聚乳酸／蒙脱土纳米复合材料的流变行为

采用熔融插层法制备了插层型的聚乳酸／蒙脱土纳米复合材料，利用旋转流变仪对其流变行为进行了研究。稳态预剪切和大振幅振荡剪切实验结果表明，蒙脱土晶粒逾渗网络结构具有剪切敏感性，但稳态预剪切更容易破坏蒙脱土晶粒的逾渗结构；反向流和起始流实验结果表明，剪切破坏的逾渗网络在静态退火过程中可以重建，而应力过冲现象的出现则是网络重建的标志；不同剪切速率下应力过冲的最大值都出现在2％应变处，这种应力与应变之间的标度关系表明蒙脱土晶粒类液晶态的形成可能是网络重建的驱动力。     

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     

SBS／蒙脱土纳米复合材料的流变行为

用毛细管流变仪测定并研究了热塑性丁苯三嵌段共聚物（SBS）／蒙脱土纳米复合材料的熔体的稳态剪切流变行为，研究结果表明：温度和压力一定的条件下，加入一定量的改性蒙脱土可以降低熔体的粘度；在较低的剪切速率下，即出现剪切变稀现象；在高剪切速率下，粘度对剪切速率的敏感性是降低的，改性蒙脱土加入量对熔体的剪切粘度影响较小，主要是由基体材料所决定的；随温度的升高熔体粘度对剪切速率的敏感性是降低的。采用转矩流变仪对材料的加工性能进行研究，发现复合材料的加工性能基本上保持了纯SBS的加工性能。     

Linear and nonlinear melt‐state viscoelastic properties of polypropylene/organoclay nanocomposites

Rheological behavior of polypropylene (PP)/organoclay nanocomposites varying in compatibilizer (PP‐g‐MA) and organoclay concentration was investigated. The samples were prepared by melt intercalation method in an internal mixer. The wide angle X‐ray diffraction patterns and results of rheological measurements showed that the compatibilizer had strong influence in increasing the interlayer spacing. The observed low frequency liquid‐like to solid‐like transition and apparent yield stress in simple shear flows, along with convergence of transient shear stress to nonzero values in stress relaxation after the cessation of flow experiments, were found to be consistent with formation of a physical network in quiescent conditions which could be easily ruptured with applying low shear rates. The values of stress overshoot strain in flow reversal experiments were independent of shear rate, organoclay, and compatibilizer content. From the results of frequency sweep experiments in different nonlinear strain amplitudes it was shown that extended Cox‐Merz analogy was valid in nonlinear dynamic deformations while the shear viscosity showed positive deviation from this analogy with higher deviations at lower shear rates. Results of storage modulus recovery and flow reversal experiments at different shear rates suggested that network structure is reformed with a much slower rate compared to the rotational relaxation of organoclay platelets. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Shear-induced orientation in the crystallization of an isotactic polypropylene nanocomposite

Isothermal crystallization of isotactic polypropylene (iPP)/organic montmorillonite (OMMT) binary composite under shear field was investigated by in situ polarized optical microscopy, rheometry and transmission electron microscopy. When shear strain was small, shear flow could enhance the crystallization of iPP, and the crystallizing entity was spherulitic in iPP/OMMT composite in which the OMMT content was below the percolation threshold. With shear strain increasing, the orientation extent became stronger and cylindrites and strings of spherulites appeared in these samples. However, for iPP/OMMT composite with OMMT content higher than the percolation threshold, when the shear strain was not big enough to destroy the fillers network in the matrix, the crystallization of iPP was similar with that of the un-sheared sample. When shear strain was large enough, the fillers network was destroyed and clay layers were aligned along the flow direction. There formed oriented crystals including cylindrites and strings of spherulites, which were much smaller in size than those formed in the previous case, because the aligned clay layers acted as heterogeneous nucleation agents to promote crystallization of iPP.     

