Damage characterization in non-isothermal stretching of acrylics. Part I: Theory

An improved version of dual-mechanism constitutive model was proposed to describe thermo-mechanical response of amorphous polymers below and above glass transition temperature (θ_g). Material property definitions and plastic flow rules were revisited to provide a smooth and continuous transition in material response around θ_g. The elastic-viscoplastic constitutive model was developed based on thermodynamics framework and was implemented in a fully coupled thermo-mechanical simulation of non-isothermal testing of PMMA in Part II [Gunel, E. M., Basaran, C., 2010. Damage characterization in non-isothermal stretching of acrylics. Part II: Experimental validation. Mechanics of Materials]. For damage evolution in complex thermo-mechanical problems such as polymer processing operation, irreversible entropy production was considered as the measure of damage.     

Effect of dispersion conditions on the thermo-mechanical and toughness properties of multi walled carbon nanotubes-reinforced epoxy

In this work, multi wall carbon nanotubes (MWCNTs) dispersed in a polymer matrix have been used to enhance the thermo-mechanical and toughness properties of the resulting nanocomposites. Dynamic mechanical analysis (DMA), tensile tests and single edge notch 3-point bending tests were performed on unfilled, 0.5 and 1 wt.% carbon nanotube (CNT)-filled epoxy to identify the effect of loading on the aforementioned properties. The effect of the dispersion conditions has been thoroughly investigated with regard to the CNT content, the sonication time and the total sonication energy input. The CNT dispersion conditions were of key importance for both the thermo-mechanical and toughness properties of the modified systems. Sonication duration of 1 h was the most effective for the storage modulus and glass transition temperature (T_g) enhancement for both 0.5 and 1 wt.% CNT loadings. The significant increase of the storage modulus and T_g under specific sonication conditions was associated with the improved dispersion and interfacial bonding between the CNTs and the epoxy matrix. Sonication energy was the influencing parameter for the toughness properties. Best results were obtained for 2 h of sonication and 50% sonication amplitude. It was suggested that this level of sonication allowed appropriate dispersion of the CNTs to the epoxy matrices without destroying the CNT’s structure.     

Effects of dispersion and interfacial modification on the macroscale properties of TiO2 polymer–matrix nanocomposites

This paper quantifies how the quality of dispersion and the quality of the interfacial interaction between TiO₂ nanoparticles and host polymer independently affect benchmark properties such as glass transition temperature (T_g), elastic modulus and loss modulus. By examining these composites with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM), we demonstrate changes in properties depending on the adhesive/wetting or repulsive/dewetting interactions the nanoparticles have with the bulk polymer. We further quantify the dispersion of TiO₂ nanoparticles in polymethylmethacrylate (PMMA) matrices by a digital–optical method and correlate those values to the degree of T_g depression compared to neat PMMA. Samples with the same weight percent of nanoparticles but better dispersion show larger shifts in T_g.     

Heterogeneity of spiral wear patterns produced by local heating on amorphous polymers

We report on spiral wear patterns produced at constant angular velocity by hot tip atomic force microscopy (HT-AFM) on surfaces of two common amorphous polymers: polystyrene (PS) and polymethylmethacrylate (PMMA). Topography of these patterns is obtained with regular AFM cantilevers. Topography cross-sections taken from a center of each spiral at a given azimuthal angle Θ relate changes of surface corrugation h_corr with tangential velocity v of a thermal cantilever. Polymer wear is characterized by a power law h_corr(v) = α(v/v_max)^−β, which yields a pre-factor α and an exponent β. Below the glass transition temperature T_g, α is polymer specific and β varies weakly between similar conditions and samples. Variations of β are hypothesized to reflect polymer relaxation processes, which are expected to vary only weakly between amorphous polymers. At and above T_g, α approaches initial thermal tip indentation depth within a polymer, β plummets, and a power law relation of h_corr with v diverges. These results are explained by heterogeneous wear around T_g due to a local nature of glass transition. At all studied temperatures, additional wear heterogeneities are found as due to position on the polymer and Θ. Variations of α and β with position on the polymer are found to be only marginally larger then uncertainties of the thermal tip–polymer interface temperature. Variations of α and β with Θ are found to be largely influenced by buckling of thermal cantilevers traveling in a spiral pattern.     

