Dynamic mechanical thermal analysis of thermally stable and thermally reactive network polymers

The temperature and frequency dependence of the dynamic mechanical properties in the glass transition was studied for a series of partially cured thermally reactive networks (low temperature cured epoxy and a dimethacrylate photocured with a conventional initiator) and more thermally stable networks (high temperature cured epoxy and two dimethacrylates photocured with a photoiniter1). The viscoelastic behavior in the transition region of the former networks changed during the experiment due to additional cure, whereas the thermally stable networks enabled the study of the effect of conversion on the transition region. The glass transition temperatures showed 1 : 1 relationships with the isothermal curing temperatures and were correlated with the degree of conversion. The breadth of the glass transition, as determined from the real and loss moduli, tan δ, and the loss compliance in the temperature and frequency domains, was found to be greater for the dimethacrylate networks than for the epoxy networks. The breadth of the transition for the dimethacrylates was not significantly dependent on the degree of cure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1348–1359, 2004     

Dynamic mechanical analysis of fiber-reinforced phenolics

Dynamic mechanical analysis (DMA) was used to investigate the thermomechanical behavior and the effects of postcuring on a range of glass-reinforced phenolics. The materials examined were a pure resol (reinforced with S- and E-glass), a pure novolac (reinforced with S-glass), and three derivatives of the resol and/or novolac: a resol/novolac blend, a phenolic–furan graft copolymer, and a rubber-modified resol (all reinforced with S-glass). The blend and copolymer were prepared to obtain phenolic resins with improved impact strength, without degeneration of their high-temperature performance. They have a more loosely crosslinked structure compared to the pure resol or novolac. The rubber-modified resol was prepared with the intention of reducing the brittleness of the resin structure by incorporating an elastomeric phase within the resol resin matrix. It was found that the stiffness and glass transition temperature (T_g) of the materials could be increased by postcuring, which also produced a decrease in their damping capacity. Knowing that the postcure process is a function of time and temperature, a master curve was constructed that allowed prediction of the T_g of the resol/novolac blend over a broad range of postcure times and temperatures. The effect of frequency on the storage modulus of the pure resol (S-glass), copolymer, and blend was also studied from 0.01 to 100 Hz. Master curves were constructed by time–temperature superpositioning that allowed prediction of the storage modulus at times and temperatures that are not experimentally accessible. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 649–658, 1999     

Dynamic mechanical study of filled semi-interpenetrating polymer networks: Influence of γ-Fe2O3 on microphase structure

The preparation of filled two-component semi-interpenetrating polymer networks (semi-IPNs) is described and the results of an investigation of their morphology by means of dynamic mechanical spectroscopy are considered. The influence of an active dispersed filler (γ-Fe₂O₃) on the semi-IPNs phase structure is studied. A comparison is made between filled and unfilled semi-IPNs consisting of compatible or incompatible polymers. In the case of a semi-IPN of compatible polymers, the introduction of γ-Fe₂O₃ was observed to cause phase separation. With a two-phase semi-IPN the introduction of the filler enhanced the phase separation. The presence of two distinct peaks (the dynamic glass transition temperatures) corresponding to those of the two initial homopolymers shows the semi-IPN to have a two-phase structure.     

Thermal analysis and mechanical characterization of maleimide‐functionalized benzoxazine/epoxy copolymers

Maleimide‐functionalized benzoxazine is copolymerized with epoxy to improve toughness and processibility without compromising the thermal properties. The incorporation of maleimide functionality into the benzoxazine monomer results in a high performance polymer. All three possible polymerization reactions are confirmed using Fourier transform infrared (FT‐IR) spectroscopy. While maleimide‐functionalized benzoxazine has a glass transition temperature, T_g, of 252°C, a further 25°C increase of T_g is observed when copolymerized with epoxy. The flexural properties are also measured, and the copolymers exhibit a flexural modulus of 4.2–5.0 GPa. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1670–1677, 2006     

Glass transition temperatures of hydrocarbon blends: Adhesives measured by differential scanning calorimetry and dynamic mechanical analysis

A comparison of calculated and measured glass transition temperatures of a series of three‐component hydrocarbon blends was performed. The blends were prepared as mixtures of an elastomer with different proportions of tackifying resin and oil. Glass transition temperature, T_g, was measured by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) at four measurement frequencies. Most of these blends had pressure‐sensitive adhesive (PSA) properties, and were used to prepare a series of PSA tapes. The adhesion of the PSA tapes was shown to be strongly dependent on T_g. Tack of PSA tapes was measured at two different temperatures, and shown to be directly correlated to the blend T_g. Several predictive methods for blend T_g that are based on individual component T_gs were evaluated. The prediction of blend T_g is far more accurate if the individual component T_g values are determined by DMA instead of DSC. In addition, the Gordon‐Taylor equation gave a significant improvement on predicted blend T_g when compared to the Fox equation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 826–832, 2000     

