A multiple-scattering model analysis of zinc oxide pigment for spacecraft thermal control coatings

Space assets inhabit a harsh thermal environment in which the high intensity of direct solar radiation can potentially raise temperatures to harmful levels. Thermal management is obtained through the use of radiators coated with thermal control coatings (TCCs) that diffusely reflect the sun’s high energy visible (VIS) and near infrared (NIR) radiation, while emitting infrared (IR) energy as a method of radiatively cooling. The current state-of-the-art TCC system utilizes a potassium silicate binder and zinc oxide (ZnO) pigment to maintain solar reflectance over a long exposure time. We are investigating improvements to TCCs that will have greater initial performance and significantly better end-of-life properties. We have utilized modeling techniques based upon Mie scattering to determine the theoretical scattering efficiency limits of the currently used materials. An optimized TCC would attain maximum diffuse solar reflectance at a lower film thickness and reduce the pigment volume concentration (PVC) required. These factors would contribute to a reduction in overall weight and possibly extend the durability of the system to longer time scales. Our results of modeling ZnO pigment embedded in a matrix similar to that of potassium silicate under solar irradiance conditions indicate that a narrow particle size distribution centered at 0.35 μm would provide the highest overall scattering coefficients, ranging from 0.75 μm⁻¹ at 1000 nm to 5.0 μm⁻¹ at 380 nm wavelengths. These results indicated that a significant improvement, 2–10 times dependent upon wavelength, in the scattering efficiency of ZnO-based TCCs can be realized by utilizing an optimized particle size distribution rather than the currently used size distribution.     

ZnO nanostructures decorated hollow glass microspheres as near infrared reflective pigment

Hollow glass microsphere/ZnO composite pigments were successfully prepared by a facile sol-gel method. ZnO coating layers composed of nanosheets, nanoplates, or nanoparticles were anchored at the surface of hollow glass microspheres by formation of Zn-O-Si bond. A reasonable growth mechanism for elucidating the formation of ZnO nanocoating was proposed. The results indicated that the near-infrared reflectance property of the composite pigments was strongly affected by the morphology of ZnO nanostructures. The nanoparticles structures exhibited higher near-infrared reflectance than that of nanosheets and nanoplates structures. The near-infrared solar reflectance of hollow glass microsphere/ZnO composite pigments was 95.7%, while the total solar reflectance of the composite pigment was as high as 97.2%. An approximately 11.1 °C decrease in outer surface temperature was obtained for the heat box coated with composite pigments. Therefore, hollow glass microsphere/ZnO composites are excellent near infrared reflective pigments for efficient solar reflective coatings designed for building facades and roofs.     

Optical properties and radiation stability of SiO2/ZnO composite pigment prepared by co-sintering method

Thermal control coatings (TCCs) are an essential part of the thermal control systems in the spacecraft. Solar absorptance and emittance are the key performance parameters of TCCs. To develop an ultra-low solar absorption and stable inorganic TCCs for surface radiator, different TCCs were prepared by co-sintering ZnO and SiO₂ nanoparticles to form Zn₂SiO₄/SiO₂ pigment in this work, and the optical properties and radiation stability were systematically studied. It is found that the coating based on composite pigment has high reflectivity in the ultraviolet band and excellent optical performance possessing the low solar absorption of 0.06. In addition, the Zn₂SiO₄/SiO₂ coating demonstrates the highest proton and electron radiation stability because that SiO₂ between Zn₂SiO₄ particles acts as the relaxation center of the defects caused by radiation.     

Electrochemical study of protective behavior of organic coating pigmented with zinc aluminum polyphosphate as a modified zinc phosphate at different pigment volume concentrations

Electrochemical impedance spectroscopy was employed to evaluate protective performance of the solvent-borne epoxy coatings pigmented with zinc aluminum polyphosphate as a representative of phosphate-based anticorrosion compounds at different Lambda values. Furthermore, the effective ratio of the pigment volume concentration (PVC) to the critical pigment volume concentration (CPVC) was determined. To compare the function of zinc aluminum polyphosphate and zinc phosphate incorporated into coatings, electrochemical noise method as well as electrochemical impedance spectroscopy was taken into consideration. The trend and magnitude of charge transfer, coating and noise resistances plus the amplitude of the current noise fluctuation indicated superiority of the modified pigment. In order to provide an insight into the mechanism by which anticorrosion pigments improve protective behavior of coating, performance of bare metals exposed to pigment extracts was assessed through taking advantage of electrochemical impedance spectroscopy and electrochemical noise method as well.     

