Natural and artificial ageing of an alkyd based wood finish

Wood protection in exterior use is generally achieved with a stain. This protective product is often obtained from an alkyd resin. A natural and artificial agening have been studied by measuring the glass transition temperature (T _g) of the finish variations in terms of time. In both ageings, theT _g variations are the same; there is an increase inT _g during the first steps of ageing and then a stabilization. A behaviour equation is proposed and is perfectly suitable to both ageings. Time constants are calculated. This equation shows that the artificial ageing machine chosen is a good means of artificial ageing. It allows the reproduction and the acceleration by 10 times of phenomena which are observed during the natural ageing.     

The effect of fiber orientation and stacking sequence on carbon/E-glass/epoxy intraply hybrid composites under dynamic loading conditions

This study investigated the dynamic mechanical properties of hybrid intraply carbon/E-glass epoxy composites with different orientations and stacking sequences under different loading conditions with increasing temperature. A neat epoxy and five various hybrid composites such as Carbon (0°)/E-glass (90°), Carbon (45°)/E-glass (135°), Carbon (90°)/E-glass (0°), Carbon/E-glass (alternating layer), and Carbon/E-glass (alternating layer 45°) were manufactured. Three-point bending test and dynamic mechanical test were conducted to understand the flexural modulus and viscoelastic behavior (storage modulus, loss modulus, and loss tangent) of the composites. Dynamic mechanical test was performed with the dual cantilever method, at four different frequencies (1, 5, 10, and 20 Hz) and temperatures ranging from 30 to 150°C. The experimental results of storage modulus, loss modulus, and loss tangents were compared with the theoretical findings of neat epoxy and various hybrid composites. The glass transition temperature (T_g) increased with the increase in frequency. A linear fit of the natural log of frequency to the inverse of absolute temperature was plotted in the activation energy estimation. The interphase damping (tanδ_i) between plies and the strength indicator (S_i) of the hybrid composites were estimated. It was observed that the neat epoxy had more insufficient storage and loss modulus and a high loss tangent at all the frequencies whereas hybrid composites had high storage and loss modulus and a low loss tangent for all the frequencies. Compared with other hybrid composites, Carbon (90°)/E-glass (0°) had higher strength and activation energy. The result of reinforcement of hybrid fiber in neat epoxy significantly increases the material's strength and stability at higher temperatures whereas decreasing free molecular movement.     

Thermal ageing of rocket propellant formulations containing ε-HNIW (ε-CL20) investigated by heat generation rate and mass loss

New types of rocket propellant batches have been formulated with the objective of achieving higher burning rates. The main ingredients are (1) the energetic plasticizers glycidyl azide polymer-α,ω-diazide (GAP)-A (short chain GAP with azide end groups), trimethylolethane trinitrate (TMETN) and 1,2,4-butanetriol trinitrate (BTTN), (2) the energetic substances ammonium perchlorate (AP) and ε-CL20 (ε-HNIW, hexanitrohexazaisowurtzitane, crystallised in ε-phase). The binder is GAP (glycidyl azide polymer, diol component) cured with the polyisocyanate Desmodur™ N100. From the point of view of stability and ageing, the interesting fact is that the formulations contain none of the typical stabilisers for the nitric acid ester components TMETN and BTTN, although their contents range up to 21 mass%. One reason for doing so is to increase the content of the high energy ingredients. Seven formulations were examined in more detail. To assess basic stability the autoignition temperature test, Dutch mass loss test and vacuum stability test were used. To investigate ageing, two measurement quantities are applied: heat generation rate (heat flow) as function of time at 70, 80 and 89 °C and mass loss as function of time at the temperatures of 70, 80 and 90 °C. The evaluation of the measurements was done with reaction kinetic models. One batch (#189) containing BTTN shows significantly lower activation energy and pre-exponential factor. From mass loss one gets as activation energy for #189 of 101 kJ mol⁻¹ in comparison to the range of 126-135 kJ mol⁻¹ for the six other batches. But, based on the ageing caused by chemical decomposition reactions, all seven batches showed a good ageing behaviour. A use time period of up to 20 years of use seems realistic.     

