Improvements of electromechanical properties of gelatin hydrogels by blending with nanowire polypyrrole: effects of electric field and temperature

Nanowire‐polypyrrole/gelatin hydrogels were fabricated by dispersion of nanowire‐polypyrrole into a gelatin aqueous solution followed by solvent casting. The electromechanical properties, thermal properties and deflection of pure gelatin hydrogel and nanowire‐polypyrrole/gelatin hydrogels were studied as functions of temperature, frequency and electric field strength. The 0.01%, 0.1%, 0.5%, 1% v/v nanowire‐polypyrrole/gelatin hydrogels and pure gelatin hydrogel possess storage modulus sensitivity values of 0.75, 1.04, 0.88, 0.99 and 0.46, respectively, at an electric field strength of 800 V mm^?1. The effect of temperature on the electromechanical properties of the pure gelatin hydrogel and nanowire‐polypyrrole/gelatin hydrogels was investigated between 30 and 80 °C; there are three regimes for the storage modulus behaviour. In deflection testing in a cantilever fixture, the dielectrophoresis force was determined and found to increase monotonically with electric field strength. The pure gelatin hydrogel shows the highest deflection angle and dielectrophoresis force at an electric field strength of 800 V mm^?1 relative to those of the nanowire‐polypyrrole/gelatin hydrogels. Copyright © 2012 Society of Chemical Industry     

On the origin of strain hardening in glassy polymers

The influence of network density on the strain hardening behaviour of amorphous polymers is studied. The network density of polystyrene is altered by blending with poly(2,6-dimethyl-1,4-phenylene-oxide) and by cross-linking during polymerisation. The network density is derived from the rubber-plateau modulus determined by dynamic mechanical thermal analysis. Subsequently uniaxial compression tests are performed to obtain the intrinsic deformation behaviour and, in particular, the strain hardening modulus. At room temperature, the strain hardening modulus proves to be proportional to the network density, irrespective of the nature of the network, i.e. physical entanglements or chemical cross-links. With increasing temperature, the strain hardening modulus is observed to decrease. This decrease appears to be related to the influence of thermal mobility of the chains, determined by the distance to the glass-transition temperature (T−T_g).     

Large deformation and ultimate properties of biopolymer gels: 1. Single biopolymer component systems

The large deformation and ultimate properties of gelatin and agarose gels were investigated, in simple tension, as a necessary preliminary to an examination of mixed bipolymer gel systems. The underlying structure of these systems is sufficiently similar in certain respects to that of a ‘rubber-like’ network, to suggest that an analysis along these lines might be fruitful. It is found that under tensile test conditions, the factorization of strain and time dependence appears to be valid over all experimental conditions encountered. Modulus values from the initial slope of stress/strain curves confirm previously derived modulus/concentration relationships. Doubly logarithmic plots of stress at break against strain at break (‘failure envelopes’) provide a means of comparing ultimate properties as a function of polymer concentration. Since both break stress and break strain exhibit strong dependence on strain rate, minimum observed values of these quantities have been chosen to characterize the failure process.     

Experimental study of mechanical behaviour of cement paste under compressive stress and chemical degradation

This paper presents experimental investigations of mechanical behaviour of a pure cement paste subjected to compressive stresses and chemical degradation. Two series of laboratory tests have been performed: decoupled and coupled chemical-mechanical tests. Hydrostatic and triaxial compression tests have first been realized respectively on sound and chemically degraded samples. The obtained results allow the characterization of basic mechanical responses of the tested cement paste and the identification of chemical degradation effects on the mechanical behaviour. In the coupled tests, the samples are simultaneously subjected to deviatoric stresses and chemical leaching by aggressive solution flow. Variations of deformation of cement paste samples are measured during chemical degradation process. The results obtained in these tests can be used for the validation of chemo-mechanical constitutive modelling.     

