Progress in Organic Coatings最新文献

Electropolymerization of organoclays and usage of synthesized polymer-clay nanocomposite as a matrix for cell adhesion 有机粘土的电聚合及合成聚合物-粘土纳米复合材料作为细胞粘附基质的应用

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-26 DOI: 10.1016/j.porgcoat.2025.109334

Sultan Sacide Gelen , Ahmet Cifci , Hacer Azak , Esra Evrim Yalcinkaya , Simge Er Zeybekler , Dilek Odaci

One of the prominent topics in nanobiotechnology is the development of multifunctional biocompatible materials at the nanoscale and the creation of an artificial extracellular matrix (ECM) through the proper design of these material surfaces. In this study, a polymer-clay nanocomposite was synthesized via electropolymerization method to investigate the adhesion of U87-MG glioblastoma cells. Initially, 2-(4H-dithieno [3,2-b:2′,3′-d] pyrrol-4-yl)-3-mercapto propanoic acid (DTP-SH) and 4-(4H-dithieno [3,2-b:2′,3′-d] pyrrole-4-yl) phenethyl) aniline (DTP-NH₂) monomers were synthesized and characterized. DTP-NH₂ monomer was incorporated between montmorillonite (MMT) clay layers by ion exchange reaction and characterized using Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy–energy-dispersive X-ray spectroscopy (SEM–EDS), and X-Ray diffraction (XRD) techniques. The obtained (DTP-NH₂)-MMT was polymerized using the cyclic voltammetry (CV) technique on screen-printed gold (Au) electrode surface to form polymer-clay nanocomposite. For the first time in literature, a conductive polymer-based polymer-clay nanocomposite was synthesized using the electrochemical polymerization as an alternative to traditional methods. After the formation of P(DTP-NH₂)-MMT on the DTP-SH-coated Au surface, the GMT8 aptamer was covalently immobilized to generate a biofunctional surface. Electrochemical characterization of the resulting surface was subsequently performed using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). U87-MG glioblastoma and L929 fibroblast (negative control) cell lines were incubated on the P(DTP-NH₂)-MMT/GMT8 surface. Finally, cell adhesion was examined using DPV technique and fluorescence imaging. The results demonstrated that the aptamer-functionalized P(DTP-NH₂)-MMT surface supported significantly higher adhesion of U87-MG cells compared to the control, indicating its promising potential as a cell adhesion platform.

纳米生物技术的一个重要课题是在纳米尺度上开发多功能生物相容性材料，并通过适当设计这些材料表面来创造人工细胞外基质（ECM）。本研究采用电聚合法制备聚合物-粘土纳米复合材料，研究其对U87-MG胶质瘤细胞的粘附作用。首先，合成了2-（4h -二噻吩[3,2-b:2 ',3 ' -d]吡咯-4-基）-3-巯基丙酸（DTP-SH）和4-（4h -二噻吩[3,2-b:2 ',3 ' -d]吡咯-4-基）苯胺（DTP-NH2）单体并进行了表征。通过离子交换反应将DTP-NH2单体掺入蒙脱土（MMT）粘土层之间，并利用傅里叶变换红外光谱（FTIR）、扫描电子显微镜-能量色散x射线能谱（SEM-EDS）和x射线衍射（XRD）技术进行表征。得到的(DTP-NH2)-MMT采用循环伏安法（CV）在丝网印刷金（Au）电极表面聚合，形成聚合物-粘土纳米复合材料。本文首次采用电化学聚合的方法合成了导电聚合物基聚合物-粘土纳米复合材料，作为传统方法的替代。在dtp - sh包覆的Au表面形成P（DTP-NH₂）-MMT后，将GMT8适配体共价固定以生成生物功能表面。随后使用循环伏安法（CV）、差分脉冲伏安法（DPV）和电化学阻抗谱（EIS）对所得表面进行了电化学表征。在P(DTP-NH2)-MMT/GMT8表面培养U87-MG胶质母细胞瘤和L929成纤维细胞（阴性对照）。最后用DPV技术和荧光成像检测细胞黏附。结果表明，适配体功能化的P（DTP-NH₂）-MMT表面对U87-MG细胞的粘附作用明显高于对照，表明其作为细胞粘附平台的潜力很大。

