Dynamic mechanical analysis of polymeric systems of pharmaceutical and biomedical significance

Dynamic mechanical analysis (DMA) is an analytical technique in which an oscillating stress is applied to a sample and the resultant strain measured as functions of both oscillatory frequency and temperature. From this, a comprehensive knowledge of the relationships between the various viscoelastic parameters, e.g. storage and loss moduli, mechanical damping parameter (tan delta), dynamic viscosity, and temperature may be obtained. An introduction to the theory of DMA and pharmaceutical and biomedical examples of the use of this technique are presented in this concise review. In particular, examples are described in which DMA has been employed to quantify the storage and loss moduli of polymers, polymer damping properties, glass transition temperature(s), rate and extent of curing of polymer systems, polymer-polymer compatibility and identification of sol-gel transitions. Furthermore, future applications of the technique for the optimisation of the formulation of pharmaceutical and biomedical systems are discussed. (C) 1999 Elsevier Science B.V. All rights reserved.

Evaluation of Postpolymerization as a Function of the Storage Time of Triethylene Glycol Dimethacrylate/2,2-Bis[4-(2-Hydroxy-3-Methacryloxy-Prop-1-Oxy)-Phenyl]-propane Bisphenyl-alpha-Glycidyl Ether Dimethacrylate Copolymers Used in Dental Resins by Differential Scanning Calorimetry and Dynamic Mechanical Analysis

The aim of this work was to evaluate the effect of the storage time on the thermal properties of triethylene glycol dimethacrylate/2,2-bis[4-(2-hydroxy-3-methacryloxy-prop-1-oxy)-phenyl]propane bisphenyl-alpha-glycidyl ether dimethacrylate (TB) copolymers used in formulations of dental resins after photopolymerization. The TB copolymers were prepared by photopolymerization with an Ultrablue IS light-emitting diode, stored in the dark for 160 days at 37 degrees C, and characterized with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared spectroscopy with attenuated total reflection. DSC curves indicated the presence of an exothermic peak, confirming that the reaction was not completed during the photopolymerization process. This exothermic peak became smaller as a function of the storage time and was shifted at higher temperatures. In DMA studies, a plot of the loss tangent versus the temperature initially showed the presence of two well-defined peaks. The presence of both peaks confirmed the presence of residual monomers that were not converted during the photopolymerization process. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 679-684, 2009

Thermal mechanical and dynamic mechanical property of biphenyl polyimide fibers

High-performance polyimide fibers possess man), excellent properties, e.g., outstanding thermal stability and mechanical properties and excellent radiation resistant and electrical properties. However, the preparation of fibers with good mechanical properties is very difficult. In this report, a biphenvl polyimide from 3,3',4,4'-biphenyltetracarboxylic dianhydride and 4,4'-oxydianiline is synthesized in p-chlorophenol by one-step polymerization. The solution is spun into a coagulation bath of water and alcohol via dry-jet wet-spinning technology. Then, the fibers are drawn in two heating tubes. Thermal gravimetric analysis, thermal mechanical analysis, and dynamic mechanical analysis (DMA) are performed to study the properties of the fibers. The results show that the fibers have a good thermal stability at a temperature of more than 400degreesC. The linear coefficient of thermal expansion is negative in the solid state and the glass transition temperature is about 265degreesC. DMA spectra indicate that the tandelta of the fibers has three transition peaks, namely, alpha, beta, and gamma transition. The alpha and gamma transition temperature, corresponding to the end-group motion and glass transition, respectively, extensively depends on the applied frequency, while the beta transition does not.

Determination of the drug solubility at the melt temperature in silicone intravaginal rings using dynamic mechanical analysis

92

Dynamic mechanical analysis of binary and ternary polymer blends based on nylon copolymer/EPDM rubber and EPM grafted maleic anhydride compatibilizer

The dynamic mechanical properties such as storage modulus, loss modulus and damping properties of blends of nylon copolymer (PA6,66) with ethylene propylene diene (EPDM) rubber was investigated with special reference to the effect of blend ratio and compatibilisation over a temperature range –100°C to 150°C at different frequencies. The effect of change in the composition of the polymer blends on tanδ was studied to understand the extent of polymer miscibility and damping characteristics. The loss tangent curve of the blends exhibited two transition peaks, corresponding to the glass transition temperature (Tg) of individual components indicating incompatibility of the blend systems. The morphology of the blends has been examined by using scanning electron microscopy. The Arrhenius relationship was used to calculate the activation energy for the glass transition of the blends. Finally, attempts have been made to compare the experimental data with theoretical models.

