Curing and barrier properties of NBR/organo-clay nanocomposite

Organo-montmorillonite/NBR nanocomposites were prepared by a melt intercalation process. The characteristics of NBR nanocomposites were characterized by oscillating-disk rheometer, water-vapour transmission and transmission electron microscopy (TEM). Changes in cure characteristics resulting from changes in clay content and the addition of silane coupling agent were investigated. The study confirmed that organo-montmorillonite/NBR nanocomposites cure characteristics, viz minimum torque, maximum torque, scorch time and curing time, change according to the change in clay content and the addition of silane coupling agent. Of the water-vapour transport properties, the clay content and silane content are the dominating factors in determining the individual water-vapour permeability of these NBR nanocomposites. TEM analysis provided clear evidence for the homogeneous dispersion of clay in the NBR matrix without regard to increases in clay content. Copyright © 2004 Society of Chemical Industry     

Preparation and characteristics of nitrile rubber (NBR) nanocomposites based on organophilic layered clay

The effect of clay modification on organo‐montmorillonite/NBR nanocomposites has been studied. Organo‐montmorillonite/NBR nanocomposites were prepared through a melt intercalation process. NBR nanocomposites were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), dynamic mechanical thermal analysis (DMTA) and a universal testing machine (UTM). XRD showed that the basal spacing in the clay increased, which means that the NBR matrix was intercalated in the clay layer galleries. On TEM images, organo‐montmorillonite (MMT) particles were clearly observed, having been exfoliated into nanoscale layers of about 10–20 nm thickness from their original 40 µm particle size. These layers were uniformly dispersed in the NBR matrix. The DMTA test showed that for these nanocomposites the plateau modulus and glass transition temperature (T_g) increased with respect to the corresponding values of pure NBR (without clay). UTM test showed that the nanocomposites had superior mechanical properties, ie strength and modulus. These improved properties are due to the nanoscale effects and strong interactions between the NBR matrix and the clay interface. Copyright © 2003 Society of Chemical Industry     

Characteristics of nitrile–butadiene rubber layered silicate nanocomposites with silane coupling agent

Nanocomposites of organophilic montmorillonite (C18‐MMT), nitrile–butadiene rubber (NBR), and a coupling agent were produced during a melt compounding process at room temperature. During the process, it was clearly observed that organo‐MMT particles were exfoliated into nanoscale layers of approximately 1–30 nm thickness, in addition to their original 40 μm thickness. These MMT layers were uniformly dispersed in the NBR matrix. The effects of a coupling agent such as 3‐(mercaptopropyl)trimethoxy silane in C18‐MMT/NBR nanocomposites were studied. The C18‐MMT/NBR nanocomposites in the presence of the coupling agent were identified and characterized by X‐ray diffraction, transmission electron microscopy, a universal testing machine, thermogravimetric analysis, and IR spectroscopy. It was observed that an additional silane coupling agent, 3‐(mercaptopropyl)trimethoxy silane, enhanced the chemical interaction and was accompanied by the formation of Si? O? Si coupling bonds between C18‐MMT and the coupling agent and Si? C coupling bonds between NBR and the coupling agent. This work resulted in improved properties of organo‐MMT/NBR nanocomposites because of the nanoscale effects and strong interaction of the coupling bonds between NBR and organo‐MMT. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2633–2640, 2003     

橡胶微观结构对NBR硫化加工特性的影响

研究了丁腈橡胶(NBR)微观结构对NBR及NBR/炭黑混炼胶硫化加工性能的影响.研究表明:丙烯腈含量增加,分子极性增加,物理交联密度增加,致使焦烧时间缩短,正硫化时间先增长后缩短,提高了胶料的加工性能,硫化速度先增加后减小.加入炭黑后,对低丙烯腈含量的NBR1846的硫化转矩影响最大,减小了因丙烯腈含量造成的流变性能的变化,缩短了硫化时间,提高了硫化转矩和硫化程度,但炭黑对NBR的硫化速度影响不明显.     