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引用次数: 0

Yam mucilage nanocomposite film incorporated silver nanoparticles extend the shelf life and preserve the postharvest quality of Agaricus bisporus 加入银纳米粒子的山药黏液纳米复合膜延长了双孢蘑菇的保质期，并保持了采后品质

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-26 DOI: 10.1016/j.porgcoat.2025.109332

Yuting Chen , Anbazhagan Sathiyaseelan , Xin Zhang , Yingshan Jin , Myeong-Hyeon Wang

The development of antimicrobial food packaging using polymers embedded with metallic nanoparticles has extended the shelf life of fresh foods by preventing food-borne illnesses. This study used yam mucilage extracts to synthesize silver nanoparticles (Yam-AgNPs) and Yam-AgNPs blended with Yam/PVA composite to form films (Yam/PVA-AgNPs). Yam-AgNPs showed maximum absorbance at 414 nm, and TEM confirmed the spherical particles with an average of 16.02 ± 7.39 nm. SEM evidenced that the Yam-AgNPs were dispersed in the Yam/PVA surface. Yam/PVA-AgNPs film (F3) possesses a good UV barrier (T₂₈₀ = 80.12 %), transparency (T₆₆₀ = 64.54 %), swelling (636.23 %), and water solubility (52.26 %) properties. Furthermore, F3 exhibited good antibacterial activity, with biofilm inhibition exceeding 73.80 % against pathogens. Compared to Yam-AgNPs, the Yam/PVA-AgNPs film had a similar effect on protein leakage in S. aureus (18.42 μg/mL) and E. coli (19.48 μg/mL). In addition, the Yam/PVA-AgNPs film (F3) used for packaging Agaricus bisporus mushrooms demonstrated a strong ability to prevent food pathogen-induced spoilage and maintain the original color and morphology during storage at 4 °C. F3 significantly inhibited the respiration rate and water loss of mushrooms, resulting in a weight loss of 11.48 % and an MDA content of 1.18 nmol/g FW, both of which were lower than those observed with the Yam/PVA film and the control (without packaging) after 12 days. Furthermore, F3 preserved active substances (total sugars and total phenolics) and inhibited the growth of psychrophilic bacteria, with a bacterial count of 4.32 ± 0.23 Log₁₀ CFU/g at 12th day. These results suggest that Yam/PVA-AgNPs film can serve as antimicrobial packaging materials for food preservation.

使用嵌入金属纳米颗粒的聚合物开发的抗菌食品包装通过预防食源性疾病延长了新鲜食品的保质期。本研究利用山药黏液提取物合成银纳米粒子（yam - agnps），并将yam - agnps与山药/PVA复合材料共混形成薄膜（yam /PVA- agnps）。Yam-AgNPs的最大吸光度为414 nm， TEM证实其平均吸光度为16.02±7.39 nm。SEM证实Yam- agnps分散在Yam/PVA表面。Yam/PVA-AgNPs薄膜（F3）具有良好的抗紫外线性能（T280 = 80.12%）、透明度（T660 = 64.54%）、溶胀性（636.23%）和水溶性（52.26%）。此外，F3具有良好的抑菌活性，对病原菌的生物膜抑制率超过73.80%。与Yam- agnps相比，Yam/PVA-AgNPs膜对金黄色葡萄球菌（18.42 μg/mL）和大肠杆菌（19.48 μg/mL）的蛋白渗漏效果相似。此外，用于包装双孢蘑菇的Yam/PVA-AgNPs薄膜（F3）在4°C的储存过程中表现出较强的防止食物病原体引起的腐败的能力，并保持原有的颜色和形态。F3显著抑制了蘑菇的呼吸速率和水分流失，使蘑菇的失重率降低了11.48%，MDA含量为1.18 nmol/g FW， 12 d后均低于山药/PVA膜处理和未包装的对照。此外，F3保存了活性物质（总糖和总酚类物质），抑制了嗜冷细菌的生长，第12天细菌数量为4.32±0.23 Log₁₀CFU/g。上述结果表明，山药/PVA-AgNPs薄膜可作为食品保鲜的抗菌包装材料。

