Preparation and characterization of two-way shape memory olefin block copolymer/silicone elastomeric blends

Very few olefin block copolymer (OBC)-based shape memory polymers (SMPs) studies were reported in the literature so far. This study investigated the preparation of OBC and silicone elastomeric blends (70/30 and 50/50) using a melt-blending technique to form the first two-way OBC-based SMPs, to our best knowledge. Two phr of ((2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (DHBP) was used to prepare flexible OBC/silicone D2 (D2 representing 2 phr of DHBP) networks. DHBP not only assisted the curing of OBC and silicone but also increased their compatibility in the blends. Despite the very low crystallinity of the OBC elastomer component, 10.4%, corresponding to only ~7% based on total resins in the OBC/silicone D2 70/30 blend, the rare two-way shape memory behavior at such a low crystallinity was still envisaged. Regarding two-way shape memory results at various loads, both entropy-driven and crystallization-driven contributions to the overall actuation magnitude (R_act) were at the highest level under 450 kPa, attributing to the highest orientation of molecular networks in the blends. With increasing the applied stress, the R_act of OBC/silicone (70/30) sample increased from 4.1% to 23.7% due to the increased strain-induced crystallization effect confirmed by the XRD (X-ray diffraction) evaluation, while the recovery magnitude (R_rec) was maintained at the high level, close to 90%, without the hindrance of high load on the recovery due to high elasticity of silicone rubber. Besides, the crystallization-driven contribution to the overall actuation magnitude was higher for the blends containing the higher amount of crystalline OBC elastomer in the blends. On behalf of silicone with outstanding thermal stability, high elastic behavior, and high hydrophobicity, OBC/silicone SMP blends with versatile properties could meet different applications.     

Thermo-responsive shape memory properties based on polylactic acid and styrene-butadiene-styrene block copolymer

This study aims to compare thermal, mechanical, and shape memory behavior of polylactic acid (PLA) blended with different structures of styrene-butadiene-styrene block copolymer (SBS), namely linear SBS (L-SBS), and radial SBS (R-SBS). The amount of L-SBS and R-SBS added was varied between 10 and 70 wt%, and the blending process was carried out using an internal mixer at 180°C before the shaping process by the compression molding. An improvement in the degree of crystallinity was observed across the entire composition range with less pronounced transition temperature change. Tensile strength and modulus of PLA/L-SBS blends were higher than PLA/R-SBS blends across all composition ranges. The results also revealed that the shape fixing ratio (R_f) and recovery ratio (R_r) of PLA/L-SBS were higher than PLA/R-SBS, with PLA70/SBS30 showed the best shape memory behavior. The morphology characteristics of the blend were also examined with the scanning electron microscope.     

Renormalized Flory-Huggins lattice model of physicochemical kinetics and dynamic complexity in self-healing double-network hydrogel

Self-healing capability offers great designability on mechanical properties of double-network (DN) hydrogel. However, the thermodynamics understanding behind such physicochemical transitions and self-healing behaviors are yet to be explored properly. This study describes a renormalized Flory-Huggins lattice model for DN hydrogels, of which the physicochemical kinetics and dynamic complexity are resulted from stress-induced bond scission and macromolecule rearrangement. Based on the Flory-Huggins lattice model and Gaussian distribution theory, an extended free-energy model was formulated by the steric repulsive free-energy function. Afterwards, the function was used to identify the working mechanisms and thermodynamics in self-healing DN hydrogels with ultra-high mechanical strength. Finally, the effectiveness of model was demonstrated by applying it to predict the mechanical behaviors of DN hydrogels, where the analytical results showed good agreements with experiment data.     