动态热机械分析法对环氧树脂固化程度的研究

以动态热机械分析仪研究环氧树脂的固化程度 ,发现样品固化不完全 ,在分析过程中的加热效应使其固化完全     

Dynamic mechanical analysis of the two glass transitions in a thermotropic polymer

A dynamic mechanical analysis has been performed on a thermotropic poly(ether ester) with biphenyl units as mesogens and spacers with methyl substituents. This polymer develops a smectic mesophase with a rather slow rate of formation, in such a way that the isotropic melt of this polymer can be easily quenched into the glassy amorphous state. A quenched amorphous sample and three specimens annealed above the glass transition for different times have been analysed. These annealed specimens exhibit different degrees of liquid crystal formation. The dynamic mechanical (and DSC) results show that the glass transition (α-relaxation) temperatures of the isotropic amorphous and anisotropic liquid crystalline states are clearly different, and when the mesophase transformation is not complete, as it happens in the two specimens annealed at intermediate times, the two glass transitions are simultaneously observed. The values of the storage modulus below the glass transition are dependent on the degree of liquid crystallinity, showing that the rigidity of the mesophase is significantly higher than the one for the amorphous component.     

联苯型液晶聚氨酯/环氧体系的动态力学性能

采用动态热力学分析方法(DMA),研究了联苯液晶聚氨酯(DLCP)/环氧树脂(E-51)固化体系的储能模量、损耗模量和力学损耗因子随温度的变化情况。在玻璃化转变温度(Tg)下,通过改变振动频率求出链段运动的活化能并探讨聚合物分子链段的运动情况。结果表明:DLCP可降低材料的内耗,提高材料的Tg。加入质量分数5%的DLCP,复合材料的储能模量可达2 700 MPa,Tg比纯树脂提高10～30℃。     

Dynamic mechanical behavior of atactic and high‐impact polystyrene

Results of the dynamic mechanical behavior of atactic polystyrene (PS) and high‐impact polystyrene (HIPS) for temperatures between 300 and 425 K at a frequency of the order of 50 kHz are presented. The storage Young's modulus, (E′), of the HIPS is lower than the PS value, being the relationship between them a function of the rubber phase volume fraction, independent of the measurement frequency. The glass transition temperature (T_g) of HIPS is shifted to lower temperature in respect to the PS. The γ relaxation appears at 308 K in PS at 50 kHz, while it seems to move toward lower temperatures in the HIPS. Both shifts are attributed to the presence of mineral oils in the HIPS. The values of E′, T_g, and the temperature of the γ relaxation at 50 kHz are discussed within the scope of the theory of viscoelasticity. Finally, the effect of thermal treatments, using different annealing times, on the behavior of both materials is shown. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 865–873, 2000     

The effect of benzenesulfonamide plasticizers on the glass transition temperature of an amorphous aliphatic polyamide

The plasticizing effect of benzenesulfonamides (BSAs) on an amorphous aliphatic polyamide (AAPA) has been studied using dynamic mechanical analysis of copper‐supported spin‐coated mixtures. It follows that N‐(n‐butyl)BSA (BBSA), an amorphous liquid hydrogen bonding BSA, is fully miscible with AAPA because their mixtures are characterized by a single glass transition (T_g) throughout the compositional range. The T_g–composition dependence, however, is not linear because experimental results suggest a 20 K fall in T_g occurring around 0.65 BBSA units per amide unit, which coincides with the system shifting from a polymer‐like to a liquid‐like glass‐forming material. When considering a crystallizable hydrogen‐bonding plasticizer such as ethylBSA (EBSA), AAPA/EBSA mixtures become fully crystalline at a 1.3 EBSA unit per amide group. Nevertheless, melting point depression together with the single T_g observed throughout the compositional range on quenched (and therefore amorphous) samples confirms the miscibility of AAPA chains with the plasticizer. N,N‐DialkylBSAs, which lack the sulfonamide proton and therefore the possibility of hydrogen bonding with amide groups, quickly phase separate from AAPA, the glass transition of the latter staying mainly unaffected apart from a small (9 K) decrease at 10–15 mol% plasticizer. © 2001 Society of Chemical Industry     

Dynamic mechanical analysis of fibre‐reinforced plastic composites based on carboxyl terminated poly(ethylene glycol) adipate modified epoxy and E glass fibre