蒙脱土改性聚丙烯体系的流变行为

对聚丙烯／蒙脱土复合材料的插层情况用X-射线衍射仪和扫描电镜作了分析，用双机筒毛细管流变仪考察了聚丙烯和聚丙烯／蒙脱土复合材料的流变行为，结果表明：在低剪切速率下，聚丙烯／蒙脱土复合材料的粘度均高于聚丙烯；在高剪切速率下，形成无序插层结构的聚丙烯／蒙脱土复合材料的粘度低于聚丙烯。     

Effect of Carbon Nanotubes on the Rheological and Electrical Percolation of PP/EPDM Blend

The rheological and electrical percolation of single-walled carbon nanotubes on a thermoplastic-elastomer based on polypropylene/ethylene-propylene-diene was investigated. Polypropylene-grafted maleic anhydride was used to improve the nanotube dispersion. The shear stress and viscosity decreased with increasing temperature from 200 to 220°C. The flow activation energy for the nanocomposites increased with increasing nanotube content. The morphology and degree of dispersion of the nanotubes in the thermoplastic-elastomer matrix were investigated using SEM. The obtained rheological and electrical properties of the nanocomposites indicate that they were affected by the nanotube-nanotube network structure, which was related to the morphological behavior of nanotubes uniform dispersion.     

Processing of polypropylene–clay nanocomposites: Single‐screw extrusion with in‐line supercritical carbon dioxide feed versus twin‐screw extrusion

This work investigates two different melt‐blending strategies for preparing compatibilized polypropylene‐clay nanocomposites, specifically: (1) conventional twin‐screw extrusion, and (2) single‐screw extrusion capable of direct supercritical carbon dioxide (scCO₂) feed to the extruder barrel. Proportional amounts (3 : 1) of maleic anhydride functionalized polypropylene compatibilizer and organically modified montmorillonite clay at clay loadings of 1, 3, and 5 wt % are melt‐blended with a polypropylene homopolymer using the two approaches. The basal spacing, degree of exfoliation, and dispersion of organoclay is assessed using X‐ray diffraction, transmission electron microscopy, and rheology. In terms of the latter, both steady shear and small‐amplitude oscillatory shear provide information about the apparent yield stress and solid‐like terminal behavior respectively. Finally, nanoindentation is performed to determine the room temperature modulus of each melt‐blended nanocomposite. The results reveal unequivocally that the high shear of the twin‐screw process is vastly superior to the single‐screw with in‐line scCO₂ addition in generating well‐exfoliated, percolated polypropylene‐clay nanocomposites. It is likely that increased contact time between clay and scCO₂ is necessary for scCO₂ to positively affect exfoliation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 884–892, 2007     

PP/PS-海泡石插层纳米复合材料的流变性能与形态结构

采用苯乙烯乳液聚合法对有机海泡石原位插层,将插层产物聚苯乙烯(PS)-海泡石与聚丙烯(PP)熔融共混制备PP/PS-海泡石插层纳米复合材料.流变测试结果表明:PP/PS-海泡石插层纳米复合材料为典型的假塑性流体,其偏离牛顿流体的程度随PS-海泡石含量增加而增大,表观黏度和零切黏度随着PS-海泡石含量的增加而减小,PS-...     

Mechanical and rheological properties of the maleated polypropylene–layered silicate nanocomposites with different morphology

Three types of maleated polypropylene–layered silicate nanocomposites with different dispersion states of layered silicate (deintercalated, intercalated, and exfoliated states) are prepared from two kinds of polypropylenes with different molecular weights, organically modified layered silicate and pristine montmorillonite to investigate the effect of the final morphology of the nanocomposite on the rheological and mechanical properties. Maleated polypropylene with high molecular weight intercalates slowly and the other with low molecular weight exfoliates fast into the organophilic layered silicates. Rheological properties such as oscillatory storage modulus, nonterminal behavior, and relative viscosity has close relationship with the dispersion state of layered silicates. The exfoliated nanocomposite shows the largest increase and the deintercalated nanocomposite shows almost no change in relative shear and complex viscosities with the clay content. The exfoliated nanocomposite shows the largest drop in complex viscosity due to shear alignment of clay layers in the shear flow. In addition, the final dispersion state of layered silicates intimately relates to the mechanical property. The dynamic storage moduli of nanocomposites show the same behavior as the relative shear and complex viscosities. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1526–1535, 2003     

Structure and electrical properties of grafted polypropylene/graphite nanocomposites prepared by solution intercalation