Viscoelastic properties of nanostructured natural rubber/polystyrene interpenetrating polymer networks

The effects of the blend ratio and initiating system on the viscoelastic properties of nanostructured natural rubber/polystyrene‐based interpenetrating polymer networks (IPNs) were investigated in the temperature range of ?80 to 150 °C. The studies were carried out at different frequencies (100, 50, 10, 1, and 0.1 Hz), and their effects on the damping and storage and loss moduli were analyzed. In all cases, tan δ and the storage and loss moduli showed two distinct transitions corresponding to natural rubber and polystyrene phases, which indicated that the system was not miscible on the molecular level. However, a slight inward shift was observed in the IPNs, with respect to the glass‐transition temperatures (T_g's) of the virgin polymers, showing a certain degree of miscibility or intermixing between the two phases. When the frequency increased from 0.1 to 100 Hz, the T_g values showed a positive shift in all cases. In a comparison of the three initiating systems (dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile), the dicumyl peroxide system showed the highest modulus. The morphology of the IPNs was analyzed with transmission electron microscopy. The micrographs indicated that the system was nanostructured. An attempt was made to relate the viscoelastic behavior to the morphology of the IPNs. Various models, such as the series, parallel, Halpin–Tsai, Kerner, Coran, Takayanagi, and Davies models, were used to model the viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by group contribution analysis; this showed that the damping was influenced by the phase morphology, dual‐phase continuity, and crosslinking of the phases. Finally, the homogeneity of the system was further evaluated with Cole–Cole analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1680–1696, 2003     

Improved Glass Transition Temperature towards Thermal Stability via Thiols Solvent Additive versus DIO in Polymer Solar Cells

The halogen‐free solvent additive, 1,4‐butanedithiol (BT) has been incorporated into PTB7‐Th:PC₇₁BM, leading to higher power conversion efficiency (PCE) value as well as substantially enhanced thermal stability, as compared with the traditional 1,8‐diiodooctane (DIO) additive. More importantly, the improved thermal stability after processing with BT contributes to a higher glass transition temperature (T _g) of PTB7‐Th, as determined by dynamic mechanical analysis. After thermal annealing at 130 °C in nitrogen atmosphere for 30 min, the PCE of the specimen processed with BT reduces from 9.3% to 7.1%, approaching to 80% of its original value. In contrast, the PCE of specimens processed with DIO seriously depresses from 8.3% to 3.8%. These findings demonstrate that smart utilization of low‐boiling‐point solvent additive is an effective and practical strategy to overcome thermal instability of organic solar cells via enhancing the T _g of donor polymer.     

Influence of glass transition temperature of crosslinked unsaturated polyester resin/styrene formulations on the final conversion after an isothermal curing at 100°C

SMC (sheet molding compound) is a composite based on fibers‐reinforced unsaturated polyester (UP) resin molded usually at 140°C to 170°C under a pressure of 60 to 100 bars. In order to develop new SMC formulations that can be molded at lower temperature (100°C) for economic and environmental reasons, the formulation of the composite had to be completely modified, both to allow a rapid reaction at 100°C, but also to avoid a vitrification phenomenon due to the fact that the glass transition temperature (Tg) of the SMC parts becomes, during the molding process, higher than the mold temperature. In this paper, the relation between the molding temperature, the glass transition temperature, and the final conversion of UP resin/styrene formulations has been underlined. The Tg of the cured resin was decreased by two different ways. The first way involved the reduction of the crosslinking density of the UP resin by using a blend of two resins, a pure maleic and a more flexible one. This blend allows to adjust the Tg over a temperature range from 197°C (Tg of the pure UP resin) to 75°C (Tg of the pure flexible resin). The second way consisted in the addition of butyl methacrylate (BuMA), a reactive plasticizer, to the formulation, allowing a decrease of the final material's Tg from 197°C to 130°C by replacing 35 wt% of styrene by BuMA. These two methods allow to obtain a final conversion of 99% after 8 minutes of molding at 100°C.     

Aging and cold crystallization of melt‐extruded poly(trimethylene terephthalate) films

We analyzed the thermal crystallization, glass‐transition behavior, and mechanical properties of melt‐extruded poly(trimethylene terephthalate) (PTT) films to investigate their physical aging and annealing effects. The physical aging and annealing of PTT films had an influence on the glass‐transition temperature, recrystallization behavior, and mechanical properties. When samples were aged at an ambient temperature, the crystallization temperature decreased largely within 5 h, the heat of crystallization increased, and the breaking stress and breaking elongation increased. The glass‐transition temperature of annealed samples, which was obtained from differential scanning calorimetry and dynamic mechanical measurements, increased with increasing annealing temperature below 80 °C but decreased above that temperature. In addition, the glass‐transition temperature and modulus of annealed samples were largely affected by the annealing time; in particular, they increased sharply within 1 h on annealing at 50 °C. Consequently, the change in the glass‐transition temperature on annealing was ascribed to the fact that the molecular constraint due to recrystallization and the mobility of rigid amorphous PTT chains competed with each other, being dependent on the annealing temperature. The mechanical properties of aged samples were closely related to their cold‐crystallization behavior. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1920–1927, 2001     

