂‐NH₂. The morphology of SiO₂, SiO₂‐NH₂, and SiO₂‐COOH nanoparticles in nylon 6 matrix was observed using SEM measurements. The results revealed that the dispersion of SiO₂‐COOH nanoparticles in nylon 6 matrix was better than SiO₂ and SiO₂‐NH₂ nanoparticles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improvement of polyamide 1010 with silica nanospheres via in situ melt polycondensation

Polyamide 1010 (PA1010) had been prepared by in situ melt polycondensation in presence of silica nanospheres with amine groups on the surfaces (SiO₂ NH₂). Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), and thermal gravimetric analysis (TGA) measurements demonstrated that the nanosphere surface was grafted with PA1010 chains. Wide angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC) measurements showed that the PA1010/SiO₂ NH₂ nanocomposites had a lower degree of crystallinity (χ_c) in comparison with PA1010 and PA1010/SiO₂ nanocomposites. Dynamic mechanical analysis (DMA) indicated that SiO₂ NH₂ nanospheres improved glass transition temperature (T_g), tensile strength and storage modulus of PA1010 since SiO₂–NH₂ nanospheres limited the mobility of PA1010 chains. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Study of the partial wetting morphology in polylactide/poly[(butylene adipate)‐co‐terephthalate]/polyamide ternary blends: case of composite droplets

The prediction of the morphology of ternary polymer blends requires a good knowledge of the values of the three interfacial tensions. We selected three polymers, either biobased or biodegradable, polyamide (PA), poly[(butylene adipate)‐co‐terephthalate] (PBAT) and polylactide (PLA), and we accurately measured their interfacial tensions using the retraction method, varying the molar mass or inverting the phases. The following values of interfacial tension were obtained: γ_PBAT/PLA = 3.3 ± 0.7 mN m^?1, γ_PA/PLA = 5.6 ± 0.3 mN m^?1 and γ_PBAT/PA = 3.0 ± 0.4 mN m^?1. These values were used to calculate the spreading coefficients giving rise to two negative coefficients and one coefficient close to zero. Ternary blends with various compositions, two different levels of viscosity for PBAT and different processing conditions were prepared. There was a very good agreement between the predictions of the spreading theory, when using the values of interfacial tension of the right order of magnitude, and the observed morphologies, whatever the polymer serving as a matrix. When PLA or PBAT was chosen as the matrix, the ternary blend morphology was composed of composite droplets, presenting a partial wetting morphology, dispersed in the polymer matrix. This morphology was observed whatever the composition, the viscosity of the PBAT phase and the processing conditions. A further calculation of the free energy confirmed this morphology. The formation process of this semi‐encapsulated morphology was observed during blending. © 2018 Society of Chemical Industry     

Interfacial interactions and properties of natural rubber–silica composites with liquid natural rubber as a compatibilizer and prepared by a wet‐compounding method

Natural rubber–silica [W(NR–SiO₂)] composites were prepared by wet‐compounding technology with liquid natural rubber (LNR) as a compatibilizer. The effects of the LNR content and wet‐compounding technology on the filler dispersion, Payne effect, curing characteristics, mechanical properties, and interfacial interactions were investigated. The results show that the incorporation of LNR promoted vulcanization and decreased the Payne effect of the W(NR–SiO₂) composites. With the addition of 5 phr LNR, the remarkable improvements in the mechanical properties of the W(NR–SiO₂) vulcanizates were correlated with the improved silica dispersion and strengthened interfacial bonding. Furthermore, the W(NR–SiO₂) vulcanizates containing LNR exhibited improvements in both the wet‐skid resistance and rolling‐resistance performance. The interfacial interactions, quantitatively evaluated by the Mooney–Rivlin equation and Lorenz–Park equation on the basis of the rubber elasticity and reinforcement theory, were strengthened in the presence of LNR. Accordingly, an interfacial structural model was proposed to illustrate the improvements in the mechanical properties of the W(NR–SiO₂) composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46457.     

