Epoxy/clay nanocomposites: further exfoliation of newly modified clay induced by shearing force of ball milling

To induce montmorillonite (MMT) to be further exfoliated and homogeneously dispersed in epoxy matrix (diglycidyl ether of bisphenol A) curing in the presence of diaminodiphenyl sulfone and obtain improved mechanical properties, a promising new method has been developed to prepare highly reinforced epoxy/MMT nanocomposites through exerting shearing force on epoxy/MMT solution by ball milling. Modifying agents, being combined with dodecylbenzyldimethylammonium chloride and meta‐xylylenediamine, were used to organically modify the clay (MMTII). Different resultant products were characterized by Fourier‐transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, etc, and the fracture surface of the mechanically tested specimens was also observed by scanning electronic microscopy. Results show that the novel MMTII possess a reactive interaction surface with the epoxy matrix. Exfoliation of the retained sandwich structure (being intercalated) or large agglomerates (undispersed MMTII) can be promoted by external shearing force of ball milling, and homogeneously dispersed MMTII nano‐sheets in epoxy matrix nanocomposites are typically observed. Mechanical properties, especially impact toughness, can be increasingly enhanced by the newly structured MMTII and ball milling. Impact strength is increased up to 48.1 kJ m^?2 from 32.1 kJ m^?2 at 3 wt% MMTII content, which is about 50 % higher than that of pristine matrix, and the flexural strength can also be enhanced by about 8 % higher. Copyright © 2004 Society of Chemical Industry     

Chemorheology of cyanate ester—organically layered silicate nanocomposites

The effect of nanoparticle addition on the flow and curing behavior of a phenolic triazine cyanate ester resin system has been studied using chemorheological, thermal and spectroscopic techniques. While the neat system exhibited Newtonian flow, the nanodispersed prepolymer exhibited pseudoplastic flow behavior, typical of polymeric fluids such as gels and pastes. Evolution of the morphology during curing has been found to be dependent on the rate of intergallery diffusion of the prepolymer and subsequent gelation and vitrification, as well as the intra and extragallery cure kinetics. Curing reactions of the cyanate ester nanocomposite system consisting of a di-functional phenol, a halogen cyanate and organically layered silicates were studied. Gel times were measured as a function of temperature by time sweeps on a controlled stress rheometer. Gelation and vitrification times and activation energies for the nanocomposite systems were lower than that of the neat resins, indicating a catalytic effect of the clays on the curing reaction. Curing kinetics experiments performed on DSC and FTIR confirmed this phenomenon. Based on above experiments, time-temperature-transformation diagrams for the different systems were constructed.     

球磨制备超细硅酸锆分段磨的实践

对广东佛山顺德盈信超细锆微粉有限公司的生产工艺流程进行了研究,将其原有流程的分级沉砂返回再磨工艺改为分级沉砂小直径研磨介质二段磨工艺,生产试验证实,球磨效率明显提高,磨料粒度D50从3.65 μm降为2.73 μm,D97从24.10 μm降为13.82 μm,球磨时间缩短了1 h,生产成本大幅下降.     

Rheological behavior of polypropylene/layered silicate nanocomposites prepared by melt compounding in shear and elongational flows

Melt rheology and processability of exfoliated polypropylene (PP)/layered silicate nanocomposites were investigated. The nanocomposites were prepared by melt compounding process in the presence or absence of a PP‐based maleic anhydride compatibilizer. PP/layered silicate nanocomposites showed typical rheological properties of exfoliated nanocomposites such as nonterminal solid‐like plateau behavior at low frequency region in oscillatory shear flow, higher steady shear viscosity at low shear rate region, and outstanding strain hardening behavior in uniaxial elongational flow. The melt processability of exfoliated PP/layered silicate nanocomposites was significantly improved due to good dispersion of layered silicates and increased molecular interaction between the PP matrix and the layered silicate organoclay. Small‐angle X‐ray scattering and transmission electron microscopy results revealed that the layered silicate organoclay was exfoliated and good interaction between PP matrix and organoclay was achieved by using the PP‐g‐MAH compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3506–3515, 2007     

Abs/iron nanocomposites prepared by cryomilling

Acrylonitrile‐Butadiene‐Styrene (ABS)/iron nanocomposites have been prepared by cryomilling (high‐energy ball milling under cryogenic temperature), and a microstructure of iron network in ABS matrix was obtained. The blending scale and homogenization of ABS/iron nanocomposites are observed by Atomic Force Microscope (AFM). The morphology and structure of cryomilled composite powders are characterized by means of Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), and X‐ray Diffraction (XRD). The results indicate that upon cryomilling for 20 h, ABS and Fe are intimately blended with the single composite particle size less than 100 nm, the Fe phase domains less than 50 nm, and Fe grain size reduced to 20 nm. Both the fast rate of homogenization and size reduction are mainly attributed to the introduction of cryogenic temperature and comilling. The evidences suggest that cryomilling is a capable and promising technique for the production of polymer/metal nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 501–505, 2006     

