Preparation and properties of hybrid magnetic materials based on phthalocyanine polymer

Dicarboxylic acid containing 1,3-benzoxazine was synthesized and chemically bonded on iron carbonyl particles by post-coating method. The novel organic–inorganic hybrid magnetic composites were prepared via the interfacial reaction between iron phthalocyanine magnetic polymer and chemically modified iron carbonyl particles. The interfacial compatibility of hybrid magnetic materials was improved by the polymer coatings. The magnetic properties of prepared magnetic composites were measured by vibrating sample magnetometer (VSM). After the metallic particles were treated, the magnetic properties of obtained composites were enhanced, and with the feed ratio of coated iron carbonyl increased from 20 to 40%, the saturation magnetization of the magnetic composites increased from 48.82 to 65.06 emu/g; meanwhile the obtained magnetic composites exhibited excellent thermal stability up to 500 °C.     

Multi-functional hybrid coatings containing silica nanoparticles and anti-corrosive acrylate monomer for scratch and corrosion resistance

Multi-functional hybrid coatings having both anti-corrosion and scratch resistance were prepared from modified silica nanoparticles and functional acrylates. To improve the dispersion properties of silica nanoparticles in the organic/inorganic hybrid coatings, the surface of the nanoparticles was modified with γ-methacryloxypropyltrimethoxysilane. The coating solution could be prepared by mixing modified silica nanoparticles, tetrasiloxane acrylate, di-acrylate monomer containing an anti-corrosion functional group, acrylic acid, and an initiator in a solvent. The mixture was then dip-coated on iron substrates and finally polymerized by ultraviolet (UV) irradiation. Corrosion and scratch resistance of the coated iron was evaluated by electrochemical impedance spectroscopy (EIS) and a pencil hardness test, respectively. From the EIS results, the coatings with tetrasiloxane acrylate and di-acrylate did not show any decrease in impedance or phase angle, even after 50 days' exposure to 0.1 M NaCl electrolyte, whereas the conventional acrylate coatings started to fail after only 24 h. A hybrid coating containing the amine-quinone functional group exhibited excellent corrosion protection properties with 4-5H pencil hardness.     

有机硅KH-570改性硅溶胶杂化涂层的制备研究

以硅溶胶、γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)为原料,将低钠型碱性硅溶胶经强酸性阳离子交换树脂离子交换后,得到酸性硅溶胶,将其与KH-570按一定比例共混搅拌,通过KH-570在酸性条件下,水解缩聚,制得有机/无机杂化溶胶。以低碳钢Q235为基材,制备出硅烷偶联剂KH-570(MEMO)改性硅溶胶的杂化涂层。以FT-IR测试方法对其结构进行了表征,采用动电位极化曲线测试涂层的耐蚀性能。以光学显微镜、SEM观察涂层与碳钢裸片在腐蚀前后的表面形貌。研究结果表明:酸性硅溶胶与KH-570的水解缩聚产物通过共缩聚反应在碳钢表面形成带有有机基团的无机交联网络,基本骨架由Si-O-Si组成,经过100℃热处理,即可得致密涂层,涂层均匀、透明,无缺陷。电化学分析表明涂层形成物理屏障,为基体提供了优良的腐蚀保护。杂化涂层显现出良好的耐蚀性能。     

Effect of amino-modified silica nanoparticles on the corrosion protection properties of epoxy resin-silica hybrid materials