Interfacial slip‐stick transition induced by reactive compatibilization in ethylene‐co‐butyl acrylate elastomer dispersed polyamide 6 blend subjected to high shear flow and extensional flow

The effect of phase interaction induced by reactive compatibilization during high shear and extensional flow in polyamide (PA6) and ethylene‐co‐butyl acrylate (EBA) blends was studied using advanced dual bore capillary rheometer. The viscosity‐composition behavior of the uncompatibilized PA6/EBA blends exhibited negative deviation behavior from log‐additivity rule. The interfacial slip mechanism, operative between the matrix PA6 and dispersed EBA during shear flow was studied by the use of Lin's and Bousmina‐Palierne‐Utracki (BPU) model for viscosity for the blends under the processing conditions. On the other hand, the compatibilized PA6/EBA‐g‐MAH^0.49/EBA blends with varying dispersed phase volume fraction show positive deviation behavior. The reactive compatibilizers EBA‐g‐MAH^0.49 and EBA‐g‐MAH^0.96 increased the phase interaction with adequate reduction in the dynamic interfacial tension, which favored the particle break‐up and stabilized the morphology in the compatibilized blends. The extensional viscosity of the blends has enhanced because of the inclusion of EBA in all the uncompatibilized and compatibilized blends. The melt elasticity and elasticity function were systematically studied from first normal stress coefficient functions (ψ₁). The variation in the recoverable shear strain (γ_R), shear rate dependent relaxation time (λ) and shear compliance (J_c) under various shear rates were thoroughly analyzed for all the blend compositions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Polyamide-6,6/in situ silica hybrid nanocomposites by sol-gel technique: synthesis, characterization and properties

The organic-inorganic hybrid nanocomposites comprising of poly(iminohexamethyleneiminoadipoyl), better known as Polyamide-6,6 (abbreviated henceforth as PA66), and silica (SiO₂) were synthesized through sol-gel technique at ambient temperature. The inorganic phase was generated in situ by hydrolysis-condensation of tetraethoxysilane (TEOS) in different concentrations, under acid catalysis, in presence of the organic phase, PA66, dissolved in formic acid. Infrared (IR) spectroscopy was used to monitor the microstructural evolution of the silica phase in the PA66 matrix. Wide angle X-ray scattering (WAXS) studies showed that the crystallinity in PA66 phase decreased with increasing silica content. Atomic force microscopy (AFM) of the nanocomposite films revealed the dispersion of SiO₂ particle with dimensions of <100 nm in the form of network as well as linear structure. X-ray silicon mapping further confirmed the homogeneous dispersion of the silica phase in the bulk of the organic phase. The melting peak temperatures slightly decreased compared to neat PA66, while an improvement in thermal stability by about 20 °C was achieved with hybrid nanocomposite films, as indicated by thermogravimetric analysis (TGA). Dynamic mechanical analysis (DMA) exhibited significant improvement in storage modulus (E′) for the hybrid nanocomposites over the control specimen. An increase in Young's modulus and tensile strength of the hybrid films was also observed with an increase in silica content, indicating significant reinforcement of the matrix in the presence of nanoparticles. Some properties of the in situ prepared PA66-silica nanocomposites were compared with those of conventional composites prepared using precipitated silica as the filler by solution casting from formic acid.     

Jet breakup and droplet formation in near-critical regime of carbon dioxide-dichloromethane system

The jet breakup and droplet formation mechanism of a liquid in the near-critical conditions of a solvent-antisolvent system is examined with high-speed visualization experiments and simulated using a front tracking/finite volume method. The size of droplets formed under varying system pressure at various jet breakup regimes is measured with a Global Sizing Velocimetry, using the shadow sizing method. A stainless steel nozzle with 0.25 mm I.D and 1.6 mm O.D was used in this study. Experiments were performed at fixed temperature of 35 °C and system pressure in the range from 61 to 76 bar in the near-critical regime of the DCM-CO₂. At the near mixture critical regime for DCM-CO₂ mixture, the miscibility between the two fluid phases increases and the interfacial tension diminishes. This phase behavior has important applications in particle formation using gas antisolvent (GAS) and supercritical antisolvent (SAS) processes. The jet breakup and droplet formation in the near-critical regime is strongly dependent on the changes in interface tension and velocity of the liquid phase. An understanding of the droplet formation and jet breakup behavior of DCM-CO₂ in this regime is useful in experimental design for particle fabrication using SAS method.     