Rheology of PBT-layered silicate nanocomposites prepared by melt compounding

Abstract

The rheological behaviour of poly(butyleneterephthalate) (PBT) based clay nanocomposites processed by melt compounding is investigated and related to the morphology of the samples. Hybrids at three weight percentages (3, 6 and 9 wt-%) of a commercial organo-modified montmorillonite were prepared by means of a twin screw extruder, using two different extrusion rates (90 and 150 rev min ^-1). The samples produced were submitted to structural and rheological investigations. X-ray and TEM analyses were carried out to provide information on the morphology (i. e. clay dispersion, degree of exfoliation, orientation) of the hybrids, whereas rheological tests in the low and high shear region (dynamic frequency sweep, steady rate sweep and stress relaxation tests) were performed to evaluate the effect of both hybrid composition and extrusion rate on the flow behaviour of the nanocomposites. Both structural and rheological results showed that a good dispersion and a high degree of silicate exfoliation in the PBT matrix are obtained under the experimental conditions. As a consequence, hybrids having clay fractions higher than 6 wt-% show a pseudo-solidlike flow behaviour at long times, as a result of the occurrence of strong polymer–silicate interactions that slow the relaxation times of the PBT chains.     

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     

PVDF/BaTiO3/carbon nanotubes ternary nanocomposites prepared by ball milling: Piezo and dielectric responses

Nanocomposites based on poly(vinylidene fluoride) (PVDF) filled with barium titanate, BaTiO₃, (BT) particles, and multiwalled carbon nanotubes (MWCNTs) were prepared by high-energy ball milling (HEBM) and subsequent hot pressing. This method of materials preparation allowed obtaining uniform dispersions of the nanofillers. The influence of the particles on the polymer structure and morphology was studied. To understand the origin of changes in the PVDF properties, thermal and electrical behaviors of the PVDF/BT/MWCNT nanocomposites were studied as a function of composition. The addition of BT, MWCNT, or its mixture had not any influence on the PVDF polymorphism. However, calorimetric results pointed out that the presence of the nanofillers exerted nucleation mainly ascribed to the surface to volume ratio of the nanoparticles. The capacitance of the composites increased as the nanofiller content increased, being the effect mainly dependent on the surface to volume ratio of the nanoparticles. The dielectric behavior of the materials as a function of frequency was modeled by a Debye equivalent circuit only below the percolation threshold respect to the amount of MWCNT. The piezoelectric behavior of the ternary nanocomposites was highly affected by the incorporation of the nanofillers only when high dielectric losses occurred above the percolation threshold. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47788.     

Characterizations of UV‐curable montmorillonite/epoxy nanocomposites prepared by a hybrid of chemical dispersion and planetary mechanical milling process

Ammonium salt, [2‐(methacyloyloxy)ethyl] trimethylammonium methyl sulfate (MAOTMA), was adopted to modify montmorillonite (MMT) via the cationic exchange process in an acidic environment and a successful enlargement of MMT lamellar spacing from 1.18 to 1.39 nm was identified by x‐ray diffraction and Fourier‐transform infrared spectroscopy. Accordingly, UV‐curable epoxy nanocomposite resins containing various amounts of MAOTMA‐modified MMT were prepared with the aid of a planetary mechanical milling process. Transmission electron microscopy revealed a uniform dispersion of exfoliated MMT lamella in epoxy matrix, leading to the distinct improvements on thermal stability and thermal expansion property of nanocomposite samples. Calcium (Ca) test indicated that the good dispersion of MMT fillers in polymer effectively suppresses the moisture permeation in sample matrix. More than twofold increment on retention time of 5% Ca hydrolysis and 20% improvement on the permeation kinetic parameters were observed in the nanocomposite sample containing 8 wt % MMT in comparison with the pristine epoxy sample. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PE/OMMT nanocomposites prepared by in situ polymerization approach: Effects of OMMT‐intercalated catalysts and silicate modifications