Thermal transitions in and structures of dried polyelectrolytes and polyelectrolyte complexes

Dynamic mechanical analysis (DMA) was used to explore the thermomechanical properties of dried polyelectrolytes and polyelectrolyte complexes (PECs) with different thermal and humidity histories. Although differences in the amount of water remaining in polyelectrolytes and PECs were small for ambient versus dessicator storage, the properties of polyelectrolyte‐based materials were drastically different for different humidity histories. Glass transition temperatures (T_gs) of poly(diallyldimethylammonium chloride) (PDADMAC) were shown to vary by 100 °C, depending on humidity and thermal histories. These parameters also change glassy storage modulus values by 100%. Furthermore, we observe that dried PDADMAC is highly lossy. DMA of dried poly(styrene sulfonate) (PSS) was more complex and did not exhibit a glass transition in the tested range. DMA of a PEC of PDADMAC and PSS revealed a humidity history‐dependent water melt in the first heating cycle, as well as storage modulus values of dried and annealed PECs that only varied by 17–26% over a 275 °C temperature range. Based on these results, we report for the first time humidity history as controlling structure and properties of polyelectrolyte‐based materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 684–691     

Unsaturated polyester resins cure: Kinetic,rheologic, and mechanical dynamical analysis. II. The glass transition in the mechanical dynamical spectrum of polyester networks

Unsaturated polyester networks with various structures built from an orthophtalic polyester, with methyl ethyl ketone peroxide as an initiator and cobalt octoate as a promoter, were studied with dynamic mechanical thermal analysis from −50 to 200 °C to characterize changes in the mechanical properties as a function of the temperature. From these measurements, the glass‐transition temperatures of the different networks were determined, their dependence on conversion being fitted to an equation related to the Couchman and DiBenedetto equations. Finally, the different transitions were analyzed as a function of the cure conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 146–152, 2001     

Influence of temperature and humidity on the mechanical properties of Nafion® 117 polymer electrolyte membrane

The dynamic mechanical properties of Nafion® 117 have been measured in‐plane parallel and perpendicular to the lamination direction in a specially designed humidity cell, which allows measurement of the stiffness and mechanic loss under fuel cell relevant temperature and humidity conditions (50–100% relative humidity, 30–120 °C). The results obtained at different temperature–humidity conditions are compared with the mechanical behavior of the dry as well as the membrane saturated with liquid water. Different regimes of change in mechanical properties were found, although in general water acts as a plasticizer in Nafion®. At elevated temperatures it stiffens the membrane by stabilizing the network of hydrophilic clusters. An intermediate increase of mechanical strength at very low humidity levels is attributed to an enforcement by formation of hydrates and hydrogen bridge bonds between vicinal sulfonic acid groups. This increase is significant for the protonated state of the membrane and disappears after ion exchange. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 786–795, 2005     

Mechanical properties and transition temperatures of crosslinked-oriented gelatin

 This second part of a systematic study of the properties of crosslinked-oriented gelatin involves the effects of orientation and water content on the glass transition temperature T _g and on the melting behavior. The samples were the same as those in the preceding study, and their transition temperatures were determined by both differential scanning calorimetry and dynamic mechanical thermal analysis. The crosslinked gelatin which had been room-conditioned showed two transition temperatures: the lower one was attributed to T _g of the water-plasticized gelatin, and the higher one was interpreted as T _g of dried gelatin superimposed by melting. A rather unusual situation arose because of the fact that the T _g and melting temperatures T _m (217 and 230 ^°C, respectively) are so similar. Using water as plasticizer not only decreases T _g but produces imperfect crystallites which melt below the T _g of the system. The presence of the amorphous phase in the glassy state would presumably make it essentially impossible to define a melting point or crystallization temperature in the normal manner, as an equilibrium between crystalline and amorphous phases. Received: 8 October 1996 Accepted: 2 November 1995     

Mechanical behaviour of isotactic polypropylenes in the lower and the upper glass transitions ranges

 The effects of physical ageing on both glass transitions of isotactic polypropylenes (homopolymer and random copolymer)are investigated by isothermal dynamic mechanical spectroscopy and by low strain creep. The ageing-time dependent expressions of the amorphous fractions which undergo each relaxation are introduced in a rheological model composed by a modified Zener model (associated to the β-relaxation) in series with a γ-element (associated to the α-relaxation). The agreement between the responses of this model and the creep and dynamic results is good over a time (or frequency) range covering up to 15 decades for three kinds of isotactic polypropylenes. Received: 2 January 1996 Accepted: 16 August 1996     

