Carbon nanotube–polyurethane shape memory nanocomposites with low trigger temperature

Ester-based polyurethane (PU) with low glass transition temperature was used to develop shape memory nanocomposites with low trigger temperature. Pristine carbon nanotubes (CNTs) and oxidized CNTs (ox-CNTs) were introduced by melt mixing to improve the mechanical and shape memory properties of the PU matrix. The dispersion of CNTs on the mechanical properties and shape memory behaviors of the nanocomposites were also investigated. The results show that better dispersion of ox-CNTs contributes to more stiffness effect below glass transition temperature (T_g) while lower storage modulus (E′) above T_g. The nanocomposites exhibit high shape fixity and recovery ratio above 98%. The ox-CNT/PU nanocomposite shows higher shape recovery ratio for the first cycle, faster recovery due to better dispersion of CNTs and have potential applications for controlling tags or proof marks in the area of frozen food. The trigger temperature can be tailored by controlling the T_g of the PU matrix or the content of the nanofillers.     

Relation between the network structure and dynamic mechanical properties of a typical amine-cured epoxy polymer

The dynamic mechanical properties of a series of epoxy polymers of known network structure have been investigated. It was shown that the distance between crosslinks could be predicted from either the shift in the glass transition temperature T_g or by use of the dynamic modulus above T_g. The front factor in the equation of state for rubber elasticity was near unity for stoichiometric equivalence of epoxy and amine and increased slowly with excess of either component.     

Shape memory effect and recovery stress property of carbon nanotube/waterborne epoxy nanocomposites investigated via TMA

Shape memory polymers (SMPs) have received great attention and scientific interest in widespread technological development during last few decades. Besides the development of novel SMPs, various techniques have been practiced for characterization of shape memory effect (SME) of SMPs. In this study, the shape memory effect and recovery stress property of the carbon nanotube (CNT)/waterborne epoxy (WEP) nanocomposites below and above the glass transition temperature (T_g) of the nanocomposites and under isostrain and isostress were systematically investigated via thermal mechanical analysis (TMA), respectively. The experimental results showed that the nanocomposites exhibit excellent shape memory effect. The shape memory fixity and recovery ratios were approximately 100% even below glass transition temperature (T_g). A remarkable point is that the strain of the nanocomposites suddenly increased with the temperature decreasing in a certain period of the heating-cooling cycles under isostress condition and the strain increment increased with temperature in general. Especially at low temperature, the recovery stress was very sensitive to temperature under isostrain condition of ±0.25 °C temperature with differential of 25.5 °C developed pressure difference of 0.20 MPa. Moreover, TMA is a practical method for quantifying the SME and recovery stress properties of SMPs and their composites.     

Dynamic mechanical analysis of multiblock (segmental) polyesterimides

Thermal, deformation-strength, and dynamic mechanical properties of films of segmental polyesterimides prepared from pyromellitic anhydride, aromatic diamines, and poly(butylene adipate) (M _n = 1000) with hydroxy terminal groups were studied. The glass transition points T _g of the samples obtained are below 0°C. The dynamic elastic modulus curves at temperatures higher than T _g are characterized by a portion in which the modulus only weakly depends on temperature.     

Shape memory polymers based on cyanate ester-epoxy-poly (tetramethyleneoxide) co-reacted system

Thermoset polymers showing shape memory properties were synthesized by reacting bisphenol A dicyanate (BADC) with diglycidyl ether of bisphenol A (DGEBA) and phenol telechelic poly(tetramethyleneoxide) (PTOH). The cure characteristics of the blend were evaluated by DSC, FTIR and rheometry. Blends with varying proportion of DGEBA/PTOH/BADC were studied for their flexural, dynamic mechanical and thermal properties. The flexural strength and thermal stability increased with increase in cyanate ester concentration, while these properties decreased with increase of PTOH concentration for a given composition. The storage modulus showed a similar trend. The transition temperature (T_trans) of the system increased with increase in cyanate ester content. The polymers showed good shape memory properties wherein the shape recovery increased with increase in PTOH content with a concomitant decrease in the shape recovery time. While the shape recovery increased proportional to the modulus ratio (E_g/E_r), the recovery time showed an inverse relationship with it. The transition temperature could be tuned by the reactant composition and the speed of shape recovery increased with increase in actuation temperature. These epoxy-cyanate ester systems possesses good thermal, mechanical and shape memory characteristics for potential use in smart actuator development.     

