Process for preparing a nylon‐6/ clay/acrylate rubber nanocomposite with high toughness and stiffness

A novel nylon‐6/clay/acrylate rubber ternary nanocomposite has been prepared using a process developed by the authors. The process consists of two steps: firstly, an acrylate rubber/clay composite (ARCC) was manufactured by spray‐drying a mixture of clay slurry and irradiated acrylate rubber latex; secondly, the nylon‐6/unmodified clay/acrylate rubber ternary nanocomposite was prepared by blending ARCC and nylon‐6. It has been found that the acrylate rubber particles and clay platelets can help each other to disperse or exfoliate in the nylon‐6 matrix. The silicate layers without organic treatment are exfoliated with the aid of irradiated acrylate rubber particles and the irradiated acrylate rubber particles are uniformly dispersed in the matrix with the aid of clay platelets. The novel nanocomposite prepared using the new process shows simultaneously high impact strength, high flexural modulus and high heat distortion temperature. Copyright © 2007 Society of Chemical Industry     

The thermal conductivity of Nylon 6/clay nanocomposites

Nylon 6/clay nanocomposites (NCNs) of different clay loadings are prepared by melt compounding. The effects of clay loading and dispersion on the thermal conductivity of NCNs are investigated using XRD, TEM, DSC, and POM. The results show that the thermal conductivity of the exfoliated NCNs decreases with an increase of clay content; but the thermal conductivity of the intercalated NCNs does not decrease, indeed, it increase markedly at high clay content. Such results observed in the exfoliated NCNs are opposite to the expectation of the classic Maxwell thermal conduction model. The further investigations indicate that such decrease observed in the exfoliated NCNs is due mainly to the exfoliation of clay layers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymorphism in polyamide 66/clay nanocomposites

Polyamide 66/clay nanocomposites (PA66CN) were prepared via melt compounding method by using a new kind of organophilic clay, which was obtained through co-intercalation of epoxy resin and quaternary ammonium into Na-montmorillonite. The silicate layers were dispersed homogeneously and nearly exfoliated in polyamide 66 (PA66) matrix. The introduction of silicate layers induced the appearance of the γ phase in PA66CN at room temperature, more clay loadings would amplify this phenomenon; the addition of clay also changed the structure of the α crystalline phase. The presence of silicate layers increased the crystallization rate and had a strong hetero phase nucleation effect on PA66 matrix. The lower Brill transition temperature of PA66CN can be attributed to the strong interaction between polyamide chains and surfaces of silicate layers.     

Polyamide 6/clay nanocomposites using a cointercalation organophilic clay via melt compounding

Polyamide 6/clay nanocomposites (PA6CN) were prepared via the melt compounding method by using a new kind of organophilic clay, which was obtained through cointercalation of epoxy resin and quaternary ammonium into Na‐montmorillonite. The dispersion effect of this kind of organophilic clay in the matrix was studied by means of X‐ray diffraction (XRD) and transmission electron microscopy (TEM); the silicate layers were dispersed homogeneously and nearly exfoliated in the matrix. This was probably the result of the strong interaction between epoxy groups and amide end groups of PA6. The mechanical properties and heat distortion temperature (HDT) of PA6CN increased dramatically. The notched Izod impact strength of PA6CN was 80% higher than that of PA6 when the clay loading was 5 wt %. Even at 10 wt % clay content, the impact strength was still higher than that of PA6. The finely dispersed silicate layers and the strong interaction between silicate layers and matrix decreased the water absorption. At 10 wt % clay content, PA6CN only absorbs half the amount of water compared with PA6. The dynamic mechanical properties of PA6CN were also studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 953–958, 2003     

PA6/蒙脱土纳米复合材料的力学性能研究

利用未改性蒙脱土和两种季胺盐改性蒙脱土与尼龙(PA)6混合,成功制备得到了不同结构的PA6/蒙脱土纳米复合材料.X射线衍射图谱和力学性能分析表明,季胺盐改性剂可以插入蒙脱土片层之间,使蒙脱土片层扩张,层间距增大.与PA6相比,制备得到的三种纳米复合材料的力学性能都有不同程度的提高.改性蒙脱土与PA6表现出良好的相容性,...     

Percolated Network Structure Formation and Rheological Properties in Nylon 6/Clay Nanocomposites

To understand the effect of the percolated clay network structure formed by the exfoliated clay layers in nanocomposites, the clay network structure in nylon‐6‐based nanocomposites is characterized using TEM and FFT analyses. A MMT volume fraction between 0.013 and 0.014 is the percolation threshold for strong network formation. The volume spanning MMT network leads to a very high flow activation energy as compared with that of neat nylon 6, resulting in the pseudo‐solid like response under molten state in N6CNs. A canonical NVT‐MD simulation was conducted in the system made up by nylon 6 molecules/Si(OH)₄ molecules. The formation of the strong interfacial interaction between nylon 6 molecules and Si(OH)₄ molecules induced by OH groups is suggested.