Effects of the type of crosslink on viscoelastic properties of natural rubber

The viscoelastic properties of various crosslinked natural rubbers, NR, were investigated by mechanical spectroscopy. The glass transition temperature, T_g, was found to be dependent on both the crosslink density and the crosslink type. Higher values of T_g were obtained for sulfur-crosslinked NR than for peroxide-crosslinked NR at the same crosslink density. The greater influence of the sulfur content on T_g may be attributed to polysulfidic crosslinks and cyclic sulfide structures favored at high sulfur contents. Sulfur-vulcanized NRs with monosulfidic crosslinks, favored at relatively high accelerator/sulfur ratios, have properties more similar to the peroxide-cured NR with simple carbon(SINGLE BOND)carbon crosslinks covalent bonds, resulting in only small shifts in T_g. A qualitative analysis of monosulfidic crosslinks and polysulfidic structures was performed with ¹³C solid-state NMR spectroscopy. The storage modulus, E′, in the rubbery plateau region increased with increasing crosslink density. However, the crosslink type did not influence the moduli values as much as it influenced the T_g values. Different methods of detecting the crosslink density were also discussed. © 1996 John Wiley & Sons, Inc.     

Optimization of organo‐layered double hydroxide dispersion in LDPE‐based nanocomposites

Low‐density polyethylene/layered double hydroxide (LDPE/LDH) nanocomposites were prepared via melt extrusion using organo‐LDH particles and maleic anhydride functionalized polyethylene as compatibilizer. Processing parameters, preparation method, and feed composition were properly modulated until obtaining nanocomposites with intercalated/exfoliated morphologies, and an uniform distribution of nanolayers, as evidenced by X‐ray diffraction and transmission electron microscopy analysis. These materials showed a significant improvement of the thermal‐oxidative stability, which increased of about 50°C during the first step of the degradation process. Moreover, a remarkable reduction of the oxygen permeability, proportional to the aspect ratio of LDH stacks dispersed in the polyolefin matrix was evidenced, indicating the possible application of nanocomposite films as food packaging materials. As highlighted by dynamic mechanical thermal analysis, interactions at the interface between LDH layers and polymer chains caused a shift of the LDPE β‐relaxation toward higher temperatures and a reduction of the peak intensity with respect to the matrix. It was also found that the storage modulus of the nanocomposites was lower in all the temperature range with respect to the reference samples. Finally, on‐line capillary rheometer measurements evidenced that the shear thinning behavior of the nanocomposites was dominated by the matrix so that the melt processability was not compromised by the presence of the filler. Copyright © 2010 John Wiley & Sons, Ltd.     

The effect of molecular structure on the secondary transitions and their influence on the decoloration kinetics of photochromic dyes in co‐polycarbonates

Photochromic dyes have restricted use in rigid polycarbonates because of slow coloration and decoloration kinetics. In this study, it is shown that the decoloration kinetics of two photochromic dyes can be controlled by tuning the chain stiffness and free volume of the host matrix. The introduction of flexible moieties in rigid BPA‐based polycarbonate chain accelerates the decoloration of these dyes whereas a rigid co‐monomer delays the decoloration kinetics. Although T_g might be used as a parameter to improve photochromism in polymer matrices, dynamic mechanical analysis demonstrates that the decoloration kinetics of the dyes in host polymer matrices having similar T_g depends primarily on the secondary relaxations and, thus, on the polymer architecture. The effect of the co‐monomer type on the characteristic ratio is also discussed underlining the potential relationship between the free volume and chain stiffness. These results open the possibility to develop transparent or semitransparent photochromic materials based on tailor‐made co‐polycarbonates. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1593–1601     

Preparation and properties of epoxy resins cured with silyl esters of phenol novolak and cresol novolak

The curing agents of epoxy resin, trimethylsilyl ethers of phenol novolak (TMSPN) and cresol novolak (TMSCN) were prepared by refluxing phenol novolak and cresol novolak respectively, with the mixture of hexamethyldisilazane and chlorotrimethylsilane in THF. The curing reaction of epoxy resin with these curing agents and the thermal properties of cured resins were examined. The Tg values of epoxy resins cured with TMSPN were a little higher than those cured with TMSCN. The maximum of Tg is 118°C for TMSPN-cured epoxy resin against 112°C for TMSPN-cured epoxy resin. The water absorption of hydrophobic epoxy resins cured with TMSPN was a little lower than those cured with TMSCN. The clear decrease of water absorption is attributed to the difficulty of the micro-void formation caused by the more tight primary structures of TMSPN. The water absorption at 25°C containing trimethylsilyl groups is about one-tenth of that of epoxy resins cured with conventional curing agents and even one-half of that of the epoxy resins cured with active esters. The low water absorption is attributed to the presence of trimethylsilyl groups, which are more hydrophobic than ester groups, and to the absence of hydroxyl groups of the cured resins. This revised version was published online in July 2006 with corrections to the Cover Date.     

