Environmental degradation of E‐glass/nanocomposite under the combined effect of UV radiation,moisture, and rain

This study seeks to investigate how the enhanced properties of the nanoclay E‐glass/epoxy composite can withstand the combined effects of ultraviolet radiation, moisture, and rain. The montmorillonite nanoclay's affinity to moisture compounded the moisture absorption ability of the nanoclay E‐glass/epoxy composites. The moisture in the polymer structure caused delamination, debonding of the fibers/matrix, microvoids, and fiber pullouts. The high clay content (2 wt %), therefore, recorded the highest rate of degradation of 15% in flexural stress for the first 20 days, compared to about 8 and 6% loss for the unmodified (0 wt %) and 1 wt % composites respectively. However, as the aging progressed beyond 20 days, the rate of degradation of the nanoclay E‐glass/epoxy composites laminates was steady at 10 and 18%, respectively, for the 1 and 2 wt %, while that of the unmodified polymer continued to degrade progressively. On the contrary, the viscoelastic properties of the nanoclay E‐glass/epoxy composites continued to deteriorate at a faster rate than the unmodified polymer composite. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1024–1029     

Delamination of organic coating on carbon steel studied by scanning Kelvin probe force microscopy

Corrosion‐induced delamination of an epoxy coating on the AISI/SAE 1045 carbon steel was studied under a humid atmospheric condition (temperature of 25 °C, 1 standard atmospheric pressure, relative humidity of 90%) by the technique of scanning Kelvin probe force microscopy (SKPFM). Surface‐polished 1045 samples were first cold‐coated with the epoxy and then subject to the atmospheric corrosion under the specified condition. At predetermined time intervals, surface Volta potential differences of the samples were measured using the SKPFM over the dry surface of epoxy coating. The map of Volta potential differences demonstrated high contrasts among three characteristic zones: intact steel‐epoxy interface, delaminated interface, and interface with active corrosion, which was then linked to the actual corrosion potential of the steel (measured using a potentiostat with respect to a saturated calomel electrode) based on a rigorous calibration procedure. It was found that the SKPFM was able to provide direct and nondestructive detection of early active corrosion and coating delamination on steels at a submicroscopic resolution, which outperformed the conventional electrochemical techniques for the same purposes. Copyright © 2012 John Wiley & Sons, Ltd.     

Investigation of coating delamination on steels by surface topography and Volta potential difference

Corrosion-induced delamination of an epoxy coating on the AISI/SAE 1045 carbon steel was studied under a humid atmospheric condition (temperature of 25 °C, one standard atmospheric pressure, and relative humidity of 90 %) by the technique of scanning Kelvin probe force microscopy (SKPFM). Surface-polished 1045 samples were first cold coated with the epoxy and then subject to the atmospheric corrosion under the humid atmospheric condition. At specified time intervals, surface Volta potential of the samples was measured using the SKPFM over the dry surface of epoxy coating. The map of Volta potentials demonstrated high contrasts among three characteristic zones: intact steel-epoxy interface, delaminated interface, and interface with active corrosion, which based on a rigorous calibration procedure were then linked to the actual corrosion potential of the steel (measured using a potentiostat w.r.t. a saturated calomel electrode). The SKPFM was found to be able to provide a mean of direct and nondestructive detection of early active corrosion and coating delamination of steels at a submicroscopic resolution, which outperformed the conventional electrochemical techniques for such purposes.     

Electrical and humidity sensing properties of synthesized hydrophosphoric acid doped polyaniline

H₃PO₄ doped polyaniline was synthesized by a single‐step chemical polymerization method using ammonium persulfate as an oxidizing agent. The material characterization was done by SEM, UV–vis spectroscopy and thermogravimetric analysis (TGA). The pellets of the synthesized material were used to study the electrical properties, using a four‐probe method. The room temperature electrical conductivity is found to be 0.2201 S/cm. The electrical resistance in response to the varying humid environment (ranging between 20 and 100% RH) is recorded to evaluate the sensitivity of the H₃PO₄ polyaniline samples toward humidity. The resistance of the samples is found to vary by three orders of magnitude for 20–100% RH and is found to decrease with increasing humidity. The response and recovery time are observed to be 12–14 and 26–30 sec, respectively. Copyright © 2007 John Wiley & Sons, Ltd.     