A study of the effect of surfactants on the properties of polystyrene‐montmorillonite nanocomposites

Polystyrene‐Organo Montmorillonite (PS‐MMT) nanocomposites were prepared by suspension free radical polymerization of styrene in the dispersed organophilic montmorillonite. The results of X‐ray diffraction (XRD) and Transmission Electron Microscopy (TEM) indicated that exfoliated nanocomposites were achieved. The effect of organic modifiers (surfactants) on the properties of the synthesized nanocomposites was studied. It is found that polystyrene‐MMT nanocomposite with 5.0 wt% of organo‐MMT gave the greatest improvement in thermal stability, and polystyrene‐MMT nanocomposites with 7.5 wt% of organo‐MMT showed the greatest improvement in mechanical properties, compared with that of pure polystyrene (PS) in our experimental conditions. The alkyl chain length of surfactant used in fabricating organo‐MMT affects the synthesized PS nanocomposites: the longer the alkyl chain length that the surfactant possesses, the higher the glass transition temperature of the PS nanocomposite, However, the organoclay in the nanocomposites seems to play a dual role: (a) as nanofiller leading to the increase of storage modulus and (b) as plasticizer leading to the decrease of storage modulus. This results in a lower storage modulus of PS‐TMOMMT and PS‐TMTMMT nanocomposites than that of PS‐TMDMMT and PS‐TMCMMT nanocomposites. Further study is needed to confirm the above hypothesis.     

Poly(etherimide)/montmorillonite nanocomposites prepared by melt intercalation

A novel aromatic amine organo‐modifier synthesized in our previous work was used to treat montmorillonite (MMT) and the organo‐modified MMT was used to prepare poly(etherimide) (PEI)/MMT nanocomposites by a melt intercalation method. MMT treated by this amine exhibited large layer‐to‐layer spacing and a high ion‐exchange ratio (>95%). The nanocomposites were characterized with X‐ray diffraction (XRD), transmission electron microscopy (TEM), dynamic mechanical analysis, a universal tester, thermogravimetric analysis, and by differential scanning calorimetry. The results of XRD and TEM showed that the nanocomposites formed exfoliated structures even when the MMT content was 10 wt %. When the MMT content was below 3 wt %, the PEI/MMT nanocomposites were strengthened and toughened at the same time. The nanocomposites also showed marked decreases in coefficient of thermal expansion and solvent uptake. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1857–1863, 2003     

Rigid PVC/(layered silicate) nanocomposites produced through a novel melt‐blending approach

On the basis of the fusion behavior of poly(vinyl chloride) (PVC), the influence of compounding route on the properties of PVC/(layered silicate) nanocomposites was studied. Four different compounding addition sequences were examined during the melt compounding of PVC with montmorillonite (MMT) clay, including (a) a direct dry mixing of PVC and nanoclay, (b) an addition of nanoclay at compaction, (c) an addition of nanoclay at the onset of fusion, and (d) an addition of nanoclay at equilibrium torque. Both unmodified sodium montmorillonite (Na⁺‐MMT) and organically modified montmorillonite (Org.‐MMT) clays were used, and the effect of the addition sequence of the clay during compounding on its dispersion in the matrix was evaluated by X‐ray diffraction and transmission electron miscroscopy. The surface color change, dynamic mechanical analysis, and flexural and tensile properties of PVC/clay nanocomposites were also studied. The experimental results indicated that both the extent of property improvement and the dispersion of nanoparticles in PVC/(layered silicate) nanocomposites are strongly influenced by the degree of gelation achieved in PVC compounds during processing. The addition of nanoclay to PVC must be accomplished at the onset of fusion, when PVC particles are reduced in size, in order to produce nanocomposites with better nanodispersion and enhanced mechanical properties. Overall, rigid PVC nanocomposites with unmodified clay (Na⁺‐MMT) were more thermally stable and exhibited better mechanical properties than their counterparts with organically modified clay (Org.‐MMT). J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Formation of polymer nanocomposites with various organoclays

The role of the type of organic modifier used with montmorillonite (MMT) on the formation of polymer/clay nanocomposites in the melt compounding process was investigated. Various organoclays including primary [12‐aminolauric acid (12ALA)], secondary [dioctylamine (DOA)], tertiary [trioctylamine (TOA)], and two commercial quaternary (Cloisite 30B and 20A) MMTs were melt compounded with carefully selected polymers including polypropylene, polystyrene, styrene–acrylonitrile copolymer, poly(methyl methacrylate), poly(vinylidene fluoride), and acrylonitrile–butadiene copolymer (NBR). X‐ray diffraction and transmission electron microscopy characterizations confirmed that the two quaternary ammonium organoclay (Cloisite 30B and 20A) have superior compatibility compared to the primary (12ALA), secondary (DOA), and tertiary (TOA) ammonium organoclay. DOA and TOA can form polymer/clay nanocomposites only with the most polar polymer (NBR). Cloisite Na⁺ and 12ALA can not form nanocomposite with any polymers. The large organic surface area of the quaternary ammonium organoclay could be the reason of the best compatibility with polar polymers. It is estimated that long alkyl ammonium chains of organic modifier can spread over the clay surface more effectively than short alkyl chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1888–1896, 2005     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate)/clay nanocomposites prepared by melt processing

