Impact fracture behaviour of nylon 6-based ternary nanocomposites

This study focuses on achieving high stiffness/strength and high fracture toughness in nylon 6/organoclay nanocomposites prepared via melt compounding by incorporating a maleic anhydride grafted polyethylene–octene elastomer (POE-g-MA) as a toughening agent. Mechanical test results indicated that the ternary nanocomposites exhibited higher stiffness than nylon 6/POE-g-MA binary blends at any given POE-g-MA content. More importantly, the brittle–ductile transition of nylon 6/POE-g-MA blends was not impaired in the presence of organoclay for the compositions prepared in this study. TEM analysis shows that organoclay layers and elastomer particles were dispersed separately in nylon 6 matrix. In the binary nanocomposite, no noticeable plastic deformation was observed around the crack tip. In the ternary nanocomposites, the presence of organoclay in the matrix provided maximum reinforcement to the polymer, while their absence in the elastomer particles allowed the latter to promote high fracture toughness via particle cavitation and subsequent matrix shear yielding. The partially exfoliated clay layers also delaminated and hence, adding to the total toughness of the nanocomposites.     

Micro- and nano-scale deformation behavior of nylon 66-based binary and ternary nanocomposites

The primary aim of this paper is to provide an insight on the effect of the location of organoclay on the micro- and nano-scale deformation processes in melt-compounded nylon 66/organoclay/SEBS-g-MA ternary nanocomposites prepared by different blending sequences. In addition, the deformation processes of the ternary nanocomposites were compared to the binary nanocomposites (nylon 66/organoclay and nylon 66/SEBS-g-MA) and neat nylon 66. The incorporation of SEBS-g-MA particles toughened nylon 66 markedly; but the flexural modulus and strength were both reduced. Conversely, the use of organoclay increased the modulus but decreased the fracture toughness of nylon 66. Nylon 66/SEBS-g-MA/organoclay ternary nanocomposites exhibited balanced elastic stiffness and toughness. Stress-whitening studies of the fracture surfaces in terms of gray level were also performed and an attempt was made to correlate the optical reflectivity characteristics with fracture toughness. It was concluded that the capability of SEBS-g-MA particles to cavitate was decreased by the presence of organoclay in the SEBS-g-MA phase, resulting in reduced toughening efficiency. The best micro-structure for toughness and other mechanical properties is thus to maximize the amount of exfoliated organoclay in the nylon 66 matrix rather than to have it embedded in the finely dispersed SEBS-g-MA particles.     

Orientation and the extent of exfoliation of clay on scratch damage in polyamide 6 nanocomposites

The major objectives of this work are to understand the effects of organoclay, its extent of exfoliation and orientation, and indenter geometry on the scratch characteristics of polyamide 6/organoclay nanocomposites. Two different organically treated clays are used for this purpose and their structural parameters in a polyamide 6 matrix quantified. It is shown that, while the material properties are important for scratching resistance, they are not the only determinants of the scratch performance of materials. Further, despite proving beneficial to scratch resistance, in terms of residual depth, the presence (and exfoliation) of organoclay promotes the formation of brittle cracks during scratching. But with no organoclay layers, plastic flow controls the scratch damage in neat polyamide 6 with large residual depths. Factors such as orientation of clay layers and variations of indenter tip geometry also exert dominant effects on scratch penetration resistance and damage. Additionally, significant plastic flow and rotation of organoclay layers from the original configuration are observed underneath the sliding indenter.     

Polyethylene organo-clay nanocomposites: the role of the interface chemistry on the extent of clay intercalation/exfoliation

High density polyethylene (HDPE)/clay nanocomposites have been prepared using three different functionalized polyethylene compatibilizers: an ethylene/vinyl acetate copolymer, a polyethylene grafted with maleic anhydride functions and a (styrene-b-ethylene/butylene-b-styrene) block copolymer. The nanocomposites were prepared via two different routes: (1) the dispersion in HDPE of a masterbatch prepared from the compatibilizer and the clay or (2) the direct melt blending of the three components. For each compatibilizer, essentially intercalated nanocomposites were formed as determined by X-ray diffraction and transmission electron microscopy. With the ethylene/vinyl acetate copolymer, a significant delamination of the intercalated clay in thin stacks was observed. This dispersion of thin intercalated stacks within the polymer matrix allowed increasing significantly the stiffness and the flame resistance of the nanocomposite. A positive effect of shear rate and blending time has also been put into evidence, especially for the process based on the masterbatch preparation, improving both the formation of thin stacks of intercalated clay and the mechanical properties and the flame resistance of the formed nanocomposites.     