Characterisation of the microstructure and deformation of high modulus cellulose fibres

This paper reports on the microstructure and deformation of one type of high modulus cellulose fibre characterised using the techniques of Raman spectroscopy and synchrotron X-ray diffraction and it compares this fibre to a lower modulus conventional viscose fibre. The crystallinity of the fibres has been determined using X-ray diffraction. The orientation parameter has been determined by measuring the width of the (200) equatorial reflections for each fibre using microfocus synchrotron radiation and it has also been shown that the crystal orientation parameter varies from the skin to core of the fibres and is different for each type. Mechanical properties of the fibres are reported and it is shown that the high modulus cellulose fibres have very different stress-strain behaviour to the viscose fibres. Finally, it is shown for the high modulus fibre that the 1414, 1260, 1095 and 895 cm⁻¹ Raman bands shift under the application of tensile deformation towards a lower wavenumber with the 1095 cm⁻¹ band giving information about the backbone chain stretching of the cellulose. The viscose fibres show less significant shifts in this peak. The crystal modulus of the high modulus cellulose fibre has also been determined by calculating the change in the c-spacing upon the application of tensile deformation to individual cellulose monofilaments. This change in the c-spacing is determined from the change in position of the (002) meridional reflection giving a crystal modulus of 77 GPa. This value is a little low compared to other published data, and reasons for this are discussed. The shear modulus between crystallites is also calculated and compared to previously published data.     

Investigation of the stress and strain state of clay pipes under fire condition

The focus of this paper is given to investigating the testing and evaluation method of stress and deformation behaviour of clay pipe elements like chimneys under cyclic high temperature. The experimental study on the temperature–time curves and on the radial deformation–temperature curves of a series of fire-resistant clay pipes was carried out. The tensile strength and the compressive strength, the elastic modulus before and after fire, the stress and deformation properties and the cracking behaviour of the clay pipes under fire conditions have been analyzed. The theoretical analysis corresponds well with the experimental results and tends to prove that the elastic deformation can be the most significant component in fixed-end clay pipes. This study is useful for evaluation of the stress–strain properties of ceramic pipes and provides a beneficial test method for the pipe member in small-scale or in full-scale tests under fire temperatures.     

Deformation behaviour during cold drawing of nanocomposites based on single wall carbon nanotubes and poly(ether ester) copolymers

Relationships between the macroscopic deformation behaviour and microstructure of a pure (PBT-b-PTMO) block copolymer and a polymer nanocomposite (PBT-b-PTMO + 0.2 wt% SWCNT) were investigated by simultaneous small- and wide-angle X-ray scattering (SAXS and WAXS) during tensile deformation using synchrotron radiation. The Young's modulus was found to be 15% higher for the nanocomposite than for the pure block copolymer as well as the yield strength, while the elongation-to-break was less than a half. This different behaviour can be explained by taking into account the different structural features revealed by SAXS and WAXS and thus considering that SWCNT act as anchors in the nanocomposite, sharing the applied stress with the PBT crystals and partially preventing the flexible, non-crystallisable PTMO chains to elongate.     

Mechanical and morphological features of agarose-guar gum gels

Summary Young's modulus, maximum rupture stress and compression energy to break values were determined for pure agarose (5g/l and 10g/l) and 1:1 agarose-guar gum mixed gels of 10g/l total polymer concentration. The enhancing effect of guar gum was noticed particularly on the tenacity parameter. Transmission electron microscopy, TEM, was used to image the supramolecular structure of 1:1 agarose-guar gum gels. Before sample preparation for TEM, the hot aqueous solutions have been submitted to slow cooling until a determined temperature was reached, and then quenched to -78°C. When this temperature was higher than the critical temperature of gelation, agarose-guar gum mixed samples formed aggregated structures, promoted by freezing. Below gelation, although guar gum continued producing aggregates, agarose appeared as continuous network structures. This result was related to the stabilizing role of guar gum.     

Numerical analysis of neck propagation in polymeric materials. Part 1 – Neck propagation behaviour of poly (ethylene terephthalate) film

Abstract

Neck formation and propagation in poly (ethylene terephthalate) (PET) films have been investigated using finite element analysis (FEA). First, the criteria for the occurrence of neck propagation are examined and a unique constitutive law for polymers is proposed. Neck propagation is associated with a steep rise of the tangent modulus in the plastic deformation region. The ability of the specimen to form a neck is determined by the ratio of the yield stress to the tangent modulus immediately after the yield point. Next, the characteristic load–displacement behaviour in neck formation and propagation is investigated using FEA. Finally, numerical results are compared with experimental data. The calculated values agree with experimental data on load–displacement behaviour, especially for the decrease in load immediately after yield. An apparent constitutive law representing the load–displacement behaviour of PET film has been successfully obtained. By comparing the experimental results with numerical predictions of the neck localisation and propagation process, it is shown that the decrease in load is related to the recovery of deformation in the region outside the neck.     