In this study, cold and melt crystallization behaviors of amorphous poly(ethylene terephthalate) (PET)/clay nanocomposites were investigated. Two nanocomposite samples with the same amount of inorganic content were prepared by melt processing using natural montmorillonite (Na‐MMT) and organo‐modified montmorillonite (org‐MMT). Depending on the clay structure, clay dispersion into PET and crystallization behavior of the samples were studied using X‐ray diffraction and differential scanning calorimetry methods, respectively. Effects of clay structure and organic groups between clay layers in org‐MMT on the melt crystallization kinetics of the samples were analyzed with various kinetic models, namely, the Ozawa, Avrami modified by Jeziorny, and Liu‐Mo. Crystallization activation energies of the samples were also determined by the Kissinger and Augis–Bennett models. Exfoliated structures were obtained in the nanocomposite samples prepared with both the Na‐MMT and org‐MMT. From the kinetics study, it was found that the melt‐crystallization rate of the sample prepared with the Na‐MMT was higher than that prepared with the org‐MMT at a given cooling rate. It can be concluded that organic ammonium groups in the org‐MMT decelerate the crystallization rate of PET chains possibly by affecting the chain diffusion and folding. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Preparation of extruded melt‐mixed polypropylene/montmorillonite nanocomposites with inline monitoring

This article advances the use of an inline optical detector to monitor the disaggregation of the montmorillonite (MMT) clay tactoids during the preparation of polypropylene (PP)/MMT nanocomposites via polymer melt compounding. During the exfoliation of the tactoids their size are reduced below the minimum particle size to produce light extinction and so, the signal of the inline detector reduces as the nanosize composite is formed. The measurement is done at the transient state with the MMT clay added as a pulse with constant weight into the PP extrusion melt flow and followed by the optical detector. The data comes out as the common residence time distribution curves having its maximum intensity related to the tactoids average particle size, keeping all other variables constants. The light extinction was measured for composites with different clays (Cloisite® 15A, 30B, Na⁺, and Sintered 20A) using the same PP grafted with maleic anhydride compatibilizer. The dissaglomeration/exfoliation efficiency increases as: ‘‘Sintered 20A’’ < ‘‘Na+ clay’’ < ‘‘organo‐modified clay’’ < ‘‘organo‐modified clay + compatibilizer’’. The best result is obtained using Cloisite® 15A and Cloisite® 20A following the expected reduction of the particle size obtained during a nanocomposite melt processing. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Exploiting the Plackett–Burman design to examine the formulation effect on curing characteristics of oil palm ash-filled acrylonitrile butadiene rubber compounds

The present paper is focused on exploiting Plackett–Burman design to examine the formulation effect of various chemical components content on the curing characteristics of oil palm ash (OPA)-filled acrylonitrile butadiene rubber (NBR) compound. The filled-NBR compound was prepared by conventional laboratory-sized two roll mill and cured using sulfuric system. Six independent variables such as content of zinc oxide, stearic acid, N-isopropyl-N′-phenyl-p-phenylenediamine, N-cyclohexyl-2-benzothiazole sulfenamide (CBS), sulfur, and even OPA filler were carried out to screen their significant effect on the curing characteristics of NBR compound. The scorch time, optimal cure time, minimum torque, and maximum torque were selected as a response. Results showed that the scorch time and the optimal cure time were significantly affected by CBS, whereas the minimum torque and maximum torque were significantly affected by OPA and sulfur, respectively, within the studied range. Among the chemical components under study, zinc oxide and stearic acid had the least effect on the curing properties of NBR compound. Analysis of variances for all factorial models demonstrated that the model was significant with P value <0.05 while the regularity (R ²) of all models was greater than 0.9. Lastly, the optimal chemical concentrations were predicted to acquire the optimal condition of the curing system for filled-NBR compound.     

Poly(ethylene terephthalate)/clay nanocomposites with trisilanolphenyl polyhedral oligomeric silsesquioxane as dispersant: simultaneously enhanced reinforcing and stabilizing effects

This paper presents a new approach for the preparation of poly(ethylene terephthalate) (PET)/clay nanocomposites using surfactant‐free clay (sodium montmorillonite, Na‐MMT) with trisilanolphenyl polyhedral oligomeric silsesquioxane (Tsp‐POSS) as dispersant. The dispersion of clay in the PET/Na‐MMT/Tsp‐POSS nanocomposites is enhanced over that in PET/Na‐MMT by using a very small amount of Tsp‐POSS, which acts as functional spacer to keep clay platelets apart and pull monomers in, and, at the same time, acts as a PET chain extender. As a result, thermomechanical properties and thermo‐oxidative stability of PET/Na‐MMT/Tsp‐POSS are improved simultaneously compared with those of PET/organoclay nanocomposites. © 2013 Society of Chemical Industry     

