Effect of Attapulgite Pore Size Distribution on Soybean Oil Bleaching

The pore size distribution and specific surface area of the attapulgite was a crucial parameter for the uptake of pigments of oil. Bleaching of the soybean oil with three attapulgites with different pore size distribution, which were assigned a, b, and c, respectively was investigated. The specific surface area and the pore size distribution of the attapulgites were characterized. The Freundlich isotherm analysis was used to evaluate the sorption capacity of the three attapulgite. Sample b gave the highest surface area and sample c the lowest. Sample b exhibited a wider pore distribution (8–65 Å) whereas samples a and c had more micropores smaller than 15 Å. Sample a, in contrast to samples b and c, was characterized by some larger pores (100–170 Å). The sorption capacity followed the sequence: attapulgite sample c > attapulgite sample a > attapulgite sample b. The sorption capacity was decided by the pore size distribution. The more pores with a distribution range 8–32 Å (i.e., close to the diameter of the pigments), the more pigments removed. The attapulgite sample c, which had most pores (8–32 Å) was the best.     

Improved mechanical and swelling behavior of the composite hydrogels prepared by ionic monomer and acid-activated Laponite

A composite hydrogel (CH) with much improved mechanical and swelling properties was prepared using an ionic monomer and acid-activated Laponite XLS which was used as a cross-linking agent. Addition of acid-activated clay solved the gelation problem when ionic monomers were added to clay mineral dispersions. Reaction of Laponite XLS with sulfuric acid yielded amorphous silica. A dispersion of the acid-activated Laponite and the monomers was used to synthesize composite hydrogels by in-situ polymerization. The FT-IR spectra and rheological results of the composite hydrogels demonstrated the formation of a network. The equilibrium swelling ratios of composite hydrogels (> 6000 g/g) were more than 18 times larger than traditional organic cross-linked hydrogels. The moduli G′ and G″ in the observed frequency range were about 4 and 10 times larger than those of organic cross-linked hydrogel (OR gel). The improvement in both the equilibrium swelling ratio and mechanical strength was attributed to the homogeneous cross-linked network structure.     

Network chain density and relaxation of in situ synthesized polyacrylamide/hectorite clay nanocomposite hydrogels with ultrahigh tensibility

Nanocomposite hydrogels (NC gel) D-AM and S-AM were synthesized through in situ polymerization of acrylamide (AM) with hectorite clays of Laponite RD and RDS, respectively. The tensile performance of the NC gel was observed at different crosshead speeds and all of the NC gels exhibited an extremely high tensibility, e.g., the elongation at break even higher than 4000%, except for two samples with the lowest Laponite content of 1 w/v%. Strong tensile hysteresis was observed in the elongation-reversion curve, indicating a slow relaxation in the NC gels. Dynamic moduli G′ and G″ within linear viscoelasticity illustrated that the network structure was formed in these gels with the junction of Laponite platelets. The Laponite RD showed stronger gelation capability than the tetrasodium pyrophosphate modified Laponite RDS. The relaxation modulus G(t) for the NC gels was found to be similar to the slow rubber relaxation with the critical exponent n of about 0.16, much lower than 0.66-0.71 for the critical gel at the sol-gel transition. In comparison, the chemically cross-linked hydrogel showed almost no relaxation during the same time interval. The effective network chain density of the NC gel was determined from equilibrium shear modulus, which was evidently lower than that of the chemically cross-linked hydrogels. The present results reveal that the high deformability of these NC gels comes from their low effective network chain density with moderate relaxation.     