Influence of porosity on the mechanical behaviour of single phase β-TCP ceramics

Processing and mechanical behaviour of fine grained (diameter ≈0.5–3 µm) and pure β-TCP materials with different levels of porosity (up to 19%) is described. Pores with diameters, d₅₀ ≈13–14 µm were formed fromcorn starch during sintering. Comprehensive mechanical characterisation –Young´s modulus, strength and toughness– has been done paying special attention to toughness determined in stable fracture tests. The dependence of Young´s modulus and strength with porosity was well fitted to the minimum solid area models while toughness values did not. The competitive processes occurring during fracture impede the degradation of toughness associated to the decrease in Young´s modulus as porosity increases. Materials present similar values of the critical energy release rate G_IC, which describes crack initiation. A maximum of the specific fracture energy, G_F, which averages crack propagation, has been obtained for the material with the highest porosity.     

Rheological non-Newtonian behaviour of ethylene glycol-based Fe2O3 nanofluids

The rheological behaviour of ethylene glycol-based nanofluids containing hexagonal scalenohedral-shaped α-Fe₂O₃ (hematite) nanoparticles at 303.15 K and particle weight concentrations up to 25% has been carried out using a cone-plate Physica MCR rheometer. The tests performed show that the studied nanofluids present non-Newtonian shear-thinning behaviour. In addition, the viscosity at a given shear rate is time dependent, i.e. the fluid is thixotropic. Finally, using strain sweep and frequency sweep tests, the storage modulus G'', loss modulus G″ and damping factor were determined as a function of the frequency showing viscoelastic behaviour for all samples.     

A gelatin/PLA-b-PEG film of excellent gas barrier and mechanical properties

A polylactic acid-polyethylene glycol block copolymer (PLA-b-PEG) was used as an additive to prepare gelatin/PLA-b-PEG blend films for the first time. The PEG molecule block enhanced the compatibility of the PLA molecule block with gelatin, which greatly improved the excellent mechanical and gas barrier properties of the gelatin film. The film contained 5 wt% PLA-b-PEG possessed the highest tensile strength and the highest elastic modulus. When the PLA-b-PEG content further increased to 20 wt%, the tensile strength, elastic modulus and elongation at the break of the blend film were all higher than pure gelatin film, suggesting that the gelatin/PLA-b-PEG blend film was pliable and tough. The blend film possessed not only excellent oxygen barrier property, but also a much-improved water barrier property. The degradation rate of the blend film was elongated controllably by regulating the content of the PLA-b-PEG copolymer. The blend film showed great potential in the application of food packaging.     

Dynamic mechanical behaviour and longitudinal crystal thickness measurements on ultra-high modulus linear polyethylene: a quantitative model for the elastic modulus

In this paper the dynamic mechanical behaviour of ultra-high modulus polyethylene is reported. The results are discussed in terms of a fibre reinforced composite model, in which the amount of fibre phase is related to the number of intercrystalline bridges determined from X-ray diffraction data. For both drawn and extruded materials a good correlation has been obtained between the plateau modulus at ?50°C and the longitudinal crystal thickness. This correlation is given a quantitative interpretation in terms of the model and the increase in modulus with increasing deformation ratio is ascribed to an increase in continuity of the crystalline phase. The increase in tensile modulus on cooling through the γ-process is related primarily to the change in the tensile modulus of the amorphous phase. The fall in modulus at high temperature, on the other hand, indicates a fall in the shear modulus of the crystalline phase, which provides a satisfactory explanation of the α-process.     