Dynamically mechanical and nano-impact (fatigue) analysis of touch screen thin films deposited on polyethylene terephthalate substrate

Nano-scale touch screen thin film have not been thoroughly investigated in terms of dynamic impact analysis under various strain rates. This research is focused on two different thin films, Zinc Oxide (ZnO) film and Indium Tin Oxide (ITO) film, deposited on Polyethylene Terephthalate (PET) substrate for the standard touch screen panels. Dynamic Mechanical Analysis (DMA) was performed on the ZnO film coated PET substrates. Nano-impact (fatigue) testing was performed on ITO film coated PET substrates. Other analysis includes hardness and the elastic modulus measurements, atomic force microscopy (AFM), Fourier Transform Infrared Spectroscopy (FTIR) and the Scanning Electron Microscopy (SEM) of the film surface.
Ten delta of DMA is described as the ratio of loss modulus (viscous properties) and storage modulus (elastic properties) of the material and its peak against time identifies the glass transition temperature (Tg). Thus, in essence the Tg recognizes changes from glassy to rubber state of the material and for our sample ZnO film, Tg was found as 388.3 K. The DMA results also showed that the Ten delta curve for Tg increases monotonically in the viscoelastic state (before Tg) and decreases sharply in the rubber state (after Tg) until recrystallization of ZnO takes place. This led to an interpretation that enhanced ductility can be achieved by negating the strength of the material.
For the nano-impact testing using the ITO coated PET, the damage started with the crack initiation and propagation. The interpretation of the nano-impact results depended on the characteristics of the loading history. Under the nano-impact loading, the surface structure of ITO film suffered from several forms of failure damages that range from deformation to catastrophic failures. It is concluded that in such type of application, the films should have low residual stress to prevent deformation, good adhesive strength, durable and good resistance to wear.

Effects of temperature and clay content on water absorption characteristics of modified MMT clay/cyclic olefin copolymer nanocomposite films: Permeability, dynamic mechanical properties and the encapsulated organic device performance

In the present study, amino-silane modified layered organosilicates were used to reinforce cyclic olefin copolymer to enhance the thermal, mechanical and moisture impermeable barrier properties. The optimum clay loading (4%) in the nanocomposite increases the thermal stability of the film while further loading decreases film stability. Water absorption behavior at 62 degrees C was carried out and compared with the behavior at room temperature and 48 degrees C. The stiffness of the matrix increases with clay content and the recorded strain to failure for the composite films was lower than the neat film. Dynamic mechanical analysis show higher storage modulus and low loss modulus for 2.5-4 wt% clay loading. Calcium degradation test and device encapsulation also show the evidence of optimum clay loading of 4 wt% for improved low water vapor transmission rates compared to other nanocomposite films. (C) 2014 Elsevier Ltd. All rights reserved.

Influence of Annealing on Microstructure and Mechanical Properties of Isotactic Polypropylene with beta-Phase Nucleating Agent

The microstructure and mechanical properties of beta-nucleated iPP before and after being annealed at different temperatures (90-160 degrees C) have been analyzed, Annealing induced different degrees of variation in fracture toughness of beta-nucleated iPP samples. namely, slight enhancement at relatively low annealing temperatures (< 110 degrees C) and great improvement at moderate temperatures (120-130 degrees C), whereas dramatic deterioration at relatively high temperatures ( > 140 degrees C) has been observed. The variation of fracture toughness of beta-nucleated iPP is observed to be dependent on the content of beta-NA. Experiments, including scanning electronic microscope (SEM), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and dynamic mechanical analysis (DMA), are performed to study the variations of microstructures as well as the toughening mechanism of the beta-nucleated iPP after being annealed.

The rheological behavior and dynamic mechanical properties of syndiotactic 1,2-polybutadiene

The rheological behavior and the dynamic mechanical properties of syndiotactic 1,2-polybutadiene (sPB) were investigated by a rotational rheometer (MCR-300) and a dynamic mechanical analyzer (DMA-242C). Rheological behavior of sPB-830, a sPB with crystalline degree of 20.1% and syndiotactic content of 65.1%, showed that storage modulus (G ') and loss modulus (G '') decreased, and the zero shear viscosity (eta(0)) decreased slightly with increasing temperature when measuring temperatures were lower than 160 degrees C. However, G ' and G '' increased at the end region of relaxation curves with increasing temperature and)10 increased with increasing temperature as the measuring temperatures were higher than 160 degrees C. Furthermore, critical crosslinked reaction temperature was detected at about 160 degrees C for sPB-830. The crosslinked reaction was not detected when test temperature was lower than 150 degrees C for measuring the dynamic mechanical properties of sample. The relationship between processing temperature and crosslinked reaction was proposed for the sPB-830 sample.