Effect of different treatments and SiO2/PVDF coatings on morphology and wettability of electrospun polyamide 6 membranes

The electrospun polyamide 6 (PA6) membranes are treated with different methods. The rough surfaces with different protuberances size and the fiber diameter are prepared by wet, dry heat, wet heat, and ethanol treatments under relaxation, and the formation mechanisms are analyzed. A relative stable structure of PA6 membrane is also prepared by ethanol treatment under tension, and its structure is as same as the untreated membrane. The dynamic water contact angles (WCAs) of the treated membranes are measured. The starting WCA of the membrane with wet heat treatment under relaxation is 90.95°, which is larger than those of wet, dry heat, and ethanol treatments under relaxation. The effects of surface morphologies with different treatments on wettability are analyzed. For obtaining hydrophobicity, the membrane with wet heat treatment under relaxation was coated by polyvinylidene fluoride (PVDF). The WCA of the membrane increases to 127.1° after coating. From another point of view, the WCA of the PVDF/treated PA6 membrane is much larger than that of the pure casting PVDF membrane, which means the rough surface of the treated PA6 membrane can improve the hydrophobicity of the PVDF membrane. Furthermore, the membrane is endowed with superhydrophobicity (WCA of 153.5°) after being coated by SiO₂/PVDF due to the multilevel structured surface roughness. It is a relative low cost and convenient operation method to prepare the superhydrophobic material. The results provide a novel preparation method of the superhydrophobic material and a treatment method of the electrospun PA6 membrane to obtain a stable structure. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48804.     

The Effect of Cadmium on GFR Is Clarified by Normalization of Excretion Rates to Creatinine Clearance

Erroneous conclusions may result from normalization of urine cadmium and N-acetyl-β-D-glucosaminidase concentrations ([Cd]_u and [NAG]_u) to the urine creatinine concentration ([cr]_u). In theory, the sources of these errors are nullified by normalization of excretion rates (E_Cd and E_NAG) to creatinine clearance (C_cr). We hypothesized that this alternate approach would clarify the contribution of Cd-induced tubular injury to nephron loss. We studied 931 Thai subjects with a wide range of environmental Cd exposure. For x = Cd or NAG, E_x/E_cr and E_x/C_cr were calculated as [x]_u/[cr]_u and [x]_u[cr]_p/[cr]_u, respectively. Glomerular filtration rate (GFR) was estimated according to the Chronic Kidney Disease (CKD) Epidemiology Collaboration (eGFR), and CKD was defined as eGFR < 60 mL/min/1.73m². In multivariable logistic regression analyses, prevalence odds ratios (PORs) for CKD were higher for log(E_Cd/C_cr) and log(E_NAG/C_cr) than for log(E_Cd/E_cr) and log(E_NAG/E_cr). Doubling of E_Cd/C_cr and E_NAG/C_cr increased POR by 132% and 168%; doubling of E_Cd/E_cr and E_NAG/E_cr increased POR by 64% and 54%. As log(E_Cd/C_cr) rose, associations of eGFR with log(E_Cd/C_cr) and log(E_NAG/C_cr) became stronger, while associations of eGFR with log(E_Cd/E_cr) and log(E_NAG/E_cr) became insignificant. In univariate regressions of eGFR on each of these logarithmic variables, R² was consistently higher with normalization to C_cr. Our tabular and graphic analyses uniformly indicate that normalization to C_cr clarified relationships of E_Cd and E_NAG to eGFR.     

Thermal and dynamic mechanical behavior of bionanocomposites: Fumed silica nanoparticles dispersed in poly(vinyl pyrrolidone), chitosan,and poly(vinyl alcohol)