Epoxy shape memory polymer (SMP): Material preparation,uniaxial tensile tests and dynamic mechanical analysis

The utilization of epoxy shape memory polymers (SMPs) as engineering materials for deployable structures has attracted considerable attention due to their excellent thermo-mechanical endurance and satisfactory processability. Knowledge of static and dynamic mechanical properties is essential for analyzing structural behavior and recovery, especially for new epoxy SMPs. In this paper, a new epoxy SMP was prepared with epoxy and aromatic amine curing agent. Uniaxial tensile tests and digital image correlation were used to obtain static mechanical properties. Dynamic mechanical analysis was carried out to evaluate glass transition temperatures that corresponded to the heat in the recovery process.It was found that elastic modulus, Poisson’s ratio and shear modulus are 1413 MPa, 0.35 and 591 MPa, respectively. The beginning of glass transition temperature of 37.4 °C could be effectively achieved by electrical heaters, validating the shape memory properties of epoxy SMPs. In general, this study could provide useful observations and basic mechanical properties of epoxy SMPs.     

Revealing defects hampering the formation of epoxy networks with extremely high thermal properties: Theory and experiments

We present a combined experimental and theoretical investigation of thermal properties of cycloaliphatic epoxy networks. The networks are prepared from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ERL-4221 as a monomer and 4-methylhexahydrophthalic anhydride as a curing agent and their glass transition temperature T_g is evaluated by dynamic mechanical and thermal mechanical analyses as well as by differential scanning calorimetry. It is found that the cured epoxy networks have high T_g values reaching 233–238 °C. The method of anharmonic oscillators is first proposed to simulate the effect of network structure on the thermal properties. It suggests that further increase of T_g values is not attained because of the formation of intramolecular cyclic structures. Studies of model reaction by mass-spectrometry confirm the formation of such structures at curing.     

The proper glass transition temperature of amorphous polymers on dynamic mechanical spectra

Glass transition is crucial to the thermal and dynamical properties of polymers. Thus, it is important to detect glass transition temperature (T _g) with a sensitive and proper method. Dynamic mechanical analysis (DMA) is one of the most frequently used methods to determine T _g due to its advantage of high sensibility. However, there is controversy in the past literatures to determine the proper glass transition temperature among three transition temperatures, i.e., T _g1, T _g2 and T _g3 in the dynamic mechanical spectra, which correspond to the temperature abscissa of intersect value of two tangent lines on storage modulus (E′), the peak of the loss modulus (E″) and the peak of the loss tangent (tan δ). In this work, these three transition temperatures were compared with the glass transition temperature determined by DSC (T _gDSC). Based on the discussion of different modes of molecular motion around the glass transition region, it is demonstrated that T _g1 and T _g2 have the same molecular mechanism as T _gDSC, i.e., local segmental motion which is enthalpic in nature and determines the proper glass transition temperature, while T _g3 is assigned to the transition temperature of entropic Rouse modes, thus cannot be used as the proper glass transition temperature.     

Amine‐cured epoxy/clay nanocomposites. II. The effect of the nanoclay aspect ratio

The thermophysical and mechanical properties of a nanocomposite material composed of amine‐cured diglycidyl ether of bisphenol A (DGEBA) reinforced with organomontmorillonite clay are reported. The storage modulus at 100 °C, which was above the glass‐transition temperature (T_g), increased approximately 350% with the addition of 10 wt % (6.0 vol %) of clay. Below the T_g, the storage modulus at 30 °C increased 50% relative to the value of unfilled epoxy. It was determined that the T_g linearly increased as a function of clay volume percent. The tensile modulus of epoxy at room temperature increased approximately 50% with the addition of 10 wt % of clay. The reinforcing effect of the organoclay nanoplatelets is discussed with respect to the Tandon–Weng and Halpin–Tsai models. A pseudoinclusion model is proposed to describe the behavior of randomly oriented, uniformly dispersed platelets in nanocomposite materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4391–4400, 2004     