Storage Stability of LiFePO4/C in Humid‐hot Air

Storage stabilities of LiFePO₄/C composite at different conditions are investigated in terms of structural and electrochemical evolutions. The results from different aging tests indicate that moisture and temperature are the key factors that have the most profound effects on the structure homogeneity which in turn influences the electrochemical performance of LiFePO₄/C. Although the storage in a humid‐hot environment, such as saturated humidity air at 50°C, does not greatly influence the discharging capacity of LiFePO₄/C, it does reduce the initial charging capacity, thus the amount of reversible Li⁺ ions in a practical LiFePO₄/graphite cell decreases. This impact is explained by the lithium extraction during the storage, forming olivine FePO₄ and associated Li₃PO₄. Elevated storage temperature also favors the delithiation process. The degree of delithiation increases from about 6% at 50°C to 18% at 80°C. It is also found that re‐calcination at 650°C effectively resolves the problem of the structural heterogeneity of the stored LiFePO₄/C. Therefore both the initial charging capacity and coulombic efficiency of the stored sample in the first cycle revert to the original value of the fresh one.     

Properties of nitrocellulose‐coated and polyethylene‐laminated chitosan and whey films

Chitosan (chitosan acetic acid salt) and whey (65% protein) films were coated with a nitrocellulose lacquer or laminated with polyethylene to enhance their water resistance and gas barrier properties in humid environments. The barrier properties were measured by the Cobb₆₀ test and water‐vapor (100% relative humidity) transmission and oxygen (90% relative humidity) permeability tests. Mechanical properties were obtained with tensile tests. Packaging properties were studied with crease and folding tests. The Cobb₆₀ test revealed that the coated films were resistant to liquid water, at least for a short exposure time, if the coating thickness was at least 10–17 μm. Water‐vapor transmission rates comparable to those of polyethylene‐laminated films were obtained for coated chitosan at a coating thickness of 5–7 μm. The coated films possessed low oxygen permeability despite the high humidity. Coated films dried for 3 weeks showed oxygen permeabilities at 90% relative humidity that were similar to values for dry ethylene‐co‐vinyl alcohol at 0% relative humidity. The lacquer partly penetrated the whey films, and this led to excellent adhesion but poor lacquer toughness. The lacquer coating on chitosan was tougher, and it was possible to fold these films 90° without the coating fracturing if the coating thickness was small. The coated whey films were readily creasable. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 985–992, 2001     

Study on porous silk fibroin materials: 3. Influence of repeated freeze–thawing on the structure and properties of porous silk fibroin materials

The influence of repeated freeze–thawing on pore structural characteristics and physical properties of porous silk fibroin materials prepared by freeze drying were studied. It showed that when quick‐frozen silk fibroin solution was repeatedly thawed and frozen before being vacuum dried, thus pore size of prepared porous silk fibroin materials increased from 67 µm to about 120 µm, and pore density decreased from 80 per square millimeter to about 28 per square millimeter; at the same time compression ratio and moisture permeability increased from 22.7% and 230 g/m² hr to about 33.7% and 308 g/m² hr, respectively, tensile strength and dissolvability in hot water decreased from 20.2 N/cm² and 42.7% to about 12.5 N/cm² and 26.1%, respectively. Both the times of repeated thawing and the thawing temperature had a certain influence on the above‐mentioned pore characteristic parameters and physical properties. Copyright © 2001 John Wiley & Sons, Ltd.     

Influence of imidazole‐based acidity control of PEDOT:PSS on its electrical properties and environmental stability

Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been studied for a wide range of applications due to its potential as a transparent electrode. Herein, the use of imidazole and its derivatives as a neutralizing additive for PEDOT:PSS dispersion and in‐depth studies of their effects in terms of electrical properties and stability is reported. Although the neutralization in general reduces the electrical conductivity of PEDOT:PSS, the conductivity after imidazole treatment (685.2 S cm^?1) is higher than that after treatment of other derivatives. Spectroscopic and thermoelectric studies show that the de‐doping effect resulted in the conductivity reduction. As a trade‐off of the conductivity reduction, greatly enhanced long‐term stability and noncorrosive characteristics are obtained after neutralization. The change in sheet resistance of imidazole‐treated PEDOT:PSS after 500 h under harsh conditions (85 °C and 85% humidity) is half that of the untreated samples, demonstrating the great enhancement of the stability. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1530–1536     

Epoxy–amine reticulates observed by infrared spectrometry. III. Modifications of the structure and hydration abilities after irradiation in a humid atmosphere

