Development of self-healing coatings based on urea-formaldehyde/polyurethane microcapsules containing epoxy resin

In this study, the synthesis of urea-formaldehyde/polyurethane (UF/PU) microcapsules containing epoxy resin for self-healing and anti-corrosion coatings with good stability has been reported. Spherical microcapsules were prepared with a diameter of about 50–720 μm and a shell thickness of 0.6–0.7 μm via in situ polymerization in an oil-in-water emulsion using 2,4-toluene diisocyanate-based pre-polymer along with the urea-formaldehyde. Scanning electron microscopy (SEM) and optical microscopy (OM) were employed to evaluate the shape and morphology of the microcapsules. Fourier transform infrared (FTIR) spectroscopy showed the absence of free isocyanate groups within the microcapsule shell confirming the completion of shell formation reactions. OM illustrated that the microcapsules were stable over a period of 30-days in toluene and xylene. Increasing microcapsule loading improved crack repairing and anti-corrosion performance of the coating layer. Low-carbon steel coupons coated with an epoxy resin containing 10 wt% microcapsules and scribed using a scalpel blade showed no visible sign of corrosion after up to 5 weeks of exposure in a standard salt spray test chamber.     

Tung oil: An autonomous repairing agent for self-healing epoxy coatings

The capability of the encapsulated Tung oil was investigated as a scratch healing agent for self-healing coatings. Encapsulation of Tung oil with urea–formaldehyde shell was carried out by in situ polymerization. Before the mechanical agitation of microcapsules into epoxy resin, their characteristics were evaluated by scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). Released Tung oil from ruptured microcapsules healed the artificial scratch in the coating matrix successfully. Corrosion resistance of healed area was evaluated by electrochemical impedance spectroscopy (EIS) and immersion test; and the results were compared with neat epoxy coating.     

Microencapsulation of oil soluble polyaspartic acid ester and isophorone diisocyanate and their application in self-healing anticorrosive epoxy resin

Isocyanate and amine solution are microencapsulated, respectively, via in situ polymerization to realize the self-healing function in epoxy matrix. First, the isophorone diisocyanate (IPDI) microcapsules prepared with different core/shell ratios, emulsifier dosages and emulsification rates are characterized by field emission scanning electron microscope (FE-SEM). They exhibit integral spherical shape when the core/shell ratio is 3:1 and emulsifier concentration is 2.52 wt %, and the diameter of IPDI microcapsules ranged from 2.66 μm to 11.25 μm is manufactured by adjusting emulsification rate over the range of 3000–9000 rpm. Besides, during the microencapsulation of polyaspartic acid ester (PAE), urea, tung oil, as well as aqueous isocyanate are proposed to improve the stability of PAE emulsion. SEM and FTIR results reveal that aqueous isocyanate can react with partial PAE and form polyurea (PU) layer to take protection effectively. Further, IPDI-PAE dual microcapsules are incorporated into epoxy coatings, the self-healing and anticorrosion performance of coatings with various amounts of microcapsules are investigated systematically. It was found that the degree of repair and anticorrosion are increased with increasing microcapsules loading, and the appropriate amount of microcapsules addition is 15 wt %, which corresponding to 93% repair efficiency. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48478.     

Improved self‐healing properties of collagen using polyurethane microcapsules containing reactive diisocyanate

Collagen is a natural polymer much available as a waste material. However, a more extensive use of collagen as an engineering material is restricted due to its low mechanical strength. This work presents a collagen–microcapsules system and evaluates the hypothesis that a self‐healing ability can be imposed on a collagen matrix to improve its tensile strength. Collagen films containing various types of microcapsules were studied using tensile tests (TTs). To evaluate the self‐repairing capacity of the developed system, samples were submitted to a 20% strain (to develop micro‐cracks in the material that could lead to the rupture of microcapsules and release of diisocyanate) and then left to stand for 20 min. A new TT was performed, named paused tensile test (PTT). The samples of pure collagen underwent no alteration with respect to their mechanical properties comparing TT and PTT results. In contrast, some samples containing microcapsules presented an increase of around 70% in mechanical strength when compared with the pure collagen results, proving that the released diisocyanates were effective in reacting with collagen and improving its mechanical strength. This type of behavior and the observed enhanced property can extend the usage of collagen to a variety of engineering applications. © 2016 Society of Chemical Industry     

