Predictive modeling of creep in polymer/layered silicate nanocomposites

A predictive creep model is developed which uses the properties of matrix and reinforcement to predict the creep of polymer/layered silicate nanocomposites. Up to this point, primarily empirical creep models such as Findley and Burgers models have been used for creep of polymer/clay nanocomposites. The proposed creep model is based on the elastic-viscoelastic correspondence principle and a stiffness model of these nanocomposites. Also, the added stiffness of polymeric matrix due to the constraining effect of layered silicates on polymer chains in the nanocomposite is considered by a parameter termed constraint factor. The results of the proposed model show good agreement with experimental creep data for different clay contents, stresses and temperatures. Comparing the model predictions with experimental data, a logical relationship between the method of processing and the constraint factor is discovered which shows that in-situ polymerization can be more efficient for improving creep resistance of polymer/layered silicate nanocomposites relative to melt processing.     

Rheology of polymer layered silicate nanocomposites

Layered silicate based polymer nanocomposites have gained significant technological interest because of the recent commercialization of nylon 6 and polypropylene based materials. Aside from the natural interests in understanding and improving the processing of these hybrids, viscoelastic measurements have also proven to be a sensitive tool to probe the mesoscale structure and the strength of polymer–nanoparticle interactions.     

Thermal analysis of polymer layered silicate nanocomposites

It has been shown, for three different polymer layered silicate (PLS) nanocomposite systems, how differential scanning calorimetry (DSC) can identify the different reactions of homopolymerisation and of crosslinking that occur in the intra- and extra-gallery regions of these nanocomposites, respectively, and hence how DSC can be used to assess the cure conditions for optimising their nanostructure. The PLS nanocomposites are based upon: (i) diglycidyl ether of bisphenol-A (DGEBA) cured with a polyoxypropylene diamine; (ii) DGEBA cured with an –NH₂ terminated hyperbranched polymer (HBP); and (iii) tri-glycidyl p-amino phenol (TGAP) cured with a diamine. In each case, the existence of both intra- and extra-gallery reactions in the DSC cure curves, and whether they occur simultaneously or sequentially, and in what order, are identified and correlated with the nanostructure as observed by small angle X-ray scattering and transmission electron microscopy. In particular, it is shown that the intra-gallery reaction must precede the extra-gallery for significant exfoliation to occur. In accordance with this scenario, the TGAP/diamine system displays the greatest degree of exfoliation, the DGEBA/diamine system the least, with the DGEBA/HBP system intermediate. For those systems in which significant exfoliation occurs, the DSC cure curves also allow the optimum cure conditions, such as the isothermal cure temperature, to be determined.     

Thermo-oxidative stability of polypropylene/layered silicate nanocomposites

Several series of experiments were carried out to check the effect of components on the stability of PP/layered silicate nanocomposites. The amount of organophilic montmorillonite (OMMT) changed between 0 and 6, while that of maleated polypropylene (MAPP) between 0 and 50 vol%. The composites were prepared in an internal mixer at 190 °C. Mixing speed and time were changed to study the effect of processing conditions on stability. The structure of the samples was characterised by various methods, while stability by the induction time of oxidation (OIT), the onset temperature of degradation (OOT) and by colour. Contrary to numerous claims published in the literature, which indicate the positive effect of layered silicates on the stability of polymer nanocomposites, our results clearly proved that both OMMT and MAPP accelerate degradation during processing and deteriorate the properties of PP composites. Residual stability decreases drastically with increasing amounts of both components, chain scission leads to the decrease of viscosity and to inferior strength and deformability. In spite of expectations, the effect of the components is independent of each other. Discoloration is caused mainly by the inherent colour of the filler and it decreases with increasing exfoliation. The most probable reason for decreased stability is the reaction of the components with the stabilisers, but this explanation needs further verification. Processing conditions influence degradation considerably, increasing shear rate and longer residence times lead to more pronounced degradation. The basic stabilization of commercial grade polypropylenes is insufficient to protect the polymer against degradation and without additional stabilization processing under normal conditions results in products with inferior quality.     

In situ monitoring of reaction-induced phase separation with modulated temperature DSC

A linearly polymerizing and network forming epoxy-amine system, DGEBA-aniline and DGEBA-MDA, respectively, will be modified with 20 wt% and 50 wt% of a high-T_g thermoplastic poly(ether sulphone) (T_g=223°C), respectively, both showing LCST-type demixing behavior. Reaction-induced phase separation (RIPS) in these modified systems is studied using Modulated Temperature DSC (MTDSC) as an in situ tool. Phase separation in the linear system can be probed by vitrification of the PES-rich phase, occurring at a higher conversion than the actual cloud point from light scattering measurements. The negative slope of the cloud point curve in a temperature-conversion-transformation diagram unambiguously shows the LCST-type demixing behavior of this system, while the relation between the composition/glass transition of the PES-rich phase and the cure temperature is responsible for the positive slope of its vitrification line. Phase separation in the network forming system appears as reactivity increases at the cloud point due to the concentration of reactive groups. Different mixture compositions alter the ratio between the rate of phase separation and the rate of reaction, greatly affecting the morphology. Information about this in situ developed structure can be obtained from the heat capacity evolutions in non-isothermal post-cures.     

