Comparison of anti-corrosion properties of polyurethane based composite coatings with low infrared emissivity

Four polyurethane resins, pure polyurethane (PU), epoxy modified polyurethane (EPU), fluorinated polyurethane (FPU) and epoxy modified fluorinated polyurethane (EFPU), with similar polyurethane backbone structure but different grafting group were used as organic adhesive for preparing low infrared emissivity coatings with an extremely low emissivity near 0.10 at 8-14 μm, respectively. By using these four resins, the effect of different resin matrics on the corrosion protection of the low infrared emissivity coatings was investigated in detail by using neutral salt spray test, SEM and FTIR. It was found that the emissivity of the coatings with different resin matrics changes significantly in corrosion media. And the results indicated that the coating using EFPU as organic adhesive exhibited excellent corrosion resistance property which was mainly attributed to the presence of epoxy group and atomic fluorine in binder simultaneously.     

Self-healing coatings containing microcapsule

Effectiveness of epoxy resin filled microcapsules was investigated for healing of cracks generated in coatings. Microcapsules were prepared by in situ polymerization of urea-formaldehyde resin to form shell over epoxy resin droplets. Characteristics of these capsules were studied by 3D measuring laser microscope, particle size analyzer, Fourier-transform infrared spectroscopy (FTIR) and differential scanning calorimeter (DSC) to investigate their surface morphology, size distribution, chemical structure and thermal stability, respectively. The results indicate that microcapsules containing epoxy resins can be synthesized successfully. The size is around 100 μm. The rough outer surface of microcapsule is composed of agglomerated urea-formaldehyde nanoparticles. The size and surface morphology of microcapsule can be controlled by selecting different processing parameters. The microcapsules basically exhibit good storage stability at room temperature, and they are chemically stable before the heating temperature is up to approximately 200 °C. The model system of self-healing coating consists of epoxy resin matrix, 10 wt% microencapsulated healing agent, 2 wt% catalyst solution. The self-healing function of this coating system is evaluated through self-healing testing of damaged and healed coated steel samples.     

Microstructure and properties of TiC-Fe36Ni cermet coatings by reactive plasma spraying using sucrose as carbonaceous precursor

This study is aimed to introduce an innovative precursor pyrolysis process to prepare Ti-Fe-Ni-C compound powder and to discuss and evaluate the relationship between microstructure and properties of TiC-Fe36Ni cermet coatings in-situ synthesized by reactive plasma spraying (RPS) of these compound powders. The main characteristic of the pyrolysis process is that sucrose (C12H22O11) is used as a source of carbon as well as a binder to bind reactive constituent particles. The compound powder with high bonding strength can avoid the problem that reactive constituent particles are separated during spraying. The TiC-Fe36Ni cermet coatings present typical splat-like morphology of thermally sprayed coatings and consist of two different areas: one is a composite reinforcement area where spherical fine TiC particles (100-500 nm) homogeneously distribute within the Fe36Ni matrix; the other is an area of TiC accumulation. The surface hardness of the coatings reaches about 90 ± 2 (HR15N). The maximum and average microhardness values of the coatings are 1930 HV_0.2 (Vicker Hardness) and 1640 HV_0.2, respectively. The average bonding strength of the coatings is about 62.3 MPa. The wear resistance property of the coatings is much more than that of Ni60 alloys coatings.     

Processing and properties of carbon nanofibers reinforced epoxy powder composites

