Thermotropic glazings for overheating protection. I. Material preselection,formulation, and light‐shielding efficiency

This article presents a systematic strategy for formulation and optimization of thermotropic layers for overheating protection purposes. Specifically, thermotropic systems with fixed domains (TSFD) which consist of a thermotropic additive finely dispersed in a matrix material are considered. Based on systematic material (component) preselection regarding thermoanalytical characteristics and refractive indices, numerous thermotropic layers were formulated. TSFD with thermoplastic matrix were produced by compounding and compression molding. TSFD with resin matrix were produced by UV curing. The thermotropic layers were analyzed as to solar optical properties, threshold temperature, switching process and residual transmittance in the opaque state applying UV/Vis/NIR spectrometry equipped with a heating stage. Best performing materials exhibited solar hemispheric transmittance in the range of 72.2–84.5% and between 59.6 and 83.7% in the clear and opaque state, respectively. Threshold temperatures between 45 and 75°C were realized. Refractive index difference between matrix and additive and solar hemispheric transmittance displayed a close correlation. Hence, refractometry was shown to be an appropriate tool for material preselection. Furthermore, investigations revealed a close correlation of thermal transitions of thermotropic additives recorded by differential scanning calorimetry and threshold temperatures of thermotropic layers formulated therewith. However, thermotropic layers formulated so far have to be optimized with respect to light‐shielding performance for efficient overheating protection. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39950.     

Thermotropic glazings for overheating protection. II. morphology and structure–property relationships

This article completes a systematic strategy for formulation and optimization of thermotropic systems with fixed domains (TSFDs) for overheating protection purposes. Focus was on characterization of morphology and on revealing optimization potential. A comprehensive characterization of scattering domain size and shape was done applying optical microscopy and scanning electron microscopy. In general, scattering domains exhibited inappropriate size and/or shape for optimum overheating protection performance. Moreover, several TSFD displayed defects (vacuoles, voids) resulting from thermomechanical or physicochemical interaction of matrix material and thermotropic additive during manufacturing. Morphological features along with solar optical and thermorefractive properties allowed for establishment of structure–property relationships. Light‐shielding efficiency of TSFD correlated well with scattering domain size and shape. The majority of TSFD showing defects exhibited an increase of solar hemispheric transmittance upon heating. Several strategies to overcome defect formation and to improve scattering morphology were suggested and proof of concept was shown partially, thus indicating a significant optimization potential of the established TSFD. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39910.     

Thermotropic systems with fixed domains exhibiting enhanced overheating protection performance

Within this study, a time saving photo‐initiated miniemulsion polymerization process (duration of polymerization was 15 min) was established in order to encapsulate a paraffin wax with an acrylate polymer shell. The obtained freeze‐dried latex was an off‐white powder exhibiting spherical particles with mean diameters around 400 nm and a concentration of paraffin wax around 56%. Mixing the reaction product with a UV‐curable resin matrix resulted in thermotropic overheating protection glazings with high light‐shielding efficiency. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40417.     

Thermogravimetric and Fourier‐transform infrared analyses on the cure behavior of polycardanol containing epoxy groups cured by electron beam

In this study, the curing behavior of polycardanol containing epoxy groups (diepoxidized polycardanol) was exploited in terms of thermal stability and the cure reaction conversion by means of thermogravimetric analysis and Fourier‐transform infrared spectroscopy, respectively. The effect of photo‐initiator type and concentration and electron beam absorption dose in the presence of cationic photo‐initiators (triarylsulfonium hexafluorophosphate (P‐type) and triarylsulfonium hexafluoroantimanate (Sb‐type) on the cure behavior of diepoxidized cardanol (DEC) resin was investigated. The thermal stability of DEC with Sb‐type photo‐initiator was higher than that with P‐type one, being increased with increasing the concentration and electron beam absorption dose. The conversion of cure reaction was gradually increased with increasing the dose, showing the maximum at 800 kGy. The results revealed that Sb‐type photo‐initiator, the concentration of 2 or 3 wt %, and electron beam absorption dose of about 800 kGy may be preferable for initiating epoxy ring opening in the DEC molecules as well as for efficiently curing the DEC resin by electron beam irradiation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41599.     

