Effect of glucose crosslinking on thermomechanical properties and shape memory effect of PET‐PEG copolymers

Poly(ethylene terephthalate) (PET) and poly (ethylene glycol) (PEG) copolymers crosslinked with glucose as a crosslinker are prepared to improve their mechanical and shape memory properties compared to the one without crosslinking. Composition of PEG and glucose is varied to search for the one with the best mechanical and shape memory properties. The highest shape recovery rate is found in the copolymer composed of 25 mol % PEG‐200 and 2.0 mol % glucose. The result that crosslinking by glucose improves the shape recovery rate and supports the high shape recovery rate under the repetitive cyclic test conditions, compared to the one without crosslinking, will be discussed in the points of the structure and shape memory mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of the cross‐linking process on the electrical resistivity and shape‐memory behavior of cross‐linked carbon black filled ethylene‐octene copolymer

The electrical resistance of carbon black (CB) filled ethylene‐octene copolymer (EOC) was monitored during the compression molding step by means of conductivity sensors. It increases strongly during the cross‐linking process due to the de‐agglomeration of CB aggregates. After completion of cross‐linking reaction CB aggregates reagglomerate causing a decay of resistance. The electrically stimulated shape‐memory (SM) behavior was found to be strongly dependent on the extent of electrical resistivity and the rigidity of CB network, which is formed during compounding and subsequent cross‐linking process. The effect of amount of peroxide and cross‐linking conditions like time and temperature on resistivity and the related SM behavior was characterized. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Flexible cross‐linking by both pentaerythritol and polyethyleneglycol spacer and its impact on the mechanical properties and the shape memory effects of polyurethane

A series of polyurethane (PU) polymers cross‐linked laterally by pentaerythritol and polyethyleneglycol (PEG) spacers were compared with linear PU. The PU was composed of 4,4′‐methylenebis(phenylisocyanate) (MDI), poly(tetramethyleneglycol), 1,4‐butanediol (BD), pentaerythritol, and PEG‐200 as a spacer. PEG‐200 connected the pentaerythritol hydroxyl groups of two PU chains with MDI as a connecting agent. The phase separation between hard and soft segments was disrupted by the PEG crosslinking, and T_m did not change with an increase in cross‐linking content. Instead, the cross‐link density increased with an increase of pentaerythritol content. A significant increase in maximum stress compared with linear PU was attained, together with an increase in strain. The combination of both pentaerythritol and PEG‐200 in the PU resulted in the improvement of both stress and strain, unlike in the conventional cross‐linking method. The shape recovery increased to 90% and did not decrease after three test cycles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Triple‐shape memory properties of polyurethane/polylactide–polytetramethylene ether blends

A facile method to prepare triple‐shape memory polymers was developed by blending polyurethane and polylactide–polytetramethylene with well‐separated glass transition temperatures. The thermal properties of the blends were characterized using modulated differential scanning calorimetry and differential scanning calorimetry. Field emission scanning electron microscopy, Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction were used to characterize the microstructures and crystal structures of the blends. The mechanical properties were also evaluated. The versatile triple‐shape memory effect and quantitative shape memory response were evaluated by consecutive thermal mechanical experiments based on a two‐step programming process and subsequent progressive thermal recovery. The results show that the blends have phase‐separated microstructures resulting in an ability to fix two temporary shapes independently and can recover to their original shapes sequentially. The blends have excellent triple‐shape memory properties and may have some applications in multi‐shape coatings, adhesives, films and temperature sensing or actuating elements. © 2015 Society of Chemical Industry     

交联型与线形水性聚氨酯的形状记忆性能比较

由聚酯多元醇、2,4–甲苯二异氰酸酯、二羟甲基丙酸等合成了水性聚氨酯乳液,对乳液性能进行了研究;对制得的聚氨酯胶膜进行了红外分析、DSC测试和形状记忆性能测试;用丙三醇和三羟甲基丙烷作为扩链制得的交联水性聚氨酯与用1,4–丁二醇制得的线形水性聚氨酯进行了性能比较,结果表明:不同扩链剂对水性聚氨酯的性能有一定的影响,与线形水性聚氨酯相比,交联型水性聚氨酯具有较好的形状记忆性能,形状恢复率可达92%～97%。     