Characterization of polypropylene/layered silicate nanocomposites prepared by single-step method

The extent of organo-modified clay (C93A) platelets dispersion in polymer matrix and crystallization and melting behavior of iPP-based nanocomposites prepared by a single-step melt-mixing method were investigated by wide-angle X-ray diffraction (WAXD), transmission (TEM), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). WAXD patterns revealed exfoliated structure of nanocomposites containing 1 wt% clay, and mixed intercalated/exfoliated structure at higher concentration of nanoclay. The isothermal crystallization proceeds faster in the matrix polymer (iPP/PP-g-MA) than in nanocomposite samples. The results obtained for T _m ^o suggest that the presence of nanoclay has induced a perfection of the formed crystals. The presence of C93A particles in PP leads to increase in crystallization peak temperature implying nucleating ability of clay particles, which was more pronounced in exfoliated than in mixed intercalated/exfoliated system.     

Isothermal crystallization of layered silicate/starch-polycaprolactone blend nanocomposites

The isothermal crystallization behavior of layered silicate/starch-polycaprolactone blend nanocomposites was studied by means of differential scanning calorimetry (DSC) measurements. The theoretical melting point was higher for the matrix than for nanocomposites. At low clay concentration, the induction time decreased and the overall crystallization rate increased acting as nucleating agent whereas at higher concentrations became retardants. Classical Avrami equation was used to analyze the crystallization kinetic of these materials. n values suggested that clay not only affected the crystallization rate but also influenced the mechanism of crystals growth. An Arrhenius type equation was used for the rate constant (k). Models correctly reproduced the experimental data.     

Nanostructure and properties of polysiloxane‐layered silicate nanocomposites

The relationship between nanostructure and properties in polysiloxane layered silicate nanocomposites is presented. Solvent uptake (swelling) in dispersed nanocomposites was dramatically decreased as compared to conventional composites, though intercalated nanocomposites and immiscible hybrids exhibited more conventional behavior. The swelling behavior is correlated to the amount of bound polymer (bound rubber) in the nanocomposites. Thermal analysis of the bound polymer chains showed an increase and broadening of the glass‐transition temperature and loss of the crystallization transition. Both modulus and solvent uptake could be related to the amount of bound polymer formed in the system. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1595–1604, 2000     

Preparation and properties of aramid/layered silicate nanocomposites by solution intercalation technique

Polymer—clay nanocomposites were synthesized from aromatic polyamide and organoclay using the solution intercalation technique. Polyamide chains were produced through the reaction of 4,4′‐oxydianiline (ODA) and isophthaloyl chloride (IPC) in N, N′‐dimethyl acetamide, using stoichiometry yielding chains with carbonyl chloride end groups. The intercalation of sodium montmorillonite (Na‐MMT) was carried out using p‐phenylene diamine as a swelling agent through an ion exchange reaction. Different concentrations of organoclay were blended with the polyamide solution for complete dispersion of clay throughout the matrix. The resulting composite films were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), mechanical testing, thermogravimetry (TGA), differential scanning calorimetry (DSC) and water absorption measurements. The XRD pattern and morphology of the nanocomposites revealed the formation of exfoliated and intercalated clay platelets in the matrix. The film containing a small amount of clay was semitransparent and had a tensile strength of the order of 70 MPa (relative to the 52 MPa of the pure aramid). Thermal decomposition temperatures were in the range of 300–450°C and the weight of the samples remaining after heating to 900°C was found to be roughly proportional to the clay loading. DSC showed a systematic increase in the glass transition temperature with increase in clay content. Water absorption of the pristine aramid film was rather high (5.7%), which reduced upon loading of organoclay. Copyright © 2008 John Wiley & Sons, Ltd.     