This article is the third part of a series devoted to the study of the responsibilities of both humidity and irradiation in the aging process of amine‐cured epoxy resins. The basic technique used in this study was infrared spectrometry. In previous articles, we described the hydration of two kinds of epoxy resins widely used in the nuclear industry. In the first article, we reported results concerning the hydration of unirradiated resins; in the second article, these resins were first submitted to ionizing radiation in a dry atmosphere. In this article, we describe the effects of irradiation in a humid atmosphere and compare these effects to what was observed after irradiation in a dry atmosphere, as described in the previous articles. These effects were subtle: the humidity of the ambient atmosphere apparently protected the resins from oxidative degradation because, after irradiation in a humid atmosphere, a smaller number of carboxylic groups were formed. However, the water uptake increased after irradiation in a humid atmosphere. Thus, the humidity of the ambient atmosphere at the same time favored the rupture of chains, which released steric hindrances and allowed a greater number of H₂O molecules to reach hydrophilic sites in the resin. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1129–1136, 2001     

Effects of posttreatment on the properties of modified PLLA/PDLA fibers

Poly(L ‐lactic acid)/poly(D ‐lactic acid) (PLLA/PDLA) blended with plasticizer poly(ethylene glycol) and nucleation agent TMC‐306 as‐spun fibers were prepared by melt spinning. The posttreatment was applied by hot drawing at 70°C and then heat‐treating at different temperatures for 30 minutes. In the process of hot drawing, orientation induced the further formation of the sc crystals and increased the degree of crystallinity of drawn fibers. When the hot drawing ratio reached 3 times, the properties of the fibers were relatively better. The highly oriented fibers containing pure sc crystals with high crystallinity were obtained by heat‐treating at a temperature above the melting point of α crystals. The posttreated PLLA/PDLA fibers with poly(ethylene glycol) and TMC‐306 (LDTP) obtained by hot drawing to 3 times at 70°C and then annealing at 170°C for 30 minutes exhibited the best antioxidative degradation and heat resistance properties. The initial decomposition temperature (T_5%) and heat resistance of posttreated LDTP fiber were about 94°C and 20°C higher than those of the commercial PLLA fiber, respectively.     

Viscoelastic phase diagram of fluorinated and grafted polymer films and proton‐exchange membranes for fuel cell applications

The influence of temperature and moisture activity on the viscoelastic behavior of fluorinated membranes for fuel cell applications was investigated. Uncrosslinked and crosslinked ethylene tetrafluoroethylene (ETFE)‐based proton‐conducting membranes were prepared by radiation grafting and subsequent sulfonation and their behavior was compared with ETFE base film and commercial Nafion^® NR212 membrane. Uniaxial tensile tests and stress relaxation tests at controlled temperature and relative humidity (RH) were carried out at 30 and 50 °C for 10% < RH < 90%. Grafted films were stiffer and exhibited stronger strain hardening when compared with ETFE. Similarly, both uncrosslinked and crosslinked membranes were stiffer and stronger than Nafion^®. Yield stress was found to decrease and moisture sensitivity to increase on sulfonation. The viscoelastic relaxation of the grafted films was found to obey a power‐law behavior with exponent equal to ?0.04 ± 0.01, a factor of almost 2 lower than ETFE, weakly influenced by moisture and temperature. Moreover, the grafted films presented a higher hygrothermal stability when compared with their membranes counterparts. In the case of membranes, a power‐law behavior at RH < 60% was also observed. However, a markedly different behavior was evident at RH > 60%, with an almost single relaxation time exponential. An exponential decrease of relaxation time with RH from 60 s to 10 s was obtained at RH ≥ 70% and 30 °C. The general behavior of grafted films observed at 30 °C was also obtained at 50 °C. However, an anomalous result was noticed for the membranes, with a higher modulus at 50 °C when compared with 30 °C. This behavior was explained by solvation of the sulfonic acid groups by water absorption creating hydrogen bonding within the clusters. A viscoelastic phase diagram was elaborated to map critical conditions (temperature and RH) for transitions in time‐dependent behavior, from power‐law scaling to exponential scaling. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1139–1148     

湿空气下制备稳定的CsPbI2Br钙钛矿太阳电池

无机钙钛矿太阳能电池由于具有良好的热稳定性,高吸光系数等优点发展迅速。但无机钙钛矿材料对水分极其敏感,一般在惰性环境下中进行制备,操作复杂。本文通过简单的一步旋涂工艺,在无手套箱空气湿度条件下制备CsPbI₂Br无机钙钛矿薄膜,通过介孔TiO₂厚度的优化,对钙钛矿薄膜的结晶、成膜及稳定性进行了分析,发现在较厚基底介孔层上制备的钙钛矿晶粒大、无孔隙;随着基底厚度的减小,其上所形成的CsPbI₂Br薄膜禁带宽度(E_g)增大;电化学阻抗测试表明在较厚基底介孔层上制备的CsPbI₂Br钙钛矿具有更好的载流子提取与传输能力。对不同厚度介孔层上沉积的钙钛矿薄膜稳定性进行测试,发现CsPbI₂Br钙钛矿的稳定性随着介孔层厚度的增加而提高,在空气中做放置144 h后无明显变化。在空气湿度条件下组装成器件,获得到了8.16%的最佳光电转换效率,并且对器件无任何修饰及封装的情况下,在相对湿地低于35%的空气中放置72 h后保持最初效率的73%。     

