Crosslinking characterization of a polyimide: AFR700B

Crosslinking in AFR700B polyimide was studied using several techniques. Crosslinking could not be detected using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). Swelling in n-methyl pyrrolidone (NMP) showed network formation occurs at cure temperatures ≥325°C (617°F), but the reaction kinetics could not be determined from the data. Dynamic mechanical analysis (DMA) studies have shown that the storage modulus (G′) increased with increasing cure temperature up to 350°C (662°F), and was constant above 350°C (662°F), indicating that crosslinking via the reverse Diels-Alder reaction was occurring. A broad secondary transition was seen in the loss modulus (G″) curves, centered between 150 and 180°C (302 and 356°F). This secondary transition appeared at a cure temperature of 300°C (572°F) and became more dominant with increasing temperature and time. This secondary transition was not seen for cures <300°C (572°F) when the chains have not crosslinked. Therefore, this is likely due to a crosslink bond rather than one in the backbone. At 1 atm, crosslinking followed second-order kinetics based on the increase in glass transition temperature (T_g). The Arrhenius plot of the rate constant showed a break in the slope, possibly indicating a change in reaction mechanism. At 1.38 MPa (200 psi), the T_g data was too scattered to determine the kinetics.     

Nonisothermal crystallization kinetics and morphology of self‐seeded syndiotactic 1,2‐polybutadiene

Subsequent melting behavior after isothermal crystallization at different temperatures from the isotropic melt and nonisothermal crystallization kinetics and morphology of partially melting sPB were carried out by differential scanning calorimetry (DSC), polarized light microscopy (POM), respectively. Triple melting‐endothermic peaks were observed for the polymer first isothermally crystallized at temperatures ranging from 141 to 149°C, respectively, and then followed by cooling at 10°C/min to 70°C. Comparing with the nonisothermal crystallization from the isotropic melt, the nonisothermal crystallization for the partially melting sPB characterized the increased onset crystallization temperature, and the sizes of spherulites became smaller and more uniform. The Tobin, Avrami, Ozawa, and the combination of Avrami and Ozawa equations were applied to describe the kinetics of the nonisothermal process. Both of the Tobin and the Avrami crystallization rate parameters (K_T and K_A, respectively) were found to increase with increase in the cooling rate. The parameter F(T) for the combination of Avrami and Ozawa equations increases with increasing relative crystallinity. The Ziabicki's kinetic crytallizability index G_Z for the partially melting sPB was found to be 3.14. The effective energy barrier Δ? describing the nonisothermal crystallization of partially melting sPB was evaluated by the differential isoconversional method of Friedman and was found to increase with an increase in the relative crystallinity. At the same time, Hoffman‐Lauritzen parameters (U and K_g) are evaluated and analyzed from the nonisothermal crystallization data by the combination of isoconversional approach and Hoffman‐Lauritzen theory. The K_g value obtained from DSC technique was found to be in good agreement with that obtained from POM technique. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1479–1491, 2006     

Rheokinetical behavior of melamine-formaldehyde resins

The effects of cure temperature and amount of catalyst on the rheokinetical behavior of a melamine-formaldehyde (MF) thermosetting system is investigated using a dynamic mechanical technique similar in nature to Torsion Impregnated Cloth Analysis (TICA) and Torsional Braid Analysis (TBA). The proposed name of the used technique is Torsional Substrate Analysis (TSA). Isothermal cures of the resin are carried out from 115°C to 160°C for varying amounts of catalyst. Each TSA measurement exposes several transitions. First, a glass-to-liquid transition during the heatup procedure is seen, indicated by sharp peaks of the loss shear modulus, G″, and loss tangent, tanδ. Later, vitrification is seen, indicated by a second G″ maximum. Finally, a completion of shift to a diffusion controlled cure reaction occurs, shown as a storage shear modulus, G′, plateau. The rheokinetical data is used to construct Time-Temperature-Transformation (TTT) cure diagrams, for each level of catalyst. High pressure differential scanning calorimetry (HPDSC) measurements are carried out in order to estimate the fractional conversion of samples that have been cured isothermally for times corresponding to a second tanδ maximum, the second G″ maximum, and the G′ plateau. The fractional conversion is determined by the residual entalphy technique. The HPDSC measurements do not give a clear answer whether the second tanδ maximum corresponds to gelation or not. It is therefore likely that TSA, like similar techniques, is not capable to detect gelation. A glass transition temperature of 130°C and 150°C is found to correspond to a fractional conversion of 0.65 and ～0.80, respectively. Preliminary measurements suggest that the maximum glass transition temperature, T_{g ∞}, of the investigated MF resin is at least 180°C.     