Electron‐beam curing of bismaleimide‐reactive diluent resins

Electron‐beam (E‐beam) curing of 4,4′‐bismaleimidodiphenylmethane (BMPM)/BMI‐1,3‐tolyl/o,o′‐diallylbisphenol A (DABPA)–based bismaleimide (BMI) systems and their mixing with various reactive diluents, such as N‐vinylpyrrolidone (NVP) and styrene, were investigated to elucidate how temperature, electron‐beam dosage, and diluent concentration affect the cure extent. The effect of free‐radical initiator on the cure reactions was also studied. It was found that low‐intensity E‐beam exposures cannot cause the polymerization of BMI. High‐intensity E‐beam exposures give high reaction conversion attributed to a high temperature increase, which induced thermal curing. It was shown that the dilution and activation of NVP in BMI cause a more complete BMI cure reaction under E‐beam radiation. BMI/NVP can be initiated easily by low‐intensity E‐beam without thermal curing. FTIR studies indicate that about 70% of the reaction is complete for BMI/NVP with 200 kGy dosage exposure at 10 kGy per pass. The sample temperature only reaches about 75°C. The free‐radical initiator, dicumyl peroxide, can accelerate the reaction rate at the beginning of E‐beam exposure, but does not affect the final reaction conversion. The increase of the concentration of NVP in the BMI/NVP systems increases the reactive conversions almost linearly. © 2004 Wiley Periodicals Inc. J Appl Polym Sci 94: 2407‐2416, 2004     

Study on spatial–temporal kinetics of photo‐initiated frontal polymerization in stacked reaction cells

The spatial–temporal kinetics for photo‐initiated frontal polymerization(PFP) of isobornyl acrylate with 2,4,6‐trimethylbenzoyldiphenyl phosphine oxide (TPO) as photobleaching initiator was studied experimentally in stacked reaction cells. FTIR and NMR spectroscopy were employed to measure the polymerization conversion, which is dependent on the exposure time, sample depth, light intensity and photo‐initiator concentration. The experimental results are consistent with the theoretical model prediction and show that prolonged irradiation time, higher light intensity and lower photo‐initiator concentration are favorable in enhancing the advance of the polymerization front. The depth‐resolved GPC analysis shows that the average molecular weight of the PFP product dramatically increases with sample depth, while the molecular weight polydispersity reduces steadily with increase in sample depth. Copyright © 2006 Society of Chemical Industry     

On the inhibiting effect of phenolic compounds in the photopolymerization of acrylates under high‐intensity and polychromatic UV/visible lights

The photopolymerization of wood coatings under UV and visible light in industrial type conditions has been investigated. The inhibiting effect of the phenolic compounds found in wood extractives, especially quercetin, on the final properties of the coating (hardness, gel content) as well as the polymerization kinetics (rates, final conversion) has been discussed. Model clear‐coating formulations — based on an acrylate oligomer, a reactive diluent and a bis‐acylphosphine oxide as photo‐initiator — have been used. This article focuses on the influence of the nature of the acrylate oligomer (polyester, epoxy, polyurethane), the type of phenolic derivative (POHs) and the irradiation conditions (UV conveyor, Xe lamp). It appears that lead to through the strong inner‐filter effect in the presence of quercetin is responsible for the loss of all the observed properties. In order to mimic what happens at the wood–coating interface, the role of the diffusion of the phenolic derivatives have been also investigated and discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3285–3298, 2007     

Synthesis and photo‐curing behaviors of silicon‐containing (vinyl ether)–(allyl ether) hybrid monomers