Effects of loading rate and temperature on tensile yielding and deformation mechanisms of nylon 6-based nanocomposites

Tensile tests were conducted on nylon 6/organoclay nanocomposites, with and without POE-g-MA rubber particles, over a range of temperatures and strain rates 10⁻⁴–10⁻¹ s⁻¹. It was shown that the 0.2% offset yield strength varied with both temperature and strain rate which could be described by the Eyring equation thus providing results on the activation energy and activation volume for the physical processes involved. In addition, their tensile deformation mechanisms were characterized using the tensile dilatometry technique to differentiate the dilatational processes (e.g., voiding/debonding caused by the organoclay and rubber particles or matrix) and shear yielding (e.g., matrix with zero volume change). Dilatometric responses indicated that the presence of POE-g-MA rubber particles did not alter the shear deformation mode of neat nylon 6. In contrast, the presence of organoclay layers changed the tensile yield deformation behavior of nylon 6 matrix from dominant shear yielding to combined shear yield plus dilatation associated with delaminations of nanoclay platelets. In nylon 6/organoclay/POE-g-MA ternary nanocomposite, the volume strain response indicated that the POE-g-MA rubber particles promoted shear deformation and suppressed delamination of the organoclay layers. Supports for the deformation mechanisms deduced from the tensile dilatometry tests were corroborated by optical microscopy and transmission electron microscopy micrographs of the studied materials.     

Clay exfoliation and organic modification on wear of nylon 6 nanocomposites processed by different routes

The role of nanoclay on the wear characteristics of nylon 6 nanocomposites processed via different routes is examined in this paper. Pristine clay and organoclay were used in melt-extrusion with the matrix resulting in a largely aggregated and a highly exfoliated morphology, respectively. High exfoliation of pristine clay was also achieved by a water-assist process in melt compounding. Nylon 6/pristine clay composite had the worst wear resistance due to the large aggregated clay particles. For the two nylon 6/exfoliated clay nanocomposites, the one with the organically modified clay outperformed that with the pristine clay exfoliated by water. Detailed study on the wear track and subsurface below of the nylon 6/clay composites using both transmission and scanning electron microscopy provided new insight into the differences in their deformation and damage mechanisms. It was revealed that the interfacial adhesion of clay to matrix, and not the exfoliated morphology of clay, played a critical role in wear. However, exfoliated clay morphology is preferred to aggregate morphology. Hence, the superior wear-performance of nylon 6/organoclay nanocomposite is brought about by a combined effect of fine dispersion of clay platelets in nylon 6, high interfacial interaction between nylon 6 and clay layers, and effective constraint on surrounding nylon 6 material exerted by the clay platelets.     

Investigation of the nanomechanical properties of nylon 6 and nylon 6/clay nanocomposites at sub-ambient temperatures

The nanomechanical properties of nylon 6, nylon 6/exfoliated clay and nylon 6/non-exfoliated clay nanocomposites have been investigated from room temperature to ?10 °C in a controlled environment with humidity less than 1% RH. The hardness, elastic modulus and creep resistance of nylon 6 were improved in the nanocomposites across the temperature range. However, the effective reinforcement of the clay depended on the temperature due to the change between the glassy and transition states in the nylon. The exfoliated clay nanocomposite showed the greater improvements than in the non-exfoliated clay nanocomposite at all testing temperatures due to the improved constraint of the polymer chains by the clay platelets in the exfoliated structure. The surface mechanical properties of nylon 6 and the nanocomposites were also found to be highly sensitive to the moisture level during the tests; increasing the humidity in the room temperature tests resulted in a dramatic decrease in hardness and stiffness due to plasticisation by water molecules. The kinetics of the re-humidification process on nylon 6 were studied by monitoring the change in nanoindentation response. Analysis of the indentation creep revealed a significant change in the strain rate sensitivity when the humidity of the near-surface region probed by nanoindentation was in the vicinity of the glass transition.     

原位聚合法制备尼龙66/蒙脱土纳米复合材料及其性能

采用原位聚合法制备了尼龙66/有机蒙脱土纳米复合材料,利用TEM观察了复合材料的微观结构,测试了其力学性能、热稳定性和阻燃性能,探讨了复合材料结构与性能之间的关系。研究结果表明:蒙脱土以纳米尺度均匀分散在尼龙66基体中,蒙脱土的加入改善了材料的力学性能、热稳定性和阻燃性能。     

尼龙6/橡胶/天然粘土纳米复合材料的制备及其力学性能

采用一种新型的超细全硫化粉末橡胶/蒙脱土复合粉末(UFPRM),可以制备出剥离型的尼龙6/橡胶/天然粘土(尼龙6/UFPRM)纳米复合材料,所用的橡胶是一种具有特殊结构的超细全硫化粉末橡胶(UFPR).微观分析表明,橡胶粒子在尼龙6基体中分散良好,同时天然粘土在橡胶粒子之间的基体中剥离.在一定份数下,复合粉末可以同时提高尼龙6的韧性、刚性及耐热性;随着复合粉末含量的增加,材料的冲击强度进一步增加.而且,复合粉末对高分子量尼龙6的增强、增韧效果好于低分子量尼龙6.进一步研究发现,在适当的剪切速率下,尼龙6/橡胶/天然粘土纳米复合材料可以获得较好的综合力学性能.     