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引用次数: 0

Multifunctional anti-corrosion coatings based on 2D/3D structure-function integrated nanomaterials for steel protection 基于二维/三维结构-功能集成纳米材料的多功能钢防护防腐涂层

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-26 DOI: 10.1016/j.porgcoat.2025.109335

Dashuai Yan , Zhen Chen , Wenjuan Zhang , Yanli Wang , Liman Chen

Most conventional organic anti-corrosion coatings cannot provide long-term protection for metals due to their limited functionality. Here, a smart anti-corrosion coating (ZLIP/EP) is developed by incorporating a 2D/3D structure-function integrated nanomaterial (ZLIP) into the coating matrix. ZLIP consists of polyethylene glycol (PEG)-encapsulated dodecahedral layered double hydroxide (LDH) nanocages, which contain corrosion inhibitor imidazoline (IM). Compared to ZIF-67 added to the coating, the 2D LDH layers of ZLIP can effectively extend the electrolyte solution's penetration path within the coating. When the composite coating is damaged, the LDH layers can capture chloride ions in the electrolyte solution, while IM is released to suppress corrosion. Moreover, the IM stored in the unique 3D hollow structure of ZLIP can also be released and subsequently adsorbed onto the steel substrate to further improve the active corrosion protection ability of the coating. The electrochemical test reveal that the |Z|_0.01Hz of ZLIP/EP remains as high as 68.8 MΩ·cm² after long-term immersion (40 days), demonstrating superior corrosion resistance. The ZLIP/EP system developed in this study shows significant promise for practical anti-corrosion applications.

大多数传统的有机防腐蚀涂层由于其有限的功能而不能为金属提供长期保护。在这里，通过将2D/3D结构-功能集成纳米材料（ZLIP）结合到涂层基体中，开发了一种智能防腐涂层（ZLIP/EP）。ZLIP由聚乙二醇（PEG）包封的十二面体层状双氢氧化物（LDH）纳米笼组成，其中含有缓蚀剂咪唑啉（IM）。与添加到涂层中的ZIF-67相比，ZLIP的二维LDH层可以有效地延长电解质溶液在涂层内的渗透路径。当复合涂层被破坏时，LDH层可以捕获电解质溶液中的氯离子，同时释放IM抑制腐蚀。此外，储存在ZLIP独特的三维中空结构中的IM也可以被释放并随后吸附到钢基体上，进一步提高涂层的主动防腐能力。电化学测试表明，ZLIP/EP经过长时间浸渍（40天）后，|Z|0.01Hz仍保持在68.8 MΩ·cm2，具有较好的耐腐蚀性。本研究开发的ZLIP/EP系统在实际防腐应用中具有重要的前景。

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引用次数: 0

Multifunctional superhydrophobic film with comprehensive icing monitoring, anti-icing, and photothermal/electrothermal deicing properties 具有综合结冰监测、防结冰、光热/电热除冰性能的多功能超疏水薄膜

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-25 DOI: 10.1016/j.porgcoat.2025.109337

Haozhong Ji , Chao Yang , Haoxi Su , Zhengpan Qi , Yao Wang , E. Cheng , Ning Hu

Superhydrophobic photothermal/electrothermal surfaces have garnered considerable attention on account of the synergistic effect of the superhydrophobic anti-icing and photothermal/electrothermal deicing, which can effectively address the issue of surface icing. However, it lacks the ability to precisely monitor the icing process, a critical component for improving their deicing efficiency. Therefore, a multifunctional superhydrophobic film with comprehensive icing monitoring, anti-icing, and photothermal/electrothermal deicing properties was prepared using the laser ablation method, which consisted of an interdigital patterned laser-ablated graphene (LAG) planar capacitance sensor and a laser-ablated polytetrafluoroethylene (PTFE) superhydrophobic surface. As a result, it was able to effectively monitor the process of ice growth and detect the thickness of ice by utilizing the differences in dielectric properties of water, ice, and air. In addition, the laser-ablated PTFE superhydrophobic surface processed a contact angle of 159.5° and a sliding angle of 3.5°, which prevented the ice formation for 4.9 min at −20 °C. Meanwhile, by harnessing the photothermal and electrothermal effects of the LAG conductive network, the surface temperature reached 108.4 °C and 43.2 °C with a light irradiance of 2 W/cm² and an applied electric power density of 0.135 W/cm², respectively, thereby allowing effective deicing. Consequently, the multifunctional superhydrophobic film, with its comprehensive icing monitoring, anti-icing, and photothermal/electrothermal deicing properties, possesses significant potential for the prevention and removal of ice.