Various bionanocomposites were prepared by dispersing fumed silica (SiO₂) nanoparticles in biocompatible polymers like poly(vinyl pyrrolidone) (PVP), chitosan (Chi), or poly(vinyl alcohol) (PVA). For the bionanocomposites preparation, a solvent evaporation method was followed. SEM micrographs verified fine dispersion of silica nanoparticles in all used polymer matrices of composites with low silica content. Sufficient interactions between the functional groups of the polymers and the surface hydroxyl groups of SiO₂ were revealed by FTIR measurements. These interactions favored fine dispersion of silica. Mechanical properties such as tensile strength and Young's modulus substantially increased with increasing the silica content in the bionanocomposites. Thermogravimetric analysis (TGA) showed that the polymer matrices were stabilized against thermal decomposition with the addition of fumed silica due to shielding effect, because for all bionanocomposites the temperature, corresponding to the maximum decomposition rate, progressively shifted to higher values with increasing the silica content. Finally, dynamic thermomechanical analysis (DMA) tests showed that for Chi/SiO₂ and PVA/SiO₂ nanocomposites the temperature of β‐relaxation observed in tanδ curves, corresponding to the glass transition temperature T_g, shifted to higher values with increasing the SiO₂ content. This fact indicates that because of the reported interactions, a nanoparticle/matrix interphase was formed in the surroundings of the filler, where the macromolecules showed limited segmental mobility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation on interfacial interaction of flame retarded and glass fiber reinforced PA66 composites by IGC/DSC/SEM

The interfacial interaction of flame retarded and glass fiber reinforced PA66 composites is a very important issue due to one of the key factors influencing the mechanical properties of materials. In this article, the interfacial interaction among the components in the composites has been studied by IGC/DSC/SEM techniques. The experimental data demonstrated that Zn²⁺-modified melamine polyphosphate (Zn-MpolyP) flame retardant could obviously enhanced the mechanical properties of the composites compared with melamine polyphosphate (MpolyP). SEM results proved that Zn-MpolyP could well disperse in the composites, and effectively improve the interfacial compatibility of the composites. Based on DSC results, Zn-MpolyP and MpolyP promoted the crystallization enthalpy (ΔH_c) and temperature (T_c) of PA66 to increase. Zn-MpolyP showed more effect in increasing the crystallization degree of PA66 than MpolyP. They exhibited the nucleating effect in PA66. The Lewis acid-base numbers (K_a and K_b) and their ratio (K_b/K_a) obtained by inverse gas chromatography (IGC) further proved that the strongest Lewis acid-base interaction between PA66 and Zn-MpolyP existed in the composites. This result is probably due to the strong complex between Zn²⁺ in Zn-MpolyP and lone pair electrons at O and N atoms of PA66 and glass fiber. Therefore, the all results of IGC/DSC/SEM techniques demonstrated that the interfacial compatibility of components in composites was better improved by Zn-MpolyP than MpolyP.     

Novel continuous process for methacrolein production in numerous droplet reactors

A continuous process for methacrolein production was constructed by filling w/o Pickering emulsions in a column reactor. Ionic liquid (IL-[HDEA]Ac) with secondary amine was designed to catalyze propionaldehyde condensation with formaldehyde through the Mannich reaction. Emulsion droplets encapsulated with IL aqueous solution were stabilized with modified SiO₂ nanoparticles and dispersed in cyclohexane, which could be observed as numerous reactors. The properties of SiO₂ stabilizer, such as wettability, surface groups, and the effect on interfacial tension were investigated. The characteristics of emulsion influenced by stabilizer properties and content were systematically studied. The droplet size, IL concentration and liquid hourly space velocity were optimized. The droplets were evaluated at 0.5 hr⁻¹ for 150 hr without IL leakage and obvious activity decreasing, indicating the excellent stability of the emulsion system. The continuous process showed a 1.25-fold enhancement in catalysis efficiency and less equipment compared to batch process.     

SiO2 migration mechanism at the joints of SiO2f/SiO2 composite brazed by bismuth glass

Joining is an indispensable process for expanding the application of ceramics and composites. Recently, glasses have been extensively explored for ceramic/composite joining owing to their unique functional needs. However, the difficulty in detecting amorphous materials and lack of enthalpy data make the interfacial reaction mechanism challenging to investigate. In this study, the interfacial reaction mechanism of joints of SiO_2f/SiO₂ composite-brazed bismuth glass was thoroughly explored. SiO₂ was dissolved from the matrix and used throughout the brazing process. In the initial stage, silica reacts with the brazing glass to form Bi₄(SiO₄)₃. Then, owing to the decomposition of Bi₄(SiO₄)₃, the silicate glass replaced the bismuth glass. Finally, some precipitation of SiO₂ occurred at the brazing seam owing to an entropy–enthalpy dominating mode. This study may instigate the design of brazing glasses for joining SiO_2f/SiO₂ composites.     