Rheology of poly(propylene)/clay nanocomposites

The linear and nonlinear shear rheological behaviors of poly(propylene) (PP)/clay (organophilic‐montmorillonite) nanocomposites (PP/org‐MMT) were investigated by an ARES rheometer. The materials were prepared by melt intercalation with maleic anhydride functionalized PP as a compatibilizer. The storage moduli (G′), loss moduli (G″), and dynamic viscosities of polymer/clay nanocomposites (PPCNs) increase monotonically with org‐MMT content. The presence of org‐MMT leads to pseudo‐solid‐like behaviors and slower relaxation behaviors of PPCN melts. For all samples, the dependence of G′ and G″ on ω shows nonterminal behaviors. At lower frequency, the steady shear viscosities of PPCNs increase with org‐MMT content. However, the PPCN melts show a greater shear thinning tendency than pure PP melt because of the preferential orientation of the MMT layers. Therefore, PPCNs have higher moduli but better processibility compared with pure PP.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2427–2434,2004     

Rheological study of the gelation of cross-linking polyhedral oligomeric silsesquioxanes (POSS)/PU composites

The gelation process of N-Phenylaminomethyl-POSS/PU (polyurethane) nanocomposites during curing and at the stable state after curing was investigated by rheology. An increase in dynamic shear moduli, G′ and G″, was observed during the dynamic temperature ramps of the sample. In time-resolved mechanical spectroscopy (TRMS), G′ and G″ increased with curing time at constant curing temperatures over a wide of frequencies. The gelation time of the composites decreased with the rise of curing temperature or with the increase of POSS concentration. The relaxation exponent n at the critical gel was around 0.73. The gel stiffness S decreased as curing temperature increased or as POSS concentration increased. After the completion of the curing reaction, the critical concentration of POSS beyond which the gelation of POSS/PU composites would happen was found around 2.5 wt%. The viscoelastic properties of crosslinking POSS/PU fitted time–temperature-superposition well which implied the incorporation of multifunctional POSS into PU increased the homogeneity of crosslinking POSS/PU composites. Surprisingly, the modulus of the fully cured materials between 2.7 wt% and 6 wt% could also be supposed onto a master curve at high temperature, which implied self-similarity of network near the critical gel. The similar microstructure of POSS/PU at stable state was also confirmed by TEM. The network formation mechanism and the fine structure of the crosslinking POSS/PU were firstly investigated which would provide technical and theoretical basis for other hybrid crosslinking systems.     

Rheological characterization of a charged cationic hydrogel network across the gelation boundary

The in situ rheological behavior across the gelation threshold has been investigated for an affine network of a completely charged cationic monomer (3-acrylamidopropyl)-trimethylammonium chloride (APTMAC1) when it is crosslinked with a neutral crosslinker (N,N′-methylenebisacrylamide) to form a fully charged novel cationic hydrogel. The elastic moduli (G′) near the gel point (during the crosslinking or ‘curing’ process) show a power law dependence of the form G′(t)=ε^z, where ε=((t−t_c)/t_c) is the distance from the gel point (t_c). The critical exponent, z, for the hydrogel series investigated is estimated to be 1.5, slightly lower than the predictions based on percolation theory (z∼1.7-1.9). From the equilibrium (after the curing process) rheological measurements of a series of samples, it is inferred that there is a critical crosslinker mole percent (X_c) with respect to the monomer concentration, required to form a well-defined three-dimensional network with a solid-like behavior. The value of this X_c is found to be between 0.5 and 1%. The theoretically predicted value of X_c using the percolation theory (for the percolation of crosslinks, G₀(X)∝[|X−X_c|/X_c]^z) and the exponent estimated from the in situ measurements (z=1.5), is X_c∼0.6, which is in good agreement with the experiments. The results may have applicability in translating from bulk systems to the nanoscale in hydrogel design.     

Dynamic rheological properties of binary PP/PA and ternary PP/PA/GF blends

The dynamic rheological behavior was investigated for binary polypropylene (PP) - polyamide-6 (PA-6) and ternary PP-PA-6-glass fiber (GF) blends. The observed trends are related to the blend morphology and the partitioning of the GF within the three component blends. The dynamic and shear viscosity results show a good overlap for the PP homopolymer, within the shear rates studied. The addition of PA-6 and/or glass fibers to the PP causes significant deviations between the two rheological behaviors. This reflects the fibrillation of PA-6 and the orientation of glass fibers during shear rheometry, which reduce the blends' shear viscosity. The effect of PA-6 content on dynamic viscosity is less significant than for shear viscosity, owing to the absence of morphological structuring. The addition of PA-6 to PP increased the principal relaxation time of the binary blends. The addition of GF to these binary blends gave a further increase in the principal relaxation time.     