Preparation and shape memory behavior of novel heat-resistance epoxy networks containing phthalide cardo structure

Heat-resistance epoxy shape memory (SM) materials were prepared based on diglycidylether of bisphenol A (DGEBA) epoxy resin with the mixture of 4,4′-diaminodiphenylether (DDM) and phthalide-containing aromatic amine (PBMI-DDM), which was synthesized by Michael addition of 3,3-bis[4-(4-maleimido phenoxy)phenyl] -phthalide (PBMI) and DDM, in different molar ratios as curing agents. The chemical structure of PBMI-DDM was confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectra. The dynamical mechanical behavior and high-temperature tensile properties, and the influence of PBMI-DDM content and number of cycles on SM performance were investigated in detail. With increasing PBMI-DDM content, the glass transition temperatures (T_g) decreased, damping loss factors increased, and shape recovery ratio (R_r) and shape fixity ratio (R_f) were improved significantly. R_r and R_f of the pure PBMI-DDM cured epoxy resins are both lager than 90% with a deformation strain above 15%. The T_g and activation energies (△E) of α-relaxation for the epoxy system with unstable SM performance are constantly increased with SM cycles due to the adjustment and rearrangement of network chains.     

Dynamic mechanical and dielectric properties of epoxidized SBS triblock copolymer

The morphological and dynamic properties of epoxidized styrene–butadiene–styrene block copolymers were studied and compared with their parent styrene–butadiene–styrene block copolymer (SBS). Two peaks were observed in the mechanical loss (tan δ) curve which can be attributed to segmental motion of epoxidized polybutadiene (EPPB) and polystyrene. Analysis by DSC thermograms also showed the linear increase of glass transition temperature for EPPB domain with the epoxy group content. Phase separated structures of epoxidized SBS as observed by TEM suggests a considerable degree of mixing occurred between phases after 80 mol % of the double bonds in SBS were epoxidized. The interfacial region displays a third peak and causes much steeper drop in modulus at higher temperature than T_g of EPPB. Parallel dielectric relaxation measurements were also made in the frequency range of 30 Hz–1 KHz as a function of temperature. In each dielectric constant (?′) curve, there is a maximum near the T_g of EPPB determined from the dielectric loss tangent curve. The shift in T_g of EPPB versus epoxy group content was consistent with that measured by the thermal and dynamic mechanic analysis. These findings indicated an 8°C shift in glass transition temperature as the epoxy group content in EPPB increased 10%.     

UV curable epoxy acrylate-clay nanocomposites

UV curable epoxy acrylates were reinforced with two different organically modified montmorillonites (MMTs) and an unmodified MMT. Conversion and rate of polymerization was monitored by real time infrared spectroscopy (RTIR) and photo-DSC. Microstructures were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and optical clarity. Optical clarity of the films containing clay was quite good as only a slight decrease was observed. Physical properties of the reinforced films were examined by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), hardness and tensile testing. Enhancements in glass transition temperature (T_g), thermal stability and mechanical properties were observed. The films reinforced with the unmodified MMT exhibit the most significant enhancements in properties.     

Thermal,mechanical and electroactive shape memory properties of polyurethane (PU)/poly (lactic acid) (PLA)/CNT nanocomposites

Polymer blend nanocomposites based on thermoplastic polyurethane (PU) elastomer, polylactide (PLA) and surface modified carbon nanotubes were prepared via simple melt mixing process and investigated for its mechanical, dynamic mechanical and electroactive shape memory properties. Chemical and structural characterization of the polymer blend nanocomposites were investigated by Fourier Transform infrared (FT-IR) and wide angle X-ray diffraction (WAXD). Loading of the surface modified carbon nanotube in the PU/PLA polymer blends resulted in the significant improvement on the mechanical properties such as tensile strength, when compared to the pure and pristine CNT loaded polymer blends. Dynamic mechanical analysis showed that the glass transition temperature (T_g) of the PU/PLA blend slightly increases on loading of pristine CNT and this effect is more pronounced on loading surface modified CNTs. Thermal and electrical properties of the polymer blend composites increases significantly on loading pristine or surface modified CNTs. Finally, shape memory studies of the PU/PLA/modified CNT composites exhibit a remarkable recoverability of its shape at lower applied dc voltages, when compared to pure or pristine CNT loaded system.     

