Elastic moduli of a liquid crystalline polymer and its in-situ composites

The elastic moduli of a liquid crystalline polyesteramide (LCP) and polycarbonate/LCP in-situ composites with 10 to 80 wt% of LCP have been measured as functions of draw ratio λ from 1 to 15 by an ultrasonic method. For the LCP, the sharp rise of the axial Young's modulus E₃ and the slight decreases of the transverse Young's modulus E₁ and the axial (C₄₄) and transverse (C₆₆) shear modulus with increasing λ result from the alignment of chains along the draw direction. E₁, C₄₄, and C₆₆ follow the lower bounds calculated using the series coupling scheme of the aggregate model. Although E₃ lies close to the lower bound at low λ, it follows the upper bound calculated according to the parallel coupling scheme at λ > 3. The elastic moduli of the composites have similar draw ratio dependences as those of the LCP. The strong increase in E₃ with increasing λ arises from the higher aspect ratio of the LCP domains in the composites and the improved molecular orientation within the domains. The reinforcement effect on the other moduli is much weaker, with E₁ and C₄₄ of the composites only 5 to 30% higher than those of polycarbonate at λ = 15. Since C₆₆ of the LCP decreases to a value below that of polycarbonate at λ > 2, there is a positive reinforcement effect at low λ but a negative effect at high λ.     

Mechanical relaxations and moduli of oriented semicrystalline polymers

A systematic investigation was carried out on the mechanical relaxations and moduli of four drawn semicrystalline polymers: polyoxymethylene, polypropylene, polyvinylidene fluoride and polychlorotrifluoroethylene. Low-frequency tensile and torsional measuremnts were made between-140 and 140°C, and ultrasonic measurements of all five moduli were made by the water-tank method between 0 and 60°C. The patterns of relaxations remain essentially unchanged upon orientation, but there is a marked reduction of the height of relaxation peaks associated with the amorphous phase and, correspondingly, a smaller drop of moduli in the relaxation region. This reflects a lowering of molecular mobility in the amorphous phase due to the constraining effect of taut tie-molecules. The modulus C₃₃ increases sharply with draw ratio λ while the other moduli show little variation, which result from the alignment of molecular chain axes and the production of taut tie-molecules. The λ-dependence of the moduli is consistent with the aggregate model only when the polymer is glassy, that is, when its amorphous phase is comparable in stiffness to the crystalline phase and the polymer can reasonably be regarded as a one-phase material for which the aggregate model is valid.     

Mechanical properties of crosslinked polyurethanes

Stress–strain and stress–relaxation behavior of polyurethane elastomers based on poly(ethylene adipate), poly(ethylene maleate), polyethylene glycol, and 4,4′-diphenylmethane diisocyanate (MDI) have been studied. The elastomers were crosslinked by an excess of MDI and by dicumyl peroxide (DiCup); the latter was supposed to form additional crosslinks on the unsaturated bonds. The determined values of Young's modulus, Mooney-Rivlin elastic parameters C₁ and C₂, relaxation moduli E(10 sec) and E(100 sec), as well as relaxation speed were used to estimate the effect of MDI- and DiCup-formed crosslinks on the mechanical behavior of polyurethanes. It was found that while the elastomers crosslinked by MDI only apparently displayed viscoelastic properties, the polyurethanes additionally crosslinked by DiCup exhibited more elastic behavior. The results obtained were explained on the basis of changes in the amount of secondary bonding due to the additional network junctions formed by DiCup at nonpolar groups.     