Preparation and characterization of microcapsules containing linseed oil and its use in self-healing coatings

Effectiveness of linseed oil filled microcapsules was investigated for healing of cracks generated in paint/coatings. Microcapsules were prepared by in situ polymerization of urea–formaldehyde resin to form shell over linseed oil droplets. Characteristics of these capsules were studied by FTIR, TGA/DSC, scanning electron microscope (SEM) and particle size analyzer. Mechanical stability was determined by stirring microcapsules in different solvents and resin solutions. Cracks in a paint film were successfully healed when linseed oil was released from microcapsules ruptured under simulated mechanical action. Linseed oil healed area was found to prevent corrosion of the substrate.     

Polyamine microcapsules featured with high storage stability used for one-component epoxy adhesive

One-component epoxy adhesives have great promising prospects in industrial applications. However, it faces the challenge to reduce the activity of curing agents for achieving long-term storage and controlled release. Microencapsulation is a feasible and effective solution. In this paper, multi-polyaniline (MPAN) was successfully encapsulated with polyetherimide (PEI), a thermoplastic resin, as the shell material by using solvent evaporation method with dichloromethane (DCM) as solvent. The impacts of different preparation parameters on the structure and properties of microcapsules were investigated by single variable control method. It is found that the resulted microcapsules under the optimal process parameters, namely PVA concentration 1 wt%, core/shell mass ratio 1:1 and stirring rate 700 rpm, exhibits a smooth and dense spherical surface with an average particle size concentrated around 17.8 μm. Compared with the pure curing agent, the encapsulated curing agent effectively prolonged the shelf life of the epoxy adhesive at 40°C for at least 60 days, indicating excellent storage stability. The microencapsulated MPAN curing agent prepared in our research is of potential applications in the fields of electronic component bonding, potting and circuit board sealing due to its high storage stability and encapsulation efficiency (74%).     

苯乙醇微胶囊的稳定性及热释放行为研究

以苯乙醇为囊芯材料,以明胶和羧甲基纤维素(CMC)为壁材,采用复凝聚法制备了苯乙醇微胶囊,其包埋率达到92%。考察了温度和时间对苯乙醇微胶囊热释放行为的影响,以及其在卷烟纸上的贮存稳定性。结果表明,苯乙醇微胶囊可粘附在纸张纤维上,120℃加热10 min时微胶囊基本无变化,能够满足卷烟纸生产工艺要求。180℃加热40 min时微胶囊内部芯材基本挥发完全。在常温下密封保存60 d时苯乙醇保留率仍达到65%,稳定性较好。     

Preparation and evaluation of self-healing microcapsules for asphalt based on response surface optimization

The purpose of this study is to explore the best preparation process of asphalt self-healing microcapsules. Response surface design and single factor design were used to optimize the preparation process parameters of asphalt self-healing microcapsules, and the prediction model of core content was established. The optimal preparation process was determined. The results of response surface design showed that the interaction among emulsifier concentration/reaction temperature, core-shell ratio/reaction temperature, and pH/reaction temperature had significant effect on the core content of microcapsules; the microcapsules prepared by the optimal process were spherical with an average particle size of 90.19 μm. The results of thermogravimetric analysis (TGA) and heating simulation test showed that the microcapsule can delay the damage of the core in high temperature environment; the results of nanoindentation test showed that the young's modulus and hardness of the microcapsules were about 2.50 and 0.28 GPa, respectively. Finally, the improvement mechanism of self-healing performance of asphalt by microcapsules was revealed by fluorescence microscope.     

环氧树脂微胶囊合成及其反应动力学

将环氧树脂E-51分散在水中形成稳定的乳液,使用三乙烯四胺固化剂,在环氧树脂液滴表面形成交联结构作为环氧树脂微胶囊囊壁,这种微胶囊为环氧树脂复合材料的科学研究和工程应用提供了无界面差异囊壁的研究模型。采用扫描电子显微镜（SEM）和光学显微镜（OM）分析了乳化剂种类及用量、反应温度和搅拌速率等工艺条件对这种微胶囊的形成过程、表面形貌、粒径大小及分布和壁厚的影响。采用红外光谱（FTIR）研究了环氧树脂微胶囊的化学结构。当合成条件为乳化剂Tween 80浓度为1%,固化剂三乙烯四胺浓度为2.5%,反应温度90℃,搅拌速度600～1000 r·min^-1,合成的环氧树脂微胶囊形状规整,表面光滑致密,平均粒径为103 μm,囊芯含量为44.65%,壁厚为5 μm。研究三乙烯四胺固化剂中伯胺和仲胺的反应速率常数和活化能等反应动力学参数,定量分析环氧树脂-三乙烯四胺的化学反应中伯胺和仲胺的反应活性差异。     