The fracture energy and acoustic emission of a short carbon fiber reinforced nylon 66 composite

Two knee points which are found in the cumulative plotting of acoustic emission (AE) events on a semi-log sheet in a monotonically increasing tensile load system of the center notched carbon fiber reinforced nylon 66 composite (FRTP) are applied to the estimation of the energy value required for the beginning of the stable crack propagation, the one for the stable crack propagation and also the one for the final fracture. They have been examined with regard to the dependence of some mechanical properties of the material on the gauge length, the fiber content and the crack length to width ratio of the specimen. Correlations between the AE characteristic nature such as AE activity (the number of AE events per unit area) and the above energy values are also investigated with regard to the results of the fractographic measurement of the fracture surface. It has been found that the energy required for the stable crack propagation decreases with an increase in the crack length to width ratio and increases with an increase in the gauge length. However, for an unstable crack propagation, it decreases with an increase in the fiber content. The dependence of the energy value on crack length to width ratio disappears in the results for a 30% specimen and this value becomes constant.     

Fracture mechanisms and fracture toughness in semicrystalline polymer nanocomposites

Polymer nanocomposites, especially nanoclay composites, have received much attention in recent years. While it is the functional properties of these composites that are the driving force, good mechanical properties are necessary in most applications. Although claims are made that the mechanical properties of nanocomposites should be excellent, in practice the mechanical properties are often disappointing. Soft or hard spherical particles can toughen semicrystalline polymers, but plate-like nanoclay particles have not produced any significant toughening action and frequently cause significant embrittlement. In this paper the toughening of semicrystalline polymers with nanoparticles, and particularly the difference in behaviour of spherical and plate-like particles is reviewed.     

Stochastic analysis of interphase effects on elastic modulus and yield strength of nylon 6/clay nanocomposites

The multifunctional properties of polymer clay nanocomposites (PCNs) can be related to the interaction of clays, polymer and interphase region. Several experimental, analytical and numerical studies have been conducted to characterize the mechanical behavior of PCNs. The elastic behavior of PCNs is well documented in the literature but their other material properties like yield strength are rather vague. On the other hand, the variation of material parameters and the stochastic nature of interphase region hinder the use of deterministic methods. In this study, a stochastic analysis along with a hierarchical multiscale method is used to analyze the effect of interphase properties on the macroscopic properties of PCNs. Since the interphase layer is expected to be weaker than the polymer matrix, a weakening coefficient is defined to describe the interphase properties based on the matrix properties. This weakening coefficient and the interphase thickness are considered as the stochastic inputs. The elastic modulus and yield strength of nylon 6/clay nanocomposites are calculated using the stochastic multiscale framework. The uncertainty propagation and sobol sensitivity analysis are performed to study the effect of random inputs on the elastic modulus and yield strength of PCNs. Despite the wide range of input variations, the accuracy of the proposed stochastic multiscale framework for the prediction of the PCNs properties is estimated by validating our results against the available experimental data in the literature.

     

Temperature effects on the fracture behavior and tensile properties of silane-treated clay/epoxy nanocomposites

We investigated the effects of clay silane treatment on the fracture behaviors of clay/epoxy nanocomposites by comparing the compliance, critical fracture load, and fracture toughness of silane-treated samples with those of untreated samples. The fracture toughnesses of untreated and silane-treated clay/epoxy nanocomposites were 8.52 J/m² and 15.55 J/m², respectively, corresponding to an 82% increase in fracture toughness after clay silane treatment. Tensile tests were performed at ?30 °C, 25 °C, 40 °C, and 70 °C. Tensile strength and elastic modulus were higher at ?30 °C than at 25 °C for both samples. However, the tensile properties decreased as temperature increased for both samples. In particular, at 70 °C, the tensile properties were less than 10% of the original value at room temperature, independent of surface treatment. The fracture and tensile properties of silane-treated clay/epoxy nanocomposites increased due to good dispersion of the clay in epoxy and improvement in interfacial adhesive strength between epoxy and clay layers.     