Mechanical and crystalline properties of monomer casting Nylon‐6/Sio2 composites prepared via in situ polymerization

A series of monomer casting (MC) nylon‐6/SiO₂ composites were prepared via in situ polymerization. It was found that the tensile strength, storage modulus, and notched charpy impact strength of the composites were improved and reached maximum at 3–5 wt% loading of SiO₂. The α relaxation peak corresponding to the glass transition temperature (T_g) shifted to high temperature with increasing SiO₂ content. Addition of SiO₂ led to an increase of the melting and crystallization temperatures, and crystallinity. It also reduced the induction time of crystallization, advance the crystallization process of MC nylon‐6, and improve the crystal growth rate. The self‐nucleation crystallization analysis indicated that SiO₂ particles played the role of facilitating the crystallization of the matrix mainly via accelerating the generation of crystal nucleus. By addition of SiO₂ particles, the fracture surface of MC nylon‐6 changed to distant striations with many yield folds accompanied by a large number of stress whitening, displaying much obvious character of tough fracture. SiO₂ particles can be pulled‐out under stress by being covered with MC nylon‐6 resin due to strong interfacial interaction and presented a skin–core structure. © 2012 Society of Plastics Engineers.     

Preparation of form-stable silica/polyethylene glycol composites using flash-drying for large-scale melt-spun fibers with thermal management property

The combination of phase change materials (PCMs) with fibers can afford smart fibers with thermal management properties. However, the issues of easy leakage and poor thermal stability of PCMs often limit their use in high-temperature spinning. Herein, we report a form-stable PCM of spherical SiO₂/PEG composite that was prepared through flash-drying using inorganic dendritic silica (D-SiO₂) as the core skeleton to support organic polyethylene glycol (PEG). The SiO₂/PEG composite not only presents high crystallization enthalpy (101.35 J/g), but also maintains a superior phase change stability. Meanwhile, it exhibits a significant temperature hysteresis effect during heating and cooling, and the endothermic and exothermic time are 381.95 and 293.57 s, respectively. Because the degradation temperature of 300°C for SiO₂/PEG is higher than the melt processing temperature of 240–270°C for the preparation of polyamide 6 (PA6) fibers, PA6/SiO₂/PEG fibers were prepared using melt spinning. The prepared PA6/SiO₂/PEG fibers exhibit high latent heat (17.14 J/g), outstanding thermal cycling stability and satisfactory temperature adjustment properties, and the temperature-adjustment time of 458.97 s and temperature difference of 10.68°C under the thermal environment. Moreover, the tensile strength of PCFs-20% reached 1.97 cN/dtex after drawing, which make PCFs meet the requirements of uses in textile industries.     

Thermolytic conversion of a bis(alkoxy)tris(siloxy)tantalum(V) single-source molecular precursor to catalytic tantala–silica materials

The new complex (ⁱPrO)₂Ta[OSi(O ^tBu)₃]₃ (1) was prepared via silanolysis of Ta(O ⁱPr)₅ with (^tBuO)₃SiOH and is a useful structural and spectroscopic (NMR, FTIR) model of Ta(V) on silica. The complex was also used to prepare tantalum-containing silica materials, via the thermolytic molecular precursor method (yielding Ta₂O₅ ⋅ 6SiO₂ and Ta₂O₅ ⋅ 18SiO₂) or by grafting 1 onto mesoporous SBA-15 silica (yielding a surface-supported tantala species, TaSBA-15). The solution phase thermolysis of 1 in nonpolar media afforded homogeneous, high-surface-area (ca. 450 m² g⁻¹) xerogels (Ta₂O₅ ⋅ 6SiO₂) that are amorphous up to approximately 1100 °C. A more silica-rich tantala–silica material (Ta₂O₅ ⋅ 18SiO₂) was prepared via a solution-phase co-thermolytic route with 1 and HOSi(O ^tBu)₃, to yield a material with a Si/Ta ratio of 9/1. It was demonstrated that tantala–silica materials are active as catalysts for cyclohexene oxidation.