Long-term weathering behavior of UV-curable clearcoats: Depth profiling of photooxidation,UVA, and HALS distributions

The long-term weathering performance of two UV-curable clearcoat systems was studied using in-plane microtomy in combination with infrared spectroscopy, UV spectroscopy, and ESR spectroscopy. Oxygen transport characteristics were also studied using the half-time method. The photooxidation versus depth profile was highly dependant on the presence of hindered amine light stabilizers (HALS) for both coating systems. Ultraviolet light absorbers (UVA) had little effect on the photooxidation profile. A photooxidation gradient was formed in both clearcoats due to a reduction in oxygen solubility when compared to standard thermoset clearcoats. This gradient was only seen in formulations not containing HALS. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

聚甲醛的光稳定化研究

采用了二苯甲酮类和苯并三唑类紫外线吸收剂(UVA)、位阻胺类光稳定剂(HALS)以及光屏蔽剂对聚甲醛进行光稳定化改性,对比了改性前后聚甲醛光降解后的物理力学性能及表面层分子量保持率。结果表明,0 5%的UVA可以显著提高POM的耐紫外光性能,苯并三唑类效果优于二苯甲酮类UVA。在酚类抗氧剂存在下,低含量的HALS(<0 25%)对聚甲醛没有光稳定化作用。     

Long-term performance of a HDPE geomembrane stabilized with HALS in chlorinated water

A high density polyethylene geomembrane (GMB) stabilized with hindered amine (light) stabilizers (HALS or HAS) is immersed in four chlorinated water solutions with a simulated free chlorine concentration range of 0.5–5 ppm at five different temperatures (25, 40, 65, 75, and 85 °C) for 70 months. Standard and high pressure oxidative induction time (OIT) tests are performed to monitor antioxidants depletion while melt flow index, tensile, and stress crack resistance (SCR) tests are conducted to monitor degradation in physical and mechanical properties. Degradation in the GMB properties occurred shortly after immersion in chlorinated water at all temperatures except at 25 °C. Increasing the free chlorine concentration resulted in faster degradation of the tensile properties and SCR. The predicted time to nominal failure based on SCR ranges between 25 years at 40 °C and 5 years at 85 °C in chlorinated water (with 0.5 ppm free chlorine). A comparison between the degradation in SCR of this GMB and a GMB with a different resin and without HALS shows significant difference in their performance in chlorinated water but not in other incubation media.     

Extended HALS algorithm for nonnegative Tucker decomposition and its applications for multiway analysis and classification

Analysis of high dimensional data in modern applications, such as neuroscience, text mining, spectral analysis, chemometrices naturally requires tensor decomposition methods. The Tucker decompositions allow us to extract hidden factors (component matrices) with different dimension in each mode, and investigate interactions among various modalities. The alternating least squares (ALS) algorithms have been confirmed effective and efficient in most of tensor decompositions, especially Tucker with orthogonality constraints. However, for nonnegative Tucker decomposition (NTD), standard ALS algorithms suffer from unstable convergence properties, demand high computational cost for large scale problems due to matrix inverse, and often return suboptimal solutions. Moreover they are quite sensitive with respect to noise, and can be relatively slow in the special case when data are nearly collinear. In this paper, we propose a new algorithm for nonnegative Tucker decomposition based on constrained minimization of a set of local cost functions and hierarchical alternating least squares (HALS). The developed NTD-HALS algorithm sequentially updates components, hence avoids matrix inverse, and is suitable for large-scale problems. The proposed algorithm is also regularized with additional constraint terms such as sparseness, orthogonality, smoothness, and especially discriminant. Extensive experiments confirm the validity and higher performance of the developed algorithm in comparison with other existing algorithms.     

紫外光固化聚合物涂层的原位光稳定化研究

选用实验室制备的四种新型反应型受阻胺类光稳定剂(r-HALS):4-甲基丙烯酰氧基-2,2,6,6-四甲基哌啶醇酯(MTMP)、4-丙烯酰氧基-2,2,6,6-四甲基哌啶醇酯(ATMP)、4-甲基丙烯酰氧基-1,2,2,6,6-五甲基哌啶醇酯(MPMP)和4-丙烯酰氧基-1,2,2,6,6-五甲基哌啶醇酯(APMP),实现了紫外光固化聚合物涂层(膜)的原位(in situ)光稳定化。通过室内人工光老化实验和在光氧化过程中黄度指数(Yellowness Index,YI)的监测,再与典型的商用HALS(Tinuvin770和Tinuvin292)进行平行实验对比,考察了r-HALS对紫外光固化聚合物涂层的光防护效果,探索一条紫外光固化聚合物涂层原位(in situ)光稳定化的新途径。     

miRNA Expression Profiling in Subcutaneous Adipose Tissue of Monozygotic Twins Discordant for HIV Infection: Validation of Differentially Expressed miRNA and Bioinformatic Analysis