Rheology and properties of melt-processed poly(ether ether ketone)/multi-wall carbon nanotube composites

Poly(ether ether ketone) (PEEK)/multi-wall carbon nanotube (MWNT) composites containing up to 17 wt% filler were prepared using a twin screw extruder. Transmission electron microscopy (TEM) images reveal that the MWNTs were homogeneously dispersed in the PEEK matrix. Linear viscoelastic measurements show that both complex viscosity and moduli increase with increasing MWNT concentration. The storage modulus, G^′ exhibits a dramatic seven order increase in magnitude around 1 wt%, leading to a solid-like low-frequency behaviour at higher loadings; the effect can be attributed to network formation at a rheological percolation threshold. Rheotens measurements show that the melt strength also increases significantly on addition of nanotubes, however, the drawability decreases. An analytical Wagner model was used to calculate the apparent elongational viscosity over a wide range of elongational rates, and to reveal significant increases on addition of MWNTs, with a similar threshold behaviour. The electrical response is also dominated by percolation effects, increasing by nearly 10 orders of magnitude from 10⁻¹¹ to 10⁻¹ S/cm, on the addition of only 2 wt% MWNTs. In contrast, the thermal conductivity and tensile elastic modulus of the composites increased linearly with nanotube content, rising by 130% and 50%, at 17 wt% MWNTs, respectively.     

Rheological behavior of multiwalled carbon nanotube/polycarbonate composites

The rheological behavior of compression molded mixtures of polycarbonate containing between 0.5 and 15 wt% carbon nanotubes was investigated using oscillatory rheometry at 260 °C. The nanotubes have diameters between 10 and 15 nm and lengths ranging from 1 to 10 μm. The composites were obtained by diluting a masterbatch containing 15 wt% nanotubes using a twin-screw extruder. The increase in viscosity associated with the addition of nanotubes is much higher than viscosity changes reported for carbon nanofibers having larger diameters and for carbon black composites; this can be explained by the higher aspect ratio of the nanotubes. The viscosity increase is accompanied by an increase in the elastic melt properties, represented by the storage modulus G′, which is much higher than the increase in the loss modulus G″. The viscosity curves above 2 wt% nanotubes exhibit a larger decrease with frequency than samples containing lower nanotube loadings. Composites containing more than 2 wt% nanotubes exhibit non-Newtonian behavior at lower frequencies. A step increase at approximately 2 wt% nanotubes was observed in the viscosity-composition curves at low frequencies. This step change may be regarded as a rheological threshold. Ultimately, the rheological threshold coincides with the electrical conductivity percolation threshold which was found to be between 1 and 2 wt% nanotubes.     

Dynamic mechanical and rheological properties of metallocene-catalyzed long-chain-branched ethylene/propylene copolymers

The dynamic mechanical and rheological properties of five long-chain branched (LCB) and three linear ethylene/propylene (EP) copolymers were investigated and compared using a dynamic mechanical analyzer (DMA) and an oscillatory rheometer. The novel series of LCB EP copolymers were synthesized with a constrained geometry catalyst (CGC), [C₅Me₄(SiMe₂N^tBu)]TiMe₂, and had various propylene molar fractions of 0.01-0.11 and long-chain branch frequencies (LCBF) of 0.05-0.22. The linear EP copolymers were synthesized with an ansa-zirconocene catalyst, rac-Et(Ind)₂ZrCl₂ (EBI), and contained similar levels of propylene incorporation as the CGC copolymers, but no LCB. In dynamic mechanical analysis, the dynamic storage moduli (G′) and loss moduli (G″) of the copolymers decreased with an increase of propylene molar fraction. The α- and β-transitions of the CGC copolymers were overlaid with each other. High damping (tan δ) values were found with the CGC copolymers at temperatures below 0 °C. In oscillatory rheological analysis, compared to the linear EBI counterparts, the LCB CGC copolymer melts showed higher zero shear activation energies, broader plateaus of δ and larger elastic contributions, which are essential characteristics of LCB polymers. It was found that the long chain branching was the determining factor in controlling rheological properties of the polymer melts while the short chain branching from propylene incorporation played a decisive role in affecting dynamic mechanical properties. This work represents the first rheological evidence of LCB in EP copolymers synthesized with CGC.     