Sol–gel preparation and characterization of antibacterial and self-cleaning hybrid nanocomposite coatings

ZnO–TiO₂, SiO₂–TiO₂, and SiO₂–TiO₂–ZnO hybrid nanocomposite coatings were synthesized based on sol–gel precursors including tetramethoxysilane (TMOS), 3-glycidoxypropyl trimethoxysilane (GPTMS), tetra(n-butyl orthotitanate) (TBT), and zinc acetate dihydrate. The hybrid network was characterized by FTIR, FESEM, and EDAX techniques. Results indicated that inorganic particles’ size was of nanoorder (20–30 nm), with very uniform distribution and dispersion. Photocatalytic and self-cleaning activities of these coatings were further investigated by degradation of methylene blue in an aqueous solution (20 ppm) at visible light irradiation, indicating photocatalytic performance of the coatings containing ZnO and TiO₂ nanoparticles. The antibacterial effect of the coatings was investigated for inhibition and inactivation of cell growth, with the results showing the same antibacterial activity for ZnO–TiO₂ and SiO₂–TiO₂–ZnO coatings against Escherichia coli and Staphylococcus aureus; the activity was, however, higher than that of SiO₂–TiO₂ hybrid nanocomposite coatings.     

Study of the anticorrosive behaviour of epoxy binders containing non-toxic inorganic corrosion inhibitor pigments

The anticorrosive performance of epoxy coatings pigmented with non-toxic corrosion inhibitors pigments was investigated in this work. The coatings used contained the following pigments: zinc phosphate (ZP), zinc phosphomolybdate (ZPM) and zinc calcium phosphomolybdate (ZCPM). For comparative studies epoxy coatings with the following compositions were made up: one only with filler (CRG); one without pigments, varnish (VR) and other with zinc chromate (ZC) pigment. The corrosion inhibitor performance of the coatings was evaluated by immersion tests in 0.01 mol L⁻¹ NaCl aqueous solutions and accelerated tests in a salt spray chamber. The corrosion inhibitor performance of the samples was monitored using open-circuit potential (E_oc) measurements and electrochemical impedance spectroscopy (EIS) technique. Complementary tests were carried out using water vapour permeability of free-standing films and thermogravimetric (TG) analysis. The permeability test showed that the addition of the studied pigments did not modify the barrier properties of the free-films in comparison that pigmented with chromate. Thermal analysis indicated that the addition of the pigments improved the thermal stability of the coatings and it suggested a resin/pigment interaction. The total immersion tests and salt spray tests demonstrated that the barrier properties of the coatings pigmented with the inhibitors were not degrading as much as that pigmented with ZC. Therefore, all the three pigments could replace ZC as an anticorrosive pigment in similar conditions to those described here. The best corrosion inhibitor performance in the total immersion test was presented by the ZPM and ZCPM coatings while in the salt spray test the corrosion inhibitor performance of all the three pigmented coatings was similar, suggesting that only in the less aggressive test is possible to detect any difference between the coatings with the non-toxic pigments.     

Estimation of the Kubelka—Munk scattering coefficient from single particle scattering parameters

Computer colour matching of paints is based on the determination of the Kubelka—Munk absorption (K) and scattering coefficients (S) of pigments. K and S are sensitive to particle size in the range of sizes employed in paint technology. The K—M theory does not provide any guidelines for the correction of the values of K and S with a change in particle size. On the other hand the Mie theory linear scattering coefficient can be calculated from a knowledge of size and refractive index of the pigment. A number of relations correlating the K—M scattering coefficient and the linear scattering coefficient have been proposed in the literature. Attempts are made to estimate the K—M scattering coefficient using a relation suggested by Mudgett and Richards and to make a comparison with experimental values. The Mie theory equations being complex, simplified equations applicable to pigment sizes for the calculation of Mie theory parameters are proposed. The viability of the simplified equations has been established by comparing the results with those obtained using the full Mie equations.The K—M scattering coefficient for titanium dioxide pigments has been determined from reflectance measurements. The particle size of titanium dioxide has been determined by a light scattering method. The K—M scattering coefficient calculated from the linear scattering coefficient obtained using the simplified expressions agrees with experimental results. This suggests a method for the correction of the values of K and S with changes in pigment particle size.     