超疏水光热/电热表面由于具有超疏水防冰和光热/电热除冰的协同作用，能够有效解决表面结冰问题，受到了广泛的关注。然而，它缺乏精确监测结冰过程的能力，这是提高其除冰效率的关键组成部分。因此，采用激光烧蚀方法制备了一种具有综合结冰监测、防结冰和光热/电热除冰性能的多功能超疏水薄膜，该薄膜由数字间图案激光烧蚀石墨烯（LAG）平面电容传感器和激光烧蚀聚四氟乙烯（PTFE）超疏水表面组成。因此，它能够有效地监测冰的生长过程，并通过利用水、冰和空气的介电特性的差异来检测冰的厚度。此外，激光烧蚀的PTFE超疏水表面处理的接触角为159.5°，滑动角为3.5°，在- 20°C下防止了4.9 min的结冰。同时，利用LAG导电网络的光热和电热效应，表面温度分别达到108.4°C和43.2°C，光辐照度为2 W/cm2，施加的功率密度为0.135 W/cm2，从而实现有效的除冰。因此，多功能超疏水膜具有全面的结冰监测、防结冰和光热/电热除冰性能，在防冰和除冰方面具有巨大的潜力。

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引用次数: 0

Fluoropolymer covalent grafted vinyl ester resin composite coatings for enhancing mechanical properties, water repellency and corrosion resistance 氟聚合物共价接枝乙烯酯树脂复合涂料，提高机械性能、拒水性和耐腐蚀性

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-25 DOI: 10.1016/j.porgcoat.2025.109346

Shaozhen Xian, Wentian Wei, Mingmei Jing, Hongbin Zheng, Shengsen Wang, Shaoheng Yang, Yang Hu, Zhuangzhuang Chu, Zhuohong Yang

Anti-corrosion coatings for metal protection should have good mechanical properties, water repellency and corrosion resistance to deal with the negative effects caused by external impact and corrosive medium erosion. Herein, a novel vinyl ester resin (VER) composite coating was prepared by covalent grafting of reactive fluoropolymer (PF-HDI) with epoxy resin (E-44), and ring-opening reaction of acrylic acid. The covalent introduction of PF-HDI has a significant effect on comprehensive properties of the coating. 0.4 wt% of PF-HDI not only endow coating excellent mechanical properties and corrosion resistance, including 81.64 % increase in tensile strength (80.94 MPa), 3 orders (42 d) and 6 orders (82 d) of magnitude increase in impedance modulus (>10¹⁰ Ω cm²), but also significantly improve the water repellency compared with pure VER. This work provides an effective strategy for the preparation of high-performance composite coatings with toughening, water repellency and corrosion resistance enhancement suitable for various applications.

金属防护用防腐涂料应具有良好的机械性能、拒水性和耐腐蚀性，以应对外界冲击和腐蚀介质侵蚀所造成的负面影响。本文采用反应性氟聚合物（PF-HDI）与环氧树脂（E-44）共价接枝，并与丙烯酸进行开环反应制备了新型乙烯基酯树脂（VER）复合涂料。共价引入PF-HDI对涂层的综合性能有显著影响。0.4 wt%的PF-HDI不仅赋予涂层优异的力学性能和耐腐蚀性，包括抗拉强度提高81.64% (80.94 MPa)，阻抗模量提高3个数量级（42 d）和6个数量级（82 d）（>1010 Ω cm2），而且与纯VER相比，防水性能显著提高。本研究为制备具有增韧、拒水性和耐腐蚀性的高性能复合涂层提供了一种有效的策略。

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引用次数: 0

Microwave-assisted modification of a solid epoxy resin with a Peruvian oil 用秘鲁油对固体环氧树脂进行微波改性