Microstructure and dynamic mechanical analysis of extruded layered silicate PVC nanocomposites

The nanostructure and dynamic mechanical properties of polyvinyl chloride (PVC) and the bentonite nanocomposites have been investigated. Nanocomposites with 5 wt% concentration of bentonite were prepared by melt extrusion followed by two‐roll‐milled processing. Atomic force microscopy (AFM) and wide‐angle X‐ray scattering (WAXS) were utilized to study the micro and nanostructure of the two‐roll‐milled sheets. The nanocomposites were compounded with two types of coupling agents: KZTPP® and Tamol 2001®. Optical microscopy showed that the materials remained optically transparent, i.e. they did not show evidence of nanoclay agglomeration. The WAXS patterns of PVC‐bentonite‐KZTPP nanocomposite were anisotropic, suggesting flow‐induced preferred orientation of the nanoplates. Moreover, the 001 reflection of the bentonite was shifted toward smaller angles, suggesting that the nanoplates were intercalated by the macromolecules. On the other hand, the WAXS patterns of PVC‐bentonite‐Tamol 2001 nanocomposite remained isotropic and did not show evidence of bentonite, suggesting exfoliation of the nanoplates. The nanocomposites showed an increase in glass transition temperature T_g, with the sequence T_g,PVC < T_g,KZTPP < T_{g,Tamol 2001}. Moreover, dynamic mechanical analysis (DMA) showed an increase in mechanical moduli and activation energy (and a decrease in the intensity of the mechanical damping Tan δ) following the same sequence. Interestingly, the improvement in mechanical moduli became more pronounced above the glass transition temperature. Copyright © 2008 John Wiley & Sons, Ltd.     

Estimation of interphase thickness and properties in PP/layered silicate nanocomposites

Nanocomposites were prepared from sodium montmorillonite (NaMMT) and organoclays (OMMT) with different particle sizes as a function of silicate content. Composite structure was characterized by various methods including X-ray diffraction (XRD), scanning electron microscopy (SEM) and rheology. Model calculations were carried out to estimate the thickness and yield stress of the interphase forming in the composites. The results proved the formation of an interphase, but the determination of interphase properties was hampered by several factors. First of all, the particle size of the filler changed quite considerably in PP/OMMT composites in spite of earlier observations and expectations. Particle characteristics changed even further when a relatively small amount (5 vol.%) of functionalized polymer (MAPP) was added to the composite. As a consequence, the estimation of the contact surface between the silicate and the polymer became extremely difficult. In spite of the uncertainties overall values of interphase properties were obtained using the results of all composites prepared. The prediction for the average thickness of the interphase is 0.23 μm and we obtained 51.2 MPa for interphase yield stress, but this estimate neglects the different interactions developing in composites containing the uncoated and the modified silicate, respectively.     

Understanding and controlling the structure of polypropylene/layered silicate nanocomposites

The miscibility and structure in polypropylene/layered silicate nanocomposites is systematically investigated utilizing a maleic-anhydride grafted polypropylene with a low degree of functionalization acting as the compatibilizer. The morphology of the hybrids can be modified from phase separated to almost completely exfoliated in a controlled way by varying the ratio α of the compatibilizer to the organophilized clay; this ratio α is found to be the most important parameter in determining the final structure whereas exfoliated structures can be obtained for α values of 9 or higher. Furthermore, utilization of a “masterbatch” procedure can enhance the degree of exfoliation even for smaller values of α; in that case, polypropylene is essentially mixed with the already dispersed “hairy” platelets. Investigation of the thermal stability of the micro- and nanocomposites shows that high degree of exfoliation is vital in increasing the temperature that the polymer starts to degrade. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2683–2695, 2008     

In situ poling and orientation stability of chromophore-bearing ladderlike polysiloxanes

A new, specially designed nonlinear optical (NLO) polymer is composed of ladderlike polysilsesquioxane as a backbone and “side-on or end-on” fixed stilbene chromophores. In-situ poling was carried out simultaneously during film formation via solvent evaporation and crosslinking which was caused by sequential hydrolysis and condensation of remained Si-H groups on macromolecules. The dipolar orientation after poling is described by an order parameter Φ which was measured using an original linear optical technique–UV dichroism. Orientation order and its decay are influenced by chromophore loading, crosslinking degree and poling condition. Compared with corresponding single chain polymers, a poled thin film of ladderlike NLO polymers demonstrates more stable poling-induced orientation.     

Synthesis of polystyrene/polybutylacrylate/layered silicate nanocomposites in aqueous medium

Synthesis of nanocomposites based on polystyrene/polybutylacrylate with layered silicates using emulsion polymerization procedure in aqueous medium allowed obtaining stable nanolatexes with sodium dodecyl sulfate as surfactant. Monomer and layered silicate nature influences the average diameter of the particles and the zeta potential appeared on the particle-disperse medium interface, as it was shown by dynamic light scattering analyses. In order to evidence the layered silicate structure, two structural evaluation methods were used. A new approach was used based on Fourier transform infrared analyses as a method to asses the clay delamination. The method was followed in conjunction with X-ray diffraction patterns and showed the pronounced delamination of the clay in the polymer matrix. The thermal stability was investigated by thermogravimetric analyses and the morphologies in solid state observed by environmental scanning electron microscope measurements.     