Influence of temperature on the microstructure and mechanical properties of stretched polypropylene

Microstructure and mechanical properties of isotactic polypropylene (iPP) stretched at different temperatures were studied. Strain‐induced fibrils were observed after stretching. Crystallinity (X_c), crystallite thickness (L_c), long period (L_pf), and diameter (D_f) of fibrils were characterized by Differential Scanning Calorimetry and Small angle X‐ray scattering. L_pf of stretched iPP below 60°C was found to be lower than undrawn iPP. X_c, L_c, and D_f increased with increasing draw temperature. Tensile test showed that Young's moduli of stretched iPPs were negatively dependent on X_c and L_c. The fraction of taut tie molecules was estimated from the mechanical model. Results showed that more tie molecules were formed in the samples stretched at lower temperatures. Dynamical mechanical analysis showed that glass transition temperature was strongly dependent on the draw temperature. The glass transition peak disappeared in stretched iPPs obtained below 80°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42622.     

The effect of aspect ratio of inclusions on the elastic properties of unidirectionally aligned composites

This paper examines the influence of aspect ratio α, from zero to infinity, on the effective elastic moduli of a transversely isotropic composite. The reinforcing inclusions, which could be flakes or short fibers, are assumed to be spheroidal and unidirectionally aligned. Of the five independent elastic constants, the longitudinal Young's modulus E₁₁ and in-plane shear modulus μ₁₂ appear to increase with increasing aspect ratio, while the transverse Young's modulus E₂₂, out-plane shear modulus μ₂₃, and plane-strain bulk modulus K₂₃, generally decrease. It is further noted that E₁₁ is more sensitive to α when α > 1 but the others are more so when α < 1. The present analysis was carried out by the combination of Eshelby's and Mori-Tanaka's theories of inclusions.     

Effect of morphology on stress relaxation of polypropylene

Samples of isotactic polypropylene having different morphologies and crystallinities were prepared and subjected to stress-relaxation experiments at different levels of strain. The relaxation moduli were determined in the range of temperature between – 20 and 40°C over a period of time from 1 to 1000 seconds. Using the time-temperature superposition principle, the activation energy values of the shift factors a_T were determined and the master curves were obtained for the various structures. Increasing crystallinity and/or crystalline aggregate size increases the relaxation modulus of the material and changes both shape and location of the spectrum of relaxation times so that no simple method can be found to correlate the various master curves.     

Mechanical anisotropy in oriented polychlorotrifluoroethylene

The dynamic tensile modulus (E) and loss (tan δ) of various oriented samples of polychlorotrifluoroethylene have been measured at 0°, 45° and 90° to the draw direction over the range of ? 100 to 160°C. For the cold-drawn samples the mechanical anisotropy at the lowest temperature is determined by the overall chain orientation resulting in E₀ >E₄₅ >E₉₀. Above the γ relaxation (20°C) a shear process is activated leading to a change in the anisotropy pattern to E₀ >E₉₀ >E₄₅. Cold-drawing followed by annealing gives rise to further changes so that E₉₀ >E₀ >E₄₅ above the β relaxation (120°C). The effect of annealing has been attributed to the relaxation of the amorphous regions and the development of lamellar texture, and the anisotropy in tan $\text{δ}\text{E}$ at the β relaxation is found to be consistent with the interlamellar shear model.     

Roller drawing of polyoxymethylene

The roller drawing of polyoxymethylene (POM) sheets was carried out in the temperature range of 140–157°C. The mechanical properties, the molecular orientation, and the microstructure of the roller-drawn POM sheets were investigated by means of tensile test, dynamic viscoelasticity, wide-angle X-ray diffraction, small-angle X-ray scattering, visible dichroic spectrum, electron microscopy, and so on. The Young's modulus and the tensile strength increased with increasing draw ratio up to draw ratio, λ of 14–15. The improvement of the mechanical properties is concerned with structural changes, such as the increase in orientation function in the crystalline and amorphous regions and the formation of taut tie molecules and crystalline bridges in the intercrystallite and interfibrillar regions. In the higher draw ratio range (λ > 15), the increase in Young's modulus and tensile strength was restricted by the formation of interfibrillar microvoids.     