基于双硫键和氢键协效的高性能自修复聚氨酯脲的研制

为解决自修复弹性体同时具有优异的力学性能和自修复性能的矛盾,首先将原料胱氨酸（CYS）进行甲酯化得到含双硫键的二胺扩链剂胱氨酸二甲酯（CDE）,然后以聚四氢呋喃醚二醇（PTMG）为软段,异佛尔酮二异氰酸酯（IPDI）和CDE为硬段,固定摩尔比为1∶3∶2,采用两步法制备了自修复聚氨酯脲（SH-PUU）弹性体,并对SH-PUU进行了红外光谱测试、拉曼光谱测试、力学性能测试、自修复性能测试、划痕修复微观形貌观察、应力松弛和动态力学性能测试。实验结果表明：SH-PUU的软段和硬段的玻璃化转变温度分别为-38.5℃和77.6℃,微相分离程度较高,SH-PUU具有良好的力学性能,拉伸强度为13.6MPa,断裂伸长率达531.3%;同时SH-PUU具有高效的自修复能力,试样在经过80℃修复2h后,基于拉伸强度的自修复效率达到97.1%,SH-PUU的力学性能和自修复性能达到较好的平衡。SH-PUU的高自修复能力是由动态双硫键和氢键协效增强引起的,其通过加热方式的自修复机理为：SH-PUU中的动态双硫键在80℃发生可逆交换反应,SH-PUU中的氢键在低于100℃时会重新形成。     

Blends of poly(ester urethane)s and polyesters as a general design approach for triple-shape memory polymers

Poly(ester urethane)s represent a widely investigated class of thermoplastic polymers that exhibit a thermally triggered dual shape memory effect. This behavior is the result of urethane-rich hard segments that define the permanent shape, while domains formed by the crystallizable polyester segments act as the memory switch. We show here that blending poly(ester urethane)s with a second polyester having a different melting temperature is a straightforward and possibly general approach to create triple-shape memory polymers, in which two different temporary shapes can be programmed. To demonstrate this, we blended a poly(ester urethane) containing crystallizable poly(1,4-butylene adipate) segments with poly(butylene succinate) or poly(hexamethylene dodecanoate). The blends microphase separate and the different polyester segments form separate semicrystalline domains, which serve as switching elements that can be activated at different temperatures. The blends retain attractive mechanical properties and the shape memory characteristics are characterized by high fixities (70%–96%) and recovery rates (82%–94%).     

The investigation on the curing process of polysulfide sealant by in situ dielectric analysis

In this work, in situ dielectric analysis (DEA) was employed for the first time to the best of our knowledge, to monitor the curing process of polysulfide (PSF) sealant using manganese dioxide (MnO₂) as the curing agent, where the gel point and ending point were determined. The obtained results were verified by rheological tests of dynamic mechanical analysis and tensile strength tests. It showed a significant difference between this curing process and those of usual thermosetting materials. The influences of the pH value of the samples and curing temperature were investigated and discussed in detail. Also, activation energies of the curing reaction of the samples with different pH values were calculated. The results proved DEA as a reliable and useful method for in situ monitoring PSF–MnO₂ curing process. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Design and properties of dynamic self-healing polyurea molecule based on disulfide bonds

Although thermosetting polymer materials have excellent mechanical properties, they are less self-healing, recycling than thermoplastic polymer materials, which may cause a serious waste of resources. Herein, a series of polyurea materials with high mechanical strength, good properties of self-healing and recycling are prepared by adjusting the ratio of polyether polyol and introducing disulfides into the synthesis of polyurea prepolymer in an innovative way. The composite polyurea (FHPUA) materials with tensile strength over 47 MPa and elongation at break of 720% are prepared. The experimental results show that by adjusting the content of aromatic disulfide, the tensile strength is further increased to 52 MPa, and the heat resistance of the material is improved. Through five self-healing experiments, the surface of the material recovers as before even after continuous heating at 70°C for 1 h. In addition, the tensile strength of the material recovers 86.56% and the elastic modulus recovers 70.21% after four recycling experiments. In practical application, it is expected to fill the shortcomings of traditional polyurea such as micro cracks, short service life and poor performance, and have great potential applications in the fields of coating layer of heavy-duty conveyor belts, encapsulation film of electronic devices and building facade coating.     