In this article, the surfactants, (2‐hydroxylethyl) octadecyl dimethylammonium nitrate (OH‐C18), hexadecyltrimethylammonium bromide(C16), and mixture of trimethylchlorosilane (TM) and OH‐C18 were ion‐exchanged with cations in the montmorillonite (MMT) to generate three organic MMTs (named as OH‐C18‐MMT, C16‐MMT, and MMMT), leading to different environments of catalyst species in MMT interlayer gallery. Et[Ind]₂ZrCl₂ (abbreviated as EI) was supported on the above three types of OMMTs to prepare the PE/OMMT nanocomposites via in situ polymerization. By contrast, EI/MMMT showed higher activity than EI/OH‐C18‐MMT and EI/C16‐MMT under the same polymerization conditions. The other two types of catalysts, such as [(tert‐Bu)NSi(Me₂)C₅Me₄]TiCl₂ (CGCT) and Bis[N‐(3‐tert‐butylsalicylidene)anilinato] titanium (IV) dichloride (FI) were also supported on the OH‐C18‐MMT for in situ ethylene polymerization. It was found that the activity of FI/OH‐C18‐MMT for ethylene polymerization was much lower than the other two corresponding catalysts under the similar reaction conditions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of resol‐layered silicate nanocomposites

Resol‐layered silicate nanocomposites were synthesized by intercalative polymerization of phenol and formaldehyde using layered clays such as an aminoacid‐modified montmorillonite (MMT) and a commercial modified MMT (Cloisite 30B). The composites were prepared by a sequential process in which one of the reactives of the phenolic resin was reacted with the organosilicate and subsequently cured with triethylamine. The nanocomposites were studied by means of X‐ray diffraction, atomic force microscopy, and thermogravimetric analysis. Results show a strong clay composition dependence on the intercalation state. The composite of resol with 2 wt % aminoacid‐modified MMT content has the best dispersion of clay layers. Thermal stability of nanocomposites was slightly increased in comparison with the neat resol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of matrix features on polypropylene layered silicate nanocomposites

The aim of this study was to examine the effect of the polypropylene based resin on the properties of organoclay-PP nanocomposites prepared by melt compounding using a twin screw extruder.The characterization of the obtained materials was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), melt flow rate (MFR) and mechanical tests.The study has shown the effect of the polymer matrix molecular weight on the possibility of producing by melt compounding nanocomposites based on PP homopolymers or heterophasic PP-PE copolymers and an organically modified montmorillonite, in presence of maleic anhydride-modified polypropylene (PP-g-MAH).An increase of mechanical properties was achieved both for homopolymers and heterophasic copolymers. However the reinforcing effect of clay dispersed in heterophasic copolymers was not as high as found for the homopolymers.     

高能球磨法制备纳米赤铁矿矿物颜料水分散体

以赤铁矿为原料,马来酸酐-醋酸乙烯酯共聚物PMV为分散剂,采用高能球磨法制备纳米级赤铁矿颜料水分散体,讨论了研磨时间、研磨介质以及分散剂用量等对分散体的粒径和Zeta电位的影响。结果表明,采用行星式球磨仪在球磨机转速为500 r/min,球磨时间为5 h,分散剂用量为0.25 g/g颜料,研磨介质为直径2 mm和0.5 mm锆珠的质量比为3∶2时,能获得粒径大小为230 nm的赤铁矿颜料水分散体,具有一定的粒径分散稳定性。     

Thermal behaviour of nanocomposites based on linear-low-density poly(ethylene) and carbon nanotubes prepared by high energy ball milling

The thermal behaviour of nanocomposites of linear-low-density-poly(ethylene) (LLDPE) and carbon nanotubes (CNT), prepared by the method of High Energy Ball Milling (HEBM) has been in-depth investigated. The CNT affect the nucleation of LLDPE, in that they act as nucleating agents for LLDPE. Moreover, as it is shown by self-nucleation experiments, in the presence of CNT a direct transition from domain I to domain III, with lack of domain II takes place. Isothermal experiments show that the crystallization rate of the nanocomposites is much higher than that of neat LLDPE. It is worthy noting that such effect is very high even for low contents of CNT in the sample (i.e. 1% by weight), then additions of CNT do not have any further effect. Lastly, the dynamic-mechanical properties of LLDPE are slightly modified in the nanocomposites.     

Methanol synthesis over Cu/ZnO catalysts prepared by ball milling

Cu/ZnO catalysts (with a Cu/Zn atomic ratio of 30/70) have been prepared by high intensity mechanical mixing of copper and zinc oxide powder in air and under vacuum. During milling in vacuum gradual amorphisation of the constituents occurs, as evidenced by broadening of the Cu⁰ and ZnO diffraction peaks in XRD, but the two original phases remain. The result of such treatment is a catalyst with low BET area and low Cu metal surface area. Consequently, the activity of the vacuum milled samples in batch methanol production from synthesis gas (CO/CO₂/H₂=20/5/75) at 50 bar and 250°C is low. Milling in air leads to oxidation of the copper metal phase and much higher BET surface area and, after reduction, Cu metal surface area. Prolonged milling times in air result in more than 90% Cu²⁺ formation as evidenced by TPR. Activity in methanol synthesis for the air milled samples is comparable to a conventional Cu/ZnO catalyst prepared by coprecipitation. It is concluded that high intensity ball milling at ambient conditions is a promising method to prepare mixed oxide catalysts or catalyst precursors. This revised version was published online in July 2006 with corrections to the Cover Date.     