     

Poly(propylene)/Clay Nanocomposites Prepared by Reactive Compounding with an Epoxy Based Masterbatch

Summary: Poly(propylene) (PP)/clay nanocomposites have been prepared via a novel reactive compounding approach, in which an epoxy based masterbatch consisting of 20 wt.‐% clay was introduced to poly(propylene) with the aid of a maleic anhydride grafted PP (MAPP). The masterbatch was prepared using a recently developed “slurry compounding” technique. After melt compounding, most clay particles have been exfoliated and dispersed into small stacks with several clay layers. WAXD data shows that the dispersion of clay is better at low clay content or high MAPP content. Due to the novelty of the preparation process and complication of the system, the tensile properties of nanocomposites exhibit some unique tendencies with varying the content of MAPP or masterbatch. It is believed that the yield strength and Young's modulus can be dramatically improved after minimizing the excess of unreacted epoxy and optimizing the dispersion of clay.

TEM micrograph of PP/clay nanocomposites prepared with epoxy based masterbatch.     

Polyamide 66/Clay Nanocomposites via Melt Intercalation

Polyamide 66/clay nanocomposites (PA66CN) were prepared via a melt compounding method using a new kind of organophilic clay, which was obtained through co‐intercalation of epoxy resin and quaternary ammonium into Na‐montmorillonite. The dispersion effect of silicate layers in the matrix was studied by means of XRD and TEM. The silicate layers were dispersed homogeneously and nearly exfoliated in the matrix as a result of the strong interaction between epoxy groups and PA66. The mechanical properties and heat distortion temperature (HDT) of PA66CN increased dramatically. The notched Izod impact strength of PA66CN was 50% higher than that of PA66 when the clay loading was 5 wt.‐%. Even at 10 wt.‐% clay content, the impact strength was still higher than that of PA66. The finely dispersed silicate layers and the strong interaction between silicate layers and the matrix reduced the water absorption, at 10 wt.‐% clay content; PA66CN only absorbs 60% water compared with PA66. The addition of silicate layers changed the crystal structure in PA66CN.     

Novel polyacrylonitrile nanocomposites containing Na-montmorillonite and nano SiO2 particle

Polyacrylonitrile (PAN)/Na-montmorillonite (Na-MMT)/SiO₂ nanocomposites were prepared via in situ emulsion polymerization. X-ray diffraction (XRD) results suggest that the Na-MMT layers are exfoliated during the polymerization process. As evidenced by the transmission electron microscope (TEM), the Na-MMT and nano SiO₂ particles exhibit good dispersion in the polymer matrix. It was found that the PAN/Na-MMT/SiO₂ nanocomposites exhibit considerably enhanced mechanical properties compared with the PAN/Na-MMT and PAN/SiO₂ nanocomposites.     

Preparation and thermal properties of resole‐type phenol resin–clay nanocomposites

Resole‐type phenol resin–clay nanocomposites have been prepared successfully by melt compounding phenol resin with organophilic clay. In the resulting phenol resin–clay nanocomposite, the silicate layers of the clay were exfoliated and dispersed as monolayers. The nanocomposite exhibited higher long‐term heat resistance when compared with unmodified phenol resin. It was surmised that the silicate layers of the clay acted as barriers to oxygen penetration into the resin, as the degree of heat degradation of the nanocomposite was much lower than that of the straight phenol resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3236–3240, 2006     

Mechanical,Thermal and Viscoelastic Behavior of Nylon 6/Clay Nanocomposites with Cotreated Montmorillonites

Nylon 6 nanocomposites were prepared using melt intercalation technique. Sodium montmorillonite (Na-MMT) was modified with octadecyl ammonium salt to evaluate the effect of clay modification on the performance of the nanocomposites. A comparative account with the nanocomposites prepared, using commercial clay cloisite 30B has been presented. X-ray diffraction (XRD) studies indicated an increase in the basal spacing of organically modified clays. Further, X-ray diffractograms of the nanocomposites displayed the absence of basal reflections suggesting the formation of an exfoliated structure. Transmission electron microscopy (TEM) investigations also confirmed exfoliation of clay galleries in the nanocomposites. Differential scanning calorimetry (DSC) measurements revealed both γ and α transitions in the matrix polymer as well as the nanocomposites. The crystallization temperature (T_c) exhibited a marginal increase in the C30B/Nylon 6 nanocomposites. Thermal stability of virgin Nylon 6 and the nanocomposites has been investigated using thermogravimetric analysis. Mechanical test revealed an increase in the tensile and flexural properties of Nylon 6 with the incorporation of nanoclays. Storage and loss modulus of virgin matrix increased with the incorporation of nanoclays. C30B/Nylon 6 nanocomposites exhibited optimum performance at 5% clay loading. Further, water absorption studies also confirmed comparatively lesser tendency of water uptake in these nanocomposites.     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Intercalated polyaniline/Na-montmorillonite nanocomposites via oxidative polymerization