In this paper, a series of organic-inorganic hybrid materials consisting of epoxy resin frameworks and dispersed nanoparticles of amino-modified silica (AMS) were successfully prepared. First of all, the AMS nanoparticles were synthesized by carrying out the conventional acid-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) in the presence of (3-aminopropyl)-trimethoxysilane (APTES) molecules. The as-prepared AMS nanoparticles were then characterized by FTIR, 13C-NMR and 29Si-NMR spectroscopy. Subsequently, a series of hybrid materials were prepared by performing in-situ thermal ring-opening polymerization reactions of epoxy resin in the presence of as-prepared AMS nanoparticles and raw silica (RS) particles. The as-prepared epoxy-silica hybrid materials with AMS nanoparticles were found to show better dispersion capability than that of RS particles existed in hybrid materials based on the morphological observation of transmission electron microscopy (TEM). The hybrid materials containing AMS nanoparticles in the form of coating on cold-rolled steel (CRS) were found to be much superior in corrosion protection over those of hybrid materials with RS particles when tested by a series of electrochemical measurements of potentiodynamic and impedance spectroscopy in 5 wt% aqueous NaCI electrolyte. The increase of corrosion protection effect of hybrid coatings may have probably resulted from the enhancement of the adhesion strength of the hybrid coatings on CRS coupons, which may be attributed to the formation of Fe-O-Si covalent bond at the interface of coating/CRS system based on the FTIR-RAS (reflection absorption spectroscopy) studies. The better dispersion capability of AMS nanoparticles in hybrid materials were found to lead more effectively enhanced molecular barrier property, mechanical strength, surface hydrophobicity and optical clarity as compared to that of RS particles, in the form of coating and membrane, based on the measurements of molecular permeability analysis, dynamic mechanical analysis, contact angle measurements and ultraviolet-visible transmission spectra, respectively.     

ELECTROPHORETIC COATINGS FOR ADVANCED MATERIALS

We have electrophoretically deposited a variety of coatings for a number of applications. We have also worked extensively with a process for electrophoretically depositing styrene acrylate polymer coatings. These coatings provide useful corrosion protection and dielectric properties for capacitors and electrical insulation. Dielectric breakdown strengths in the order of 1000 V/micrometer have been observed for capacitors with this coating as the dielectric. Various particles have also been dispersed in the electrolyte; these mixtures yield composite coatings of unusual materials such as fissile uranium in a carbon matrix. The process can also be adapted to form very thin, free-standing styrene acrylate films or pellicles. We have also explored the feasibility of depositing a variety of colloidal inorganic particles from liquid suspensions. Our results show that isopropanol works relatively well as a dispersing medium for a large number of powders. Isopropanol slurries can be used to deposit a number of uniform ceramic or glass coatings on metal substrates. Important coating considerations with regard to whether useful coatings can be deposited using this latter type of electrophoretic process include: (1) the average size, size distribution, and shape of the particles, (2) the charge assumed by the powder particles when they are dispersed in a liquid such as isopropanol, and (3) the coefficients of thermal expansion of the substrate and the coating material from the standpoint of the heat treatment or sintering required to obtain sufficient cohesion and adhesion.     

掺杂纳米CeO2对ZrO2-Y2O3热障涂层隔热性能的影响

以纳米ZrO₂-8 wt%Y₂O₃(YSZ)和在纳米ZrO_2-8wt%Y₂O₃中分别掺杂25wt%和50wt%纳米CeO₂团聚处理后作为隔热层材料,NiCrAlY(Ni-25Cr-5Al-0.5Y,wt %)作为粘结层材料,用等离子喷涂(APS)方法在GH30高温合金表面制备三种材料体系的热障涂层(TBC) 。通过扫描电镜(SEM)和X射线衍射仪(XRD)对掺杂了25wt%纳米CeO₂涂层的微观组织结构进行分析研究,测定了三种材料涂层在室温和 300、500、700℃时的热导率,并在相同边界条件下测试了它们的隔热性能。结果表明：掺杂纳米CeO₂涂层组成相为稳定的t相(t-ZrO₂、t-Zr_0.82Y_0.18O_1.91、t-Zr_0.82Ce_0.18O₂)和c相(c-CeO₂) , 涂层中存在闭合的孔隙和微裂纹;掺杂纳米CeO₂能够降低涂层的热导率,并且隔热性能随CeO₂含量的增加而提高。对于 400μm厚的CeO₂/ZrO₂-Y₂O₃涂层(CYZ , 掺杂25wt%CeO₂)对基体产生的温降比纳米YSZ涂层提高了10.7%,当CeO₂的含量从25wt%提高到50wt%时,隔热性能也提高了7.1%。     

Funktionelle Schichten auf Metallen: Maßgeschneiderte Eigenschaften durch Sol‐Gel‐Technologie

Functional Layers on Metals: Tailored Properties by Sol‐Gel Technology The value of metal articles can be substantially enhanced by convenient surface coatings. Beside organic layers (e. g. paints) and inorganic layers (e. g. enamel) wellknown as coating materials, so‐called inorganic‐organic hybrid polymers set out to combine the advantages of both coating groups. For the manufacture of such hybrid materials functional particles with sizes of a few nanometers – so‐called nanoparticles – are synthesized in the sol‐gel process. The versatility of this procedure allows to cover an extreme variety of properties of the resulting layers. Thus, depending on their composition, sol gel coatings are suited as corrosion protection, as primer, as abrasion‐reducing coating or as easy‐to‐clean layer. A sufficient wetting and adhesion on vitually any substrate can be achieved by proper choice of functional groups and pretreatment steps.     