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-25 DOI: 10.1016/j.porgcoat.2025.109333

Daniel Obregón , Antonella Hadzich , Lunjakorn Amornkitbamrung , G. Alexander Groß , Santiago Flores

A solid epoxy resin was modified with drying vegetable oils via microwave heating to produce one-component epoxy ester resins. These hybrid bio-based resins have an epoxy network that cures at room temperature due to the auto-oxidative capacity of unsaturated fatty acid chains. The influence of the fatty acid source, temperature, and reaction time on viscosity was evaluated using a response surface design. Structure (Fourier transform infrared (FTIR) spectroscopy and proton nuclear magnetic resonance (¹H NMR)), drying behavior, thermal stability (thermogravimetry/ differential thermal analysis (TG/DTG)), and molecular weight distribution (gel permeation chromatography (GPC)) of selected resins were also studied. Paints prepared with representative epoxy ester resins were analyzed to compare the effect of the fatty acid source on anticorrosive properties by electrochemical impedance and salt spray tests. The design of experiments simplified the selection of synthesis conditions to obtain optimal resin film properties. Microwaved-synthesized epoxy ester resins prepared with Peruvian oil are potential raw materials for developing functional anticorrosive paints, as they provide the best corrosion resistance. Its high unsaturation content gives sacha inchi oil the curing properties needed to replace linseed oil in the coatings industry.

用干燥植物油对固体环氧树脂进行微波加热改性，制得单组分环氧酯树脂。由于不饱和脂肪酸链的自氧化能力，这些杂化生物基树脂具有在室温下固化的环氧树脂网络。采用响应面设计评价了脂肪酸来源、温度和反应时间对粘度的影响。研究了所选树脂的结构（傅里叶变换红外（FTIR）光谱和质子核磁共振（1H NMR））、干燥行为、热稳定性（热重/差热分析（TG/DTG））和分子量分布（凝胶渗透色谱（GPC））。通过电化学阻抗和盐雾试验，比较了不同脂肪酸源对环氧酯树脂涂料防腐性能的影响。实验设计简化了合成条件的选择，以获得最佳的树脂膜性能。用秘鲁油制备的微波合成环氧酯树脂具有良好的耐腐蚀性，是开发功能性防腐涂料的潜在原料。它的高不饱和含量赋予了茶树油在涂料工业中取代亚麻籽油所需的固化性能。

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引用次数: 0

Benzotriazole inbuilt hollow mesoporous CeO2 microsphere encapsuled by polydopamine/polyethyleneimine co-deposition layer for dual active corrosion protection of waterborne epoxy coated steel 聚多巴胺/聚乙烯亚胺共沉积层包封苯并三唑内嵌中空介孔CeO2微球用于水性环氧涂层钢的双活性防腐

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-25 DOI: 10.1016/j.porgcoat.2025.109331

Peng Xu, Tianguan Wang, Jingsha Tan, Wenfeng Ge, Huixuan Qian, Yanwei Zeng, Bing Lei, Honglei Guo, Zhiyuan Feng, Guozhe Meng

In this work, a new type of hollow mesoporous CeO₂ microsphere (HMCM), synthesized through a template-free approach, was utilized as both an inhibitor and a nanocontainer for loading the corrosion inhibitor benzotriazole (BTA). These microspheres were encapsulated with a co-deposition layer composed of polydopamine (PDA) and polyethyleneimine (PEI) to construct smart containers (PDA-PEI@HMCM-BTA) with pH-responsive release properties. The corrosion inhibition effect of PDA-PEI@HMCM-BTA nanocontainers was assessed and the release rate of BTA and Ce ions from the nanocontainers was greatly accelerated in the presence of acidic solutions. Electrochemical impedance spectroscopy (EIS) was conducted to evaluate the barrier properties and active anti-corrosion performance of the coatings. The results showed that the integration of nanocontainers within the waterborne epoxy coating significantly improved the corrosion resistance and self-healing capabilities, thereby providing efficient corrosion protection for carbon steels. The method offered a simplified synthesis route for Ce-based nanocontainers and presented a strategy for producing waterborne epoxy coatings with active anticorrosive properties.