Thermogelling polysaccharides for aqueous gelcasting—part III: mechanical and microstructural characterization of green alumina bodies

The use of gelling additives, such as polysaccharides, in colloidal processing provides adequate mechanical properties to the green bodies to be handled. In this work, the green density and the mechanical behaviour (stress–strain relationships, elastic modulus, bend strength and fracture mechanism) at room temperature of gelcast alumina bodies are studied, in order to establish the influence of the type and the concentration of additive. Furthermore, the previous concentration of polysaccharide solutions is also taken into account as an important variable. Agar, agarose and carrageenan were used as gelling additives. Values of the bend strength up to 4 MPa are obtained, significantly higher than those corresponding to slip cast alumina without gelling additives, and they increase with the final concentration of polysaccharide, while Young's modulus values are mainly influenced by the concentration of additive in the precursor solution. For bodies with a large final concentration of additive, extensive plastic deformation during fracture is observed.     

Uniaxial compaction behaviour and elasticity of cohesive powders

The compression and compaction behaviour of bentonite, limestone and microcrystalline cellulose (MCC) — three cohesive powders widely used in industry were studied. Uniaxial compression was performed in a cylindrical die, 40 mm in diameter and 70 mm high, for three selected cohesive powder samples. The initial density, instantaneous density and tablet density were determined. The influence of maximum pressure and deformation rate was examined. The secant modulus of elasticity E_sec was calculated as a function of deformation rate v, maximum pressure p and powder sample. After compaction experiments in hydraulic press at three pressures - p = 30, 45 and 60 MPa - and two different deformation rates, the strength of the produced tablets was examined in a material strength testing machine.From uniaxial compression tests performed on the universal testing machine for loading and unloading, the modulus of elasticity E was calculated on the basis of the first linear phase of unloading. The total elastic recovery of tablets was also obtained.     

Gelatin shells strengthen polyvinyl alcohol core–shell nanofibers

In this study, polyvinyl alcohol (PVA) and gelatin are coaxially electrospun into core–shell nanofibers to derive mechanical strength from PVA and bioactivity from gelatin. The core–shell nanofibers with PVA in the core and gelatin in the shell display an increased Young's modulus, improved tensile strength, and reduced plastic deformation than PVA nanofibers. When the order of gelatin and PVA is reversed in the core–shell nanofibers, however, the mechanical strengthening effects disappear. It thus suggests that the bioactive yet mechanically weak gelatin shell improves the molecular alignment of PVA in the core and transforms the weak, plastic PVA into a strong, elastic PVA. The use of a gelatin shell as a biological coating and a protecting barrier to strengthen the core in electrospinning presents a new strategy for fabricating advanced composite nanofibers.     

A study of the large strain deformation and failure behaviour of mixed biopolymer gels via in situ ESEM

A mixed biopolymer gel, consisting of a protein (gelatin) and polysaccharide (maltodextrin) mixture has been investigated. By controlling the composition it was possible to construct an ‘emulsion-like’ structure, with included spherical particles of one phase (maltodextrin) within a continuous matrix of the second (gelatin). Large strain deformation and failure behaviour of this system has been examined via in situ environmental scanning electron microscopy (ESEM). ESEM has been employed to explore the changes in the structure of the material, whilst allowing the sample to stay hydrated as it was subjected to tensile strain, thereby allowing simultaneous imaging and determination of stress-strain data of the native sample. Ductile behaviour was observed, which has been attributed to the stretching, tearing and fracture of gelatin ligaments and debonding at the interface between the maltodextrin particles and continuous gelatin matrix. Deformation and fracture of the maltodextrin particles during tensile testing was also observed. The interfacial fracture energy of the composite has been calculated following an elastomer composite-debonding model, although there are several limitations to this approach for the mixed gel. It was found in samples tested after different ageing times that the debonding stress and strain was decreasing with ageing leading to a lower interfacial fracture energy. Samples were also tested after successive loading cycles, which resulted in a mechanical strength decrease after each cycle.     