Characterization of polystyrene and doped polymethylmethacrylate thin layers

About 1 μm thick films of polystyrene (PS) and polymethylmethacrylate (PMMA) were prepared from solutions using spin-coating method. The PMMA films were doped with diphenylsulfoxide (DS) up to 45 wt%. Glass transition temperature (T _g ) of doped PMMA films was determined by DSC technique and relative permittivity (ε) as a function of the sample temperature was determined from capacitance measurement. The dependence of polarization (P) on electric field (E) and the temperature was measured using a standard Sawyer-Tower circuit. Spectral dependence of film refractive index was measured using a refractometer. The glass transition temperature T _g of PMMA/DS composite was found to be decreasing function of the DS concentration. Relative permittivity ε of unpolar PS is lower than that of polar PMMA. The PS permittivity does not depend on the sample temperature. For PMMA the permittivity is increasing function of both, DS dopant concentration and sample temperature. The dependence of the polarization on the electric field on PS film does not exhibit a hysteresis and indicate no polarization contrary to PMMA. PMMA/DS composites exhibit easier and larger polaribility and a permanent dipole moment. Resulting polarization is an increasing function of DS concentration. Refractive index of both pristine PS and PMMA decreases with increasing wave length. The refractive index of PMMA/DS composites depends on the DS concentration.     

The effect of physical ageing on the relaxation time spectrum of amorphous polymers: the fractional calculus approach

Empirical models corresponding to a constitutive equation with fractional derivatives are proposed for linear viscoelastic polymers. For these models, the relaxation modulus, the dynamic moduli, the relaxation time spectra, and other material functions can be calculated as a function of a few parameters that characterise the behaviour of a viscoelastic polymer. The fractional calculus approach allows us to calculate the relaxation time spectrum H() via the Stieltjes inversion in the linear viscoelastic zone. Polymethylmethacrylate (PMMA) is chosen as a model amorphous polymer in a temperature range from T_g + 90°C to T_g + 25°C. This polymer is characterised by a non-equilibrium state between at least the and relaxations. The structural recovery of PMMA has been investigated using dynamic mechanical thermal analysis (DMTA) by varying the preparational history. The effect of time and temperature on the model parameters and on the relaxation time spectra are also investigated in the neighbourhood of the glass transition.     

Novel nanocomposites based on epoxy resin/epoxy-functionalized polydimethylsiloxane reinforced with POSS

The purpose of the present study is to develop novel nanocomposites based on diglycidylether of bisphenol A (DGEBA) combined with diglycidylether-terminated polydimethylsiloxane (DG-PDMS), reinforced with 10 wt.% (mono-/octa) epoxy POSS nanocages (MEP or OEP-POSS). DG-PDMS and POSS compounds were covalently incorporated into DGEBA resin via copolymerization of epoxy groups. The effect of both DG-PDMS and POSS nanoparticles on the curing reaction, glass transition temperature (T_g), thermal stability, hardness and morphology of DGEBA/DG-PDMS ± POSS nanocomposites were studied by DSC, FTIR, DMA, TGA, SEM/EDX, AFM and contact angle measurements. SEM/EDX and AFM results prove that OEP-POSS is well dispersed within DGEBA/DG-PDMS polymer matrix, while MEP-POSS forms large POSS aggregates. The thermo-mechanical properties of POSS based nanocomposites are also in good correlation with morphology features. MEP-POSS based nanocomposite with heterogeneous dispersion of POSS aggregates exhibits lower T_g value and thermal stability in comparison with OEP-POSS nanocomposite which exhibits a nanoscale dispersion of the POSS cages. The obtained T_g of OEP-POSS based nanocomposite increases with 31 °C in comparison with the unreinforced matrix. Moreover, this nanocomposite shows the highest storage modulus (E′) and hardness.     

Tuning of the emission chromaticity of Eu,Gd, Be-containing copolymers

Eu, Gd, Be-containing copolymers were synthesized through copolymerization of reactive complexes with methyl methacrylate (MMA). Their structure was characterized by FT-IR and UV analysis. The glass transition temperature T_g of the copolymers was 24 °C higher than that of PMMA. XRD analysis indicates that the complexes were bonded and dispersed uniformly in polymer matrix. The copolymers showed the emission peaks of red, green and blue monomers under the UV excitation of 365 nm. When the feed ratio of Eu, Gd, Be was 1.5:15:2, the CIE coordinate was calculated as (0.34, 0.33), being located in white light range, and the relative quantum yield (η_S) was calculated to be 0.112. Therefore, this kind of luminescent material is promising for application in white light-emitting diodes.     