Room-temperature self-healing and reprocessing of Diselenide-containing waterborne polyurethanes under visible light

Realizing environmentally friendly polymers that could heal themselves at room temperature is an important challenge for sustainable societies. Herein, environment-friendly self-healing waterborne polyurethanes (WPUs) containing diselenide groups were synthesized. The healing efficiency could reach up to more than 90% after exposed to visible light for 48 hours and the fractured location was allowed to be healed repeatedly. Meanwhile, a fast room-temperature self-healing could also be achieved in 4 hours with a healing efficiency of ~84%. The healing process was a combination of rapid closure of crack surfaces at the beginning due to the rebuilding of hydrogen bonds and gradual restoration of mechanical property derived from diselenide metathesis across the fractured interface. At the same time, room-temperature reprocessing could be also achieved with the aid of external pressure under visible light. Moreover, the prepared diselenide-containing WPUs exhibited excellent emulsion stability. The present work would be hopefully developed into a methodology of design and fabrication of environmentally friendly photo-sensitive polymers with self-healing and reprocessing abilities. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47071.     

Influence of chloroacetate group on physical properties of natural rubber and its interaction with fillers

Filler–rubber composites were prepared by mixing chloroacetated natural rubber (CNR) with silica, carbon black (CB), or calcium carbonate using a two‐roll mill. The interactions between the CNR and fillers, including silica, carbon black, and calcium carbonate, were characterized based on glass transition temperature (T_g) and shear storage modulus (G′). The results showed that both the T_g and G′ values of the CNR‐Si composite were found to be higher than those of the CNR–CB and CNR–CaCO₃ composites, indicating the existence of the CNR and silica interaction. The outstanding direct interaction between the CNR rubber matrix and silica without using a coupling agent was believed to be due to hydrogen bonds that formed between the hydroxyls of the silanol groups of silica and the carbonyls in the chloroacetate groups of CNR molecules. Moreover, it was also found that silica dispersed and distributed in the CNR matrix much better than in the natural rubber matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43076.     

Novel multifunctional microcapsule and its cyanate ester resin composites with self-healing ability and gamma radiation shielding ability

Resin-based composites used in spacecraft face risks from space debris and high-energy charged particles during their long-term service in the space environment. This work proposes a novel microcapsule (MC) and its cyanate ester (CE) resin-based composites (CE/MCs) with self-healing ability and gamma radiation shielding ability. The multifunctional epoxy/lead tungstate (EP@PWO) microcapsules are developed through self-assembly method and in-situ precipitation method. These microcapsules and curing agent 4,4′-diaminodiphenylsulfone (DDS) are incorporated into the CE resin to form resin-based composites with low curing temperature, self-healing ability, and gamma radiation shielding ability. Various approaches including chemical characterizations (X-ray diffractometer, fourier-transform infrared, energy dispersive spectrometer), microscopy (optical microscope, scanning electronic microscope), and thermal analysis (differential scanning calorimeter, thermogravimetric analysis) are utilized to demonstrate the successful encapsulation of the EP resin by PWO shell and good thermal stability of this material. The mechanical property, self-healing ability, and gamma radiation shielding property are investigated via fracture toughness test and using a NaI (Tl) spectrometer. In comparison with pure CE resin, the fracture toughness of the CE/MCs composites can increase by 66.5%, and the self-healing efficiency can reach up to 56%, indicating that the microcapsules have good toughening and self-healing abilities. The microcapsules and their composites also exhibit good gamma radiation shielding properties.     

Rheological and mechanical properties of dynamic covalent polymers based on imine bond

Dynamic covalent polymers based on imine bond (FPIs), which are capable of reorganizing their constitution on the molecular level, are prepared from bio-based dimer fatty acids. The irregular structure of carbon chains in dimer fatty acids leads to the amorphous nature of FPIs. The effect of imine bond on the glass transition temperature of FPIs is studied by differential scanning calorimetry. The linear viscoelasticity of FPIs is investigated by small amplitude oscillatory shear tests and analyzed by using the Likhtman-McLeish theory. It is found that the rheological behavior of FPIs is similar with that of static, linear entangled polymers predicted by Likhtman-McLeish theory, when the dynamic chain arrangements caused by imine-bond exchange is not active enough. For FPIs, the temperature variation of viscosity is still following the Arrhenius law with an activation energy of ~50 kJ mol⁻¹. Owing to the thermal adaptability, FPIs demonstrate great malleability, self-healing capability and processing stability at elevated temperatures.     