Fibre reinforced plastic (FRP) composites prepared from E glass woven fabrics as reinforcing agent and carboxyl terminated poly(ethylene glycol) adipate (CTPEGA) modified epoxy as a matrix, were subjected to dynamic mechanical thermal analysis at a fixed frequency of 5 Hz. The volume fraction of glass was about 0.45. The concentration of CTPEGA in the matrix was varied gradually from 0 to 40 phr (phr stands for parts per hundred parts of resin), to investigate the effect of CTPEGA concentration on the dynamic properties of the composites. It was found that the tan δ peak temperature and storage modulus gradually decrease with incorporation of CTPEGA. However, the tan δ peak value increases up to 20 phr of CTPEGA concentration and decreases thereafter. The same trend was obtained in the case of impact strength. © 2000 Society of Chemical Industry     

The Use of Dynamic Mechanical Methods to Study the Effect of Absorbed Water on Temperature-dependent Properties of an Epoxy Resin-Carbon Fibre Composite

Dynamic mechanical methods were used to study the effect of absorbed moisture on the properties of an epoxy resin matrix CFRP. The glass transition temperature (T_g)of the matrix resin, determined as the onset of the characteristic fall in dynamic modulus with increasing temperature, was found to decrease with increasing moisture content. Maximum shifts in T_g of 80 to 90°C, relative to the dry material, were observed for a resin moisture content of 5.2% by weight. The effects of sample geometry, fibre orientation, and frequency of oscillation, on the dynamic mechanical properties are discussed. Results are given of an analysis of the observed dependence of T_g on water content using two theoretical models.     

The effect of citrate esters as plasticizers on the thermal and mechanical properties of poly(methyl methacrylate)

Plasticizers play a key role in the formulation of polymers and in determining their physical properties and processability. This study examines the effects of citrate esters, triethylcitrate, and triacetine as plasticizers on the thermal and mechanical properties of poly(methyl methacrylate). The samples were characterized by differential scanning calorimetry, dynamical mechanical analysis, and mechanical testing under different plasticizer contents. Both citrate esters proved to be effective as plasticizers, DSC data for the triacetine additive fits with Fox equation. Microstructure and relaxation properties were studied by dynamic mechanical analysis where loss modulus shows clearly that absorbed plasticizer shifts the α‐transition to lower temperature and β‐relaxations associated to ester side groups are unchanged even up to 30 wt % plasticizer. Mechanical properties were evaluated with an Instron testing machine. Both additives produced (1) an initial plasticization, with a decrease in tensile strength and modulus; (2) an antiplasticization, reflected as an increase in tensile strength; and modulus and (3) a final plasticization, with a notable decrease in tensile strength and modulus and an increase in elongation where a 35 wt % of triethylcitrate added to the poly(methyl methacrylate) increased in 200% its elongation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Dynamic mechanical properties of polystyrene–aluminum nitride composite

A composite of aluminum nitride (AlN) particles dispersed around polystyrene matrix particles was synthesized in this study. The purpose of using this microstructure is to improve the thermal properties of a polymer at a low filler content with a minimal increase in the dielectric constant of the polymer composite to meet the material requirements for electronic packaging. The dynamic mechanical properties of this type of polystyrene–AlN composite were investigated here. The experimental results indicate that the dynamic mechanical property of the polystyrene–AlN composite is a function of the polystyrene particle size, AlN filler concentration, and temperature under this dispersion state. The addition of an AlN concentration into polystyrene increases both the storage modulus and the α‐transition temperature. The smaller polystyrene particle size gives a higher storage modulus and damping peak. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1348–1353, 2000     

Semiinterpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. I. Thermodynamic state and dynamic mechanical analysis

Semiinterpenetrating polymer networks (semi‐IPNs) based on polyurethane (PU) and polyvinylpyrrolidone (PVP) have been synthesized, and their thermodynamic characteristics, thermal properties, and dynamical mechanical properties have been studied to have an insight in their structure as a function of their composition. First, the free energies of mixing of the two polymers in semi‐IPNs based on crosslinked PU and PVP have been determined by the vapor sorption method. It was established that these constituent polymers are not miscible in the semi‐IPNs. The differential scanning calorimetry results evidence the T_g of polyurethane and two T_g for PVP. The dynamic mechanical behavior of the semi‐IPNs has been investigated and is in accordance with their thermal behavior. It was shown that the semi‐IPNs present three distinct relaxations. If the temperature position of PU maximum tan δ is invariable, on the contrary, the situation for the two maxima observed for PVP is more complex. Only the maximum of the highest temperature relaxation is shifted to lower temperature with changing of the semi‐IPNs composition. It was concluded that investigated semi‐IPNs are two‐phase systems with incomplete phase separation. The phase composition was calculated using viscoelastic properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 852–862, 2001     

Dynamic mechanical analysis of FRP composites based on different fiber reinforcements and epoxy resin as the matrix material