Aliphatic polyamidoamine hyperbranched polymers/layered silicate nanocomposites

Polyamidoamine hyperbranched polymer (Hyp)/clay nanocomposites were synthesized by using both of montmorillonite and laponite clays. Poly amidoamine hyperbranched polymer (Hyp) was prepared by one‐pot polymerization via couple monomer methodology. Afterward, the amino ends of Hyp were modified with methyl methacrylate (MMA), styrene (St) and butyl methacrylate (n‐BuMA) polymers which were previously prepared via ATRP (atom transfer radical polymerization) to form the corresponding new hyperbranched polymers Hyp₁, Hyp₂ and Hyp₃. Those formed polymers were inserted into the modified clay, such as montmorillonite and laponite to form their nanocomposites. The formed polymer/clay nanocomposites were characterized via XRD, TEM, and thermal analyses. The formed hyperbranched polymers generally showed intercalation behavior more than the exfoliation one mostly because of the bulkiness of the hyperbranched skeleton. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mixed-conducting polyaniline-Fuller's Earth nanocomposites prepared by stepwise intercalation

A series of polyaniline-Fuller's Earth (PANI-FE) nanocomposites were prepared by the successive intercalation of anilinium ions followed by polymerisation within the interlayer spaces of Fuller's Earth (a type of calcium montmorillonite). The first member in the series is prepared by exchanging the calcium ions in Fuller's Earth for ammonium ions and subsequently for anilinium ions and polymerising the latter using an externally introduced oxidant. The emeraldine salt form of polyaniline formed is then neutralised with ammonium hydroxide and more anilinium ions are exchanged for ammonium ions and polymerised to get the second member. In this manner, by making use the unique chemistry of clay and polyniline, four members of PANI-FE are prepared. In the last member, the negative layer charges of Fuller's Earth is completely neutralised by the positive charges of the polymer. The extent of polymer loading in each stage, the effect polymer has on the host structure and the electronic and ionic components of the conductivities of the new PANI-FE nanocomposites are investigated. The Fe(III) sites in FE are capable of spontaneously polymerising aniline within its intergalleries. The extent of spontaneous polymerisation is limited by the amount of Fe(III) present in the FE. The deliberate polymerisation of remaining anilinium ions by externally introduced oxidant results in highly conductive emeraldine salt-FE (EMS-FE) nanocomposites. The FE host accommodates higher amount of emeraldine salt and the repetitive insertions of the polymer could be done four times for complete layer charge neutralisation whereas with Bentonite the layer charge saturation takes place with three successive insertions. The new EMS-FE nanocomposites exhibit more than order of magnitude greater tuneable ionic and electronic conductivities compared to those of the same polymer incorporated in Bentonite.     

Styrene-acrylonitrile (SAN) layered silicate nanocomposites prepared by melt compounding

Poly(styrene-co-acrylonitrile) (SAN) nanocomposites were successfully made by melt compounding and exhibited improved thermal stability and reduced flammability. The organoclays used in these nanocomposites were based upon fluorinated synthetic mica (FSM) or montmorillonite (MMT). Four different organic treatments were used on the clay surface to study the effect of organic treatment on clay dispersion: dimethyl, bis(hydrogenated tallow) ammonium (DMHTA), methyl tallow bis-2-hydroxyethyl ammonium (MTBHA), triphenyl, n-hexadecyl phosphonium (TPHDP), and 1,2-dimethyl-3-n-hexadecyl imidazolium (DMHDI). Along with studying the effect of clay organic treatment on the nanocomposite formation and flammability, the effect of acrylonitrile content in the SAN on nanocomposite formation and flammability was also studied. The overall findings suggest that dispersion of clay into SAN is rather facile, but certain combinations of organic treatment and clay type resulted in microcomposites rather than nanocomposites. Flammability of these materials was measured by pulse-combustion flow calorimetry (PCFC), also known as micro-cone calorimetry.     

Synthesis of resol–layered silicate nanocomposites by reaction exfoliation with acid‐modified montmorillonite

Resol–layered silicate nanocomposites were prepared by the intercalative polymerization of phenol and formaldehyde in the presence of acid‐modified montmorillonite (HMMT). The nanocomposites were studied by means of X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic mechanical analysis (DMA), and rheological measurements. The exfoliation of HMMT was promoted by the intragallery reactions catalyzed by protons in the galleries of the clay, whereas the extragallery polymerization catalyzed by ammonia went on simultaneously. The nanocomposites showed higher glass‐transition temperatures in the DMA diagram compared with the resol counterparts. The impact strength was improved significantly by the incorporation of the clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 791–797, 2004