Miscibility, crystallization and mechanical properties of PPC/PBS blends

In this paper, melt blends of poly(propylene carbonate) (PPC) with poly(butylene succinate) (PBS) were characterized by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), tensile testing, wide-angle X-ray diffraction (WAXD), polarized optical microscopy and thermogravimetric analysis (TGA). The results indicated that the glass transition temperature of PPC in the 90/10 PPC/PBS blend was decreased by about 11 K comparing with that of pure PPC. The presence of 10% PBS was partially miscible with PPC. The 90/10 PPC/PBS blend had better impact and tensile strength than those of the other PPC/PBS blends. The glass transition temperature of PPC in the 80/20, 70/30, and 60/40 PPC/PBS blends was improved by about 4.9 K, 4.2 K, and 13 K comparing with that of pure PPC, respectively; which indicated the immiscibility between PPC and PBS. The DSC results indicated that the crystallization of PBS became more difficult when the PPC content increased. The matrix of PPC hindered the crystallization process of PBS. While the content of PBS was above 20%, significant crystallization-induced phase separation was observed by polarized optical microscopy. It was found from the WAXD analysis that the crystal structure of PBS did not change, and the degree of crystallinity increased with increasing PBS content in the PPC/PBS blends.

The mechanical and thermal behaviors of glass bead filled polypropylene

Notch Izod impact strength of poly(propylene) (PP)/glass bead blends was studied as a function of temperature. The results indicated that the toughness for various blends could undergo a brittle-ductile transition (BDT) with increasing temperature. The BDT temperature (T-BD) decreased with increasing glass bead content. Introducing the interparticle distance (ID) concept into the study, it was found that the critical interparticle distance (IDc) reduced with increasing test temperature correspondingly. The static tensile tests showed that the Young's modulus of the blends decreased slightly first and thereafter increased with increasing glass bead content. However, the yield stress decreased considerably with the increase in glass bead content. Dynamic mechanical analysis (DMA) measurements revealed that the heat-deflection temperature of the PP could be much improved by the incorporation of glass beads. Moreover, the glass transition temperature (T-g) increased obviously with increasing glass beads content. Differential scanning calorimetry (DSC) results implied that the addition of glass beads could change the crystallinity as well as the melting temperature of the PP slightly.

Mechanical and thermal properties of glass bead-filled nylon-6

The mechanical and thermal properties of glass bead-filled nylon-6 were studied by dynamic mechanical analysis (DMA), tensile testing, Izod impact, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) tests. DMA results showed that the incorporation of glass beads could lead to a substantial increase of the glass-transition temperature (T-g) of the blend, indicating that there existed strong interaction between glass beads and the nylon-6 matrix. Results of further calculation revealed that the average interaction between glass beads and the nylon-6 matrix deceased with increasing glass bead content as a result of the coalescence of glass beads. This conclusion was supported by SEM observations. Impact testing revealed that the notch Izod impact strength of nylon-6/glass bead blends substantially decreased with increasing glass bead content. Moreover, static tensile measurements implied that the Young's modulus of the nylon-6/glass bead blends increased considerably, whereas the tensile strength clearly decreased with increasing glass bead content.

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3-butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T-g) and the melting temperature (T-m) of PLA. Moreover, crystallinity of PLA increased with increasing the con-tent of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break.

Binary alloys of nylon 1010 and ethylene-propylene copolymer: Chemical, morphological, and mechanical analysis

The modification of ethylene-propylene copolymer (EPM) has been accomplished by melt grafting of maleic anhydride (MAH) molecules promoted by radical initiators. The resulting EPM-g-MAH and EPM have been used to obtain binary nylon 1010/EPM or nylon 1010/EPM-g-MAH blends by melt mixing. It was found that the EPM-g-MAH copolymer used as the second component has a profound effect upon the properties of the resulting blends. This behavior has been attributed to a series of chemical and physicochemical interactions taking place between the two components. The interactions are due to the presence of the anhydride functionality on the copolymer and do not occur when this functionality is absent. The interaction has been confirmed by Fourier-transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, and scanning electron microscopic.

A dynamic mechanical method for determining the silicone elastomer solubility of drugs and pharmaceutical excipients in silicone intravaginal drug delivery rings

The silicone elastomer solubilities of a range of drugs and pharmaceutical excipients employed in the development of silicone intravaginal drug delivery rings (polyethylene glycols, norethisterone acetate, estradiol, triclosan, oleyl alcohol, oxybutynin) have been determined using dynamic mechanical analysis. The method involves measuring the concentration-dependent decrease in the storage modulus associated with the melting of the incorporated drug/excipient, and extrapolation to zero change in storage modulus. The study also demonstrates the effect of drug/excipient concentrations on the mechanical stiffness of the silicone devices at 37°C.