Mica/polypyrrole (doped) composite containing coatings for the corrosion protection of cold rolled steel

Micas/polypyrroles (PPys) doped with molybdate, p-toluene sulfonate, dodecyl benzene sulfonate, and 2-naphthalene sulfonate composite pigments were synthesized by chemical oxidative polymerization and characterized in coatings for corrosion protection on cold rolled steel substrate by various electrochemical techniques. Synthesized composite pigments were characterized for morphology by scanning electron microscopy, which indicated physical formation of PPy on the surface of mica. Chemical composition of the composite pigments was analyzed by X-ray photoelectron spectroscopy which chemically confirmed doped PPy formation on the mica surface. Coatings were formulated at 20% pigment volume concentration (composite pigments or as-received mica pigment) and were applied on cold rolled steel substrate. Coatings were exposed to salt spray test conditions (ASTM B117) for 30 days and were periodically assessed for corrosion with electrochemical impedance spectroscopy (EIS), open circuit potential (OCP), and potentiodynamic polarization. EIS and circuit modeling results demonstrated higher coating resistance (R _c) for mica/PPy (doped) composite coatings as compared to as-received mica pigment containing coating after 30 days of salt spray exposure. Lower current density and more positive corrosion potential values were observed for mica/PPy (doped) composite coatings as compared to mica pigment-based coating in potentiodynamic polarization measurements, indicating improved corrosion protection for cold rolled steel substrate. OCP measurements revealed more positive values for mica/PPy (doped) composite coatings as compared to mica pigment-based coating suggesting superior corrosion protection for mica/PPy (doped) composites.     

低成本铁红水性防锈涂料的制备

介绍了以氧化铁红为体质防锈颜料、磷酸锌和氧化锌为化学防锈颜料、红云母为片状颜料,苯丙乳液为基料的水性防锈涂料的制备。对影响其性能的因素进行了分析,并与溶剂型防锈涂料进行了性能对比。     

Synthesis of Zn-SBA-15 as a new pigment for spacecraft white thermal control coatings

Thermal control coatings (TCCs) help to maintain the thermal equilibrium of spacecraft at a level acceptable for vital components, usually around 20°C. This is done by either minimizing the solar absorbance or maximizing the thermal emittance. In the present study, with the aim of introducing new TCCs with enhanced optical properties, two TCCs were prepared by incorporating presynthesized pigments including SBA-15 (mesoporous material) and Zn-SBA-15 into potassium silicate binder. After application and drying, the TCC containing SBA-15 showed very low hiding power, so optical tests for this TCC were not done. The results of solar absorptance measurements revealed that the TCC containing Zn-SBA-15 was a proper reflector in the ultraviolet (UV) radiation range, making it much less susceptible to solar radiation in comparison with conventional TCCs. Also, thermal emittance tests demonstrated that the surface of this TCC had greater ability to emit heat. Furthermore, lower pigment-to-binder ratio and dry film thickness were attainable with this TCC, leading to weight reduction, improvement of mechanical properties, and lower porosity.     

Influence of pH in the synthesis of ferric tannate pigment for application in antifouling coatings

Ferric tannate was synthesized at pH 4 and pH 7 (FT4 and FT7, respectively) as a new class of environmentally friendly antifouling pigments. The solubility of both pigments was evaluated by gravimetric tests, showing that FT4 is more soluble than FT7. A mixture of rosin/acrylic resin (9:1 w/w) was sufficient to form an antifouling coating due to improved matrix properties. Electrochemical impedance spectroscopy (EIS) measurements were used to determine the apparent water coefficient of diffusion (D) and coating behavior. The D in the coating formulated with FT4 exhibited better values than that obtained with FT7. EIS results showed that both coatings present Fickian behavior at the initial stages of immersion, while flat Nyquist plots revealed penetration of water in the films. The physicochemical characteristics of FT4 pigment were determined by thermogravimetry and Fourier transform infrared. Immersion tests in the Mediterranean Sea demonstrated the excellent efficacy of the FT4-containing coating against marine fouling after six months of immersion.     