Effects of reaction and cure temperatures on morphology and properties of poly(ester‐urethane)

Poly(ester‐urethane) was synthesized from poly(ethylene glycol adipate) (PEG) and 2,4‐toluene diisocyanate (TDI) to study the effects of reaction temperature and cure temperature on the crystallization behavior, morphology, and mechanical properties of the semicrystalline polyurethane (PU). PEG as soft segment was first reacted with TDI as hard segment at 90, 100, and 110°C, respectively, to obtain three kinds of PU prepolymers, coded as PEPU‐90, PEPU‐100, and PEPU‐110. Then the PU prepolymers were crosslinked by 1,1,1‐tris (hydroxylmethyl) propane (TMP) and were cured at 18, 25, 40, 60, and 80°C. Their structure and properties were characterized by attenuated total reflection Fourier transform infrared, wide‐angle X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis, and tensile testing. With an increase of the reaction temperature from 90 to 100°C, the crystallinity degree of soft segment decreased, but interaction between soft and hard segments enhanced, leading to the increase of the glass transition temperature (T_g) of soft domain and tensile strength. When the cure temperature was above 60°C, miscibility between soft and hard segments of the PEPU films was improved, resulting in relatively low crystallinity and elongation at break, but high soft segment T_g and tensile strength. On the whole, all of the PEPU‐90, PEPU‐100, and PEPU‐110 films cured above 60°C possessed higher tensile strength and elongation at break than that of the films cured at other temperatures. The results revealed that the reaction temperature and cure temperature play an important role in the improvement of the crosslinking structure and mechanical properties of the semicrystalline PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 708–714, 2006     

Effects of glass bead content and surface treatment on viscoelasticity of filled polypropylene/elastomer hybrid composites

The dynamic mechanical properties of A‐glass bead filled polypropylene (PP)/ethylene–propylene–diene monomers polymer (EPDM) ternary composites have been measured over a temperature range from −80 °C to 100 °C and at a fixed frequency of 1 Hz, using a dynamic mechanical analyser (DMA), to identify the effects of the filler content and its surface treatment with a silane coupling agent on the dynamic viscoelastic behaviour. The results show that the storage modulus (E′_c) and loss modulus (E ″_c) of these composites with 10% volume fraction of EPDM at 25 °C increase non‐linearly with increasing volume fraction of glass beads (ϕ_g). At the same test conditions, the E′_c value of the PP/EPDM filled with pretreated glass beads is higher than that of the uncoated glass bead filled PP/EPDM system, especially at higher ϕ_g, while the difference in E ″_c between both systems is very small. The mechanical damping for the former decreases with increasing ϕ_g, but the opposite is true for the latter. The glass transition temperature of these composites varies irregularly with ϕ_g. The dynamic complex viscosity increases nonlinearly with an increase of ϕ_g. In addition, the interfacial structure between the matrix and inclusions has been observed by means of a scanning electron microscope. © 1999 Society of Chemical Industry     

Dispersion of multiwalled carbon nanotubes in thermoplastic elastomer gels: Morphological,rheological, and electrical properties