Three-ply composite laminates prepared from E-glass or N-glass chopped strand mats (CSMs) and jute (J) fabrics as reinforcing agents and amine-cured epoxy resin as the matrix material were subjected to dynamic mechanical thermal analysis at a fixed frequency of 1 Hz over a temperature range of 30–180°C. The volume fraction of fibers ranged between 0.21 and 0.25. The reinforcing effect for the three fibers is in the order E-glass > N-glass ≫ jute. Glass-reinforced composites show a higher storage modulus (E′) than that of jute-reinforced composites. The E′ values of glass-jute hybrid composites lie between those of glass-reinforced and jute-reinforced composites. Odd trends in temperature variability of the loss modulus (E′) and the damping parameter, tan δ, and in the glass transition temperature (T_g) for the three different unitary and four different hybrid composites are interpreted and understood on the basis of odd differences in (1) the chemical nature and physical properties of the three different fibers (E-glass, N-glass, and jute), (2) the void content and distribution, (3) the thermal expansion coefficients of the main phases in the composites, (4) the degree of matrix stiffening at or near the fiber-matrix interface, and (5) the extents of matrix softening in the zone next to the interface. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2467–2472, 1997     

Synthesis and characterization of high temperature cyanate-based shape memory polymers with functional polybutadiene/acrylonitrile

New thermosetting shape memory cyanate polymers (SMCPs) modified with polybutadiene/acrylonitrile (PBAN) were synthesized and compared with polyethylene glycol (PEG)-modified SMCPs for integration into the family of high temperature shape memory polymers with controllable glass transition temperatures (T_g) used in the aerospace industry. The materials were characterized in terms of microstructure, thermal properties, mechanical properties and shape memory properties by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and tensile tests. Differing from the SMCP with PEG, the new cyanate-based shape memory polymer with PBAN (T_g ∼255.1.0 °C) had better shape memory properties and higher thermal stability (relatively high initial degradation temperature and high char residue value at 800 °C). Both of the SMCPs with PBAN and PEG displayed exceedingly high glass transition temperatures over 241.3 °C and higher toughness than unmodified polycyanurate. These qualities render them desirable candidates as matrices in polymer composites, particularly for space applications.     

Effect of thermal exposure on the properties of phenolic composites: Dynamic mechanical analysis

Changes in the dynamic response of glass‐reinforced phenolic composites following thermal exposure at 180^oC for periods of time up to 28 days were monitored using dynamic mechanical analysis. Four phenolic resins were investigated: a resol/novolac blend, a phenolic–furan novolac/resol graft copolymer, a novolac, and a resol. Reactive blending and copolymerization of phenolic resins are currently being investigated to determine if these techniques will produce phenolic resins (and composites) that have improved impact properties and retain the excellent high‐temperature properties of resol and novolac phenolic resins. The results indicate that thermal aging at 180^oC for 1 day led to a more complete cure of all four phenolic resins as indicated by an increase in the temperature of the maximum of plots of both loss modulus (E″) and tan δ versus temperature. The storage modulus (E′) of the composites at 40^oC varied little following thermal aging at 180^oC for 1 day but decreased with increasing exposure time for samples aged 2, 7, and 28 days. Thermal aging led to an increase in E′ at higher temperatures and the magnitude of E′ at a given temperature decreased with increasing exposure time. The magnitude of E″ and tan δ decreased with aging time for all resins, although E″ and tan δ were larger for the blend and copolymer composites than for the novolac and resol composites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 385–395, 2001     

Dynamic Mechanical Analysis of Amorphous-Phase Organization in Acrylic Polymers

Factors affecting polymer network organization were studied in highly crosslinked acrylics of the type used in dental adhesive resins. The variables tested were comonomer content and processing conditions. BisEMA (2,2,-bis[4-(2-methacryloyloxyethoxy)-phenyl]-propane) and BisEMA + TEGDMA (triethyleneglycol dimethacrylate) were cured with and without 25% comonomer. Comonomers had characteristics that are expected to influence intrachain organization in amorphous phases: TEGDMA, crosslinking; methyl methacrylate (MMA), monomer conversion; isobornyl methacrylate (IBM), low cure shrinkage; tetrahydrofurfuryl methacrylate (THFM), antiplasticization. Dynamic mechanical analysis temperature scans were run at 0.1 Hz 2h or 24h after ambient cure, or 24h postcure after heating at 75° or 125°C. After 24h, tan δ maxima occurred in ranges centering on approximately -30°, 75° and 150°C (T_g). Heating at 125°C nearly eliminated all peaks except T_g, reduced tan δ peaks and increased T_g by 0–14°. T_g increased in the order: TEGDMA>125°C>IBM>MMA>75°C>2h>24h>THFM. The ability to crosslink, and postcure heating at 125°C, were the more important factors found to increase intrachain organization in amine-promoted, unfilled BisEMA resins of the type used in dental sealants, luting cements and bulk-filling resin composite materials.