Commercially available CNFs (diameter 30–300 nm) have been used to develop both bulk and coating epoxy nanocomposites by using a solvent-free epoxy matrix powder. Processing of both types of materials has been carried out by a double-step process consisting in an initial physical premix of all components followed by three consecutive extrusions. The extruded pellets were grinded into powder and sieved. Carbon nanofibers powder coatings were obtained by electrostatic painting of the extruded powder followed by a curing process based in a thermal treatment at 200 °C for 25 min. On the other hand, for obtaining bulk carbon nanofibers epoxy composites, a thermal curing process involving several steps was needed. Gloss and mechanical properties of both nanocomposite coatings and bulk nanocomposites were improved as a result of the processing process. FE-SEM fracture surface microphotographs corroborate these results. It has been assessed the key role played by the dispersion of CNFs in the matrix, and the highly important step that is the processing and curing of the nanocomposites. A processing stage consisted in three consecutive extrusions has reached to nanocomposites free of entanglements neither agglomerates. This process leads to nanocomposite coatings of enhanced properties, as it has been evidenced through gloss and mechanical properties. A dispersion limit of 1% has been determined for the studied system in which a given dispersion has been achieved, as the bending mechanical properties have been increased around 25% compared with the pristine epoxy resin. It has been also demonstrated the importance of the thickness in the nanocomposite, as it involves the curing stage. The complex curing treatment carried out in the case of bulk nanocomposites has reached to reagglomeration of CNFs.     

Plasma treatment of carbon fibers: Non-equilibrium dynamic adsorption and its effect on the mechanical properties of RTM fabricated composites

The effect of oxygen plasma treatment on the non-equilibrium dynamic adsorption of the carbon fabric reinforcements in RTM process was studied. 5-Dimethylamino-1-naphthalene-sulfonylchloride (DNS-Cl) was attached to the curing agent to study the change of curing agent content in the epoxy resin matrix. Steady state fluorescence spectroscopy (FS) analysis was used to study this changes in the epoxy resin at the inlet and outlet of the RTM mould, and XPS was used to study the chemical changes on the carbon fiber surfaces introduced by plasma treatment. The interlaminar shear strength (ILSS) and flexural strength were also measured to study the effects of this non-equilibrium dynamic adsorption progress on the mechanical properties of the end products. FS analysis shows that the curing agent adsorbed onto the fiber surface preferentially for untreated carbon fiber, the curing agent content in the resin matrix maintain unchanged after plasma treatment for 3 min and 5 min, but after oxygen plasma treatment for 7 min, the epoxy resin adsorbed onto the fiber surface preferentially. XPS analysis indicated that the oxygen plasma treatment successfully increased some polar functional groups concentration on the carbon fiber surfaces, this changes on the carbon fiber surfaces can change the adsorption ability of carbon fiber to the resin and curing agent. The mechanical properties of the composites were correlated to this results.     

Influence of high temperature annealing on the structure, hardness and tribological properties of diamond-like carbon and TiAlSiCN nanocomposite coatings

Diamond-like carbon (DLC) and TiAlSiCN nanocomposite coatings were synthesized and annealed at different temperatures in a vacuum environment. The microstructure, hardness and tribological properties of as-deposited and annealed DLC-TiAlSiCN nanocomposite coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Raman spectroscopy, nano-indentation and friction tests. The TEM results reveal that the as-deposited DLC-TiAlSiCN coating has a unique nanocomposite structure consisting of TiCN nanocrystals embedded in an amorphous matrix consisting of a-Si₃N₄, a-SiC, a-CN and DLC, and the structure changed little after annealing at 800 °C. However, XPS and Raman results show that an obvious graphitization of the DLC phase occurred during the annealing process and it worsened with annealing temperature. Because of the graphitization, the hardness of the DLC-TiAlSiCN coating after annealing at 800 °C decreased from 45 to 36 GPa. In addition, the DLC-TiAlSiCN coating after annealing at 800 °C has a similar friction coefficient to the as-deposited coating.     