KH-560改性SiO2绝缘薄膜的制备及性能研究

软磁合金是新一代质子/重离子同步加速器加速器的核心材料,在其表面涂覆绝缘涂层可有效降低高频涡流损耗。同时,高温热处理(~600 ℃)可有效减少软磁合金冷压成形产生的缺陷和位错而引起的内部残余应力。因此,软磁合金用绝缘涂层还需满足耐高温要求。SiO₂涂层是最常见的无机涂层材料,具有良好的绝缘性能和耐高温性能。本工作在植酸催化TEOS+MTES制备硅溶胶的基础上,加入硅烷偶联剂KH-560进一步提高硅溶胶的成膜性能,系统研究了KH-560对SiO₂涂层结构与性能的影响,并系统分析了KH-560提高SiO₂涂层性能的机理。研究表明,添加适量的KH-560可有效提高薄膜的稳定性和成膜性。特别是当KH-560添加量为0.04 mol时,SiO₂涂层质量最好,SiO₂-0.04 KH涂层表现出最佳的耐腐蚀性和电绝缘性。在100 V时,SiO₂-0.04 KH涂层的方块电阻仍保持2.95×10¹¹Ω/□。综上,本研究利用植酸催化和KH-560改性协同作用制备出高质量的SiO₂涂层,涂层具有良好的耐高温和优异的绝缘性能。     

Electromagnetic properties of phosphate-coated ferrite composite materials

Sintered ferrite was treated with phosphoric acids to form phosphate-coated powders. The formation of the coating layer was verified by the improvement of oxidation resistance, microscopic morphologies, and evident reduction of conductivity of the powders. The coated powders were then blended with silicone to fabricate composite materials. The electromagnetic properties of the composites at the frequency range of 1?MHz to 1?GHz were investigated and found to be noticeably affected by the surface condition of the powders. The coating layer significantly reduced the imaginary part of permittivity of the composite owing to the improvement of insulation, while the resonance frequency was scarcely affected. The magnetization curves revealed that, compared to the composite containing as-prepared powder, the coated powder filled composites exhibited enhanced demagnetizing field, which consequently contributed to an obvious depression in magnetic permeability. Due to the modification of electromagnetic properties, the phosphate-coated ferrite composites were found to be practical materials as a substrate of radio frequency identification (RFID) metal tag. The impedance measurement results revealed that the phosphate-coated ferrite composites could remedy destructive interference imposed by metal and was beneficial for fabrication of RFID metal tag.     

硅钢绝缘涂层的研究进展

本文系统介绍了取向硅钢与无取向硅钢表面绝缘涂层，包括有机涂层、无机涂层和半无机涂层三大类。无机涂层具有良好的耐热和焊接性能，但其冲制性和粘结性不佳。半无机涂层具有良好的冲制性和粘结性，但其耐热性和焊接性不及无机涂层。另外，最新研究的取向硅钢表面物理气相沉积ＴｉＮ、ＣｒＮ和ＴｉＣ绝缘涂层可使硅钢获得极低的铁损，大大提高了硅钢的磁通量密度，并具有优异的耐热、焊接、冲制和粘结性。     

Transparent anti-stain coatings with good thermal and mechanical properties based on polyimide-silica nanohybrids

In this work, we synthesized polyimide/silica hybrid materials via sol-gel method using a fluorinated poly(amic acid) silane precursor and a variety of perfluorosilane contents. We studied the influence of a hybrid coating film with the following characteristics; hydrophobicity, oleophobicity, optical transparency, and surface hardness of the coating films. The hybrid coatings with the fluorosilane contents up to 10 wt% are optically transparent and present good thermal stability with a degradation temperature of > 500 degrees C as well as a glass transition of > 300 degrees C. Both water contact angle and oil contact angle increase rapidly with introducing small amount of the fluorosilane in the hybrids and reaches the maximum of 115 degrees and 61 degrees, respectively. The hardness of the hybrid coatings increases up to 5H with an increase of the FTES content in the hybrids. These colorless, transparent, and thermally stable hybrid materials could be suitable for applications as anti-stain coatings.     