Thermal stability and water uptake of high performance epoxy layered silicate nanocomposites

Intercalated and ordered exfoliated layered silicate nanocomposites based on three different epoxy resins of different structures and functionalities were synthesized using an octadecyl ammonium modified smectite clay. Water uptake properties of series of each nanocomposite system with different organoclay concentrations were determined by gravimetric measurements over a period of time. The diffusion coefficients were determined and the effect of the absorbed water on the thermal relaxations investigated. The equilibrium water uptake of all nanocomposites was reduced compared to the neat epoxy system but the rate of water diffusion remained unaffected. Further, the thermal stability of the different nanocomposites was determined using thermogravimetric analysis. The nanocomposites showed slightly reduced thermal stability, as indicated by a slight decrease in onset of degradation, whilst the final char concentration increased for greater organoclay concentrations.     

Polymer–silicate nanocomposites produced by in situ atom transfer radical polymerization

Polymer–silicate nanocomposites were synthesized with atom transfer radical polymerization (ATRP). An ATRP initiator, consisting of a quaternary ammonium salt moiety and a 2‐bromo‐2‐methyl propionate moiety, was intercalated into the interlayer spacings of the layered silicate. Subsequent ATRP of styrene, methyl methacrylate, or n‐butyl acrylate with Cu(I)X/N,N‐bis(2‐pyridiylmethyl) octadecylamine, Cu(I)X/N,N,N′,N′,N″‐pentamethyldiethylenetriamine, or Cu(I)X/1,1,4,7,10,10‐hexamethyltriethylenetetramine (X = Br or Cl) catalysts with the initiator‐modified silicate afforded homopolymers with predictable molecular weights and low polydispersities, both characteristics of living radical polymerization. The polystyrene nanocomposites contained both intercalated and exfoliated silicate structures, whereas the poly(methyl methacrylate) nanocomposites were significantly exfoliated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 916–924, 2004     

聚甲基丙烯酸甲酯/层状硅酸盐复合材料的研究

本文对聚甲基丙烯酸甲酯/层状硅酸盐纳米复合材料的国内外研究进展,层状硅酸盐的结构及有机化改性做了详细的综述.同时,对PMMA/层状硅酸盐粘土复合材料的结构及表征手段、制备原理及方法、物理和化学性能及应用前景做了系统的总结.最后,在我们研究工作的基础上对此领域的研究方向进行了预测.     

DC electrorheological response of polyethylene/organically modified layered silicate nanocomposites

The present work reports the electrorheological (ER) response of high‐density polyethylene (HDPE)/organically modified silicate layers nanocomposites based on four commercially available HDPE matrices. Two single‐site catalyzed bimodal resins, one single‐site catalyzed unimodal resin and one Ziegler–Natta catalyzed unimodal resin are studied. It is revealed that the distinct separation of the two modes of the bimodal HDPE resins significantly enhances the ER response. It is proposed that the slower structural relaxation modes introduced by higher molecular weight species in the bimodal HDPE matrices enhance the ER response of the nanocomposites. This is ascribed to the longer induction time for leaking current density, which is an indicator of mobility and release of immobilized cationic surfactants at the silicate layers surface induced by field exposure. It is found that the screening effect of prematurely released cationic surfactants leads to a weaker ER response in nanocomposites whose matrices have faster relaxation modes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1298–1309     

Bio‐based nanocomposites from functionalized plant oils and layered silicate

Some discovery work was done on the synthesis of clay nanocomposites based on renewable plant oils. Functionalized triglycerides, such as acrylated epoxidized soybean oil, maleinized acrylated epoxidized soybean oil, and soybean oil pentaerythritol maleates, combined with styrene were used as the polymer matrix. The miscibility of these monomers and clay organomodifier was assessed by solubility parameters. The formation of nanocomposites was confirmed by both X‐ray data and transmission electron microscopy. The morphology showed a mix of intercalated and partially exfoliated sheets. The flexural modulus increased 30% at only 4 vol % clay content, but there was no significant effect on flexural strength, glass‐transition temperature, and thermal stability. Property enhancement was related to the degree of exfoliation that depends on both the polarity and flexibility of the monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1441–1450, 2004     

Mechanical properties of polyamide-12 layered silicate nanocomposites and their relations with structure

The mechanical properties of polyamide-12/Cloisite 30B (PA12/C30B) nanocomposites prepared by melt compounding were studied as a function of clay volume fraction φ under various processing conditions. All measured mechanical characteristics, Young's modulus, yield stress, strain at break and stress at break, exhibit a transition at φ_p1%, identified with a percolation threshold. Also, the linear and non-linear mechanical properties appeared to depend on the degree of exfoliation of the structure, which can be tuned by the processing conditions. The three-phase Ji's theoretical model was used to predict Young's modulus as a function of clay concentration, focusing on the influence of the degree of exfoliation. Experimental yield stress data were fitted to Pukanszky's model and discussed in terms of PA12/C30B interfacial adhesion.