Thermally Stable Super Ionic Conductor from Carbon Sphere Oxide

A highly stable proton conductor has been developed from carbon sphere oxide (CSO). Carbon sphere (CS) generated from sucrose was oxidized successfully to CSO using Hummers’ graphite oxidation technique. At room temperature and 90 % relative humidity, the proton conductivity of thin layer CSO on microsized comb electrode was found to be 8.7×10^?3 S cm^?1, which is higher than that for a similar graphene oxide (GO) sample (3.4×10^?3 S cm^?1). The activation energy (E_a) of 0.258 eV suggests that the proton is conducted through the Grotthuss mechanism. The carboxyl functional groups on the CSO surface are primarily responsible for transporting protons. In contrast to conventional carbon‐based proton conductors, in which the functional groups decompose around 80 °C, CSO has a stable morphology and functional groups with reproducible proton conductivity up to 400 °C. Even once annealed at different temperatures at high relative humidity, the proton conductivity of CSO remains almost unchanged, whereas significant change is seen with a similar GO sample. After annealing at 100 and 200 °C, the respective proton conductivity of CSO was almost the same, and was about ～50 % of the proton conductivity at room temperature. Carbon‐based solid electrolyte with such high thermal stability and reproducible proton conductivity is desired for practical applications. We expect that a CSO‐based proton conductor would be applicable for fuel cells and sensing devices operating under high temperatures.     

Superior heat‐resistant and oil‐resistant blends based on dynamically vulcanized hydrogenated acrylonitrile butadiene rubber and polyamide 12

High‐performance thermoplastic vulcanizates (TPVs) are the new generation of TPVs that provide superior heat and oil aging behavior. TPVs based on hydrogenated acrylonitrile butadiene rubber and polyamide 12 (PA12) have been first developed by the dynamic vulcanization process, in which selective cross‐linking of the elastomer phase during melt mixing with the thermoplastic phase (PA12) was carried out simultaneously. In this present investigation, hydrogenated acrylonitrile butadiene rubber (HNBR)/PA12 and partially hydrogenated carboxylated acrylonitrile butadiene rubber (XHNBR)/PA12 with blend ratio of 50:50, 60:40, and 70:30 wt% were prepared at 185°C at a rotor speed of 80 rpm for 5 min. Di‐(2‐tert‐butyl peroxy isopropyl) benzene was chosen as the suitable cross‐linking peroxide to pursue the dynamic vulcanization. TPV based on 50:50 HNBR/PA12 and XHNBR/PA12 show better physico‐mechanical properties, rheological behavior, thermal stability, dynamic mechanical analysis, and creep behavior among all the TPVs. Morphology study reveals that dispersed phase morphology has been formed with an average dimension of the rubber particles in the range of 0.8–1.5 µm. For aging test, TPVs were exposed to air and ASTM oil 3, respectively. Air aging tests were carried out in hot air oven for 72 hr at 125°C, while the oil aging tests were carried out after immersion of the samples into the oils in an aging oven. After aging, there is only slight deterioration in the physico‐mechanical properties of the TPVs. In case of 50:50 blends of HNBR/PA12 and XHNBR/PA12, the retention of the properties upon after aging was found excellent. These TPVs are designed to find potential application in automotive sector especially for under‐hood‐application, where high‐temperature resistance as well as high oil resistance is of prime importance. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of Humidity on Crystal Growth of CuSCN for Perovskite Solar Cell Applications

Copper(I) thiocyanate (CuSCN) is one of the most robust hole-transport materials for perovskite solar cells (PSCs). However, the power conversion efficiency of CuSCN-based PSCs is low due to difficulty in crystallization of CuSCN. In this study, we focused on humidity conditions during the aging process of CuSCN-based PSCs to improve their performance. PSCs aged in humid air, i. e., at a relative humidity of 70 %, exhibited better performance (efficiency; 10.6 %) than those aged in lower humidity (5.9 %) due to improved crystallinity of CuSCN layers. The results of the study provide insights into how to improve fabrication process of CuSCN-based PSCs for higher stability and efficiency.     