S-SIMS and MetA-SIMS study of organic additives in thin polymer coatings

In the present study a methodology for TOF-S-SIMS measurements is developed to gain information on the distribution of molecules on and in polymer coatings (thickness ∼100 μm). Experiments were carried out on model systems consisting of one or more additive-containing polyvinylbutyral coatings. Several organic additives were selected: carbocyanine dyes, basonyl blue and the pharmaceutical risperidone. The additives have been measured as pure compounds on a Si substrate to obtain good reference spectra. After optimisation of the sample preparation method, the coatings were embedded in epoxy resin and stored in an oven (60 °C) for 24 h. Cross-sections were made by means of a microtome. S-SIMS spectra were taken on the prepared cross-sections before and after Au was deposited on the sample surface. Compared to the untreated samples, the Au covered samples give rise to more intense secondary ion signals. Generally, signals of the intact cations were more intense than those of the fragment ions. Apart from mass spectra, images of the additive distribution in the coatings could also be acquired by recording structural ion signals. It was possible to make secondary ion images of the additive molecule ions with a (sub)-micrometer lateral resolution.     

Structural and tribological properties of nitrogen doped amorphous carbon thin films synthesized by CFUBM sputtering method for protective coatings

Nitrogen doped amorphous carbon (a-C:N) films are a material that may successfully compete with DLC coatings, which have high hardness, high wear resistance, and a low friction coefficient. The a-C:N films were prepared on silicon substrate by a closed-field unbalanced magnetron sputtering method with a graphite target and using the Ar/N₂ mixture gases. And, we investigated the effects of various DC bias voltages from 0 to −300 V on the structural and tribological properties of the a-C:N films. This study was focused on improving physical properties of the a-C:N film by controlling process parameters like negative substrate DC bias voltage. The maximum hardness of the a-C:N film was 23 GPa, the friction coefficient was 0.08, and the critical load was 25 N on a Si wafer. Consequently, the structural and tribological properties of the a-C:N film showed a clear dependence on the energy of ions bombardment and the density of the sputtering and the reaction gases during film growth.     

Self-lubricative coating grown by micro-plasma oxidation on aluminum alloys in the solution of aluminate-graphite

Aluminum trioxide ceramic coatings with high hardness were grown on surfaces of 2024 Aluminum alloys by micro-plasma oxidation in an aluminate electrolytic solution, which highly improve wear-resisting properties of 2024 Aluminum alloys. However, ceramic coating surfaces are porous and very coarse, which is disadvantageous to practical applications. In this paper, in order to increase the density of the pores and decrease the friction coefficient of the ceramic coatings, different concentrations (2-8 g/l) of graphite were added into the aluminate electrolytic solution. The thickness and hardness of the produced ceramic coatings were measured by HVS-100 micro-hardness tester and thickness tester. The friction coefficient of the coatings was studied by a frictionometer. The phase composition and surface morphology of the MPO films were evaluated through X-ray diffraction (XRD) and scanning electron microscope (SEM). The results show that the thickness of the ceramic coating is about 22 ± 1 μm, surfaces of the ceramic coatings are very uniform and that the coatings consist of mainly aluminum trioxides and a certain amount of graphite, which indicates graphite have entered the ceramic films during the micro-plasma oxidation process. Wear properties results show that the friction coefficient of the ceramic coatings decreased when graphite entered the ceramic films. When the concentration of graphite is 4 g/l, the wear properties of the coatings is the most excellent and the friction coefficient decreases to the lowest, that is 0.09.     

Microwave absorption properties of Sr2FeMoO6 nanoparticles

The microwave absorption properties of nanosized double perovskite Sr₂FeMoO₆ and epoxy resin composites were investigated in the frequency range of 2-18 GHz using the coaxial method. The Sr₂FeMoO₆ composites with an optimal 20 wt% epoxy resin showed a strong electromagnetic attenuation of −49.3 dB at 8.58 GHz with a matching thickness of 2.15 mm. Moreover the optimum absorption frequency at which the reflection loss is less than −20 dB, which corresponds to 99% reflection loss of the incident microwave, is from 5.7 to 13.2 GHz with the matching thickness ranging from 3.0 to 1.5 mm. The excellent microwave-absorption properties are a consequence of a proper electromagnetic match due to the existence of the insulating matrix of anti-site defects and anti-phase domains, which not only contribute to the dielectric loss but also to the reduced eddy current loss.     