Multi‐point monitoring of cross‐linking reactions

The feasibility of deploying optical fiber sensors to obtain qualitative and quantitative information on the cross‐linking characteristics of thermosetting resin systems has been demonstrated by a number of researchers. This article is concerned with the demonstration of a low‐cost fiber‐optic Fresnel sensor system for monitoring the cross‐linking reactions at multiple locations. Cross‐linking reactions can be influenced by a number of parameters including the stoichiometry of the resin and hardener, and the heat‐transfer rates in and out of the preform as a function of the cross‐section of the preform. In situations where there is a variation in the thickness of the preform or when large components are processed, a facility to monitor the cross‐linking reactions at multiple locations will be valuable because the rate and extent of the cross‐linking can be inferred. In this article, six Fresnel sensors were immersed in individual vials containing an epoxy/amine resin system and processed (cross‐linked) in an air‐circulating oven. One additional vial with a Fresnel sensor immersed in the neat epoxy resin (no hardener) was co‐located in the oven to enable the effect of temperature to be monitored. The feasibility of using the multiplexed Fresnel sensors for cure monitoring was demonstrated successfully. The sensors in the post‐cross‐linked samples were used to study the effects of heating and cooling cycles. The feasibility of detecting the glass transition temperature using the Fresnel sensor is discussed along with the factors that give rise to variability in the output Fresnel signals. © 2014 The Authors. Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41088.     

Electrospun nonwovens of shape‐memory polyurethane block copolymers

Synthesized shape‐memory polyurethane (PU) block copolymers were used to prepare electrospun nonwovens via electrospinning. PU solutions were prepared with a mixed solvent of N,N‐dimethylformamide and tetrahydrofuran. The electrospun PU nonwovens were prepared with hard‐segment concentrations of 40 and 50 wt %. The morphology of the electrospun fibers was investigated with scanning electron microscopy. The average diameter of low‐viscosity (ca. 130–180 cPs) electrospun fibers was about 800 nm, and the morphology of the electrospun nonwovens was beaded‐on fibers. In contrast, the average diameter of high‐viscosity (ca. 530–570 cPs) electrospun fibers was about 1300 nm. In an investigation of the mechanical properties of the electrospun PU nonwovens, it was found that the tensile strength increased as the hard‐segment concentration increased within a similar range of viscosities. Also, the tensile strength of the electrospun PU nonwovens in the machine direction was higher than that in the transverse direction because of a difference in the velocities of the drum collectors. The electrospun PU nonwovens with hard‐segment concentrations of 40 and 50 wt % were found to have a shape recovery of more than 80%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 460–465, 2005     

Shape memory effect and properties memory effect of polyurethane

The relationship between shape and properties memory effect, especially viscoelastic properties of polyurethane under study is the main aim of this research work. Tensile tests have been performed in order to introduce 100% of deformation in the polyurethane samples. Under this deformation, stress–relaxation experiments have been performed in order to eliminate the residual stresses. This deformation of the samples has been fixed by cooling. Recovery tests, then, were carried out at different isothermal temperatures that varied from 30°C to 60°C. Viscoelastic behavior has been studied by a biparabolic model and by using the Cole–Cole method. It was shown that this model describes the behavior of the polymer at the different states of shape memory tests. The constants of this model then have been determined. This study leads to a better understanding of the mechanism of shape memory effect. The comparison between the virgin polymer and the polymer after a recovery test by DMTA (dynamic mechanical thermal analysis) and by Cole–Cole method has illustrated that the polymer does not obtain its initial properties even when it was totally regained its initial shape. These results have been confirmed by three successive shape memory tests on the same sample and by comparing the mechanical characteristics of different cycles because “shape memory effect” and “properties memory effect” do not follow the same mechanisms. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

High‐temperature‐resistant polymer gel system with metal–organic mixed cross‐linking agents

A high‐temperature (200°C)‐resistant polymer gel system was developed from partially hydrolyzed polyacrylamide (HPAM), chromium lactate (CrL), and water‐soluble phenol/formaldehyde resin (WPF) mixed cross‐linkers. Rheological measurements indicated that the gelation process of the gel system could be divided into four successive steps: induction, first cross‐linking with metal cross‐linker, secondary cross‐linking with organic cross‐linker, and stabilization. Effects of various parameters that affect the gelation time and gel strength including polymer concentration, cross‐linker concentration, salinity, pH, and the gelation temperature were evaluated. Gelant formulated with 0.5 wt % HPAM, 0.1 wt % CrL, and 0.9 wt % WPF and treated at 80°C for 48 h showed sufficient gelation time, high rigidity, and good thermal stability. Morphology observation by scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed that the gel had compact network microstructure. A cross‐linking mechanism for the gel system was proposed based on the gelation process and experimental results. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42261.     