本文采用无模板法合成了一种新型中空介孔CeO2微球（HMCM），作为缓蚀剂苯并三唑（BTA）的缓蚀剂和纳米容器。这些微球被聚多巴胺（PDA）和聚乙烯亚胺（PEI）组成的共沉积层包裹，构建具有ph响应释放特性的智能容器（PDA-PEI@HMCM-BTA）。考察了PDA-PEI@HMCM-BTA纳米容器的缓蚀效果，发现在酸性溶液存在下，BTA和Ce离子从纳米容器中释放速度大大加快。利用电化学阻抗谱（EIS）对涂层的阻隔性能和活性防腐性能进行了评价。结果表明，纳米容器在水性环氧涂层中的集成显著提高了涂层的耐蚀性和自愈能力，从而为碳钢提供了有效的防腐保护。该方法简化了ce基纳米容器的合成路线，为制备具有活性防腐性能的水性环氧涂料提供了一种策略。

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引用次数: 0

Depth profiling of wrinkled coil coatings - new insights into gradient structures and coating degradation 起皱线圈涂层的深度轮廓分析——对梯度结构和涂层降解的新见解

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-24 DOI: 10.1016/j.porgcoat.2025.109325

D. Leidlmair , J. Duchoslav , G. Mayr , H. Gsaller , B. Strauß , H. Groiss , D. Stifter

For the desired low-gloss appearance of applications such as outdoor roofing systems, organic coatings with a certain degree of surface corrugation are commonly used. Despite various mechanical and chemical mechanisms contributing to wrinkle formation in curing coatings have been extensively discussed in in the past, a comprehensive in-depth characterization of the internal microstructure of textured finishes is yet to be reported. In this work, the interior chemical structure of a state-of-the art wrinkled coil coating system consisting of a polyester-melamine topcoat and a polyester-polyurethane primer applied on a galvanized steel substrate was thoroughly examined by combining advanced surface analysis techniques with cryo-ultra-low-angle microtomy (cryo-ULAM). Plane-view depth-resolved analysis by means of focal-plane-array Fourier-transform infrared (FPA-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) mappings readily enabled to determine chemical gradients inside the topcoat layer related to the formation of a melamine-enriched and pigment-depleted skin on top of the coating system. Furthermore, correlative depth-resolved analysis additionally allowed to directly assess and compare the degradation of a high-end wrinkle coating system after accelerated artificial ageing as well as after exposure to atmospheric conditions, which consistently showed that the most significant alterations of the coating chemistry induced by progressive weathering particularly occurred at the melamine-enriched coating surface.

对于室外屋顶系统等应用所需的低光泽外观，通常使用具有一定程度表面波纹的有机涂层。尽管过去已经广泛讨论了各种促进固化涂层起皱形成的机械和化学机制，但对纹理饰面内部微观结构的全面深入表征尚未有报道。在这项工作中，通过结合先进的表面分析技术和低温超低角显微切开术（cryo-ULAM），彻底检查了由聚酯-三聚氰胺面漆和聚酯-聚氨酯底漆组成的最先进的起皱卷材涂层系统的内部化学结构。通过焦平面阵列傅里叶变换红外（FPA-FTIR）光谱和x射线光电子能谱（XPS）映射的平面视图深度分辨分析，可以很容易地确定与涂层系统顶部三聚氰胺富集和色素耗尽皮肤形成相关的顶层涂层内的化学梯度。此外，相关的深度分辨分析还可以直接评估和比较高端褶皱涂层系统在加速人工老化和暴露于大气条件后的降解情况，结果一致表明，由渐进风化引起的涂层化学变化最显著，特别是发生在富含三聚氰胺的涂层表面。

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引用次数: 0

Preparation and investigation of a urethane methacrylate containing a tert-butyl terminal group in urethane/acrylate hybrid latexes 氨基甲酸乙酯/丙烯酸酯杂化乳胶中端叔丁基甲基丙烯酸乙酯的制备与研究

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-24 DOI: 10.1016/j.porgcoat.2025.109324

Yongan Hu, Mark D. Soucek

A urethane methacrylate with a tert-butyl terminal group, 2-((tert butylcarbamoyl)oxy) ethyl methacrylate (tBEM), was synthesized and incorporated into a series of homogeneous and core-shell model acrylate latexes. Unlike urethane methacrylates with linear or cyclic alkyl terminal groups, the tert-butyl group seems to preclude urethane formation, other than a direct approach of reacting tert-butyl isocyanate with 2-hydroxethyl methacrylate (HEMA) was employed. The effect of tBEM content on latex performance was investigated using minimum film formation temperature (MFFT) tester, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile tests and Fourier transform infrared spectroscopy (FTIR). Increasing the loading level of tBEM led to an increase in film stiffness and tensile strength.