Annealing effects on magnetic properties of silicone-coated iron-based soft magnetic composites

This paper focuses on novel iron-based soft magnetic composites synthesis utilizing high thermal stability silicone resin to coat iron powder. The effect of an annealing treatment on the magnetic properties of synthesized magnets was investigated. The coated silicone insulating layer was characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. Silicone uniformly coated the powder surface, resulting in a reduction of the imaginary part of the permeability, thereby increasing the electrical resistivity and the operating frequency of the synthesized magnets. The annealing treatment increased the initial permeability, the maximum permeability, and the magnetic induction, and decreased the coercivity. Annealing at 580 °C increased the maximum permeability by 72.5%. The result of annealing at 580 °C shows that the ferromagnetic resonance frequency increased from 2 kHz for conventional epoxy resin coated samples to 80 kHz for the silicone resin insulated composites.     

Microstructure and mechanical properties of CrN films fabricated by high power pulsed magnetron discharge plasma immersion ion implantation and deposition

CrN films with strong adhesion with the substrate have been fabricated on Ti6Al4V alloy using novel plasma immersion ion implantation and deposition (PIII&D) based on high power pulsed magnetron sputtering (HPPMS). A macro-particle free chromium plasma is generated by HPPMS while the samples are subjected to high voltage pulses to conduct PIII&D. The CrN coatings have a dense columnar structure and low surface roughness. The grains in the films have the face-center cubic (fcc) structure with the (2 0 0) preferred orientation. An excellent adhesion is achieved with a critical load up to 74.7 N. An implantation voltage of 18 kV yields a hardness of 18 GPa and better wear resistance and a low friction coefficient of 0.48 are achieved.     

A study of TiMoN nano-multilayer coatings deposited by CFUBMSIP using DC and HIPIMS power

TiMoN nano-multilayer hard coatings have been deposited using the closed field unbalanced magnetron sputter ion plating (CFUBMSIP) technique. In one set of experiments, standard DC power supplies were used on four magnetrons in the CFUBMSIP system (4DC magnetrons). The second set of experiments was also in the same magnetic field configuration of CFUBMSIP, but three magnetrons were as again powered with standard DC whilst one magnetron with Ti target was supplied by a high power impulse magnetron sputtering (HIPIMS) power generator (3DC + 1HIPIMS magnetrons). Two elemental titanium sputtering targets and two of molybdenum were used to produce the TiMoN nano-multilayer coatings. Analysis of the coatings was carried out to investigate the differences in terms of properties, compositions and microstructures of the coatings deposited by these two sets of experiments. It was found that the coatings deposited by both sets of the experiments exhibited similar properties of high hardness, good adhesion and exceptional wear resistance, with a lower sliding friction than more commonly used hard coatings including TiN, CrN, TiAlN, CrTiAlN etc. Although the initial TiN coating as formed at the coating-substrate interface using the process of 3DC + 1HIPIMS magnetrons appeared to show a less oriented microstructure in comparison with that of the coating produced by the process using 4DC magnetrons, the compositions and cross sectional microstructures of the bulk of the coatings did not show significant differences, as observed by the cross sectional Transmission Electron Microscopy microstructures of these two types of TiMoN coatings.     

The influence of the dielectric on the properties of dielectromagnetic soft magnetic composites. Investigations with silica and silica hybrid sol–gel derived model dielectric

Dielectromagnetics made from organic–inorganic hybrid silica-coated iron powders were characterised by determination of their physical, mechanical and magnetic properties. The influence of three main factors, dielectric composition, addition level and heat treatment conditions were investigated. Results showed that these factors have significant effects on the performance of the dielectromagnetics. Increase in the organic phase content in these dielectric coatings tends to increase both the electrical resistivity and magnetic permeability of dielectromagnetics, although the strength and density are slightly impaired. Increasing the coating thickness leads to improvements in resistivity and thus reduced eddy current losses, but these are offset by reductions in density, strength and particularly magnetic permeability. A hybrid organic–inorganic coating formulation based on 40 mol% MTMS and 60 mol% TEOS precursors was found to be the optimum composition investigated. Addition levels between 0.1% and 0.3% were found to offer a good compromise between maximum permeability (μ_max>400) and minimum loss (typically <8 W/kg) for operation at 50 Hz/1 T, and the system can be optimised within this range for the desired performance.     