Effect of steam on structure and mechanical properties of biomedical block copolymers

The effect of steam on the micro‐phase structure and mechanical properties of different block copolymers used in biomedical devices is investigated via FT‐IR, tensile tests and dynamic mechanical analysis (DMA). Steam sterilization, commonly performed on medical devices and simulated in this work, affects the copolymers' morphology, due to high temperature and humidity conditions. FT‐IR analysis reveals that steam induces a modification in the crystalline conformations of copolymers with a pre‐existing hydrogen bonding network, that is, thermoplastic polyurethanes (TPU) and poly(ether‐block‐amide) (PEBA), while it does not significantly affect the domain conformation in styrenic block copolymers (SEBS), due to weak interaction with water. As a consequence, relevant changes of the mechanical properties, closely related to the microdomain structure, are found for TPU and PEBA after sterilization, while SEBS mechanical behavior remains stable, as demonstrated by tensile tests and DMA results. For this reason, SEBS is suggested as the best choice in terms of durability in biomedical applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1337–1346     

Correlation between hydrogen‐bonding interaction and mechanical properties of polyimide fibers

Novel co‐polymerization polyimide (PI) fibers based on 4,4′‐oxydianiline (ODA)‐pyromellitic dianhydride (PMDA) were prepared. 2‐(4‐Aminophenyl)‐5‐aminobenzimidazole (PABZ) containing the N? H group was introduced into the structure of the fibers as the proton donor. The results of Fourier transform infrared (FTIR) and dynamic mechanical analysis (DMA) showed that hydrogen bonding occured between the N? H group and chains, which strongly enhanced interchain interaction. This hydrogen bonding interaction increased the tensile strength and initial modulus of the PI fibers up to 2.5 times and 26 times, respectively, compared to those of homo‐PI PMDA‐ODA fibers with no hydrogen‐bonding interaction because of the absence of proton donors after the imidization process. In the mean time, glass transition temperature (T_g) of the modified PI fibers was found to be 410–440°C, which was higher than that of the homo‐PI PMDA‐ODA fibers. From the result, a novel access to molecular design and manufacture of high performance PI fibers with good properties could be provided. Copyright © 2009 John Wiley & Sons, Ltd.     

Response of semiconducting metal oxides to water vapor as a result of water molecules chemical transformations on catalytically active surfaces

The sensitivity (response) of six semiconducting metal oxide (SMO) structures on the basis of SnO₂ to water vapor was studied in dry and humid air over the H₂O vapor concentration range 0–2.9 vol % (0–100% RH) as the temperature of the samples changed from 200 to 600°C. The temperature dependence of the conductivity and response of SMOs to H₂O vapor had extrema at 300–400 and 250–400°C, respectively, and the sensitivity to water vapor did not decrease below 1.7–1.9 up to 600°C. Data on changes in the conductivity of SMOs and the number of OH⁻ groups in the oxygen-hydroxyl layer on the surface of SMOs depending on temperature and air humidity were obtained. A sharp change in conductivity as air humidity increased from 0 to 10% RH could be related to either a sharp change in the number of OH⁻ groups in the oxygen-hydroxyl layer because of the high polarity of water molecules or a decrease in the intergrain energy barrier. The phenomena observed and the behavior of SMO conductivity in dry and humid air were interpreted. The experimental data were used to suggest a mechanism of the formation of hydroxyl groups on the surface of SMOs. The paper contains practical recommendations concerning the temperature conditions under which the influence of humidity on changes in the conductivity of SMOs is weakest.     

聚氧化丙烯醚对SiO2减反膜性质的影响

采用溶胶-凝胶制备的SiO2减反膜具有优良的光学特性和高损伤阈值,可以用做高反膜和减反膜的低折射率匹配层.在高功率激光领域具有十分诱人的应用前景.     

UV cured transparent films including non‐aqueous conductive microgels

UV cured transparent films containing non‐aqueous conductive microgels coated with poly(aniline)/dodecyl benzenesulfonic acid(DBSA) were obtained. The conductive microgels were prepared by interface polymerization of aniline/DBSA in the presence of non‐aqueous polymeric microgels. The electrical conductivity and the particle size of the prepared conductive microgel were 0.5 S/cm and 58 nm, respectively. The prepared conductive microgels were easily blended with a UV curable coating formulation, and then were cured to make highly optically transparent films. For the UV cured film containing about 35 wt% of the conductive microgels, a surface resistance in the range of 10⁷ to 10⁸ Ω/square was obtained. In a polar cosolvent, such as NMP and m‐cresol, the critical volume was shifted to the lower range, with a value of 10 wt%. The UV cured films containing the conductive microgels exhibited good electrical stability against the thermal aging and humidity. Copyright © 2002 John Wiley & Sons, Ltd.