Bleaching rapeseed and soybean oils with synthetic adsorbents and attapulgites

Efficiencies of synthetic adsorbents and attapulgites in bleaching alkali-refined rapeseed and soybean oils ranged from 13–53% and 93–97%, respectively. The Freundlich equation was more applicable than the Langmuir equation to the experimental adsorption isotherms of β-carotene on attapulgites. Bleaching with attapulgites reduced tocopherols by 12.5–29.5% in rapeseed oil and by 18.9–44.8% in soybean oil. Cosmetic-grade attapulgite was superior to the others in bleaching efficiency, equilibrium amount adsorbed and removal of free fatty acids.     

Rheological behavior of cycloolefin copolymer/graphite composites

In this study, morphological and rheological properties of cycloolefin copolymer (COC)/graphite composites prepared in a twin screw extruder by using various amounts of graphite (G) and expanded graphite (EG) were investigated in detail. Rheological behaviors of the samples were measured in a dynamic oscillatory rheometer in the melt state. Rheology data were analyzed in different ways in order to quantify the microstructural features which indicate the solid‐state physical properties of the composite materials. In the linear viscoelastic region, increasing of storage modulus (G′) with the filler amount and the van Gurp‐Palmen plots were used to determine the percolation threshold which is the critical filler amount for the physical network formation by the G sheets. Percolation threshold values were found to be about 21.5 phr and 3.8 phr for the G‐ and EG‐loaded samples, respectively. Microstructures of the samples which include quite higher amount of filler than the percolation were observed in a scanning electron microscopy. It was found that the sheets of pristine G maintained their original stack form while the EG was successfully dispersed in the COC phase and formed three dimensional house‐of‐card structures without a compatibilizer. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Strengthening acrylonitrile-butadiene-styrene (ABS) with nano-sized and micron-sized calcium carbonate

ABS was reinforced by both micron-sized (MCC) and nano-sized precipitated calcium carbonate (NPCC) particles through melt compounding. The MCC/ABS composites were found to have higher modulus but lower tensile and impact strength than neat ABS. In contrast, NPCC increased modulus of ABS whilst maintained or even increased its impact strength for a certain NPCC loading range. SEM examinations revealed that NPCC particles/agglomerates were distributed in much smaller sizes in the composites than its MCC counterparts. The larger interfacial area between NPCC and ABS and cavitation-induced shear yielding in the ligament are believed to be the main reasons of the mechanical property improvement of the NPCC/ABS composites. NPCC/ABS also shows completely different rheological behavior from MCC/ABS, such as the loss of Newtonian region, high G′ at low frequencies and the appearance of yield phenomenon. A NPCC network structure was believed to be formed in the composites and induced these pseudo-solid-like rheological behaviors.     

改性凹凸棒土填充硬质PVC的制备与性能研究

用硅烷偶联剂甲基丙烯酰氧丙基三甲氧基硅烷（MPTMS）和甲基丙烯酸甲酯（MMA）和凹凸棒土（AT）进行表面接枝改性，用傅立叶红外光谱分析了改性凹凸棒土的表面化学结构。以改性的凹凸棒土填充硬质聚氯乙烯（PVC），测试了材料的力学性能和热性能，结果表明，改性凹凸棒的填充可使PVC复合材料的拉伸强度，缺口冲击强度，弯曲强度，弯曲模量和热稳定性等均有所提高，用透射电镜观察了凹凸棒土及其在PVC基体中的微观分散状况，凹凸棒上具有纳米尺寸的针状结构，在PVC基体中以直径20nm-60nm,长度100nm-500nm的短纤维状分散在其中。     

Rheological and conductive percolation laws for syndiotactic polystyrene composites filled with carbon nanocapsules and carbon nanotubes