Biodegradable polyester layered silicate nanocomposites based on poly(ϵ‐caprolactone)

Nanocomposites based on biodegradable poly(?‐caprolactone) (PCL) and layered silicates (montmorillonite, MMT) were prepared either by melt interaction with PCL or by in situ ring‐opening polymerization of ?‐caprolactone as promoted by the so‐called coordination‐insertion mechanism. Both non‐modified clays (Na⁺ ‐MMT) and silicates modified by various alkylammonium cations were studied. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. Even at a filler content as low as 3 wt% of inorganic layered silicate, the PCL‐layered silicate nanocomposites exhibited improved mechanical properties (higher Young's modulus) and increased thermal stability as well as enhanced flame retardant characteristics as a result of a charring effect. It was shown that the formation of PCL‐based nanocomposites depended not only on the nature of the ammonium cation and related functionality but also on the selected synthetic route, melt intercalation vs. in situ intercalative polymerization. Interestingly enough, when the intercalative polymerization of ?‐caprolactone was carried out in the presence of MMT organo‐modified with ammonium cations bearing hydroxyl functions, nanocomposites with much improved mechanical properties were recovered. Those hybrid polyester layered silicate nanocomposites were characterized by a covalent bonding between the polyester chains and the clay organo‐surface as a result of the polymerization mechanism, which was actually initiated from the surface hydroxyl functions adequately activated by selected tin (II) or tin (IV) catalysts.     

A comparative study on curing characteristics and thermomechanical properties of elastomeric nanocomposites: The effects of eggshell and calcium carbonate nanofillers

After‐hatching eggshell (AHES) nanobiofiller and nanocalcium carbonate (nano‐CA) were separately added to various elastomers, such as acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), and natural rubber (NR), in various amounts of 5, 10, and 15 phr. The effect of particle size and dispersion of such nanofillers on thermomechanical properties and curing characteristics were then investigated. The ultimate tensile properties of SBR and NR nanocomposites were improved to some extent when 5 phr of AHES nanofiller was added to the rubber compound compared to CA. In the case of NBR nanocompounds, however, the mechanical properties were seemingly comparable, irrespective of the type of nanofiller. This contradictive behavior could be attributed to the alteration of crosslink density due to particular filler–matrix interaction while using mineral and natural fillers. The results of the rheometric study revealed that using AHES rather than CA slightly increases the scorch time of all types of prepared nanocomposites, whereas a significant drop in the optimum curing time was seen for NBR nanocomposites containing AHES biofiller. Moreover, thermogravimetric analysis showed similar thermal stability for SBR nanocomposites containing AHES and CA fillers. Finer particle size of CA and higher porosity of AHES at high and low loading levels were respectively the main reasons for improvement of ultimate properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of polystyrene–clay nanocomposites by free‐radical polymerization

The polymerizable cationic surfactant, vinylbenzyldimethylethanolammouium chloride (VBDEAC), was synthesized to functionalize montmorillonite (MMT) clay and used to prepare exfoliated polystyrene–clay nanocomposites. The organophilic MMT was prepared by Na⁺ exchanged montmorillonite and ammonium cations of the VBDEAC in an aqueous medium. Polystyrene–clay nanocomposites were prepared by free‐radical polymerization of the styrene containing intercalated organophilic MMT. Dispersion of the intercalated montmorillonite in the polystyrene matrix determined by X‐ray diffraction reveals that the basal spacing is higher than 17.6 nm. These nanocomposites were characterized by differential scanning calorimetry (DSC), transmission electron micrograph (TEM), thermal gravimetric analysis (TGA), and mechanical properties. The exfoliated nanocomposites have higher thermal stability and better mechanical properties than the pure polystyrene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1370–1377, 2002     

Effect of hybrid reinforcement based on precipitated silica and montmorillonite nanofillers on the mechanical properties of a silicone rubber