A series of silicon‐containing (vinyl ether)–(allyl ether) hybrid monomers used in nano‐imprint lithography resists were synthesized and subjected to photo‐initiated polymerization. The surface energies of the monomers and the resulting polymer films were then investigated. The surface energies of the monomers were very low at less than 15 mJ m^–2. The photo‐curing behaviors of the five hybrid monomers were investigated using real‐time Fourier transform infrared spectroscopy. The monomers were sequentially initiated with cationic (PAG201) and mixed (cationic initiator PAG201, radical initiator ITX or TPO) initiators. The vinyl ether double bond polymerized both rapidly and completely, whereas the allyl ether double bond remained when PAG201 was used as the photo‐initiator and polymerized completely with mixed initiators. The different double bonds of the silicon‐containing (vinyl ether)–(allyl ether) hybrid monomer increased the efficiency of the polymerization and overcame the intrinsic limitations of the free radical and cationic polymerization processes, including strong oxygen inhibition, large volume shrinkage and high humidity sensitivity. The five monomers with low viscosity, low surface energy, good thermal stability and good photo‐polymerization properties were suitable for nano‐imprint photoresists. © 2013 Society of Chemical Industry     

Dual-curable PVB based adhesive formulations for cord/rubber composites: The influence of reactive diluents

In this study, the effects of reactive diluent type on the adhesion strength of cord/rubber surfaces were investigated. For this purpose, a urethane acrylate oligomer was synthesized by the reaction of 2,4-toluene diisocyanate (TDI), 2-hydroxyethyl methacrylate (HEMA) and polyvinyl butyral (PVB) in the presence of di-n-butyltin dilaurate (T12) as catalyst. The structure of the oligomer was characterized by nuclear magnetic resonance (NMR) spectroscopy. Then the oligomer was included in adhesive formulations together with trimethylolpropane trimethacrylate (TMPTMA) and tricyclodecane dimethanol diacrylate (TCDDA) as reactive diluents and thermal and photo initiator respectively. Polyester/polyamide cord fabrics were dipped into the adhesive solution and cured by UV-light. Then coated fabrics were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Contact angle measurement was employed to investigate the wettability properties of the coated fabrics. Thermal curing between the coated fabric and rubber was performed under heat and pressure. The adhesion strength between the cord/rubber surfaces was determined by T-peel test. The highest adhesion strength of 100.4 N/cm with the lowest contact angle value of 70.2° were obtained in the sample containing TCDDA as reactive diluent, due to a higher functionality resulting in a greater crosslinking density.     

Photo‐Induced Hydrogel Formation Based on g‐C3N4 Nanosheets with Self‐Cross‐Linked 3D Framework for UV Protection Application

Composite hydrogels of graphitic carbon nitride nanosheets (CNNS) and polyacrylamide (PAM) with superior UV absorption and visible transparence capabilities are reported. CNNS is employed not only as a photocatalytic initiator to trigger the polymerization of acrylamide, but also as a cross‐linker to 3D connected PAM chains via hydrogen bonds. The obtained CNNS/PAM hydrogels are highly moldable for preparing various forms, and have good mechanical properties, self‐healing ability, and photo‐stability. Furthermore, the composite hydrogels have a wide spectral range for UV absorption compared to conventional UV protective materials. Besides the complete screening of UVB (280–315 nm) in sun radiation, the CNNS/PAM hydrogel film can also filter >95% UVA radiation (315–400 nm) by regulating the coating thickness, meanwhile retaining a high visible transmittance. Therefore, the CNNS/PAM hydrogels have potential applications for shielding UV radiation. Additionally, this strategy provides a common and facile route to fabricate functional composite hydrogels via photo‐induced polymerization.     

A versatile radiochromic dosimeter for low‐medium gamma radiation and its application to food irradiation

This article presents a novel radiochromic film for selective detection of low‐medium (0–10 kGy) gamma radiation (⁶⁰Co) doses. This dosimeter is based on a printed fluorescent multilayer structure comprising a paper substrate having layers of copper phthalocyanine (DY220) (a green emitter material) on the bottom, and layers of poly[2‐methoxy‐5(2′‐ethylhexyloxy)‐p‐phenylenevinylene] (MEH‐PPV) (a green‐light absorber, red emitter, and radiation sensitive polymer) on the top. The effect of gamma radiation on the optical properties of DY220/MEH‐PPV was described: it was observed as a strong correlation between radiation dose and fluorescent, color coordinates for CIE (1931) chromatic diagram, and Pantone color reference of the dosimeter. The rate of these changes can be altered by manipulation of top–bottom layers to represent easily the radiation dose to be determined in a wide range. This versatile dosimeter has many uses in the field of food radiation for monitoring, quality assurance, and control of the gamma radiation process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45729.     