Influence of reactive gas and temperature on structural properties of magnetron sputtered CrSiN coatings

CrSiN coatings were deposited on stainless steel (Grade: SA304) and silicon Si(1 0 0) substrates, with varying argon-nitrogen gas proportions and deposition temperature, using reactive magnetron sputtering technique in the present work. The influence of sputtering (Ar) and reactive gas proportions (N₂) and temperature on the structural properties of the CrSiN coating was investigated. A small amount of silicon content (3.67 at.% Si) plays a crucial role in addition to the nitrogen content for the formation of different phases in the CrSiN coatings as observed in the present work. For example, the coating with comparatively low nitrogen content, 40% N₂, during deposition, formed a crystalline structure consisting of nano-crystalline CrN which is separated by an amorphous SiN phase, as evident from X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The formation of CrN(1 1 1) and Cr₂N(1 1 1) phases has occurred at 30% N₂ with 3.67% Si content, which transformed in to CrN(1 1 1) and CrN(2 0 0) with increase in N₂ content but with same Si content. The surface topography and morphology of the coatings were analyzed by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM), respectively. A less columnar growth is observed in CrSiN coatings deposited at low argon content, Ar:N₂ (20:80), and with 3.67 at.% Si in the coatings. However, it becomes dense with increase in nitrogen content and temperature. The XRD analysis showed that the intensity of a dominating peak (1 1 1) is decreasing from (80:20) to (60:40) argon:nitrogen environment. With a further increase of nitrogen content, from (60:40), in the sputtering gas mixture, to (40:60) argon-nitrogen, there is a sudden increase in (1 1 1) peak and above (40:60), the peak reduction rate is very slow than the previous one. The (1 1 1) and (2 0 0) peak intensity variations are very limited due to high nitrogen content, above 50%, and considerable amount of Si atoms, 3.67 at.%, present in the CrN coatings.     

Texture structure and ablation behavior of TaC coating on carbon/carbon composites

TaC coatings with hybrid, (2 0 0) and (2 2 0) texture structure were prepared on carbon/carbon (C/C) composites by isothermal chemical vapor deposition with TaCl₅-Ar-C₃H₆ system. The residual stress, hardness and ablation behaviors of the different coatings were characterized by Raman spectra, nano-indentation and oxyacetylene flame ablation machine respectively. Results shown tensile stress exists in the TaC coatings and increases when texture orientation turns from hybrid to (2 2 0) and (2 0 0), while nano-indentation hardness of the coatings also obeys the same trend. The deposited coatings could improve the ablation-resistance properties of C/C composites effectively. The texture structure also had great effects on the ablation properties and ablation morphologies of the coatings. The mass ablation rate obviously decreases when the texture structure changes from hybrid orientation to (2 0 0) and (2 2 0) orientations. The hybrid orientation and (2 0 0) texture coatings exhibit coarse oxide morphologies with crater or some breakage existed; while the (2 2 0) texture coating shows dense, molten oxide morphology. The main ablation behaviors of the hybrid, (2 0 0) and (2 2 0) texture TaC coatings are oxidation and particle denudation and block denudation, oxidation and block denudation, oxidation and mechanical erosion and block denudation, respectively.     