Effect of chain extender on microphase structure and performance of self-healing polyurethane and poly(urethane-urea)

In this work, four aliphatic chain extenders, hexanediol (HDO), hexane diamine (HDA), cystamine (CY), and cystine dimethyl ester (CDE), were chosen to synthesize four kinds of polyurethane and poly(urethane-urea)s (PUs), respectively. HDO extended polyurethanes, HDA extended poly(urethane-urea), CY extended poly(urethane-urea), and CDE extended poly(urethane-urea) were denoted as OPU, APU, CPU, and SPU, respectively. The effect of chain extender type on microphase structure and performance of four PUs was investigated. Our research showed that mechanical strength increased in the following order: OPU < SPU < CPU < APU, and self-healing performance increased in the opposite direction. This result is attributed to the increasing degree of microphase separation: OPU < SPU < CPU < APU. The optimal sample SPU has not only excellent mechanical properties (tensile strength of 27.1 MPa and elongation at break of 397.7%), but also exhibits superior self-healing performance (self-healing efficiencies of 95.3% and 93.5% based on tensile strength and elongation at break). The moderate degree of microphase separation between the soft segments and the hard segments, the introduction of disulfide bonds and low degree of hydrogen bonding are responsible for preparing a polyurethane or poly(urethane-urea) system with high mechanical strength and excellent self-healing performance simultaneously. This work provides useful information for us to develop self-healing polyurethane or poly(urethane-urea) materials in the future.     

Effect of orientation and content of carbon based fillers on thermal conductivity of ethylene‐propylene‐diene/filler composites

In this study, synthetic graphite, carbon fiber, and carbon nanotube were used as thermal conductive fillers and ethylene‐propylene‐diene (EPDM) as matrix. Oriented EPDM/filler composites were prepared with two‐roll mill, and the effects of orientation and content of carbon based fillers on thermal conductivity and tensile strength of the composites were investigated. Parallel thermal conductivity of the oriented composites is significantly higher than normal thermal conductivity of the oriented composites. Especially, at 31.6% graphite content, parallel thermal conductivity of oriented composites is 7.14 W/mK. Very high thermal conductivity was achieved for oriented EPDM/graphite composites. Orientation of the fillers using two‐roll mill significantly improves the thermal conductivity in the orientation direction. For all the EPDM/filler composites, tensile strength of orientation direction is higher than that of normal direction. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41000.     

Tailoring the nonlinear conducting behavior of silicone composites by ZnO microvaristor fillers

Silicone composite filled with zinc oxide microvaristors possesses excellent nonlinear conducting behavior as ZnO varistor does. For better adjusting the composite's electrical behavior to satisfy the practical field‐grading requirement, this article studied the influence of ZnO filler's property on the nonlinearity of the composite. Several groups of ZnO‐silicone composite samples in different filler volume fraction and filler diameter were prepared, the measured J‐E characteristics show that the percolation threshold of ZnO‐silicone composite is around 35%, above which the composites present reliable nonlinear behavior. The switching voltage of the composite exhibits a considerable decrease as filler's diameter increases or filler's volume fraction increases, while the nonlinear coefficient remains stable. Moreover, filler's size also has a little influence on composite's percolation limit. The conclusion above fits very well with the theory of the conducting composites and percolation process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42645.     

The effect of epoxy resin to reduce the compression set of polysulfide sealant

In this article, modified polysulfide sealants with lower compression set were prepared by a simple method of introducing the diglycidyl ether of bisphenol A resin (DGEBA epoxy resin) into sealants. The investigation on reactivity analysis and gel faction test verified that the incorporation of epoxy resin in sealants was just a blending process rather than copolyaddition with polysulfide resin. Stress–strain behavior during compression revealed that the epoxy resin could reduce the compression stress when the sealants were loaded to a certain strain, which effectively lessened crosslink breakages and benefited to compression resistance. Also the rigid phenyl structure in epoxy resin may retard incidental slide between polysulfide chains and prevent interchange reactions between disulfide linkages. The incorporation of 2 phr epoxy resin distinctly reduced compression set of polysulfide sealant from 28.3% to 11.2% after compressed 25% at 23°C for 1 day. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Plasticization effect of hydrogenated transgenic soybean oil on nitrile‐butadiene rubber