合成了一种末端叔丁基的甲基丙烯酸氨基乙酯（2-（叔丁基氨基甲酰基）氧基）甲基丙烯酸乙酯（tBEM），并将其掺入一系列均相核壳型丙烯酸酯乳液中。与具有线性或环烷基末端基团的氨基丙烯酸酯不同，叔丁基似乎阻止了氨基丙烯酸酯的形成，而不是采用异氰酸叔丁基与甲基丙烯酸2-羟乙基（HEMA）直接反应的方法。采用最小成膜温度（MFFT）测试仪、差示扫描量热法（DSC）、动态力学分析（DMA）、拉伸试验和傅里叶变换红外光谱（FTIR）等方法研究了tBEM含量对乳胶性能的影响。随着加载水平的提高，薄膜的刚度和抗拉强度均有所提高。

引用次数: 0

The persistence of interphase regions in epoxy-amine coatings 环氧胺涂层中相间区域的持久性

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings

Pub Date : 2025-04-23 DOI: 10.1016/j.porgcoat.2025.109327

Suzanne Morsch , Yanwen Liu , Stuart B. Lyon , Claudio Di Lullo

It has recently been established that interfacial segregation of polymer precursors occurs during the step-growth polymerization of epoxy thermosets. In composite coating formulations, this leads to the establishment of nanoscale, structurally distinct interphase regions around filler or pigment particles. Whilst these under-developed regions are widely considered to be a critical factor in determining corrosion resistant barrier coating performance, the longevity and fate of the interphase, rich in reactive chemical functionality, remains largely unexplored. Here, we investigate the evolution of nanoscale chemical gradients in exemplary systems comprised of diglycidyl ether of bisphenol-A (DGEBA) and triethylenetetraamine (TETA) binder filled with powdered synthetic hematite, (Fe₂O₃). In these systems, it is known that interphase functionality is primarily dependent on entropic segregation processes, since only weak electrostatic binding occurs between the amine and particle surfaces. Surprisingly, here we demonstrate that rather than exclusively segregating upon mixing, unreacted material continues to accumulate in the interphase throughout the ambient cure (including post-vitrification). Moreover, when a post-cure heating regime known to accelerate molecular diffusion and etherification is applied, it is found that the interphase persists and is remarkably unreactive, yielding relatively soft, partially cured regions 50–100 nm in depth around embedded particles.

近年来研究发现，在环氧热固性聚合物的阶梯生长聚合过程中，高分子前驱体的界面偏析发生。在复合涂层配方中，这导致在填料或颜料颗粒周围建立纳米级，结构上不同的相间区域。虽然这些未开发的区域被广泛认为是决定耐腐蚀屏障涂层性能的关键因素，但富含活性化学功能的界面相的寿命和命运在很大程度上仍未被探索。在这里，我们研究了由双酚a二甘油酯醚（DGEBA）和三乙烯四胺（TETA）粘合剂填充粉状合成赤铁矿（Fe2O3）组成的示例系统中纳米级化学梯度的演变。在这些系统中，众所周知，相间功能主要依赖于熵分离过程，因为在胺和颗粒表面之间只发生弱静电结合。令人惊讶的是，我们在这里证明，在混合时，未反应的物质不是完全分离的，而是在整个环境固化过程中（包括玻璃化后），未反应的物质继续在间期积累。此外，当已知的固化后加热可以加速分子扩散和醚化时，发现间相持续存在并且非常不活泼，在嵌入颗粒周围产生相对柔软的、部分固化的50-100 nm深度区域。

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引用次数: 0