Dicumyl peroxide cross‐linking of nitrile rubbers with different content in acrylonitrile

The scope of this article is the study of peroxide curing of two nitrile rubbers with low and high nitrile content. The peroxide efficiency can be much higher than one, and the polymer structure determines the mechanism of cross‐linking. In the rubber with low nitrile content, the peroxide radical may give rise to a polymerization reaction between adjacent double bonds generating a heterogeneous network with a negative effect on the vulcanizate properties. On the contrary, in the nitrile rubber with high nitrile content, this negative effect it is not present or is present to a lesser extent, and their vulcanizates show good physical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1–5, 2005     

Synthesis and characterization of vinyl‐polyhedral oligomeric silsesquioxanes‐reinforced silicone resin with three‐dimensional cross‐linking structure

A novel thermal stability and highly transparent silicone resin‐type material was prepared via hydrosilylation of vinyl‐polyhedral oligomeric silsesquioxanes (POSS)‐grafted methylhydrosilicone oil and vinylmethylsilicone oil in the presence of Karstedt catalyst. The morphology, mechanical property, thermal stability, optical transmittance, thermal‐oxidation resistance of the vinyl‐POSS‐reinforced silicone resins were systematically investigated. Scanning electron microscopy showed that the vinyl‐POSS‐reinforced silicone resins had good compatibility with polydimethylsiloxane (PDMS) systems. The mechanical analysis and thermo gravimetric analysis indicated that the mechanical properties and thermal stability increased with increasing quantity of vinyl‐POSS. However, the optical transmittance increased with the increasing amount of vinyl‐POSS rather than decreased. In addition, the incorporation of vinyl‐POSS did not improve the thermal resistance of the PDMS polymers. The product has the potential application for LED packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42187.     

Microstructural and mechanical property evolutions of shape memory polyurethane during a thermodynamic cycle

To better understand the shape memory behaviors of synthesized shape memory polyurethane (SMPU) sealant with a tailored transition temperature (T_t) for concrete pavement joints, the thermal and dynamic mechanical properties of SMPU were first characterized to determine the shape memory switching temperature of SMPU. Then the microstructural and mechanical property evolutions of SMPU in the original, programmed, and recovered states during a five‐step thermodynamic cycle were discussed, respectively. The results indicate that the tailored T_t of prepared SMPU can be used as the shape memory switching temperature to match its working temperature. Further, the programming causes the phase separation in SMPU, leading to an obvious anisotropy. The SMPU has satisfactory shape memory performance. The orientation of molecular chains in soft segments is confirmed along the stretching direction. The oriented molecular chains can restore to the naturally curled state during the free recovery. Finally, the programming improves the mechanical properties of SMPU. The recovered SMPU shows a slight decrease in mechanical properties because of the partially impaired crystal structures and broken molecular segments during the programming and recovery. It is concluded that the synthesized SMPU with the specially tailored T_t is suitable to use as a sealant of concrete pavement joints. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45703.     

Evaluation of cross‐linking after accelerated photo‐ageing of silicone rubber

Silicone formulations based on polydimethylsiloxane (PDMS) were investigated by using a number of analytical techniques. Horizontal attenuated total reflectance Fourier‐transform infrared (HATR‐FTIR) spectroscopy studies have confirmed the stability of these materials towards photo‐oxidation. No significant oxygenated products were detected after 5000 h of accelerated photo‐ageing. However, by using thermoporosimetry, hardness measurements and densitometry, an important vulnerability of these formulations towards the cross‐linking reactions provoked by UV visible radiation was identified. Thermoporosimetry, using the solid‐solid cyclohexane transition as a textural probe, was also used to visualize the profile of cross‐linking inside the materials by calculation of the mesh size distribution in successive slices of 40 µm in thickness. Copyright © 2003 Society of Chemical Industry     