Ball milling: An effective technique for the preparation of exfoliated clay filled unsaturated polyester toughened epoxy nanocomposite

This paper investigates the possibility of improving the mechanical and thermal properties of epoxy and unsaturated polyester toughened epoxy resins through the dispersion of octadecyl ammonium ion-exchanged montmorillonite (organoclay) through exfoliated mechanism. The nanocomposites prepared are characterized for their structural change and studied for their crystallite size, mechanical, thermal and water absorption (hydrophilicity) properties. The mechanical data indicates significant improvement in the flexural and tensile properties over the neat epoxy and UP-epoxy matrix according to the percentage content of organoclay. The thermal behavior too shows noticeable enhancement in glass transition temperature T _g and high thermal stability. Hydrophilicity of all the composites decreases irrespective of the concentration of organoclay on the epoxy and UP-epoxy matrices. The homogeneous morphology of epoxy and UP toughened epoxy nanocomposite hybrid systems is ascertained using scanning electron microscope (SEM). X-ray results point out that the cetyl ammonium modified clay filled composites exhibited the exfoliated structure.     

Dynamic Mechanical Properties of Activated Carbon–Filled Epoxy Nanocomposites

Nano-activated carbons obtained from oil palm empty fiber bunch (AC-EFB), bamboo stem (AC-BS), and coconut shells (AC-CNS) were reinforced in epoxy matrix to fabricate epoxy nanocomposites. The dynamic mechanical analysis of epoxy nanocomposites was carried out, and 5% AC-CNS treated with KOH-filled epoxy composites displayed the highest storage modulus of all the activated carbon–filled epoxy composites. The incorporation of a small amount of AC-BS, AC-EFB, and AC-CNS to the epoxy matrix enhanced the damping characteristics of the epoxy nanocomposites. The 5% AC-EFB treated with H₃PO₄ filled epoxy composites showed the highest glass transition temperature (T_g) in all temperature ranges.     

Dynamic mechanical analysis

Using dynamic mechanical analysis (DMA) we have studied thermal degradation for a system containing a diglycidyl ether of bisphenol A (DGEBA) and 1,3-bisaminomethylcylohexane (1,3-BAC). The changes of dynamic mechanical properties during thermal degradation indicated a shift of the glass transition temperature (T _g) to higher temperatures and a decrease in the peak value of the dynamic loss factor (tan δ) with an increasing of aging time. The value of dynamic storage modulus (E′) at the rubbery state showed an increase with aging time, whiteE′ at the glassy state only underwent a moderate change with increased thermal degradation. From these results it can be argued that thermal degradation during the stage prior to the onset of the severe degradation involves structural changes in the epoxy system, as further crosslinking and loss of dangling chains in the crosslinked network.     

Epoxy‐cyanate ester shape memory thermoset: some aspects of phase transition,viscoelasticity and shape memory characteristics

A shape memory thermoset comprising of a co‐reacted system of epoxy resin (diglycidylether of bisphenol A), cyanate ester (bisphenol A dicyanate ester) and phenol telechelic poly(tetramethylene oxide) (PTOH) was investigated for its morphology, viscoelasticity and shape memory characteristics at the transition temperature regime. The system exhibited a switching temperature (T_switch) centered at about 105°C. Atomic force microscopy analyses at different temperatures provided evidences for the existence of a discrete phase at T_switch regime. Polarized light microscope images gave evidence for the birefringence and tubular crystal formation due to PTOH segments in the shape memory thermoset. It is concluded that the T_switch has its origin from melting transition of PTOH and T_g of the thermoset matrix, the latter being lowered through plasticization by PTMO segments. Reversibility of T_switch, and stress relaxation behavior of the blend were investigated by dynamic mechanical analysis (DMA). The reversibility of transition temperature was ascertained by cyclic DMA. Temperature dependency of shape memory properties implied fast recovery of original shape above the T_switch. The cured system manifests shape memory properties even below T_switch though it is a slow process. The extent of shape recovery increased with temperature and became faster in league with the trend in temperature dependency of stress relaxation of the polymer. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis of a random copolymer and its compatibility for thermotropic liquid crystalline polymer/poly(ether ether ketone) blends