硅烷改性环氧树脂自修复微胶囊的制备及应用

采用硅烷偶联剂γ-（2,3-环氧丙氧基）丙基三甲氧基硅烷（KH-560）对环氧树脂E-51进行改性,并以此为芯材,三聚氰胺-脲醛树脂（MUF）为壁材,原位聚合法合成微胶囊,探讨了微胶囊制备工艺,并用光学显微镜（OM）、扫描电子显微镜（SEM）、红外光谱仪（FTIR）、热重分析仪（TGA）等对其表面形貌、化学结构及热性能等进行了表征和测试;之后将改性后的微胶囊应用到自修复环氧树脂涂层中,考察了自修复涂层的力学性能和电化学性能。结果表明,当芯壁比为1.5：1、乳化剂质量分数为1.4%时,微胶囊为规则球形,表面粗糙、致密,大小均匀,平均粒径约为100μm,具有良好的热稳定性。当涂层中改性微胶囊质量分数为3%时,涂层的拉伸强度、弯曲强度、黏结强度及冲击强度均较高,且其较未改性微胶囊自修复涂层分别提高了14.9%、14.3%、16.0%和9.6%;与未改性微胶囊自修复涂层相比,改性微胶囊自修复涂层的电化学性能增强,且电化学阻抗值显著提高。     

Preparation of polyurea microcapsules containing pyrethroid insecticide with hexamethylene diisocyanate isocyanurate

Polyurea microcapsules containing a pyrethroid insecticide were prepared by the reaction between hexamethylene diisocyanate isocyanurate and ethylenediamine in an oil‐in‐water emulsion. This study was performed to establish the operational conditions of preparing microcapsules by interfacial polymerization and to investigate how the operational conditions affected the characteristics of microcapsules such as the morphology, wall thickness, mean diameter, and particle size distribution. Microcapsules prepared in this study were found to be spherical and monocore. The microcapsule yields, ranging from 94 to 98%, were almost equal to the theoretical values. The wall thickness of the microcapsules increased with the diameter of the microcapsules and the concentration of hexamethylene diisocyanate isocyanurate. In comparison with the results for microcapsules prepared with a mixture of hexamethylene diisocyanate uretidione and isocyanurate, the diameters and wall thickness of the microcapsules were found to be larger. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of polyurea/polyurethane double‐shell microcapsules containing butyl stearate through interfacial polymerization

Double‐shell microcapsules containing butyl stearate were prepared through interfacial polymerization. The outer shell is polyurea formed through polymerization of toluene‐2,4‐diisocyanate (TDI) and diethylene triamine, and the inner shell is polyurethane (PU) formed through polymerization of TDI and polypropylene glycol 2000 (PPG2000). Styrene maleic anhydride copolymer was used as emulsifier. The effects of core to monomer ratio and dosage of PPG2000 on core content and encapsulation efficiency of microcapsules were investigated. The core content has a maximum at core to monomer ratio of 3–4, and the encapsulation efficiency has a maximum value of 95% at core to monomer ratio of 2. The prepared microcapsules were smooth and compact and have an obvious latent heat of 85 J/g. The shell structure of microcapsules was polyurea and PU. The average diameter of the microcapsules was 1–5 μm. The stabilities of the double‐shell microcapsule, such as anti‐ethanol wash and antiheat properties are obviously improved than those of single‐shell microcapsule. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of polyurethane coatings based on acrylic polyols and trimer of isophorone diisocyanate