Semicrystalline syndiotactic polystyrene (sPS) composites with carbon nanocapsule (CNC) and carbon nanotube (CNT) fillers were prepared and good filler dispersion confirmed by electron microscopy. Their rheological and electrical properties were investigated to reveal the effect of filler aspect ratio. Amorphous atactic polystyrene (aPS) was used to prepare composites with a CNT filler to elucidate the effect of matrix tacticity. Percolation scaling laws are applied and the threshold concentration and exponent are determined. Above a threshold, the magnitudes of storage modulus (G′) and conductivity are related to the level of percolation network as well as the intrinsic properties of the matrix and filler. Master curves are obtained provided that an appropriate percolation function is selected. Different scaling laws are validated for the G′ and conductivity results.Composites with CNTs show a much lower threshold than those with CNCs. A lower threshold is derived from the G′ results compared to that obtained from the conductivity data regardless of the filler aspect ratio and matrix tacticity. Owing to the pronounced nucleating effects of CNT, crystalline sPS composites exhibit a four times larger conductivity threshold compared to their amorphous aPS counterparts, although their rheological thresholds are similar.     

凹凸棒土的改性及其吸附2,2′-二硝基联苄废水的研究

采用XRD、FTIR以及TG等手段对改性凹凸棒土进行了分析和表征,对比分析了十六烷基三甲基溴化铵改性凹凸棒土、凹凸棒土负载TiO2、纯凹凸棒土对2,2′-二硝基联苄生产废水的处理效果。结果表明:十六烷基三甲基溴化铵改性凹凸棒土和负载TiO2凹凸棒土对废水COD的去除率分别为37.3%、30.1%,均高于纯凹凸棒土对COD的去除率(15.1%),改性后的凹凸棒土的亲有机性得到了改善,对废水COD的去除效果明显提高。     

Influence of electrorheological characteristics of polymer mixture melts on the structure and properties of non-cloth materials

Electroforming from melts of polyamide-6 and polycarbonate polymer mixtures produced non-cloth material with fibers of average diameter 10 μm. It was shown that introducing a low-molecularweight additive could decrease the diameter of the produced fibers to 2.5 μm owing to a decrease of the melt viscosity. Polycarbonate was extracted selectively from the produced material. The fiber structure after the extraction was studied. The filtering properties of the non-cloth material were measured.     

Rheological behavior and microstructure of aqueous suspension of carboxylated core‐shell structured latex particle

Core‐shell type carboxylated particles form a flocculated structure in aqueous suspension with neutralization of carboxyl groups. Rheological behaviors of the suspension have been studied at various temperatures, and microstructures of the suspension have been discussed from the rheological behaviors and SAXS measurements. At 25°C, G′ is larger than G″ in all ω regions, and G′ is almost independent of ω, and the diffraction peak is detected by SAXS. These results mean that a three‐dimensional network of interconnected lattice‐like flocculated structure is formed. With increasing temperature, ω dependency of G′ becomes stronger and distance of the particles of the structure does not changed. These mean the network linkage is disrupted partially by thermal motion, and the interconnected lattice‐like flocculated structure changes to an isolated lattice‐like one with increasing temperature. With increasing the degree of neutralization, an isolated structure changes to an interconnected three‐dimensional structure decreasing the thermal motion just like decreasing temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1627–1633, 2001     

Dehnungsinduzierte gefügeänderungen in hochorientierten teilkristallien polymeren,nachgewiesen durch esr-untersuchungen

By high energy irradiation free redicals are formed in the crystalline regions of oriented fibers of polyethylene, polypropylene, polyamide-12, polyamide-6, and polyethyleneterephthalate. The kinetics of their subsequent reactions are followed by ESR. Straining of fibers of polyethylene, polypropylene, polyamide-12 and polyethyleneterephthalate after irradiation caused enhancements of reaction rates, whereas no changes of the rates are observed for polyamide-6. Since the rates depend on the chain mobilities in the crystalline regions straining causes modifications of the structure of crystalline regions of polyethylene, polypropylene, polyamide-12 and polyethyleneterephthalate but not for polyamide-6. The bearing of these results for the explanation of free radical formation in oriented polymer fibers is discussed.