An investigation was reported here with an aim to prepare nanocomposite thermoplastic elastomer gels by dissolving polystyrene‐b‐poly(ethylene/butylene)‐b‐polystyrene (SEBS) triblock copolymer in selective hydrocarbon oils with the presence of multiwalled carbon nanotubes (MWCNTs). The properties related to morphology, viscoelasticity, electrical and mechanical properties, and thermal stability were explored and discussed. Dynamic rheological measurements of the resultant nanocomposite thermoplastic elastomer gels (NCTPEGs) confirmed that addition of MWCNTs affects the linear viscoelastic properties in which dynamic storage and loss moduli increase to some extent. At a temperature between 30°C and 40°C below the gel point the NCTPEGs have dynamic storage modulus greater than loss modulus (G′ and G″), thereby indicating that at room temperature a physical network is still present despite the addition of MWCNTs. The morphological properties revealed that MWCNTs were dispersed and exfoliated within the swollen TPE. The incorporation of small quantity of MWCNTs improved the thermal stability and mechanical properties of NCTPEGs. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis and characterization of graft copolymers of syndiotactic polystyrene with polybutadiene and 4‐methylstyrene

The basic method for synthesizing syndiotactic polystyrene‐g‐polybutadiene graft copolymers was investigated. First, the syndiotactic polystyrene copolymer, poly(styrene‐co‐4‐methylstyrene), was prepared by the copolymerization of styrene and 4‐methylstyrene monomer with a trichloro(pentamethyl cyclopentadienyl) titanium(IV)/modified methylaluminoxane system as a metallocene catalyst at 50°C. Then, the polymerization proceeded in an argon atmosphere at the ambient pressure, and after purification by extraction, the copolymer structure was confirmed with ¹H‐NMR. Lastly, the copolymer was grafted with polybutadiene (a ready‐made commercialized unsaturated elastomer) by anionic grafting reactions with a metallation reagent. In this step, poly(styrene‐co‐4‐methylstyrene) was deprotonated at the methyl group of 4‐methylstyrene by butyl lithium and further reacted with polybutadiene to graft polybutadiene onto the deprotonated methyl of the poly(styrene‐co‐4‐methylstyrene) backbone. After purification of the graft copolymer by Soxhlet extraction, the grafting reaction copolymer structure was confirmed with ¹H‐NMR. These graft copolymers showed high melting temperatures (240–250°C) and were different from normal anionic styrene–butadiene copolymers because of the presence of crystalline syndiotactic polystyrene segments. Usually, highly syndiotactic polystyrene has a glass‐transition temperature of 100°C and behaves like a glassy polymer (possessing brittle mechanical properties) at room temperature. Thus, the graft copolymer can be used as a compatibilizer in syndiotactic polystyrene blends to modify the mechanical properties to compensate for the glassy properties of pure syndiotactic polystyrene at room temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamic mechanical properties of oil-extended reinforced SBR rubbers

The dynamic mechanical behavior of six samples of styrene–butadiene random copolymers (SBR with 24% styrene) containing different amounts of carbon black and oil extender has been investigated in the temperature range ?50° to 80°C. The measurements were carried out using a Fitzgerald apparatus working in the frequency range of 0.1 to 1.0 kHz. Master curves for all materials were obtained by the method of reduced variables. The master curves show that increasing amounts of carbon black in SBR in crease both the elastic (G′) and the viscous (G″) components of the complex shear modulus. The loss factor (tan δ) decreases markedly with increasing amounts of carbon black. Increasing amounts of oil extender increase the loss factor within the reduced frequency range here reported (2 < log ωa_T < 7).     

Characterization of two polypentadienes of differing tacticity by physical methods

The preparation of isotactic and syndiotactic 1,4-polypentadienes with a cis content of at least 70%–75% using i-Bu₂AlH/Ti(i-OPr)₄ and AlEtCl₂/thiophene/Co(acetylacetonate)₂ catalysts, respectively, is reported. Physical characterization of the vulcanizates, prepared by a common recipe, involving infrared analysis, DTA, simple stress–strain and swelling measurements, and dynamic mechanical measurements over a frequency range of 2 decades and temperature range of ?60°C to +20°C indicated that no isomerization had taken place during vulcanization and that stereoregularity of the polymer chains affected the resultant cure: the isotactic form was found to have a greater crosslink density than the syndiotactic form. Master curves covering an extended frequency range were constructed from the reduced dynamic mechanical data and the calculated quantities—thermal expansion coefficients of free volume and the fractional free volumes at the glass transition temperatures—agree with the accepted values. Glass transition temperatures of the isotactic and syndiotactic polymers are ?37°C and ?42°C, respectively, and for their vulcanizates, ?33°C and ?40°C, respectively.     