Dielectric properties of doped polystyrene and polymethylmethacrylate

About 1 μm thick films of polystyrene (PS) and polymethylmethacrylate (PMMA) doped with diphenylsulfoxide (DS) up to 40 wt.% were prepared from solutions using spin-coating method. Glass transition temperature (T _g) of doped polymer films was determined by DSC technique. The depth profile and surface concentration of DS dopant were measured by RBS and XPS methods, respectively. The temperature dependence of relative permittivity of the films was determined from capacitance measurement. The dependence of polarization (P) on electric field (E) was measured using a standard Sawyer–Tower circuit. The glass transition temperature T _g of both composites was found to be decreasing function of the DS concentration. The DS doping leads to an increase of relative permittivity of the PS and PMMA films. RBS and XPS measurements reveal an outward diffusion of DS dopant in PS/DS films at elevated temperature. No such effect was observed in PMMA/DS films. PMMA/DS layers were found to be more thermally stable comparing to PS/DS.     

Tensile behaviour of blends of poly(vinylidene fluoride) with poly(methyl methacrylate)

Blends of poly(vinylidene fluoride) (PVF₂) and poly(methyl methacrylate) (PMMA) were prepared over a wide concentration range and tested in tension at the same relative temperature below the glass transition. Testing was performed at strain rates ranging from 10 to 0.01 min^–1 at test temperatures fromT _g-40 toT _g-10. By normalizing the test temperature to fixed increments belowT _g, blends and homopolymers can be compared on the basis of PVF₂ and PMMA composition and crystallinity. In nearly all blends, under conditions favouring disentanglement, (decrease in strain rate, or increase in test temperature), the yield stress and drawing stress decreased while the breaking strain increased. For materials with about the same degree of crystallinity, those with a higher proportion of amorphous PVF₂ exhibited brittle-like behaviour as a result of interlamellar tie molecules. In the semicrystalline blends, yield stress remains high as the test temperature approachesT _g, whereas in the amorphous blends the yield stress falls to zero nearT _g. Results of physical ageing support the role of interlamellar ties which cause semicrystalline blends to exhibit ageing at temperatures aboveT _g.     

Synthesis and mechanical properties of cardanol-formaldehyde (CF) resins and CF-poly(methylmethacrylate) semi-interpenetrating polymer networks

Cardanol-formaldehyde (CF) resins (both novolac and resol) and CF-poly(methylmethacrylate) (PMMA) semi-interpenetrating polymer networks were synthesized and their mechanical properties and thermal transitions were evaluated. The lower tensile strength of CF resins compared to phenol-formaldehyde (PF) resins may be understood on the basis of the structure of the C₁₅ side chain imparting steric hindrance and reduction in intermolecular interactions. Interpenetration of CF with PMMA increased the mechanical properties only marginally. Scanning electron micrographs of the semi-IPNs showed two distinct phases. Thermomechanical analysis gave two glass transition temperatures,T _g, for the IPNs, the lowerT _g corresponding to the PMMA phase and the higherT _g to the CF phase. However, the unusual increase inT _g of the CF from 128°C to 144°C suggests restrictions in the segmental motion of the CF phase brought about by mixing with another rigid polymer such as PMMA.     

Quantitative characterization of clay dispersion in polypropylene-clay nanocomposites by combined transmission electron microscopy and optical microscopy

This paper presents a novel method to describe the microstructure of polymer/clay nanocomposites quantitatively. Based on the image analyses of transmission electron microscopy (TEM) and optical microscopy micrographs, two parameters, degree of dispersion (χ) and mean interparticle distance per unit volume of clay (λ_V) are proposed to describe the level of clay dispersion. The degree of dispersion gives the percentage of exfoliation, and λ_V is a measure of spatial separation between particles relative to clay loading. A polypropylene/clay system was chosen as an example to show the effects of processing conditions and biaxial stretching on clay dispersion using the proposed quantifiers. It provides insights into the ‘real’ clay dispersion using a combination of both microscopical and macroscopical aspects.     