A novel process was developed to prepare electrically conducting maleic anhydride grafted polypropylene (gPP)/expanded graphite (EG) nanocomposites by solution intercalation. The conducting percolation threshold at room temperature (Φ_c) of the nanocomposites was 0.67 vol %, much lower than that of the conventional conducting composites prepared by melt mixing (Φ_c = 2.96 vol %). When the EG content was 3.90 vol %, the electrical conductivity (σ) of the former reached 2.49 × 10^?3 S/cm, whereas the σ of the latter was only 6.85 × 10^?9 S/cm. The TEM, SEM, and optical microscopy observations confirmed that the significant decrease of Φ_c and the striking increase of σ might be attributable to the formation of an EG/gPP conducting multiple network in the nanocomposites, involving the network composed of particles with a large surface‐to‐volume ratio and several hundred micrometers in size, and the networks composed of the boards or sheets of graphite with high width‐to‐thickness ratio and particles of fine microscale or nanoscale sizes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1864–1869, 2003     

Characterization of the rheological behavior of UHMWPE gels using parallel plate rheometry

The effects of shear flow, temperature, and gel concentration on the rheological behavior of the ultrahigh-molecular-weight polyethylene (UHMWPE) gel in gel spinning process were investigated. The gel point was determined using parallel plate rheometry in rotation mode with controlled stress. Likewise, the flow curves at various temperatures were determined with controlled shear rate from 10⁻² to 10 s⁻¹. Whereas the shear storage modulus (G′) was obtained in oscillation mode with controlled strain from 1 to 100%. The result shows that the gel point of the UHMWPE gel increases with increasing gel concentration. The result from the strain sweep indicates that G′ of the gel is 1.5 × 10³ Pa, and it exhibits a plateau at low strain, but it is reduced with increasing strain. At low shear rates, for temperatures above gel point, all flow curves exhibit a plateau, then go down with increasing shear rate. Studying contributions from UHMWPE gel concentration, temperature, and shear rate for rheological view, we found that spinning at 6% UHMWPE (MW : 1.4 × 10⁶ g/mol) gel and 140°C gives the best effect on formation of fiber structure. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1009–1016, 1998     

Linear and nonlinear melt rheology and extrudate swell of acrylonitrile‐butadiene‐styrene and organoclay‐filled acrylonitrile‐butadiene‐styrene nanocomposite

Melt viscoelastic behavior and the die swell of Acrylonitrile‐Butadiene‐Styrene (ABS) and ABS/clay nanocomposites varying in organoclay loading were studied. A pronounced low‐frequency nonterminal behavior exhibited in linear viscoelastic experiments along with an apparent yield stress in transient startup flow tests suggested the existence of a network type, because of interconnection of rubber particles in ABS matrix. From the results of linear and nonlinear viscoelastic measurements, it was found that the incorporation of organoclay can lead to the formation of an additional network formed between organoclay tactoids that caused reduced temperature dependency of linear viscoelastic properties of the nanocomposite samples compared with ABS matrix. The swelling behavior of samples was interpreted using the results of stress relaxation experiments after cessation of steady shear flow. The great reduction in the die swell of nanocomposite samples could be explained in terms of great surface area and anisometric nature of organoclay tactoids and/or platelets, which promote energy consumption and less energy to be stored in chains. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Dynamic rheological behavior of polypropylene melts with pulsatile pressure flow in a dynamic capillary rheometer

A self‐made dynamic capillary rheometer (DCR) was designed to investigate the dynamic viscoelastic characteristic of polypropylene (PP) melt during the pulsatile pressure extrusion. A vibration force field was parallel superposed upon steady shear flow in this DCR by means of a vibration driven piston. During the pulsatile pressure extruding process in DCR, the PP melt displayed apparent viscoelasticity. The experiment results proved the pressure pulsatile extrusion could reduce the viscosity of polymer melts effectively. The phase difference between the shear stress and the shear rate decreased with the superposed vibration. But, at large amplitude conditions, the viscosity has an increasing tendency. This maybe illuminated that large amplitude could be harmful for the vibration‐assistant polymer processing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1834–1838, 2006     

Effect of hydrogen bonding on the rheology of polycarbonate/organoclay nanocomposites