This work focuses on the preparation, characterization and electrical conductive properties of intercalated polyaniline/Na-montmorillonite nanocomposites. These materials consisting of polyaniline and Na-montmorillonite were prepared by oxidative polymerization with benzoyl peroxide as oxidizing agent. The synthesized nanocomposites were investigated by a series of characterization techniques; including Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and thermal analysis. X-ray diffraction and scanning electron microscopy images showed that the polyaniline was inserted into the clay layers. The modest increase in layer spacing was as much as 0.53 nm. The thermogravimetric analysis and differential thermal analysis demonstrated the improved thermal stability of the intercalated nanocomposites relative to the pure polyaniline due to the incorporated Na-montmorillonite. The room temperature electrical conductivity of nanocomposites varied from 1.0 × 10⁻⁷ to 5.8 × 10⁻⁵ Scm⁻¹.     

Polymer/layered silicate nanocomposites by combined intercalative polymerization and melt intercalation: a masterbatch process

Poly(ε-caprolactone) (PCL) and poly(vinyl chloride) (PVC) layered silicate nanocomposites were prepared by combination of intercalative polymerization and melt intercalation. In a first step, high clay content PCL nanocomposites were prepared by in situ polymerization of ε-caprolactone intercalated between selected organo-modified silicate layers. The polymerization was catalyzed with dibutyltin dimethoxide in the presence of montmorillonites, the surface of which were previously exchanged with (functionalized) long alkyl chains ammonium cations. Then, these highly filled PCL nanocomposites were added as masterbatches in commercial PCL and PVC by melt blending. The intercalation of PCL chains within the silicate layers by in situ polymerization proved to be very efficient, leading to the formation of intercalated and/or exfoliated structures depending on the organo-clay. These masterbatches were readily dispersed into the molten PCL and PVC matrices yielding intercalated/exfoliated layered silicate nanocomposites which could not be obtained by melt blending the matrix directly with the same organo-modified clays. The formation of nanocomposites was assessed both by X-ray diffraction and transmission electronic microscopy. Interestingly, this so-called ‘masterbatch’ two-step process allowed for preparing PCL nanocomposites even with non-modified natural clay, i.e. sodium montmorillonite, which showed a material stiffness much higher than the corresponding microcomposites recovered by direct melt intercalation. The thermal stability of PCL nanocomposites as a function of clay content was investigated by thermogravimetry (TGA).     

良好分散尼龙6/多壁碳纳米管复合材料的研究

采用柔和混合法制备纳米粒子良好分散的尼龙-6/多壁碳纳米管(PA6/MWNTs)复合材料,采用差示扫描量热仪(DSC)和广角X射线衍射法(XRD)研究了MWNTs对PA6基体结晶熔融行为的影响。DSC结果表明,MWNTs的加入大幅度地提高了PA6的结晶温度(最高提高约20℃),基体的结晶度也有所提高,说明良好分散的MWNTs在PA6结晶过程中呈现明显的异相成核作用;XRD结果证实,分散良好的MWNT促进PA6形成α晶型,抑制γ晶型的形成。同时,MWNT的加入导致复合材料出现熔融双峰现象,其形状随MWNT含量的变化而改变,双峰结构可能是由于熔融过程中伴随着重结晶而引起的。     

Fiber breakage and dispersion in carbon‐fiber‐reinforced nylon 6/clay nanocomposites

In this paper, short carbon‐fiber‐reinforced nylon 6/clay nanocomposites are prepared via melt compounding, and fiber breakage and dispersion during processing are studied. The influences of clay and processing conditions on fiber breakage and dispersion are taken into consideration. It is found that the presence of organoclay can improve fiber dispersion, which is due to dispersion at the nanoscale of exfoliated clay sheets with large aspect ratio. The bimodal distribution of fiber length is observed in fiber‐reinforced nanocomposites, which is similar to that in conventional fiber‐reinforced composites. The improvement of fiber breakage at moderate organoclay loadings is also observed, which is ascribed to the rheological and lubricating effects induced by organoclay. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Nylon 6 nanocomposites prepared by a melt mixing masterbatch process