Stability of pentacene organic field effect transistors with a low-k polymer/high-k oxide two-layer gate dielectric

This paper reports on the processing and the characterization of pentacene organic field effect transistors (OFETs) with a two-layer gate dielectric consisting of a polymer (PMMA) on a high-k oxide (Ta₂O₅). This dielectric stack has been designed in view to combine low voltage operating devices, by the use of a high-k oxide which increases the charge in the accumulation channel and the gate capacitance, and highly stable devices which generally could be achieved with polymer dielectrics but not necessarily with strongly polar high-k oxides. Bi-layer dielectric devices were compared to those with only Ta₂O₅ or PMMA gate insulators. Bias stress at room temperature was used to assess the electrical stability. A very low operating voltage was achieved with Ta₂O₅ but these devices exhibit hysteresis and degraded characteristics upon bias stress. OFETs with PMMA revealed very stable but operate at rather a high voltage due to the low dielectric constant of PMMA. Reasonably stable devices operating at about 10 V could have been obtained with PMMA/Ta₂O₅ two-layer dielectric. The origin of observed threshold voltage shift and mobility decrease upon bias stress are discussed.     

Isothermal and non-isothermal sublimation kinetics of zirconium tetrachloride (ZrCl4) for producing nuclear grade Zr

Sublimation of ZrCl₄ is important for the production of nuclear grade metallic Zr in Kroll's process. The sublimation kinetics of ZrCl₄ was investigated by thermogravimetric analysis under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl₄ increased with increasing temperature under isothermal conditions. ZrCl₄ sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl₄ sublimation under isothermal conditions was 21.7 kJ mol⁻¹. The activation energy for non-isothermal sublimation was 101.4 kJ mol⁻¹ and 108.1 kJ mol⁻¹ with the Kissinger method and Flynn–Wall–Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ mol⁻¹). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl₄ sublimation is 104.8 (±3.4) kJ mol⁻¹. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ mol⁻¹ and 21.7 kJ mol⁻¹, respectively.     

Mechanical and radiographic properties of a shape memory polymer composite for intracranial aneurysm coils

An intracranial aneurysm can be a serious condition that can go undetected until the aneurysm ruptures, causing hemorrhaging within the subarachnoid space surrounding the brain. The typical treatment for large aneurysms is by embolization using platinum coils. However, in about 15% of the cases treated by platinum coils, the aneurysm eventually re-opens as a result of the bio-inertness of platinum. One solution to this is to develop suitable materials with increased bio-activity to use as coil implants. In this research, a shape memory polymer (SMP), Calomer™, produced by The Polymer Technology Group, Inc., was investigated as a candidate for aneurysm coils. The SMP was tested to determine its thermo-mechanical properties and the strength of the shape recovery force. Composite SMP specimens containing tantalum filler were produced and tested to determine the mechanical effect of adding this radio-opaque metal. Thermo-mechanical testing showed that the material exhibited a shape recovery force a few degrees above the glass transition temperature, T_g. The effects of the addition were small and included a decrease in T_g and recovery force. SMP coils deployed inside a simulated aneurysm model demonstrate that typical hemodynamic forces do not hinder the shape recovery process. The radio-opacity of the Ta-filled material was characterized with clinical fluoroscopy.     

Synthesis and thermoelectric characterization of bulk-type tellurium nanowire/polymer nanocomposites

A simple method to fabricate three-dimensionally (3-D) aligned thermoelectric nanowires attached polymer particle was demonstrated by combination of solution casting of thermoelectric nanostructures (e.g., tellurium nanowires (Te NWs)) on the surface of thermoplastic polymer (e.g., poly(methyl methacrylate (PMMA)) microbeads followed by hot compaction of thermoplastic matrix. The percolation threshold of composite with 3-D assembled Te NWs (i.e., 3.45 vol%) significantly was lower than that of a randomly dispersed Te NWs (i.e., 5.26 vol%), which resulted in an order of magnitude greater thermoelectric figure of merit (ZT of 2.8 × 10^?3) compared to randomly dispersed Te NWs in PMMA matrix (ZT of 6.4 × 10^?4) at room temperature by enhancing the electrical conductivity without increasing thermal conductivity.     