Nitrile‐butadiene rubber (NBR) compounds were prepared with different amounts of hydrogenated transgenic soybean oil (HTSO) as renewable plasticizers. For comparison, similar compounds were prepared with petroleum‐based dioctyl‐phthalate (DOP), one of the most common plasticizers for NBR. Four HTSOs with different degree of hydrogenation were used, of which three HTSOs are prepared by hydrogenation reaction at different reaction conditions and one is commercial available. The plasticization effects of HTSO and of DOP were studied by Mooney viscometry, capillary rheometry, differential scanning calorimetry (DSC), and rubber processing analysis (RPA). The results showed that all the HTSOs had better plasticization effect than DOP on NBR. The swelling index result showed that the highly‐hydrogenated‐HTSO plasticized NBR vulcanizate have higher crosslinking density than the low‐hydrogenated ones. It is worthy to mention that, the introduction of high‐hydrogenated‐HTSO greatly improved both the processability of the NBR compounds and the mechanical performance of the final products, which is hard to achieve for most of the plasticizers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40643.     

Low dielectric and high thermal conductivity epoxy nanocomposites filled with NH2‐POSS/n‐BN hybrid fillers

Hybrid fillers of mono‐amine polyhedral oligomeric silsesquioxane/nanosized boron nitride (NH₂‐POSS/n‐BN) were performed to fabricate NH₂‐POSS/n‐BN/epoxy nanocomposites. Results revealed that the dielectric constant and dielectric loss values were decreased with the increasing addition of NH₂‐POSS obviously, but increased with the increasing addition of BN fillers. For a given loading of NH₂‐POSS (5 wt %), the thermal conductivities of NH₂‐POSS/n‐BN/epoxy nanocomposites were improved with the increasing addition of n‐BN fillers, and the thermal conductivity of the nanocomposites was 1.28 W/mK with 20 wt % n‐BN fillers. Meantime, the thermal stability of the NH₂‐POSS/n‐BN/epoxy nanocomposites was also increased with the increasing addition of n‐BN fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41951.     

HPAM-TGA复配絮凝除Cu2+、去浊研究

采用阴离子型聚丙烯酰胺和巯基乙酸复配絮凝除Cu^2＋、去浊,研究了除Cu^2＋的机理和几个因素对Cu^2＋去除率的影响.实验表明：（1）含Cu^2＋水样中不含致浊物质时,Cu^2＋的去除率能达到98%;（2）当Cu^2＋和致浊物质共存时,两者会促进彼此的去除,Cu^2＋的去除率接近100%,致浊物质的去除率也能达到90%以上;（3）pH在2～5.5范围内,pH越高越有利于Cu^2＋的去除.     

Morphology,interfacial interaction,and properties of a novel bioelastomer reinforced by silica and carbon black

A novel poly(diisoamyl itaconate‐co‐isoprene) (PDII) bioelastomer was prepared by redox emulsion polymerization based on itaconic acid, isoamyl alcohol, and isoprene. Carbon black (CB), silica, and silica with coupling agent (bis(3‐(triethoxysilyl)‐propyl)tetrasulfide [TESPT]‐silica) were used as fillers to reinforce the novel elastomer. The difference in morphology, interfacial interaction, thermal properties, and mechanical properties of PDII composites filled with different fillers was studied. The homogeneous dispersion of silica and CB in the PDII matrix was confirmed by scanning electron microscopy and transmission electron microscopy. Silica had homogenous dispersion possibly because of the formation of hydrogen bonds between the silica silanols and the PDII macromolecular chains. PDII/silica and PDII/TESTP‐silica have lower crosslink density and crosslinking rate than PDII/CB owing to the adsorption of accelerators by the silanols in the silica surfaces. PDII/silica had comparable tensile strength but higher elongation at break than PDII/CB. The tensile strength of PDII/TESPT‐silica was higher than PDII/CB and PDII/silica. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013