Preparation and Characterization of Bioblends from Gelatin and Linear Low Density Polyethylene (LLDPE) by Extrusion Method

Abstract

Bioblends are composites of at least one biodegradable polymer with a non-biodegradable polymer. Successful development of bioblends requires that the biodegradable polymers be compatible with other component biodegradable/synthetic (non-biodegradable) polymers. Bioblends from LLDPE and gelatin were prepared by extrusion and hydraulic heat press technique. The gelatin content in the bioblends was varied from 5 to 20 wt%. Various physico-mechanical properties such as tensile, bending, impact strength (IS), thermal ageing and soil degradation properties of the LLDPE/gelatin bioblends with different gelatin contents were evaluated. The effect of thermal ageing on mechanical properties was studied. The mechanical properties such as tensile modulus (TM), bending strength (BS), bending modulus (BM) were found to increase with increasing gelatin content up to 20 wt%, however tensile strength (TS) and elongation at break (%E _b) were decreased with increasing gelatin content. Impact strength value increased with increasing gelatin content up to 10 wt% and then decreased slightly with increasing gelatin content. The blend containing 20 wt% gelatin showed relatively better mechanical properties than other blends. The values of TS, TM,%E _b, BS, BM and IS for the bioblend with 20 wt% gelatin content are 5.9MPa, 206.3MPa, 242.6%, 12.1MPa, 8 MPa and 13.7 J/cm², respectively. Water uptake increases with increasing soaking time in water and weight loss due to soil burial also increases with increasing gelatin content in the blends but both are significantly lower than that of pure gelatin sheet. Weight loss values after thermal ageing increase with time, temperature and increasing gelatin content in the blend but are much lower than pure gelatin. Mechanical properties such as TS, TM are increased and %E _b is decreased after thermal ageing at 60°C for 30 min. Consequently, among all of the bioblends prepared in this work the blend having 20% gelatin content yields properties such that it can be used as a semi-biodegradable material.     

Mechanical properties and characterisation of very thin CNx films synthesised by IBAD

Nanoindentation has been used to investigate the mechanical properties of very thin (<1 μm) CN_x films deposited by IBAD in order to understand the variation of properties with process parameters. The structural features of the films were characterised by EELS, XPS and ERDA. Examining the load–displacement (P–δ) curves in detail revealed a number of film responses such as pure elastic behaviour, densification and elastic-plastic deformation. The film-only hardness was calculated using a recently developed energy based model while the Hertzian contact analysis and laser-acoustic measurements were used to determine the Young's modulus. Generally, the film hardness and modulus exhibit two different regimes depending on the deposition parameters. Films deposited at high temperature contain less nitrogen and have lower hardness and Young's modulus than those deposited at room temperature. All films examined displayed P–δ curves exhibiting unusually large elastic recovery (80% or more) during unloading. Because of this, resultant indentation sizes always appear to be very small thus apparently producing very high hardnesses. However, our results clearly establish that the film behaviour is better viewed as that of a ‘super-hard rubber’ in which a large proportion of the contact load is supported elastically.     

Large deformation mechanical behavior of gelatin–maltodextrin composite gels

The large deformation failure behavior of gelatin–maltodextrin composite gels was assessed. All the studied compositions were selected to lie within the incompatibility domain of the gelatin–maltodextrin phase diagram at 60°C, which produced gelatin continuous (maltodextrin included) and maltodextrin continuous (gelatin included) composites. Composite microstructural evaluation was performed using confocal laser scanning microscopy (CLSM). The large deformation mechanical behavior was measured in tension and compression experiments. Crack–microstructure interactions were investigated by dynamic experiments on the CLSM. The gelatin continuous composites exhibited pseudo-yielding behavior during tension and compression testing, and there was a significant decrease in modulus that arose from interfacial debonding. Conversely, the maltodextrin continuous composites exhibited an essentially brittle failure behavior, and there was an approximately linear increase in stress with increasing strain until fracture (which occurred at significantly lower strains than for the gelatin continuous composites). The CLSM observation of the failure of the notched samples also demonstrated interfacial debonding in the crack path; however, this occurred at significantly smaller strains than for the gelatin continuous samples with minimal elastic–plastic deformation of the maltodextrin matrix. The Poisson ratio was estimated to be close to 0.5 for these composites for all examined compositions. Compositions corresponding to a tie line of the phase diagram were also investigated to assess the influence of the relative phase volume (for constant phase compositions) on the failure behavior. The majority of the parameters subsequently extracted from the stress–strain curves were apparently functions of the individual phase volumes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 124–135, 2001