Uniaxial tensile tests and dynamic mechanical analysis of satin weave reinforced epoxy shape memory polymer composite

The utilization of epoxy shape memory polymer composite (SMPCs) as engineering materials for deployable structures has attracted considerable attention in recent decades due to high strength and satisfactory stiffness in comparison with shape memory polymers (SMPs). Knowledge of static and dynamic mechanical properties is essential for analyzing structural behavior and recovery properties, especially for new epoxy SMPCs. In this paper, a new weave reinforced epoxy shape memory polymer composite was prepared with satin weave technique and resin transfer molding technique. Uniaxial tensile tests and dynamic mechanical analysis were carried out to obtain basic mechanical properties and glass transition temperatures, respectively.The tensile strength and breaking elongation of warp specimens were comparable with those of weft specimens. The increment of elastic modulus and hysteresis loop areas became smaller with loading cycles, meaning that cyclic tests could obtain approximate stable mechanical properties. For dynamic mechanical properties, glass transition temperature (T_g) obtained from storage modulus curves was lower than that determined from tan delta curves and T_gs in the warp and weft directions were similar (29.4 °C vs 29.7 °C). Moreover, the storage modulus in response to T_g was two orders of magnitude less than that with respect to low temperature, which demonstrated the easy processibility of epoxy SMPCs near glass transition temperature. In general, this study could provide useful observations and basic mechanical properties of new epoxy SMPCs.     

Dynamic mechanical analysis of ethylene tetrafluoroethylene (ETFE) foils in use for transparent membrane buildings

Glass transition temperature and tan delta (the ratio of loss modulus to storage modulus) are indispensable parameters for determining appropriate application range of ETFE foils. In this study, ETFE foils in terms of specimen number, material direction and thickness were investigated with dynamic mechanical analysis (DMA) over a temperature range of -70-100 °C at frequencies of 0.1, 1, and 10 Hz. Glass transition temperatures were obtained with storage modulus, loss modulus and tan delta curves. It is found that frequency effect on glass transition temperature was proportional and that frequency effect was more significant than material direction effect. Moreover, a comparison study showed that elastic modulus determined with quasi-static experiments was greater than storage modulus calculated with dynamic mechanical experiments. To propose suitable glass transition temperature ranges for engineering application, an approach to determine confidence interval based on statistical analysis was employed. The resulting intervals with confidence coefficient of 95% were 31.2–32.7 °C, 60.5–66.4 °C and 79.6–83.3 °C for storage modulus, loss modulus and tan delta, respectively. In general, this study could provide useful observations and values for evaluating dynamic mechanical properties of ETFE foils.     

Effect of benzenesulfonamide plasticizers on the glass‐transition temperature of semicrystalline polydodecamide

The effect of various benzenesulfonamide (BSA) plasticizers on the amorphous phase of semicrystalline polydodecamide (PA‐12) has been investigated. MonoBSAs appear as efficient glass‐transition temperature (T_g) depressors because of their miscibility with the host polyamide (PA), low glass transition, and small molecule size. PA‐12's T_g shifts from 50 to about 0 °C at 20 mol % of the most efficient molecules. Comparatively, the more bulky bisBSAs appear to induce less important absolute T_g decreases (30 K at 20 mol %), although these appear as more important when considering the polymer T_g to plasticizer T_g difference. This unexpected observation could be ascribed to both the amide‐sulfonamide interactions and the sterically generated disorder within the polyamide because of the plasticizer molecule's size. Phase‐separation behavior of BSA plasticizers within the host PA has also been investigated. Crystalline phenyl‐SO₂NH₂, for instance, dephased beyond 20 mol % in PA‐12, forming distinct 1–2 micrometer wide crystalline domains as a result of its high propensity to crystallize upon cooling from the melt. By contrast, slow crystallizing N,N‐dimethylBSA, which lacks any specific interaction for PA‐12, remained nevertheless dispersed at a molecular level (metastable state, no phase separation) when vitrification of the host PA‐12 amorphous phase occurred on cooling. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2208–2218, 2002