Dynamic mechanical signatures of Viton A and plastic bonded explosives based on this polymer

The complex shear moduli of the fluorelastomer Viton A and four plastic bonded explosives LX‐04, LX‐07, LX‐10, and LX‐11, which use this polymer as a binder, have been investigated. LX‐10, LX‐07, LX‐04 and LX‐11 are composites of 94.5, 90, 85 and 80% 1, 3, 5, 7‐tetranitroazacyclooctane (HMX) explosive, respectively, and Viton A. Viton is a random copolymer of 7 vinylidene fluoride and 2 perfluoropropene monomers. In the temperature range from ?150 to 120°C, two relaxations, the β relaxation at ?80°C and the glass transition at ?22°C, were observed as peaks in the loss modulus in Viton A at 0.1 Hz. A third relaxation, T_α, was found above T_g in all four explosive formulations. The plastic bonded explosives (PBX's) showed antiplasticization phenomena. T_g of the explosives increased 2–3°C as the concentration of binder was reduced in 5% steps. Samples from the same original lot of LX‐04 were evaluated after 20–23 years of service. The alpha relaxation occurred at 60°C as a peak in the loss modulus at 1 Hz. Both the beta and alpha relaxations were very broad and an accurate maximum for these relaxations was difficult to determine.     

Dynamic mechanical analysis of fibers. I. Effect of experimental variables and material type

Depending upon the fiber material, some of the experimental variables can have a profound effect on the dynamic tensile modulus vs. temperature data. With the use of an experimental fiber (25°C < T_g < 75°C; T_m > 220°C; hot stretched), the effect of several variables, e.g., moisture/volatiles, annealing/relaxation, frequency (strain rate), pretension, and % strain on the modulus retention term [(E_100°C/E_25°C) × 100] have been studied. Of these variables, pretension and especially % strain dramatically increase the modulus retention and this effect is attributed to the elastic orientation under force (EOF), i.e., it exists only in the presence of tensile forces and is reversible. Such an effect was insignificant for Kevlar (T_g ? 375°C) and absent for steel wire. Dynamic modulus measurements at 25°C using sonic techniques also support the EOF phenomenon in polyethylene yarns (T_g ～ ?30°C) but not in Kevlar polymide yarns (T_g ～ 375°C).     

X-ray investigations on annealed fibers of poly(p-phenylene-1,3,4-oxadiazole)

The influence of annealing on the supermolecular structure of commercial, thermostable fibers, spun from solutions of poly(p-phenylene-1,3,4-oxadiazole) (POD) in H₂SO₄, is examined. The crystalline α-modification of thermally treated POD fibers has an orthorhombic unit–cell probably of space group P2₁2₁2₁. The symmetry of the single POD chain in these crystallites is 2₁. The unit–cell dimensions are a = 1.235 nm, b = 0.655 nm, c = 1.40···1.47 nm, where c depends on the annealing temperature T_a. The unit cell contains 4 chains of two monomers each. Annealing up to T_a of about 755 K causes increases in crystallite size, crystalline orientation, and linear degree of order, combined with an improved axial Young's modulus E. Thermal degradation at higher temperatures leads to the breaking of tie molecules in general, while UV-radiation selectively damages tie molecules that are not taut.     

Relationship between orientation of amorphous chains and modulus in highly oriented polypropylene

By using oriented polypropylene prepared by forced quenching in a zone-drawing-type apparatus, the effect of taut tie molecules on the modulus is studied by measuring the changes of superstructure with an increasing draw ratio and the temperature at which the oriented polypropylene was annealed. Superstructure is analyzed by means of an x-ray method, differential scanning calorimetry, thermal shrinkage, birefringence, and infrared spectrum. Modulus increases with an increasing orientation function of amorphous chains, ?_a, and is decided only by the value of ?_a, so long as the higher value of orientation function of the crystal c axis does not change with the draw ratio or annealing. The taut tie molecules in ultrahigh-modulus polypropylene are loosened by annealing at temperatures below 420 K, but would be incorporated into folded lamellar crystals above the annealing temperature of 420 K. The taut tie molecules does not always have a 3₁ helix conformation.     