MFC-structured biodegradable poly(l-lactide)/poly(butylene adipate-co-terephatalate) blends with improved mechanical and barrier properties

Both polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are biodegradable polymers. They are thermoplastics which can be processed using conventional polymer processing methods. In this study, microfibrillar-reinforced composites (MFC) based on PLA/PBAT (PLA/Ecoflex^®) blends in different weight ratios were prepared under industry-relevant conditions by melt extrusion followed by continuous cold drawing of the extrudates. Strip-like specimens (films) and plates (laminates) of the drawn blends were prepared by compression molding (CM) at processing temperature above the melting temperature (T _m) of PBAT, but below T _m of PLA. SEM and WAXS observations show that the extruded blend components are isotropic, but become highly oriented after drawing, and they are converted into MFC-structured polymer–polymer composites after CM. An effect of PLA microfibrils on the non-isothermal crystallization of the Ecoflex during cooling from the melt, associated with the formation of crystalline regions of the matrix around the fibrils, was observed. Depending on the blend composition, the compression-molded samples possess a 3- to 7-time higher tensile strength as well as a 15–30 higher modulus than the neat Ecoflex. In addition, the MFC-structured plates exhibited superior barrier properties compared to the neat Ecoflex, e.g., the oxygen permeability decreased by up to 5 times.     

Further development of a data reduction method for the nonlinear viscoelastic characterization of FRPs

According to the well-known Schapery’s formulation, the nonlinear viscoelastic response of any material is controlled by four stress and temperature dependent parameters, g₀ g₁, g₂ and a_σ, which reflect the deviation from the linear viscoelastic response. Based on Schapery’s formulation, a new methodology for the separate estimation of the three out of four nonlinear viscoelastic parameters, g₀, g₁ and a_σ, was recently developed by the authors. In the present article, a further development of the previously developed methodology is attempted leading to an analytical estimation of the fourth nonlinear parameter, g₂, which additionally includes the viscoplastic response of the system. Thus, a full nonlinear characterization of the composite system under consideration is achieved. The validity of the integrated model was verified through creep-recovery experiments, applied at different stress levels to a unidirectional carbon fibre reinforced polymer.     

Synthesis of bactericidal polymer coatings by sequential plasma-induced polymerization of 4-vinyl pyridine and gas-phase quaternization of poly-4-vinyl pyridine

Plasma-based technology is an alternative to produce universal polymer coatings with the appropriate requirements of robustness and stability for antibacterial applications. Here, we proposed a sequential two-step alternative to synthesize antibacterial polymer coatings. A non-isothermal plasma reactor, operated at atmospheric pressure (P_atm) and room temperature (T_room), was used to induce free radical polymerization of 4-vinyl pyridine (4VP) on high-density polyethylene (PE). In a subsequent step, the poly-4VP (P4VP) films were treated with a bromoethane/He gas stream to produce quaternized P4VP (P4VPQ) films. Chemical structure of polymer films was validated by infrared and UV–visible spectroscopy, and morphology was evaluated by optical and atomic force microscopy; scanning electron microscopy was used to determine films thickness, which was then used to estimate the surface charge density. The bactericidal capacity was determined with a standard test by using Escherichia coli. Both types of films had an estimated charge density in the order of 10¹⁶ positive charges per cm²; P4VP films removed about 95–99% of bacteria, whereas 4PVPQ films eliminated 100%. The methodology proposed for the synthesis of antibacterial polymer coatings is simpler, faster, and more environmentally friendly than other plasma-based methods; operation at T_room and P_atm may also have a significant effect on the economics and the ease of implementation of the process at commercial scale. The suggested approach may facilitate the development of new universal coatings, and operating plasma conditions could be extrapolated for engineering antibacterial coatings in industrial areas where bacterial attachment is of concern.     

Innovative one-step immobilization of TiO2 on polymer material by the sol–gel method under IL/MW conditions

An innovative one-step immobilization of titanium dioxide (TiO₂) nano-particles on organic polymer (PMMA) substrate at ambient condition is reported in this article. This immobilization can be achieved by the sol–gel method under ionic liquid/microwave heating conditions. In this method, a sol–gel reaction is conducted at specific sites of the polymer surface. These sites are the tiny cavities of the rough surface resulting from the softening and swelling effect of an alcohol, such as isopropyl alcohol, on the polymer surface under microwave irradiation. The roughness of the polymer surface is an important factor for the effective immobilization. In addition, ionic liquid can induce low temperature surface anatase crystallization of immobilized titanium dioxide in a short time. From the field emission scanning electron microscopy and energy dispersive spectroscopy observation, the TiO₂ particles could be effectively immobilized on the PMMA substrate. Raman spectra analysis data showed that the immobilized TiO₂ was anatase phase. The experimental data also shows that the immobilized TiO₂ prepared by this novel method has good immobilization stability and photocatalytic water treatment performance.