Dynamic mechanical properties of Al2O3/poly(ether ether ketone) composites

The dynamic mechanical properties of high‐performance polymer matrix composites based on semicrystalline poly(ether ether ketone) (PEEK) and aluminum oxide (Al₂O₃) were evaluated in the temperature range of 30–250°C with a three‐point‐bending mode at a frequency of 1 Hz. The storage modulus and loss modulus changed significantly with the variation of the Al₂O₃ content in the PEEK matrix. The Al₂O₃ reinforcement was more pronounced above the glass‐transition temperature (T_g). A composite containing 60 wt % (33 vol %) Al₂O₃ exhibited about a 78% increase in the storage modulus at 50°C and about a 200% increase at 200°C. However, there was no significant change in the mechanical loss factor and T_g associated with the peak of the mechanical loss factor or loss modulus with the addition of Al₂O₃. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 568–575, 2007     

Strengthening due to interlamellar constraint in oriented syndiotactic styrene–p‐methyl styrene copolymer

Channel die compression has been used to form highly oriented syndiotactic styrene–p‐methylstyrene copolymer in the solid state. The highest forming temperatures were at or near the nominal unoriented melting point (247°C). The oriented materials produced at 245 and 220°C were examined by differential scanning calorimetry, wide‐angle X‐ray diffraction, and dynamic mechanical thermal analysis. The measured increases in modulus, which resulted from the forming of the copolymer could be related to the microstructural changes in the material. The analysis of mechanical properties with a simple Takayanagi model showed that the high modulus above the glass transition temperature in oriented samples was at least partly due to an interlamellar constraint of the kind suggested by Arridge and co‐workers. The magnitudes of the constraint factor that were estimated in the modeling process were consistent with the observed microstructural changes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2312–2321, 2002     

Dynamic mechanical properties of extruded nylon–wood composites

Dynamic mechanical properties determine the potential end use of a newly developed extruded nylon–wood composite in under‐the‐hood automobile applications. In this article, the dynamic mechanical properties of extruded nylon–wood composites were characterized using a dynamic mechanical thermal analyzer (DMTA) to determine storage modulus, glass transition temperature (T_g), physical aging effects, long‐term performance prediction, and comparisons to similar products. The storage modulus of the nylon–wood composite was found to be more temperature stable than pure nylon 66. The T_g range of the nylon–wood composite was found to be between 23 and 56°C, based on the decrease in storage modulus. A master curve was constructed based on the creep curves at various temperatures from 30 to 80°C. The results show that the relationship between shift factors and temperature follows Arrhenius behavior. Nylon–wood composites have good temperature‐dependent properties. Wood fillers reduced the physical aging effects on nylon in the wood composites. The comparison of the nylon–wood composite with other similar products shows that nylon–wood composites are a promising low cost material for industrial applications. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Dynamic mechanical analysis study of the curing of phenol‐formaldehyde novolac resins

The curing reaction of typical commercial phenol‐formaldehyde novolac resins with hexamethylentetraamine (HMTA) was followed by dynamic mechanical analysis. The evolution of the rheological parameters, such as storage modulus G′, loss modulus G″, and tanδ (G″/G′), as a function of time, for samples of the phenolic resins on cloth, was recorded. The curing reaction, leading to the formation of a crosslinked structure, is described by a third‐order phenomenological equation. This equation takes into account a self‐acceleration effect, as a consequence not only of the chemical reaction of crosslinking after the gel point but of phase segregation as well. This rheokinetic model of the curing of phenolic novolac resins permits the determination of the numerical values of the kinetic equation constants. The influence of the composition, structure, and physical treatment on the curing kinetics of the novolac resins is evaluated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1902–1913, 2001     

Damage Tolerance and Extensive Plastic Deformation of β‐Yb2Si2O7 from Room to High Temperatures