A random copolymer (RCP) containing poly(ether ether ketone) (PEEK) and thermotropic liquid crystalline polymer (TLCP) segments was synthesized. Its chemical structure and liquid crystalline properties were characterized by FT‐IR, differential scanning calorimetry (DSC) and polar light microscopy (PLM) respectively. A single glass transition temperature (T_g) at 134.0°C, a melting temperature (T_m) at 282.0°C and a temperature of ignition (T_i) at 331.3°C can be observed. Blends of PEEK and TLCP with and without RCP as compatibilizer were prepared by extrusion and the effect of RCP on the thermal properties, dynamic mechanical properties, morphology and static tensile mechanical properties of blends was investigated by means of DSC, dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), etc. Dynamic mechanical measurements indicated that there appeared to be only a single tan δ peak resulting from the glass transition of the PEEK‐rich phase and the T_g value shifted towards higher temperature due to the presence of compatibilizer, as suggested partial compatibility. Morphological investigations showed that the addition of RCP to binary blends reduced the dispersed phase size and improved the interfacial adhesion between the two phases. The ternary compatibilized blends showed enhanced tensile modulus compared to their binary blends without RCP. The strain at break decreased for the ternary blends due to embrittlement of the matrix by the incorporation of some RCP to the matrix phase. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and properties of phosphorus-containing bio-based epoxy resin from itaconic acid

A phosphorus-containing bio-based epoxy resin (EADI) was synthesized from itaconic acid (IA) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO). As a matrix, its cured epoxy network with methyl hexahydrophthalic anhydride (MHHPA) as the curing agent showed comparable glass-transition temperature and mechanical properties to diglycidyl ether in a bisphenol A (DGEBA) system as well as good flame retardancy with UL94 V-0 grade during a vertical burning test. As a reactive flame retardant, its flame-resistant effect on DGEBA/MHHPA system as well as its influence on the curing behavior and the thermal and mechanical properties of the modified epoxy resin were investigated. Results showed that after the introduction of EADI, not only were the flame retardancy determined by vertical burning test, LOI measurement, and thermogravimetric analysis significantly improved, but also the curing reactivity, glass transition temperature (T _g), initial degradation temperature for 5% weight loss (T _d(5%)), and flexural modulus of the cured system improved as well. EADI has great potential to be used as a green flame retardant in epoxy resin systems.     

Influence of carboxyl‐terminated (butadiene‐co‐acrylonitrile) loading on the mechanical and thermal properties of cured epoxy blends

A mixture of epoxy with liquid nitrile rubber, carboxyl‐terminated (butadiene‐co‐acrylonitrile) (CTBN) was cured under various temperatures. The cured resin was a two‐phase system, where spherical rubber domains were dispersed in the matrix of epoxy. The morphology development during cure was investigated by scanning electron microscope (SEM). There was slight reduction in the glass transition temperature of the epoxy matrix (T_g) on the addition of CTBN. It was observed that, for a particular CTBN content, T_g was found to be unaffected by the cure temperature. Bimodal distribution of particles was noted by SEM analysis. The increase in the size of rubber domains with CTBN content is due probably to the coalescence of the rubber particles. The mechanical properties of the cured resin were thoroughly investigated. Although there was a slight reduction in tensile strength and young's modulus, appreciable improvements in impact strength, fracture energy, and fracture toughness were observed. Addition of nitrile rubber above 20 parts per hundred parts of resin (phr) made the epoxy network more flexible. The volume fraction of dispersed rubbery phase and interfacial area were increased with the addition of more CTBN. A two‐phase morphology was further established by dynamic mechanical analysis (DMA). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2531–2544, 2004