Improving the ceramic yield of polycarbosilane by radiation cross‐linking in the presence of multifunctional monomers

An interesting method for radiation cross‐linking polycarbosilane (PCS) at high efficiency and low cost was developed by adding multifunctional monomers (trimethylolpropane trimethacrylate (TMPTMA) or divinylbenzene (DVB)). The effect of multifunctional monomers on the radiation cross‐linking and ceramic yield of PCS was investigated. The results revealed that the addition of a small amount of multifunctional monomer can substantially improve the ceramic yield and reduce the absorbed dose by promoting cross‐linking. The ceramic yields of radiation cross‐linked “PCS/2%DVB (300 kGy)” and “PCS/2%TMPTMA (300 kGy)” were 74 wt% and 78 wt%, respectively, while that of the radiation cross‐linked “PCS (300 kGy)” was only 64 wt%. The presence of double bonds in multifunctional monomers stimulated the combination reactions of free radicals in PCS induced by γ‐ray irradiation and subsequently enhanced the efficiency of cross‐linking. Furthermore, it was found that the incorporation of a small amount of multifunctional monomer hardly affected the chemical composition and crystallization behavior of the final SiC ceramics.     

Study on the liquefied‐MDI‐based shape memory polyurethanes

A series of liquefied‐MDI‐based polyurethanes having shape memory behavior, with various soft segments, chain extenders, and micro‐phase separation promoters were synthesized. Their morphology and properties were investigated in terms of thermal properties, dynamic mechanical properties, and shape recovery behavior. The results indicate that the soft segment formed with longer chain segment incline to crystallize during the cooling scans and the resulting SMPU have the higher crystallinity. Meanwhile, the chain extenders, which can enhance the polarity of hard segment, incline to have excellent shape memory properties with bigger storage modulus in rubbery state too. It was also found that the micro‐phase separation promoters have great influence on the shape memory behavior due to the enhancement of micro‐phase separation of SMPU. Furthermore, it was proved again that SMPU with longer soft segment and lower hard segment contents usually showed good shape memory behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Surface layer modification of AEMs by infiltration and photo‐cross‐linking to induce monovalent selectivity

Surface modification of anion exchange membranes (AEMs) by attaching a negatively charged layer is the main method for preparing monovalent anion selective membranes. However, tremendous increase of membrane resistance and poor long‐term stability of the modified membranes face great challenges. In this work, a photosensitive molecule (4,4‐diazostilbene‐2,2‐disulfonic acid disodium salt [DAS]) was infiltrated into the membrane surface and immobilized in the structure by cross‐linking under UV irradiation. This method introduced negative charge to the surface layer of the AEMs without increasing membrane thickness, leading to high performance membrane with high monovalent anion selectivity. The optimized membrane (D‐5) shows the highest perm‐selectivity of 11.21, which is superior to the commercial selective membrane Selemion^® ASV and previously reported monovalent anion selective AEMs. Furthermore, the newly developed membrane exhibits excellent long‐term stability, which can maintain constant selectivity during the 80 h ED experiment. © 2017 American Institute of Chemical Engineers AIChE J, 64: 993–1000, 2018     

Effect of gel spinning accompanied with cross‐linking using boric acid on the structure and properties of high‐molecular‐weight poly(vinyl alcohol) fiber

To enhance the thermal stability of poly(vinyl alcohol) (PVA) fiber, the fiber was prepared from the gel spinning of high molecular weight (HMW) PVA by using dimethyl sulfoxide/water (8/2, v/v) as a solvent, accompanied with the cross‐link by boric acid (B‐PVA). In addition, the structure and properties of the B‐PVA fiber were compared with those of the HMW PVA fiber obtained by using the same spinning system without cross‐linking (NB‐PVA). Through a series of experiments, it turned out that cross‐linking actualized by an optimum amount of boric acid (0.3 wt % based on PVA) and zone drawing caused significant changes in the properties of HMW PVA gel fiber. That is, cross‐linking increased thermal degradation temperatures at each degradation step and amounts of final residues, resulting in improving thermal properties of the PVA fiber. On the contrary, it was found that in the case of the B‐PVA fiber, some broadening of the original PVA unit cell occurred, which was identified by the peak shift to lower angle in X‐ray diffractogram. The tensile strength and Young's modulus of B‐PVA fiber with draw ratio of 15 are 23.1 and 308.3 g/d, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of dynamic cross‐linking on melt rheological properties of polypropylene/ethylene‐propylene‐diene rubber blends