β‐Yb₂Si₂O₇ is a promising environmental barrier coating (EBC) material and recently attracted attention for its damage tolerance. To investigate the mechanisms of its damage tolerance and possible plasticity, dense β‐Yb₂Si₂O₇ sample was synthesized by in situ reaction/hot‐pressing method, and its mechanical properties were measured from room to high temperatures. The low magnitudes of hardness to Young's modulus ratio H_V/E, shear modulus to bulk modulus ratio G/B, and high fracture toughness to strength ratio K_IC/σ provide evidences of damage tolerance of β‐Yb₂Si₂O₇. β‐Yb₂Si₂O₇ exhibits extensive plastic deformation in Hertzian contact tests at both room and high temperatures. Transmission electron microscopy (TEM) observations show that the deformation mechanisms are different at low and high temperatures. Deformation twinning and parallel dislocation arrangement occur in plastic deformation at room temperature. Above the brittle‐to‐ductile transition temperature (between 1200°C and 1300°C), plastic deformation brings out extensive slip and climb of dislocations, while twinning is seldom observed. Measurement of temperature‐dependent dynamic Young's modulus demonstrates excellent elastic stiffness retention up to 1300°C.     

Thermomechanical behavior of poly(vinyl chloride) in the process of degradation

The thermomechanical behavior of poly(vinyl chloride) (PVC) was investigated during its thermal degradation by using torsional braid analysis. In thermomechanical behavior as a function of temperature, the relative rigidity G_r decreased initially with increasing temperature, then began to increase passing through a minimum at about 200°C, and finally decreased at 340°C. Increase in G_r from 200°C was caused by formation of a conjugated polyene chain accompanied by dehydrochlorination and by crosslinking reaction, and decrease in G_r at 340°C was related to scission reactions of the crosslinking network by oxidation. In the change in logarithmic decrement Δ, three peaks were observed: at 90°C, coinciding with the glass transition of the polymer; at about 200°C, due to the melting transition of crystallites, and at about 300°C, due to a loss of mechanical energy in the rheological transition of the polymer from a liquid state to a glassy state passing through a viscoelastic region. The thermomechanical properties of PVC with different molecular weights were also measured, and the effect of molecular weight G_r and Δ are discussed. In isothermal measurements of the relative rigidity in air, exponentially increasing curves were observed as a function of time. These curves were analyzed kinetically as a first-order reaction, and an activation energy of 22.7 kcal/mole was obtained.     

Dynamic rheological properties for HDPE/CB composite melts

A study on the dynamic viscoelastic properties of carbon black (CB)‐filled high‐density polyethylene (HDPE) in the molten state was carried out. When the temperature was above 180°C in an air atmosphere, the storage modulus G′, loss modulus G″, and loss tangent δ showed particular characteristics. In the low‐frequency region, the modulus increased with increase of the testing time while the tan δ obviously decreased. Also, the higher the temperature, the more notable was the change. We can detect these changes from the deviation of G′ (G″) against ω plots from the linearity and the appearance of a characteristic plateau phenomenon. The width and height of the modulus plateau increased with increase of the temperature. When temperature was below 180°C, the testing time and the temperature had no effect on the viscoelastic parameters of HDPE. However, if we used 99% nitrogen gas as the atmosphere, substituting for air, the viscoelastic parameters revealed an undiscernible change, different from that in an air atmosphere. No changes were found under the protection of the antioxidant B215. This phenomenon indicated that HDPE can be oxidized at a temperature higher than 180°C. Nitrogen gas and an antioxidant agent can prevent HDPE from crosslinking. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2160–2167, 2003     

Properties of poly(vinyl chloride) fibers crosslinked by 2-dibutylamino-4,6-dimercapto-1,3,5-triazine

PVC fibers, fastened to a needle frame, were crosslinked by 2-dibutylamino-4, 6-dimercapto-1,3,5-trizine in the presence of tetra-n-butylammonium bromide and alkali in water at 96°C. Solvent resistance, characterized by the gel fraction of THF, improves markedly. Mechanical properties of the fibers investigated by tensile tests at 20°C show that both the modulus and tensile strength at break increase, while elongation at break decreases over 40% gel content. Creep tests indicate that the resistance to heat deformation improves by crosslinking. The heat distortion temperature increases by 12°C at 75% gel content. Results of dynamic tests show that the T_g of PVC fibers determined by a peak in the loss modulus (E'') increases from 40% gel content. Dynamic modulus (E') increases by 74% at 23°C and the T_g by 37°C in the case of crosslinked PVC fibers having a 92% gel content. The shrinkage of PVC fibers in hot water at 94°C for 30 min decreases more than 50% over 75–80% gel content indicating the improved resistance to heat deformation.     