Behavior of quaternary ammonium salt photobase generators on initiating free radical photo‐polymerization

Series of quaternary ammonium tetraphenyl borates salt photobase generators (PBGs) were synthesized using p‐methoxyphenacylmethylene and 2‐naphthoymethylene as chromophores, and triethylene diamine, pyridine or 3‐methyl pyridine as tertiary amine. The kinetics for polymerization of trimethylolpropane triacrylate (TMPTA) monomer using PBGs as free radical photo‐initiator was monitored by differential photo‐calorimeter (DPC). It was found that all the quaternary ammonium tetraphenyl borate salt photobase generators synthesized could initiate free radical polymerization of the acrylate monomer TMPTA by exposure to UV irradiation, but the activity was relatively low. Addition of a small amount of polar solvent to the system could largely increase the polymerization rate and final conversion. Photo‐polymerization was also improved by increasing light intensity or raising reaction temperature. PBGs with p‐methoxyphenacylmethylene as chromophore had higher absorbance at around 280 nm and showed higher activity in initiating photo‐polymerization than those with N‐(2‐naphthoylmethyl) as chromophore. Copyright © 2006 Society of Chemical Industry     

Poly(vinyl alcohol)–bismuth oxide composites for X-ray and γ-ray shielding applications

Polymer composites, which are light in weight, cost effective, and less toxic, have potential applications in X-ray and γ-ray shielding and protection. In this work, we have explored the efficacy of poly(vinyl alcohol)–bismuth oxide composites as radiation shielding materials. Poly(vinyl alcohol) composites with different wt % (0–50) of bismuth were prepared by a simple solution casting technique. Structural and thermal characterization of these samples was carried out using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). TGA revealed the enhanced thermal stability of these composites. AC conductivity measurements and optical spectroscopy were used to analyze their electrical behavior. The composites showed low conductivity, and the energy gap obtained also showed their tendency to be insulators. The radiation attenuation properties were investigated using X-ray (5.895 and 6.490 keV) and γ-ray (59.54 and 662 keV) transmission measurements. The shielding efficiency of the composites increased with filler wt %. The 40 wt % composites exhibited mass attenuation coefficients of 122.68 and 93.02 cm²/g at photon energies of 5.895 and 6.490 keV, respectively, while the 50 wt % composites showed 1.57 and 0.092 cm²/g at photon energies of 59.54 and 662 keV, respectively. The effective atomic number quantifies the probability of interaction of radiation with matter. The effective atomic number of the composites calculated by the direct method was in good agreement with the theoretical value obtained from Auto-Zeff software. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47949.     

近年来辐射固化材料的研究进展

综述了光化学、光自由基聚合、光引发剂UV固化、UV固化剂、电沉积光敏抗蚀剂和涂料、UV水基和粉末涂料及UV固化纳米复合材料的研究进展。     

Photopolymerization kinetics and thermal properties of dimethacrylate based on bisphenol‐S

A dimethacrylate based on bisphenol‐S (DBSMA) was prepared and characterized by Fourier Transform infrared spectroscopy (FTIR), Electrospray Ionisation Tandem Mass Spectrometry (ESI/MS) ¹H NMR, and ¹³C NMR. DBSMA was investigated by a real‐time infrared spectroscopy (RTIR), under different conditions such as varying photoinitiator type and concentration, with and without oxygen, mixing with different amounts of a reactive diluent [1,6‐hexanediol dimethacrylate (HDDMA)]. The mechanical and thermal properties of these curing films were also investigated by dynamic mechanical analysis and thermogravimetric analysis. The results showed homopolymer of DBSMA has better thermal stability than copolymers of DBSMA/HDDMA systems. Also, the cured DBSMA polymer exhibited higher glass transition temperature (T_g) and better thermal stability compared with commercial available resin 2,2‐Bis[4‐(2‐hydroxy‐3‐methacryloxypropoxy)phenyl]propane (BIS‐GMA) (CN151). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Controllable surface modifications of polyamide by photo‐induced graft polymerization using immobilized photo‐initiators