The linear dynamic viscoelastic properties and non-linear transient rheology of polycarbonate (PC)/clay nanocomposites were investigated at temperatures ranging from 240 to 280 °C. For the study, nanocomposites of PC and natural montmorillonite (Cloisite Na⁺) or chemically modified clay (Cloisite 30B) were prepared by melt blending in a twin-screw extruder. Cloisite 30B is a natural montmorillonite modified with methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium chloride (MT2EtOH). In both PC/Cloisite Na⁺ and PC/Cloisite 30B nanocomposites the concentration of clay was varied from 2.3 to 4.3 wt%. In situ Fourier transform infrared (FTIR) spectroscopy results show that at temperatures ranging from 30 to 280 °C the carbonyl groups in PC and the hydroxyl groups in MT2EtOH of Cloisite 30B in PC/Cloisite 30B nanocomposites formed hydrogen bonds, while no evidence of hydrogen bonding was observed in the PC/Cloisite Na⁺ nanocomposites. There are no discernible sharp reflections in the X-ray diffraction (XRD) patterns of PC/Cloisite 30B nanocomposites, after Cloisite 30B having the d₀₀₁ spacing of 1.85 nm was mixed with PC, whereas the d₀₀₁ spacing changes little (1.17 nm) before and after the mixing of Cloisite Na⁺ to PC. Transmission electron microcopy (TEM) images show that organoclay platelets are well dispersed in PC/Cloisite 30B nanocomposites, while the untreated clay platelets are poorly dispersed in PC/Cloisite Na⁺ nanocomposites. The observed differences in XRD patterns and TEM images between the two nanocomposite systems are explained by in situ FTIR spectroscopy. The results of rheological measurements (linear dynamic viscoelasticity, non-linear transient shear flow, and steady-state shear flow) support the conclusions drawn from the results of XRD, TEM, and FTIR spectroscopy.     

Shear and extensional properties of short glass fiber reinforced polypropylene

Shear and extensional properties of a commercial short glass fiber reinforced polypropylene were carefully investigated using commercial rheometers and a novel on‐line rheometer. This on‐line slit rheometer, installed on an injection molding press, has been designed to measure the steady shear viscosity, the first normal stress difference, and the apparent extensional viscosity of polymer melts and composites for high strain rates up to 10⁵ s⁻¹ in shear and 200 s⁻¹ in extension. Our results show that the steady‐state viscosity measurements using the on‐line rheometer are in excellent agreement with those obtained using commercial rheometers. The steady‐state and the complex viscosities of the composites were found to be fairly close to that of the matrix, but the Cox‐Merz rule was not verified for the composites at high rates. The elasticity of the composites was found to be equal to that of the polypropylene matrix. The apparent extensional viscosity was obtained from the pressure drop in the planar converging die of the slit rheometer using the analyses proposed by Cogswell [1] and Binding [2]. The extensional viscosity of the polypropylene was found to be much larger than the shear viscosity at low strain rates with a Trouton ratio of about 40 that decreased rapidly with increasing strain rate down to the value of 4 at 200 s⁻¹. The extensional viscosity of the composites was also found to be close to that of the matrix, with values 35 and 5% larger for the 30 and 10 wt% reinforced polypropylenes, respectively. These results are compared with the predictions of the Goddard model [3], which are shown to overpredict our experimental results. POLYM. COMPOS. 26:247–264, 2005. © 2005 Society of Plastics Engineers.     

Evaluation of amine functionalized polypropylenes as compatibilizers for polypropylene nanocomposites

The compatibilization effects provided by amine functionalized polypropylenes versus those of a maleated polypropylene, PP-g-MA, for forming polypropylene-based nanocomposites were compared. Amine functionalized polypropylenes were prepared by reaction of maleated polypropylene, PP-g-MA, with 1,12-diaminododecane in the melt to form PP-g-NH₂ which was subsequently protonated to form PP-g-NH₃⁺. Nanocomposites were prepared by melt processing using a DSM microcompounder (residence time of 10 min) by blending polypropylene and these functionalized materials with sodium montmorillonite, Na-MMT, and with an organoclay. X-ray and transmission electron microscopy plus tensile modulus tests were used to characterize those nanocomposites. Composites based on Na-MMT as the filler showed almost no improvement of tensile modulus compared to the polymer matrix using any of these functionalized polypropylenes, which indicated that almost no exfoliation was achieved. All the compatibilized nanocomposites using an organoclay, based on quaternary ammonium surfactant modified MMT, as the filler had better clay exfoliation compared to the uncompatibilized PP nanocomposites. Binary and ternary nanocomposites using amine functionalized polypropylenes had good clay exfoliation, but no advantage over those using PP-g-MA. The PP-g-MA/organoclay and PP/PP-g-MA/organoclay nanocomposites showed the most substantial improvements in terms of both mechanical properties and clay exfoliation.     