A melt mixing masterbatch process for preparing nylon 6 nanocomposites that provides good exfoliation and low melt viscosities has been investigated. It is known that high molecular weight (HMW) grades of nylon 6 lead to higher levels of exfoliation of organoclays than do low molecular weight (LMW) grades of nylon 6. However, LMW grades of nylon 6 have lower melt viscosities, which are favorable for certain commercial applications like injection molding. To resolve this, a two-step process to prepare nanocomposites based on nylon 6 is explored here. In the first step, a masterbatch of organoclay in HMW nylon 6 is prepared by melt processing to give exfoliation. In the second step, the masterbatch is diluted with LMW nylon 6 to the desired montmorillonite (MMT) content to reduce melt viscosity. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain analysis were used to evaluate the effect of the clay content in the masterbatch on the morphology and physical properties of the final nanocomposite. The melt viscosity was characterized by Brabender Torque Rheometry. The physical properties of the nanocomposites prepared by the masterbatch approach lie between those of the corresponding composites prepared directly from HMW nylon 6 and LMW nylon 6. A clear trade-off was observed between the modulus and melt processability. Masterbatches that have lower MMT content offer a significant decrease in melt viscosity and a small reduction in modulus compared to nanocomposites prepared directly from HMW nylon 6. Higher MMT concentrations in the masterbatch lead to a less favorable trade-off.     

三元乙丙橡胶/黏土纳米复合材料

利用熔融插层和双羟基甲基十二烷基氯化铵插层剂改性黏土的方法，制备了三元乙丙橡胶／黏土纳米复合材料。X射线衍射(XRD)和透射电镜(TEM)的测试结果表明，形成的纳米复合材料为剥离型。探索了制作该纳米复合材料的最佳工艺方法。研究了这种材料的力学性能及老化性能，分析了该有机黏土增强橡胶的机理。结果表明，在对黏土进行有机改性时，插层剂中的双羟基与黏土中的氧原子形成了氢键，而使黏土层间的相互作用减弱，层间距增大，使三元乙丙橡胶(EPDM)分子链插入黏土层间而导致黏土剥离是该纳米材料形成的主要原因。有机黏土用量为15份时，试样的拉伸强度高迭24．9MPa，扯断伸长率为666％；前者比纯EPDM提高了3～4倍，后者上升了140％。试样的撕裂强度也有明显的改善，而邵尔A型硬度却随有机黏土用量的增加没有明显的变化。同时，试样的耐热老化性能也有了明显的改善．     

Transport properties of natural rubber latex layered clay nanocomposites

Natural rubber latex layered clay nanocomposites were prepared with low loadings of nanoclay using conventional compounding technique. A higher loading of clay resulted in processing difficulties due to viscosity build up. X‐ray analysis showed that nanocomposites in which layered silicate layers were either delaminated or ordered as in an intercalated structure was obtained. Partially exfoliated structure was observed from TEM photographs of nanocomposites with 3 phr nanoclay. The transport properties, sorption, diffusion, and permeation coefficients were measured using the solvent toluene at 303 K. A higher decrease for the diffusion coefficient for nanocomposites directs the presence of tortuous path for the diffusing molecules. Thermodynamic parameters show a better compatibility for the silicates with rubber resulted in the formation of an elastomeric network. Gas permeability results of the nanocomposites suggest a better barrier resistancefor oxygen molecules even in lower loading of nanoclay and different gas transport models (Nielsen, Bharadwaj, Cussler) were applied to describe the behavior of these nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of polymer/organosilicate nanocomposites based on unmodified LDPE

Low‐density polyethylene (LDPE)/silicate nanocomposites were prepared by the melt compounding and solution blend methods using unmodified LDPE polymer and layered silicates with different aspect ratio. X‐ray diffraction (XRD) analysis performed on composites obtained by dispersing the organosilicates in molten LDPE evidenced an exfoliated or partially exfoliated structure for the low aspect ratio silicate (laponite) in contrast to the high aspect ratio silicate (montmorillonite), which led to the formation of intercalated nanocomposites. With regard to the preparation method, the melt compounding method was more effective in forming exfoliated/highly intercalated LDPE nanocomposites compared with the solution blend method (using CCl₄ as a solvent). A gradual increase in crystallization temperatures (T_c) with increasing laponite content for LDPE‐organolaponite nanocomposites was revealed by differential scanning calorimetry (DSC) measurements. Thermogravimetric analysis and tensile measurements results indicated that thermal stability and elastic modulus increment were more prevalent for nanocomposites prepared using organomontmorillonite as filler. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009