A novel two‐step UV initiated grafting method has been developed and applied on surface modification of polyamide. Anthraquinone‐2‐sulfonate sodium, an acid dye, was chosen as the photo‐initiator. In the first step, photo‐initiators were ionically bonded onto polyamide through a normal acid dye dyeing process. Vinyl monomers such as acrylic acid were then grafted onto polyamide surface in the following step. During UVA irradiation, not only monomers were grafted onto polymer surface, photo‐initiator itself was also covalently bonded onto polymer. The grafted polymers were characterized by Fourier transform infrared spectrometer (FTIR), X‐ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM).The degree of photo‐grafting can be controlled by adjusting concentrations of photo‐initiator and monomer, as well as UVA exposure time. This process demonstrated the feasibility of efficiently modifying polymer surface under low UV intensity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

防辐射无机玻璃性能研究

核科学技术在国防、医学、工业、农业和科研等领域的应用日益广泛,各种辐射如X射线、γ射线和中子辐射对人体、环境、仪器设备等有很大的危害,并引起国际辐射防护领域的极大关注.透明防辐射玻璃是防辐射材料的重要研究方向之一,本文采用熔融浇注法制备了透明防辐射无机玻璃,对其γ射线和中子辐射的防护能力进行了表征,同时对玻璃透过率、软化点等性能进行了表征.结果显示该防辐射无机玻璃对γ射线和中子辐射具有良好的防护能力,且透过率较高,热稳定性和耐热性能好.由于该防辐射无机玻璃综合性能良好,在辐射防护领域有良好的应用前景.     

Pulsed Laser Activation of Carbene Bioadhesive Boosts Bonding Strength

Light‐activated tissue adhesives are limited to low light doses (50 J) and intensities (<1 W cm^?2) due to photo‐to‐thermal heat generation. Low intensities have the disadvantage of limited penetration depths with retarded crosslinking kinetics, which impairs carbene‐based crosslinking strategies that compete with nitrogen evolution and gas nucleation. These limitations are circumvented by a trade‐off between high‐intensity activation while reducing the exposure surface area. Continuous or pulsed activation by line scanning the carbene precursor adhesive allows curing a higher surface area/volume ratio while preventing localized heat generation. By optimizing irradiation with a pulsed laser scan, the adhesion strength is improved by 17‐fold over ultraviolet A (UVA) light emitting diodes (LEDs) and is on par with bioadhesive gold standard of topical cyanoacrylates. Overall, this improved method of photo‐activation applies to other industrial and clinical photocuring adhesives where limits on UVA dose constrain exposure intensities.     

辐射防护材料的研究进展

简述了核辐射中各种高能粒子的特点,提出了核辐射防护的主要目标。详述了X射线、γ射线及中子屏蔽材料的屏蔽机制、材料设计方法及研究进展。最后,指出了核辐射防护材料的发展方向:屏蔽性能与其他各性能之间的结合,重、轻元素的配合以及模拟方法的应用。     

The development of a highly efficient photo‐initiator system and its application in the photo‐immobilization of activated sludge

In this study, a highly efficient photo‐initiator system was developed, which contained potassium persulfate, N, N, N ′, N ′‐tetramethylethylethylenediamine plus benzil dimethyl ketal. The photo‐initiator system could successfully initiate poly (ethylene glycol) dimethyl‐acrylate prepolymer to polymerize and crosslink under the irradiation of UV rays, in the presence of concentrated activated sludge, finally leading to the formation of immobilized activate sludge pellet beads. The presence of O₂ and thickness of the reaction solution did not influence the photo‐immobilization process. Respiratory measurement result demonstrated that most activated sludge kept alive during the photo‐immobilization. Mechanical strength of the immobilized cells could be improved by optimizing contents and ratio of the initiator system. The corresponding mechanism was also discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39838.