This paper presents a study on the effect of NCO/OH ratio and an increase in hydroxyl content of acrylic polyols on the properties of polyurethane (PU) coatings. Coating properties studied are gloss, scratch resistance, flexibility and adhesion, mechanical properties include tensile strength, modulus, percent elongation and Shore hardness, while physicochemical properties include chemical resistance and solvent absorption of coated PU samples. A series of acrylic polyols (copolymers) based on butyl acrylate (BA), methyl methacrylate (MMA), styrene and 2-hydroxy ethylacrylate (HEA) were prepared by selecting different percentage of hydroxyl content. Trimer of isophorone diisocyanate (IPDI) was also synthesized in the laboratory. This trimer has trifunctionality. Isocyanurate ring of trimer increases thermal properties of PU. Polyurethanes from these acrylic polyols (containing different percent hydroxyl) and trimer of IPDI were prepared with two different NCO/OH ratios viz, 1.1:1 and 1.2:1. Polyurethanes were coated on substrates for measuring coating properties. Mechanical properties were measured on cast films of the PUs. The experimental results revealed that all polyurethane coatings based on acrylic polyols and IPDI trimer showed good gloss, scratch resistance and excellent adhesion. Thermal stability of these PU samples was found to be better. Physicochemical properties reflected that these PU have excellent chemical and solvent resistance.     

Synthesis and characterization of polyurea microcapsules containing essential oils with antigerminative activity

In this paper we report on the preparation and characterization of polyurea‐based microencapsulated systems, containing essential oils as core materials, for potential applications in controlled‐release formulations of agrochemicals. Microcapsules were synthesized by interfacial polymerization in o/w emulsion between polyfunctional isocyanates and diamines, to investigate the effect of the monomer kind on the morphology and properties of the produced samples. The synthetic conditions that gave the best results were used to microencapsulate four essential oils, able to interfere with the seed germination and radicle elongation of some test plants. The produced samples were characterized, with the aim to analyze their morphology and to verify the effectiveness of essential oil microencapsulation. Moreover, preliminary bioassay based on seed germination and subsequent radical growth were carried out to study the effects of the microencapsulated essential oils. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Hollow polylactide microcapsules with controlled morphology and thermal and mechanical properties

Hollow polylactide microcapsules were prepared by multistage premix membrane emulsification of polylactide/dichloromethane/oil solutions in water (nonsolvent). The effects of the different oils on the morphology, thermal, and mechanical properties of the hollow microcapsules were investigated. All oils resulted in hollow microcapsules with controlled shell thickness of ～60 nm except for eugenol, in which irregular, massive capsules were obtained. The properties of the microcapsules were strongly dependent on the oil used, for example the thermal transition temperatures found for hollow capsules were lower than for solid particles prepared without any oil. The crystallinity and transition temperatures of the capsules prepared with linear alkanes were higher than for cyclic alkanes; terpenes gave the lowest transition temperatures. The shell stiffness, measured with atomic force microscopy, was highly dependent on the oil used. Capsules prepared with dodecane showed higher stiffness (3.3 N m^?1) than with limonene (2 N m^?1) or cyclohexane (1.4 N m^?1). © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Thermal and fire behavior of isophorone diisocyanate based polyurethane foams containing conventional flame retardants

This work reports on the fire behavior of isophorone diisocyanate‐based polyurethane foams containing different conventional flame retardants (FRs) such as melamine, ammonium polyphosphate, aluminum hydroxide, expandable graphite, and their combinations. The foams were obtained in a laboratory scale and characterized in terms of their morphology, density, thermal stability, and fire behavior. According to atomic force microscopy, the incorporation of FRs decreased the phase separated domain size. The cellular structure of the foams was examined qualitatively by scanning electron microscopy while the quantitative analysis of the surrounding skin was performed by optical microscopy and Image J. The FR containing foams showed more and smaller cells. The thermogravimetric analysis showed that the FRs had no influence in the initial degradation temperature of the foams. However, the obtained residue values were higher than the theoretical ones, indicating that there was some type of interaction between the FRs and the foams. The fire behavior of polyurethane foams was studied by the cone calorimeter and the data showed that the introduction of expandable graphite and combinations of ammonium polyphosphate/melamine to the reference foam gave rise to a significant reduction in the total heat release. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45944.     