Production and properties of highly oriented polypropylene by die drawing

A comprehensive examination of the die-drawing behavior of polypropylene has been carried out, examining the effects of draw temperature, haul-off speed, and initial billet size. A range of oriented products was obtained and characterized, primarily by the determination of Young's modulus at room temperature, the maximum modulus being 20 GPa for a draw ratio R_A of 23.2. Using a large-scale machine, it was found possible to produce drawn products at speeds up to 2 m min^?1 at a draw temperature of 155°C and R_A of 19.3. The dynamic mechanical behavior of several drawn materials was studied over the temperature range ?30 to +80°C. It was of particular interest that the β relaxation was found to be absent in samples of high draw ratio.     

Structure-property relationships of chlorinated polyethylenes

This experimental study of suspension-chlorinated linear polyethylenes (CPE), (degree of chlorination 25 to 48% Cl), covers dynamic mechancial behavior at 3.5 and 110 Hz in the temperature range ? 100 to 120°C. The semicrystalline samples, with a maximum degree of crystallinity of 25%, showed the main relaxations α and β. The effect of thermal treatment was examined. In the amorphous specimens, in addition to the Tg relaxation, other low temperature damping peaks were observed. The mechancial spectra indicate structure heterogeneity and increasing stiffness with increasing chlorine substitution. For the most prominent β relaxation, the apparent activation energy was determined from the frequency shift of tan δ and E″ maxima. The effect of structure, crystallinity and frequency on Young's moduli are also discussed. For the amorphous γ ray-Crosslinked elastomeric samples the photoelastic properties were examined at near equilibrium conditions between 30° and 80°C at various degrees of crosslinking. The polarizability anisotropy of the optical link and the Mooney-Rivlin elasticity constants were determined and an attempt was made to relate the result to the specimens' structure. A compatibility study was also made for a 42% Cl, CPE/high cis polybutadiene polyblend. The damping mechanical spectra indicate a noninteracting system whose Young's moduli can be correlated with those of the pure components using a phenomenological model proposed by Takayanagi.     

The elastic property of polyvinyl alcohol gel with boric acid as a crosslinking agent

The elastomers of polyvinyl alcohol gel were made from the polyvinyl alcohol polymer, with boric acid added as a crosslinking agent, in the mixed solvent of dimethyl sulfoxide and water. From the experimental results, the viscosity of polyvinyl alcohol solution is found to increase not only with an increment of boric acid content, but also with the temperature in the range of 70°C ∼ 100°C, although the viscosity is decreased in the range of 30°C ∼ 70°C. Moreover, the molecular mass between junctions of polyvinyl alcohol gel is calculated from the rubber elastic theory and found to be decreased with the increment of boric acid content. We also evaluated the values of Young's modulus of polyvinyl alcohol gel, E, E*, and the elastic parameters C₁ and C₂ of the Mooney‐Rivlin equation, according to Hook's law and theory of rubber elasticity. Based on these, the polyvinyl alcohol gel behaves as a good rubberlike elastic property. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3046–3052, 1999     

Hybrid‐filler filled polypropylene/(natural rubber) composites: Effects of natural weathering on mechanical and thermal properties and morphology

Comparison was made between the properties of recycled newspaper (RNP)/carbon black (CB) and recycled newspaper (RNP)/silica hybrid filled polypropylene (PP)/natural rubber (NR) composites. The properties studied were mechanical, thermal, and morphological. These composites were also subjected to natural weathering, i.e., the tropical climate in Penang, Malaysia, for 6 months. The incorporation of CB and silica at all weight ratios of RNP/CB and RNP/silica hybrid gave increases in tensile strength, elongation at break (E_B), Young's modulus, melting temperature (T_m), heat of fusion of composites (ΔH_f(com)), crystallinity of composites (X_com), and the crystallinity of PP (X_PP). As expected, the tensile properties (except for Young's modulus), T_m, ΔH_f(com), X_com, and X_PP of the composites exhibited lower values after weathering than before weathering. The extent of chemical degradation was studied by Fourier transform infrared spectroscopy, and the results showed the formation of several functional groups, i.e., hydroxyl, hydroperoxide, vinyl, carboxylic acid, and ketone. At the same filler weight ratio, the composites filled with RNP/CB hybrid showed higher values of tensile strength and E_B but lower values of Young's modulus, ΔH_f(com), X_PP, and X_PP, as compared to those with the RNP/silica hybrid under weathering conditions. The good retention in tensile properties indicated that the replacement of RNP by CB and silica improved the weatherability performance of the PP/NR composites. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers     