Glass‐transition and gas‐transport characteristics of polymer nanocomposites based on crosslinked poly(ethylene oxide)

The glass‐transition and gas‐transport properties of rubbery polymer nanocomposites based on crosslinked poly(ethylene oxide) and metal oxide nanoparticles were studied. Nanocomposite samples were prepared by the UV photopolymerization of poly(ethylene glycol) diacrylate (n ～ 14) in the presence of magnesium oxide or silica nanoparticles. The thermomechanical properties of the composites were investigated with dynamic mechanical and dielectric spectroscopy methods. The inclusion of nanoparticles in the crosslinked poly(ethylene glycol) diacrylate network led to a systematic increase in rubbery modulus and a modest positive offset (～6°C) in the measured glass‐transition temperature for both systems. Bulk density measurements indicated only minimal void volume fraction in the composites, and CO₂ and light gas permeability decreased with particle loading; for example, the CO₂ infinite dilution permeability at 35°C decreased from 106 barrer in the unfilled polymer to 55 barrer in a nanocomposite containing 30 wt % magnesium oxide nanoparticles. The inclusion of toluene diluent in the prepolymerization mixtures produced a limited enhancement in sample permeability, but the sizeable increases in gas transport with particle loading reported for certain other rubbery nanocomposite systems were not realized in the crosslinked poly(ethylene glycol) diacrylate composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Evaluation of adhesion and mechanical properties of plasma sprayed NiCrAl/Al2O3-13wt.%TiO2 coatings

Plasma sprayed NiCrAl/Al₂O₃-13wt.%TiO₂ coating was fabricated and annealed at 300–900 °C in air atmosphere. The Elastic modulus (E), micro-hardness (H_V) and fracture toughness (K_ca) were evaluated by Vickers Indentation Fracture technique. The microstructure was studied by scanning electron microscopy. It can be concluded that with the increasing of annealing temperature, E and H_V at the interface of Substrate/Bond layer (S/B) are firstly increased and retain the highest value at 600 °C then decreased with higher annealing temperatures due to the phase transformation. E of the ceramic coating rised initially with annealing temperature increasing, reached the highest value at 400 °C, and then decreased with the further increasing of the temperature. The K_ca of the S/B interface firstly increased as the heating temperature increasing, confirming the crack initiation resistance increasing after annealing with the temperature below 700 °C. However, the K_ca decreased for further annealing temperature, even lower than that of the as-sprayed coating. Thereby, a proper annealing temperature can improve the mechanical properties of the coating since the coating becomes denser, ceramic lamellar structure becomes ambiguous and cracks are partially healed.     

Rectorite/thermoplastic polyurethane nanocomposites. II. Improvement of thermal and oil‐resistant properties

Organ‐rectorite/thermoplastic polyurethane (OREC/TPUR) nanocomposites were synthesized via melt intercalation. The dynamic mechanical properties by dynamic mechanical analysis (DMA), thermal and oil‐resistant properties were investigated. The results show that the storage modulus (E′), loss modulus (E″), and glass‐transition temperature (T_g) of the nanocomposites have an increase to some extent than those of pure TPUR. The thermal stability of nanocomposites was also studied in detail by thermal gravity analysis (TGA), which was higher than that of pristine TPUR matrix when the content of organic REC is at 2 wt %, and the decomposition temperature at 10% weight loss of OREC/TPUR is greatly increased up to 330°C from 315°C. Oil uptake of the composites is also significantly reduced in comparison with TPUR matrix, which is ascribed to the good barrier effect of nanosheets of OREC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1165–1169, 2005