Silicone rubber (SR) nanocomposites containing precipitated silica (PS), montmorillonite (MMT), and PS/MMT hybrid fillers were prepared through melt‐mixing technique. In the SR/PS/MMT nanocomposite, the hybrid filler weight ratio was increased progressively from 0.4 to 1.7 while keeping the MMT weight constant. The viscosity, cure characteristics, and mechanical properties of the nanocomposites were subsequently measured. The optimum cure time increased, and the scorch time and rate of cure decreased. Furthermore, when the hybrid filler weight ratio was raised to its optimum, the tensile strength, Young's modulus, modulus at 100 and 300% elongation (M100 and M300), elongation at break, stored energy density at break, and hardness of the nanocomposite improved. The stress–strain properties of the nanocomposite with the hybrid filler improved at high deformation in comparison with those containing the PS and MMT fillers. The MMT filler exfoliated in the SR/MMT nanocomposite but did not in the nanocomposites containing the hybrid filler. Notably, the mechanical properties of the nanocomposite benefitted from the hybrid filler. This was due to the filler–filler and filler–rubber network formation in the rubber by the PS particles. Finally, effect of the PS, MMT, and hybrid fillers on the energy loss or hysteresis of the rubber was measured. POLYM. ENG. SCI., 54:1909–1921, 2014. © 2013 Society of Plastics Engineers     

Preparation,structure and properties of nitrile–butadiene rubber–organoclay nanocomposites by reactive mixing intercalation method

The nanocomposites of nitrile–butadiene rubber (NBR) and organo‐montmorillonite modified by hexadecyltrimethyl ammonium bromide (HMMT) were prepared by the reactive mixing intercalation method in the presence of the resorcinol and hexamethylenetetramine complex (RH). The structure of the NBR–RH–HMMT nanocomposites was characterized by XRD, TEM, FTIR, determination of crosslinking density, and so on. The results showed that the d‐spacing of HMMT increased substantially with RH addition and the layers of HMMT were dispersed in rubber matrix on a nanometer scale. The mechanical properties of the NBR–RH–HMMT nanocomposites were far superior to those of NBR–HMMT composites, and the glass transition temperature of NBR–RH–HMMT nanocomposite was higher than that of NBR. The reactive mixing intercalation method by introducing RH could enhance the interface combination between the rubber and the organoclay through the interactions of RH with NBR and modified clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1905–1913, 2006     

淀粉对蒙脱土/丁腈橡胶纳米复合材料结构和性能的影响

采用蒙脱土水悬浮液/橡胶乳液共混-共凝复合技术制备蒙脱土/丁腈橡胶纳米复合材料时,在蒙脱土水悬浮液和丁腈胶乳的混合体系中加入淀粉,考察了淀粉用量对蒙脱土/丁腈橡胶纳米复合材料结构和性能的影响。结果表明,淀粉的加入有利于蒙脱土片层形成剥离型结构。当蒙脱土用量为5份、淀粉用量为10份时,蒙脱土几乎呈完全剥离状态;随着淀粉用量的增加,该复合材料的邵尔A硬度、100%定伸应力、拉伸强度、扯断伸长率和撕裂强度均有所提高。     

Influence of annealing treatment on the heat distortion temperature of nylon‐6/montmorillonite nanocomposites

It has been recognized that the incorporation of nanoscale montmorillonite (MMT) layers into polymer matrix enhances significantly the heat resistance of the resultant nanocomposites, especially for nylon‐6 (N6)/clay nanocomposites (NCNs). In the present work, the heat distortion temperature (HDT) of NCNs, including the intercalated N6/Na‐montmorillonite (Na‐MMT) and the exfoliated N6/organo‐montmorillonite (OMMT) ones, have been investigated for both non‐annealed and annealed testing specimens in comparison with the neat N6. As expected, the incorporation of MMT obviously improved HDT of NCNs, with the highest HDT value obtained in the N6/OMMT system due to its exfoliated nano‐structure. After an annealing treatment at 80°C for 6 hr, the HDT revealed noticeable increase for all the samples, particularly for the intercalated N6/Na‐MMT nanocomposite that showed the highest increment of 34°C. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared (FTIR) techniques were employed to clarify the origin of the variation in HDT after annealing, and the results suggest that the increases in the crystallinity, the glass transition temperature, and the order degree of hydrogen bonding may account for the noticeable increases in the HDT of the nanocomposites after annealing. POLYM. ENG. SCI., 45:1247–1253, 2005. © 2005 Society of Plastics Engineers     

Nanocomposite structure depending on the degree of surface treatment of layered silicate

Nanocomposite structures depending on the degree of surface modification of montmorillonite (MMT) were studied. To change the degree of surface modification, MMT was treated with a controlled amount of stearylamine. The structures of MMTs and nanocomposites were investigated by X‐ray diffraction. To confirm the extent of surface coverage of the stearylamine as a organophilic modifier, TGA and elemental analysis experiments were performed. Different structures (intercalated or exfoliated) of a polymer/clay nanocomposite were obtained according to the interfacial characteristics between the polymer chains and the clay by controlling the degree of surface coverage. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2143–2147, 2002