Combined AntiRetroviral Treatments (cARTs) used for HIV infection may result in varied metabolic complications, which in some cases, may be related to patient genetic factors, particularly microRNAs. The use of monozygotic twins, differing only for HIV infection, presents a unique and powerful model for the controlled analysis of potential alterations of miRNAs regulation consequent to cART treatment. Profiling of 2578 mature miRNA in the subcutaneous (SC) adipose tissue and plasma of monozygotic twins was investigated by the GeneChip^® miRNA 4.1 array. Real-time PCR and ddPCR experiments were performed in order to validate differentially expressed miRNAs. Target genes of deregulated miRNAs were predicted by the miRDB database (prediction score > 70) and enrichment analysis was carried out with g:Profiler. Processes in SC adipose tissue most greatly affected by miRNA up-regulation included (i) macromolecular metabolic processes, (ii) regulation of neurogenesis, and (iii) protein phosphorylation. Furthermore, KEGG analysis revealed miRNA up-regulation involvement in (i) insulin signaling pathways, (ii) neurotrophin signaling pathways, and (iii) pancreatic cancer. By contrast, miRNA up-regulation in plasma was involved in (i) melanoma, (ii) p53 signaling pathways, and (iii) focal adhesion. Our findings suggest a mechanism that may increase the predisposition of HIV⁺ patients to insulin resistance and cancer.     

聚合物抗氧剂技术进展

抗氧剂是重要的聚合物稳定化助剂，文章全面而系统地综述了聚合物抗氧剂工业的理论研究进展和技术开发趋势，进而归纳了近十年来国内外抗氧剂品种的主要结构和应用特征，旨在推动国内抗氧剂工业的技术进步。     

Mathematical modeling of photoinitiated coating degradation: Effects of coating glass transition temperature and light stabilizers

A mathematical model, describing coating degradation mechanisms of thermoset coatings exposed to ultraviolet radiation and humidity at constant temperature, was extended to simulate the behavior of a coating with a low glass transition temperature. The effects of adding light stabilizers (a UV absorber and a radical scavenger) to the coating were also explored. The extended model includes photoinitiated oxidation reactions, intrafilm oxygen permeability, water absorption and diffusion, reduction of crosslink density, absorption of ultraviolet radiation, a radical scavenger reaction, and simulates the transient development of an oxidation zone. Simulations are in good agreement with experimental data for a fast degrading epoxy-amine coating with a glass transition temperature of −50 °C. It was found that the degradation rate of the non-stabilized coating was influenced significantly by the diffusion rate of oxygen in the oxidation zone, whereas light absorption by the photoproducts formed was only a secondary effect. On the other hand, the degradation rate of the stabilized coating was mainly influenced by the light absorption capability of the coating and in this case there was no oxygen diffusion resistance. Finally, simulations showed that the rate constants of the photoinitiating and oxidation reactions, taking place within the epoxy-amine family of coatings, are strong functions of the specific crosslinker used and must be estimated, in each case, by calibration of the model against adequate experimental data series.     

N—取代烷氧基受阻胺光稳定剂及其应用

介绍了N-取代烷氧基受阻胺的结构、性能、代表性品种及其在聚合物稳定化中的应用。     

Photooxidation and stabilization of photooxidized polyethylene and of its monopolymer blends

The increasing use of products from recycled polymers, or from blends with recycled polymers exposed to the outdoors, implies the need for good weathering resistance. This is particularly important when the recycled material comes, in turn, from products exposed during their lifetime to the sun. In this case the presence of C?O groups in the macromolecular chains strongly increases the photooxidative degradation kinetics of these secondary materials. In this work the change of the photooxidative degradation of blends of virgin and photooxidized polyethylene was evaluated as a function of the C?O content present in the material. As expected, the presence of the C?O groups strongly increases the photooxidation kinetics, as revealed by the increase of the carbonyl compounds, and by the decrease of the elongation at break. It was confirmed that the increase of C?O groups is dependent on the content of the same groups, whereas this is not true for the mechanical properties. The use of UV stabilizer strongly improves the weathering resistance of these materials, which become almost insensitive to the initial amount of C?O groups. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2244–2255, 2004