Essential work of fracture and failure mechanisms of polypropylene-clay nanocomposites

The fracture behavior of polymer nanocomposites (PNCs) based on a polypropylene with organo-modified clays (2 wt.%) and different coupling agents was studied by means of essential work of fracture (EWF). The PNC microstructure was characterized by clay particle dispersion at the micron scale (>1 μm) and sub-micron scale (200 nm to 1 μm), with good intercalation and partial exfoliation (<100 nm). Tensile testing showed significant improvements (+25-50%) corresponding to nanoparticle reinforcement effects. Fracture surfaces revealed that fracture occurred by void initiation at larger clay particles, followed by void growth and coalescence as the surrounding matrix stretched into ligaments. EWF improvements (+20%) were noted for PNCs that had fewer micron scale particles and showed higher tensile improvements. Toughness improvements were attributed to higher voiding stresses and improved matrix resistance attributed to finer, more oriented clay nanoparticles.     

Graphene oxide: the mechanisms of oxidation and exfoliation

Graphene oxides (GOs) with large sheets and more perfect aromatic structure were prepared by a novel modified Hummers method. We demonstrated that the graphite did not need to be oxidized to such a deep degree as described in Hummers method because the space distance increased little when the oxidation proceeded to a certain extent and the obtained graphite oxides (GTOs) could be fully exfoliated to single layers with high thermal stability. The oxidation mechanism and chemical structure model of GO were proposed by analyzing the evolution of the functional groups with oxidation proceeded based on thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The layer spacing calculated by molecular dynamics simulations coincided with the X-ray diffraction results. Furthermore, the size distribution and thickness of GOs were also studied. The results confirmed that the GOs prepared by the modified method were fully exfoliated to uniform single layers, and this method may be important for efficient exfoliation of GTO to GO and large-scale production of graphene.     

Effects of rubbery phase and absorbed water on impact-modified nylon 66

The fatigue crack propagation (FCP) response of impact-modified nylon was investigated as a function of rubbery second phase content and absorbed water level. Particular attention was given to the influence of these material variables on the amount of hysteretic heating as measured With an infrared microscope. FCP resistance was raised when heating was localized near the crack tip, but lowered by more generalized specimen heating. Variations in FCP behaviour were found to depend strongly on changes in the dynamic storage and loss moduli resulting from hysteretic heating, with the heating-induced modulus changes being more important than the absolute temperature increase of the sample. The combination of rubbery phase end absorbed water produced greater specimen heating and, in general, produced poorer FCP resistance than with the presence of either factor ahne.     

Influence of clay incorporation on the physical properties of polyethylene/Brazilian clay nanocomposites

High density polyethylene/Brazilian clay nanocomposites were prepared by the melt intercalation technique. A montmorillonite sample from Boa Vista/PB, Northeast of Brazil, was organically modified with esthearildimethylammonium chloride (Praepagen WB) quaternary ammonium salt. The unmodified and modified clays with the quaternary ammonium salt were introduced in 1, 2, 3 and 5 wt% in a PE polymer matrix. The dispersion analysis and the interlayer distance of the clay particles were obtained by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The mechanical properties of tensile and the flammability of the nanocomposites were studied. In general, the mechanical properties of the systems presented superior values compared to the matrix. The systems showed a reduction on the burning rate, indicating that the flammability resistance of nanocomposites was improved.     

Impact strength of nylon 6 and 66 in the dry and moist states

The impact strength of nylon was determined by the modified Charpy test with double-V notches described in DIN 53753, because it cannot be reliably assessed by the notched Charpy and Izod tests. This test was adjusted to obtain a sensitive, accurate and reproducible method for the determination of impact strength in the dry and moist states. In the light of the criterion thus gained, it is shown that the dry “as-moulded” state is unstable and that the impact strength decreases exponentially with storage timE. Therefore, comparison tests are not valid unless the measurements are performed within a restricted period of time after the specimens had been demoulded. If the age of the specimens is unknown, a reproducible “as-moulded” state can be regenerated by an annealing procedure. The state of “conventional” moisture content that is taken as a reference for comparing data obtained on moist nylon is the equilibrium moisture content in a standard laboratory atmosphere. Various methods are discussed for attaining this state rapidly by accelerated conditioning. An atmosphere of 70‡ C and 62% relative humidity allows accurate adjustment to the “conventional” moisture content but does not result in a stable reference state; for instance, the impact strength decreases within several weeks after conditioning.     

纤维状凹凸棒增强尼龙6的微观结构及力学性能

采用熔融共混的方法在双螺杆挤出机上制备尼龙6/凹凸棒(AT)纳米复合材料。利用X射线衍射仪(XRD)和扫描电镜(SEM)观察、分析了复合材料的晶体结构和断面相貌。通过微观组织相貌和结晶形态探讨了凹凸棒对尼龙6基体的增强机理,实验结果表明,复合材料的拉伸强度随凹凸棒含量的增加而增加,在凹凸棒质量分数为10%时,比纯尼龙6的拉伸强度提高了32.6%,复合材料的简支梁缺口冲击强度在凹凸棒质量分数为5%时达到最大,较纯尼龙6提高31%。材料的热稳定性也有一定程度的提高。