Dynamic young's and shear moduli of graphite fiber-reinforced high-temperature matrix resins

The resonant frequencies of unidirectional graphite fiber-reinforced polyimide (Skybond 703) and polyquinoxaline resin composite beams were determined. The Timoshenko beam theory was employed to compute both the longitudinal Young's modulus (E₁₁) and the effective transverse-longitudinal shear modulus (G₁₂) from the set of resonant frequencies of the beams. E₁₁, E₂₂, and G₁₂ were determined for a 64% by volume Modmor II-reinforced polyimide (Skybound 703) composite, and E₁₁ and G₁₂ were determined for cured and postcured Modmor II-reinforced polyquinoxaline (PQ) composites. Dynamic E₁₁ and E₂₂ results were found to agree with experimentally determined static flexural moduli. Voids present in these high-temperature resin composites to an extent of 5–13% by volume appeared to lower the effective shear and longitudinal moduli of the composites.     

Mixed monolayer and mixed micelle formation in binary mixture of surfactants—Systems for trioxyethylenated dodecyl sulfonate and some polyoxyethylenated fatty alcohol ether nonionic surfactants

The interaction and synergism of some polyoxyethylenated fatty alcohol ether (POE) nonionic surfactants (C₁₂E₂, C₁₂E₃, C₁₀E₅, C₁₀E₇, where C_x indicates number of carbon atoms in the chain and E_y indicates number of oxyethylene glycol ethers) with trioxyethylenated dodecyl sulfonate (C₁₂E₃S) in mixed monolayer formation at the surface and in mixed micelle formation in aqueous solutions were studied at 25 and 40°C by calculating interaction parameters (β_α, β_M) from surface tension-concentration data by use of Rosen's equations based on the nonideal solution theory. All the systems investigated adapt reasonably well to the nonideal model, with negative values of β_σ and β_M (where M means micelle and σ refers to the air-liquid interface) indicating a favorable interaction between the mixed surfactants. Either at a monolayer or in a mixed micelle, the attractive interaction becomes stronger when the alkyl chain in the POE surfactant is longer, i.e., when the POE becomes more hydrophobic. The interaction increases in the order C₁₀E₇<C₁₀E₅<C₁₂E₃, C₁₂E₂. For the two C₁₀E _n (n= 5,7)/C₁₂E₃S systems, as temperature increases from 25 to 40°C, the interaction increases in a mixed micelle, but it decreases in a mixed monolayer. Synergism in mixed micelle formation exists for C₁₂E₃S/C₁₀E _n mixtures when X₁ ^M , the mole fraction of POE in a mixed micelle, is ≈0.4–0.8, whereas synergism does not occur in the systems of C₁₂E₃S/C₁₂E _m due to the large difference between CMC₁ and CMC₂, i.e., large |In(C ₁ ^M /C ₂ ^M )| value (where CMC=critical micelle concentration). The degree of synergism in mixed micelle formation is temperature independent and is 0.23, 0.18, and close to zero for C₁₀E₅/C₁₂E₃S, C₁₀E₇/C₁₂E₃S, and C₁₂E _m (m=2,3)/C₁₂E₃S systems, respectively. Synergism in surface tension reduction effectiveness occurs in C₁₂E₃S/C₁₂E₂ and C₁₂E₃S/C₁₂E₃ systems. The mole fractions of POE in the solution phase are 0.302 and 0.333 for the two mixtures at the point of maximum synergism.