Thermal-Diffusivity Measurement of Ceramic Coatings at High Temperature using “Front-Face” and “Rear-Face” Laser Flash Methods

Thick ceramic coatings deposited by plasma spraying techniques are widely used as wear and corrosion resistant coatings at high temperature. To measure accurately the thermal diffusivity of such coatings, the diffusivimeter of LNE has been set up to allow multilayered material studies up to 1,400°C by rear-face and front-face laser flash methods. These two methods have been compared in a large temperature range by measuring the thermal diffusivity of homogeneous (Armco iron and Poco graphite) and multilayered materials (chromium oxide coating deposited on iron alloy substrate). The thermal-diffusivity values measured by using front-face and rear-face techniques are in good agreement, with a relative deviation of less than 5% depending on temperature and materials.     

Antimicrobial coatings — obtaining and characterization

In this paper, we present inorganic–organic hybrid coatings with polymer matrix (water soluble) that contain silver nanoparticles (AgNPs). The structure and morphology of coating materials were determined by infrared spectroscopy (FT–IR) and scanning electron microscopy (SEM). Therefore, the antimicrobial activities and mechanisms of coatings for several pathogenic bacteria (Bacilius cereus and Staphylococcus aureus) were investigated. It was demonstrated that the obtained material with silver nanoparticles keep their antimicrobial effect even if they are subjected to several cycles of washing with water and detergent.     

有机硅溶胶-凝胶防腐蚀涂层研究进展

有机硅溶胶-凝胶涂层是指以烷基烷氧基硅烷为前驱体通过溶胶-凝胶技术制备的涂层。有机硅是分子水平上的有机-无机杂化分子,因此有机硅溶胶-凝胶涂层兼具了有机材料和无机材料的性能,并且能通过合理的调控有机和无机成分来获得所需的性能。其热稳定、耐刮擦性与无机材料的结合性能明显高于普通的有机材料,柔韧性与有机材料的结合性能明显高于一般的无机涂层。近年来,这种新型的、具有特殊性能的涂层被广泛研究用来保护金属材料(如铝、铁、镁、铜基材料)。介绍了有机硅溶胶-凝胶涂层涉及的基本反应、硅烷在金属表面上的成键机理以及在不同金属上的应用等方面的研究进展,并展望了有机硅溶胶-凝胶涂层应用前景及未来的研究方向。     

Preparation and characterization of sol-gel silica based neutral optical density coatings by the addition of graphite particles

Silica based coatings with various thicknesses (600-3000 nm) were prepared from the gellation of aqueous suspensions composed of colloidal silica particles, small graphite particles and inorganic binder materials, the latter were included to improve the coating structure. The graphite particles added in amounts of 0.8-3.6 wt.%, in the dried coating, absorb visible light with the same efficiency, which results in coatings with neutral optical density in this range of the spectrum. The optical density of the coatings can be changed from basically 0, in coatings without graphite, to more than 2 in thick coatings with 3.6 wt.% of graphite. The structural characterization of the coatings was carried out using X-ray diffraction, Raman scattering and atomic force microscopy.     

Hydrophobic properties and color effects of hybrid silica spin-coatings on cellulose matrix

A novel sol–gel derived organic–inorganic hybrid silica sol consisting of organic direct red dye 4BS and inorganic silica (SiO₂) is successfully synthesized by adding coupling agent γ-chloropropyltriethoxysilane (CPTS). Hybrid silica coatings are deposited on cellulose matrix surface via spin-coating approach to introduce effective hydrophobic and color properties. Compared to the dye hybrid silica sol (DHSS), the particle size of CPTS/dye hybrid silica sol (CDHSS) increases from 64.51 to 129.70 nm, while the surface tension reduces from 34.27 × 10⁻³ N m⁻¹ to 31.22 × 10⁻³ N m⁻¹. The hydrostatic pressure of the cellulose matrix coating with CDHSS is 4530.5 Pa, the contact angle is 131.48°, and the wetting time is ~150 min, which attributes to the alkyl chloride aliphatic chain and sharp micro-surface roughness of the hybrid coatings validated directly by AFM and SEM images. The K/S value (5.15) of the cellulose matrix coated with CPTS/dye hybrid silica (CMCCDHS) is 12.44% higher than that of the cellulose matrix coated with dye hybrid silica (CMCDHS), and increased by 30.38% relative to the control coated sample. The maximum absorption wavelengths of the matrixes treated with different processes are the same as the maximum absorption wavelength of the silica sols (510 nm).     