Microstructures and tribological properties of CrN/ZrN nanoscale multilayer coatings

Nanoscale multilayer CrN/ZrN coatings with bilayer thicknesses ranging from 11.7 to 66.7 nm were prepared by reactive magnetron sputtering techniques. The structure of the thin films was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). X-ray diffraction results showed that CrN individual layers presented a <1 1 1> preferred orientation in the multilayer coatings. The diffraction peaks of CrN shifted continuously to low diffraction angle with decreasing bilayer thickness. TEM observations showed that the multilayer did not form a superlattice structure instead of the coexistence of nanocrystalline CrN and ZrN layers. Columnar growth for all the coatings was observed by cross-sectional SEM. Nanoindentation tests showed that the multilayer coatings had almost a constant nanohardness of 29 GPa in spite of the variations of bilayer thickness. Pin-on-disk tests indicated that both the friction coefficients and wear rates increased when decreasing bilayer thickness. However, in comparison with the monolayer coating, the multilayer coatings exhibited excellent wear resistance.     

Structure and mechanical properties of Al/AlN multilayer with different AlN layer thickness

Nanometer scale Al/AlN multilayers have been prepared by dc magnetron sputtering technique with a columnar target. A set of Al/AlN multilayers with the Al layer thickness of 2.9 nm and the AlN layer thickness variation from 1.13 to 6.81 nm were determined. Low angle X-ray diffraction (LAXRD) was used to analyze the layered structure of multilayers. The phase structure of the coatings was investigated with grazing angle XRD (GAXRD). Mechanical properties of these multilayers were thoroughly studied using a nanoindentation and ball-on-disk micro-tribometer. It was found that the multilayer hardness and reduced modulus showed no strong dependence on the AlN layer thickness. Al2.9 nm/AlN1.13 nm multilayer had more excellent tribological properties than single layers and other proportion multilayers with a lowest friction coefficient of 0.15. And the tribological properties of all the multilayers are superior to the AlN single layer.     

3-D holographic lithography of organic-inorganic hybrids

Fabrications of ordered three-dimensional structures with submicron lattice constants were performed on organic-inorganic hybrids using a holographic lithography technique recently reported in the literature. The possibility of such a patterning has previously been demonstrated from single nanosecond laser pulse irradiation of thin films of epoxy photoresist and mixtures of methacrylate-alkoxy-silane with Zr or Ti alkoxides. In the present work, UV irradiation of similar hybrid resins were carried out through repeated laser pulses of low energy with a twofold objective: (i) to study the interference stability for future chemical gas phase decomposition experiments and (ii) to obtain patterning through large film thickness (e.g. 1 mm). The influence of several parameters on the structuration was examined from observations by scanning electron microscopy and optical diffraction. Many interdependent parameters were considered in different steps of the process, namely (i) hybrid resin preparations with required properties of stability, transparency and viscosity, (ii) film coating on different substrates, (iii) UV irradiation (energy and number of laser pulses), (iv) ultrasonic dissolution of monomer, and (v) sample drying. As results, different structuration resolutions were observed as a function of these parameters. But if the influence of a few parameters was easily understood and controlled, it has also appeared that it was not the case of all of them.     

Interfacial and adhesional aspects in polyurethane (PUR) membrane coating on Si3N4 surface of ISFET gate for REFET fabrication

Polyurethane membrane coatings on: (i) packaged ISFET (ion-sensitive field-effect transistor) devices and (ii) those in the form of chips have been investigated. The study has revealed that for reliable membrane deposition, proper film adhesion at polyurethane-silicon nitride and polyurethane-cured epoxy interfaces of ISFET was necessary. Membranes formed on packaged ISFETs were found to lift off after a short time period (<1 h) when immersed in pH 6.86 buffer solution. This was because the adhesion between polyurethane and surrounding cured epoxy was insufficient. If the membrane coating was performed on the chip, and the chip was subsequently packaged (protecting the coating on the sides with epoxy and curing the epoxy to fasten the membrane), the coating was not attacked in buffer solution. Based on these studies, a process for depositing reliable, long-lasting polyurethane membranes on ISFET gate surfaces has been proposed. Membrane reliability has been confirmed by storing the membrane-coated ISFET in buffer solution over seven days and periodically observing it microscopically. Membranes have been characterized through pH sensitivity and gate-source impedance measurements. pH sensitivities of ISFETs with polyurethane membranes were measured to be ≤4.2 mV/pH.