Synthesis of durable microcapsules for self-healing anticorrosive coatings: A comparison of selected methods

Self-healing materials have the ability to ‘repair’ themselves upon exposure to an external stimulus. In the field of coatings, extensive laboratory research has been conducted on these so-called smart materials in the last decade. In the present work, a self-healing concept for epoxy-based anticorrosive coatings, based on incorporation of microcapsules, filled with reactive agents, into the coating matrix, is investigated. Upon small damages to the coating, the reagents are released from the capsules and react, thereby forming a cross-linked network, which heals the crack. However, for the concept to work, microcapsules have to be strong enough to remain intact during storage and coating formulation and application. Furthermore, the capsules must remain stable for many years in the dry coating. Laboratory experiments, using four out of several encapsulation methods available in the literature, have been conducted to investigate the challenges associated with the synthesis of stable microcapsules. It was found that the nature of the core material strongly affects the microcapsule stability and performance. Furthermore, it was evident that experimental procedures developed for certain core materials were not suitable for encapsulation of other compounds without modifications. This is a severe limitation as not many of the encapsulation procedures have been developed for industrially relevant core materials such as epoxy resin. Results of experiments, aiming at finding optimal conditions for robust microcapsule production, are discussed.     

Detailed experimental and theoretical investigation of the thermomechanical properties of epoxy composites containing paraffin microcapsules for thermal management

Microencapsulated phase change materials (PCMs) are being increasingly employed as functional fillers in polymer matrices for thermal management. Therefore, the effect of PCM microcapsules on the rheological, microstructural, thermal and mechanical properties of the host polymer matrices must be understood. This work concerned the preparation of epoxy polymers filled with PCM microcapsules (MC) in various concentrations and their subsequent characterization. The MC phase increases the viscosity of epoxy before curing, thereby reducing castability and hindering elimination of air bubbles. The latter was reflected in an increase in porosity for highly filled compositions, as elucidated by density measurements and microscopic investigation. SEM micrographs showed that the adhesion between the capsule shell and the epoxy matrix was not optimal. The interfacial weakness and the intrinsic low stiffness and strength of MC caused a reduction in mechanical properties, as evidenced by the Nicolais-Narkis and Pukanszky models. On the other hand, at zero or low deformation levels, the interface presents no gaps and is able to transfer load and heat, as demonstrated by the data of elastic modulus, modeled with the Halpin-Tsai and Lewis-Nielsen models, and those of thermal conductivity, in excellent agreement with the Pal model. POLYM. ENG. SCI., 2020. © 2020 Society of Plastics Engineers     

Shell thickness and chemical structure of polyurea microcapsules prepared with haxamethylene diisocyanate uretidione and isocyanurate

To investigate the dependence of the shell thickness on both the microcapsule size and the concentration of hexamethylene diisocyanate (HMDI) and to analyze the chemical structure of the polyurea shell, polyurea microcapsules were prepared by using the reaction between HMDI uretidione/isocyanurate and ethylene diamine (EDA) in an oil‐in‐water emulsion. In the experiment, the concentrations of hexamethylane diisocyanate and EDA were changed. The shell thickness was correlated well with the mean size and the concentration of HMDI on the surface area per unit volume of microcapsule. From the solid‐state ¹³C NMR spectroscopy analysis, the uretidione and isocyanurate ring structures were found to be not changed before and after the reaction. From the wide‐angle X‐ray diffraction analysis, it was suggested that the chemical structure of the polyurea shell was amorphous. From the FTIR spectra analysis, it could be concluded that polyurea microcapsules were prepared by the reaction between HMDI uretidione/isocyanate and EDA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

癸酸相变微胶囊的制备及热性能

以尿素、甲醛及癸酸为原料,利用原位聚合法制备了脲醛树脂包覆癸酸的相变微胶囊。以芯壁质量比、乳化剂用量、乳化转速及固化剂含量为变量设计正交实验,采用ESEM、FTIR和DSC分别表征癸酸微胶囊的微观形貌、化学结构及热性能,利用渗漏率实验测试癸酸微胶囊的防渗性能。结果表明,m(OP-10)∶m(Span-80)=4∶1的复合乳化剂有利于改善癸酸微胶囊颗粒特性。癸酸微胶囊P(芯壁质量比3∶2、乳化剂用量占芯材质量5%、乳化转速1400 r/min、固化剂间苯二酚用量占尿素质量12%)在微观形貌上分散良好且大小均一,相变潜热为123.91 J/g,渗漏率和包覆率分别为6.95%和69.7%,与癸酸微胶囊S(芯壁质量比1∶1、乳化剂用量占芯材质量6%、乳化转速1100 r/min、固化剂用量占尿素质量10%)相比,癸酸微胶囊P的渗漏率降低了57.2%,包覆率反而提高了132.3%,具有良好的热性能。