Aerosol route to functional nanostructured inorganic and hybrid porous materials

The major advances in the field of the designed construction of hierarchically structured porous inorganic or hybrid materials wherein multiscale texturation is obtained via the combination of aerosol or spray processing with sol-gel chemistry, self-assembly and multiple templating are the topic of this review. The available materials span a very large set of structures and chemical compositions (silicates, aluminates, transition metal oxides, nanocomposites including metallic or chalcogenides nanoparticles, hybrid organic-inorganic, biohybrids). The resulting materials are manifested as powders or smart coatings via aerosol-directed writing combine the intrinsic physical and chemical properties of the inorganic or hybrid matrices with defined multiscale porous networks having a tunable pore size and connectivity, high surface area and accessibility. Indeed the combination of soft chemical routes and spray processing provides "a wind of change" in the field of "advanced materials". These strategies give birth to a promising family of innovative materials with many actual and future potential applications in various domains such as catalysis, sensing, photonic and microelectronic devices, nano-ionics and energy, functional coatings, biomaterials, multifunctional therapeutic carriers, and microfluidics, among others.     

A study on hybrid bioceramic coatings of HA/poly(vinyl acetate) co-deposited electrochemically on Ti–6Al–4V alloy surface

A novel electrochemical co-deposition approach was developed to prepare hybrid bioceramic coating of hydroxyapatite (HA)/poly(vinyl acetate) on the surface of Ti–6Al–4V alloy. The aim is to improve the adhesion between the HA coating and the metal substrate. Surface characterization showed that the composition of inorganic phase in the composite bioceramic coatings was mainly HA and the content of organic phase was more than 4% (W/W). Significant surface morphology changes were observed. The shear-testing experiments indicated that the bonding strength of the hybrid coating to metal substrate was increased by as much as 3 MPa.     

氧化石墨烯改性环氧隔热涂层的耐蚀和隔热性能研究

用氧化石墨烯(GO)浓缩浆分散法制备GO改性环氧隔热涂层，在浓度(质量分数)为3.5% 的NaCl溶液(50℃)中进行腐蚀实验并测试其腐蚀前后的隔热性能。432 h的腐蚀电化学测试结果表明，用0.5%(质量分数) 的GO改性显著提高了涂层低频阻抗，涂层的耐蚀性优于无GO改性和1.0% GO改性的涂层；SEM分析结果表明，用0.5%和1.0% GO改性的隔热涂层腐蚀432 h后表面形貌完好，涂层/基体界面处没有出现裂纹和腐蚀产物，而未经GO改性的涂层出现了明显腐蚀破坏。腐蚀试验前，0.5%、1.0% GO改性的涂层与没有改性的涂层的隔热性能没有明显的区别；腐蚀432 h后涂层对250℃热源分别降温98℃、123℃、115℃，粘结强度分别降低了3.9、1.0、2.3 MPa。实验结果表明，用0.5% GO改性的涂层耐蚀和隔热性能最好。     

粉末粒度对等离子喷涂Al2O3-13%TiO2陶瓷涂层组织结构及性能的影响

等离子喷涂粉末的粒度影响涂层组织结构与性能。选用4种不同粒度的Al2O3-13%TiO2(AT13)粉末等离子喷涂陶瓷涂层,研究了喷涂粉末粒度对涂层组织结构、孔隙率、显微硬度和沉积效率的影响。结果表明:采用较细的喷涂粉末制备的AT13涂层致密、均匀,孔隙率低;随着喷涂粉末粒度增大,涂层的孔隙率增加,显微硬度降低,沉积效率先增后减;采用粒度为38～44μm的粉末喷涂涂层时沉积效率最高,达到51%,涂层组织也较致密,这是等离子喷涂AT13陶瓷层较理想的粒度。