Study of melts rheological properties of unvulcanized and dynamically vulcanized polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, at blending ratios 10–40 wt %, EPDM, are reported. Blends were prepared by melt mixing in an internal mixer at 190°C and rheological parameters have been evaluated at 220°C by single screw capillary rheometer. Vulcanization was performed with dimethylol phenolic resin. The effects of (i) blend composition; (ii) shear rate or shear stress on melt viscosity; (iii) shear sensitivity and flow characteristics at processing shear; (iv) melt elasticity of the extrudate; and (v) dynamic cross‐linking effect on the processing characteristics of the blends were studied. The melt viscosity increases with increasing EPDM concentration and decreased with increasing intensity of the shear mixing for all compositions. In comparison to the unvulcanized blends, dynamically vulcanized blends display highly pseudoplastic behavior provides unique processing characteristics that enable to perform well in both injection molding and extusion. The high viscosity at low shear rate provides the integrity of the extrudate during extrusion, and the low viscosity at high shear rate enables low injection pressure and less injection time. The low die‐swell characteristics of vulcanizate blends also give high precision for dimensional control during extrusion. The property differences for vulcanizate blends have also been explained in the light of differences in the morphology developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1488–1505, 2000     

The influence of cross‐linking reaction on the mechanical and thermal properties of polyarylene ether nitrile

The processing of cross‐linked polyarylene ether nitrile (PEN), which has a triazine rings structure, has been investigated under different reaction times and temperatures. In this study, the PEN films prepared by the tape‐casting formed the thermally stable triazine rings by catalytic cross‐linking reaction gradually, which was characterized by Fourier transform infrared spectroscopy. The chemical cross‐linking reaction occurred as the CN group absorption of PEN at 2221 cm⁻¹ decreased and a new absorption peak, at 1682 cm⁻¹, was observed, and the absorption peak intensity would be progressively larger, with the extension of the processing time. After the formation of cross‐linking networks, the cross‐linking degree and thermal and mechanical properties of the processed films were improved substantially, compared with the untreated films. The film with added ZnCl₂ as the catalyst was more rapidly cross‐linked, and its properties were better than that without catalyst at the same treatment conditions. The glass‐transition temperature (T_g) of PEN films processed at 350°C for 4 h (213.65°C) was higher than that of PEN films before the treatment (161°C), and the tensile strength was also improved significantly. The PEN was processed at 350°C for 2 h, whose initial decomposition temperature increases by about 10°C, compared with that of untreated film, at one time. The rheology behavior of the cross‐linked films was processed on dynamic rheometer to monitor and track the process of polymer cross‐linking reaction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of dynamic crosslinking on tensile yield behavior of polypropylene/ethylene‐propylene‐diene rubber blends

Tensile yield behavior of the blends of polypropylene (PP) with ethylene‐propylene‐diene rubber (EPDM) is studied in blend composition range 0–40 wt % EPDM rubber. These blends were prepared in a laboratory internal mixer by simultaneous blending and dynamic vulcanization. Vulcanization was performed with dimethylol phenolic resin. For comparison, unvulcanized PP/EPDM blends were also prepared. In comparison to the unvulcanized blends, dynamically vulcanized blends showed higher yield stress and modulus. The increase of interfacial adhesion caused by production of three‐dimensional network is considered to be the most important factor in the improvement. It permits the interaction of the stress concentrate zone developed at the rubber particles and causes shear yielding of the PP matrix. Systematic changes with varying blend composition were found in stress‐strain behavior in the yield region, viz., in yield stress, yield strain, width of yield peak, and work of yield. Analysis of yield stress data on the basis of the various expressions of first power and two‐thirds power laws of blend compositions dependence and the porosity model led to consistent results from all expression about the variation of stress concentration effect in both unvulcanized and vulcanized blend systems. Shapes and sizes of dispersed rubber phase (EPDM) domains at various blend compositions were studied by scanning electron microscopy. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2104–2121, 2000