A model for filler—matrix debonding in glass-bead-filled viscoelastic polymers

This article deals with the stress—strain behavior of two viscoelastic polymers, polypropylene and polyamide 6, filled with rigid particles in the range of axial strain of 0 to 8%. These materials, when subjected to a constant strain rate test lose stiffness via two mechanisms: filler—matrix debonding and the viscoelastic softening of the matrix. A model that combines the concepts of damage mechanics and the time dependence of the interfacial strength is described and compared to the experimental results of polypropylene and polyamide 6 filled with up to 50 vol % of untreated and silane-treated glass beads. The matrix behavior is described in terms of an empirical equation selected to fit the stress—strain behavior of neat polymers in the range of strain rates between 0.12 and 0.5% s⁻¹ and strains between 0 and 8%. The stiffness of the damaged, partially debonded composite is calculated using the Kerner—Lewis equation assuming that debonded particles do not bear any load. The model is able to generate stress—strain curves that are in good agreement with the experimental data. The void volume attributable to debonding calculated using the model is much smaller than the experimental total determined void volume (which is a sum of several deformation mechanisms). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2013–2024, 1997     

The effect of loading rates and particle geometry on compressive properties of polypropylene/zinc oxide nanocomposites: Experimental and numerical prediction

Compressive properties, of particulate filled polymer matrix composites, are affected (to a certain extent) by the geometry of the particles, as well as the loadingrates. Therefore, this article presents the results on the compressive properties of polypropylene/zinc oxide nanocomposites across strain rates from 10⁻² to 10⁻³ s⁻¹. The specimens were tested using a Universal Testing Machine for static loading and a conventional Split Hopkinson Pressure Bar apparatus for dynamic loading. Results show that the yield stress and 2.5% flow stress, of both PP/ZnO nanocomposites, showed a positive increment with increasing strain rates. However, the yield strain shows a contradictory pattern, where it decreased with increasing strain rates. PP/ZnO‐white seal recorded higher strain rate sensitivity, dissipation energy, stiffness, and strength properties, than that of PP/ZnO‐pharmaceutical, over a wide range of strain rates investigated. Interestingly, the Eyring theory almost agreed with the experimental results. Overall, based on the experimental and numerical results, we do believe that particle geometry, as well as strain rates, has a significant influence on the compressive properties of polypropylene/zinc oxide nanocomposites specimens. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Preparation of polypropylene–clay nanocomposites by the co‐intercalation of modified polypropylene and short‐chain amide molecules

The effect of short‐chain amide (AM) molecules on the intercalation of montmorillonite clay has been investigated by the melt blending of polypropylene (PP) with clay in the presence of AM molecules such as 13‐cis‐docosenamide (erucamide). Polypropylene–clay nanocomposites (PPCNs) were prepared by the co‐intercalation of maleic anhydride grafted polypropylene (PP–MA) and an AM compound. The resulting nanocomposite structures were characterized with X‐ray diffraction (XRD) and transmission electron microscopy, whereas the thermal characterization of the PPCNs was conducted by thermogravimetric analysis. XRD results showed that the AM molecules intercalated into clay galleries and increased the interlayer spacing, a result confirmed by surface energy (contact angle) and melt flow index measurements. This additive allowed the formation of an intercalated nanocomposite structure, but an exfoliated PPCN structure was also formed with the use of AM with a PP–MA‐based compatibilizer. A new preparation method for PPCNs was, therefore, developed by the co‐intercalation of AM and PP–MA; this resulted in a significantly improved degree of intercalation and dispersion. The enhanced thermal stability of PPCN, relative to pure PP, further demonstrated the improved clay dispersion in the nanocomposite structures prepared by this method. A possible mechanism for the co‐intercalation of AM and PP–MA into the clay galleries is proposed, based on hydrogen bonding between these additives and the silicate layers. Consideration is also given to possible chemical reactions and physical interactions in this rather complex system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009