Characterization of pigment-leached antifouling coatings using BET surface area measurements and mercury porosimetry

In this work BET surface area measurements and mercury porosimetry are used to characterize leached layers formed when seawater-soluble pigments (Cu₂O and ZnO) dissolve during accelerated leaching of simple antifouling coatings. Measurements on single-pigment coatings show that an increasing fraction of Cu₂O or ZnO pigment particles becomes unavailable for dissolution when the concentration of the pigment decreases in the coating and the interparticle distance in the binder matrix becomes larger. Experimental data for a coating initially containing a mixture of Cu₂O and TiO₂ pigments suggest that a substantial fraction of the smaller and inert TiO₂ particles may be lost from the coating upon dissolution of the larger Cu₂O particles. This inert particle translocation effect is important to take into account when interpreting polishing and leaching data and when developing mathematical models of antifouling coating behaviour because the active binder surface area and porosity of the leached layer are substantially increased. A similar effect was not observed for a coating with a mixture of ZnO and TiO₂ pigments. The two experimental methods are expected to be useful for practical analysis of leaching of seawater-soluble components from commercial antifouling coatings.     

The effects of zinc aluminum phosphate (ZPA) and zinc aluminum polyphosphate (ZAPP) mixtures on corrosion inhibition performance of epoxy/polyamide coating

The epoxy/polyamide coating was loaded with different pigment mixtures of the zinc phosphate (ZP), zinc aluminum phosphate (ZPA) and zinc aluminum polyphosphate (ZAPP) pigments. The electrochemical impedance spectroscopy (EIS) and salt spray test were used to investigate corrosion inhibition performance of the coatings. The adhesion strengths of the coatings were measured by a pull-off test. Results revealed lower coating pull-off strength loss when the ZPA and ZAPP pigments were used. A significant decrease in number of blisters together with low pull-off strength loss and best corrosion inhibition properties were observed when the mixture of 80:20 of ZAPP:ZPA was used.     

Synthesis of high near infrared reflection wurtzite structure green pigments using Co-doped ZnO by combustion method

A high near-infrared reflective green pigment with a low cobalt content, Zn_0.96Co_0.04O, was prepared by solution combustion synthesis. The pigment was characterized by XRD, SEM, TG-DSC, UV–vis and CIE L*a*b*C*h* colorimetric. The resulting green pigment showed that the chromaticity performance is better. The doping Co did not affect the main crystalline structure, all samples were retained ZnO wurtzite structure. The better green hue is a* = ?15.35 and achieved a near-infrared reflectivity up to 40%, when CoO content was x?=?0.04, combustion agent was glycine, calcination temperature was 1000?°C. The synthesized pigments have a better thermal stability, chemical stability and a small amount of cobalt oxide (2.8?wt%), and the preparation process is simple. Therefore, the green pigment of ZnO wurtzite structure has great potential in serving as cool pigments for building coatings.     

Anticorrosive behaviour of alkyd paints formulated with ion-exchange pigments

Hexavalent chromium compounds (chromates) have been widely used as inhibitive pigments in the formulation of anticorrosive paints. However, their high toxicity and carcinogenic effects are forcing the development of effective chromate-free organic coatings. One such alternative, which is very attractive from a scientific point of view, is the use of ion-exchangeable pigments (IEPs).

The few studies conducted with this type of pigment are not conclusive about their anticorrosive efficiency and controversy surrounds their functioning mechanisms, interchange capacity and anticorrosive performance.

In the present research, which focuses on the anticorrosive protection of this type of pigment, alkyd paint coatings formulated with vanadate-hydrotalcite (HT/V) (anionic) and calcium/silica (Ca/Si) (cationic) IEPs have been applied on low carbon steel specimens. A traditional zinc chromate pigment has also been used for comparative purposes.

The effect of these non-toxic pigments on the protective properties of coatings has been tested by means of natural and accelerated corrosion tests (humidity, salt spray and Kesternich, 0.2 l SO₂) and electrochemical impedance spectroscopy (EIS).

None of the IEPs equalled the anticorrosive behaviour of the zinc chromate in the different tests. The anionic pigment (HT/V) seems to present good behaviour in chloride environments (salt spray, NaCl solutions, etc.) while the cationic pigment (Ca/Si) performs well in the humidity condensation and SO₂ tests.     

Corrosion inhibition of aluminum by organic coatings formulated with calcium exchange silica pigment

One of the first commercial ion-exchange anticorrosive pigments to be developed was Shieldex^® (Si/Ca). Its proposed corrosion protection mechanism, based on the retention of aggressive cations and the subsequent release of calcium cations, has created certain controversy. A number of studies have focused on the anticorrosive behavior of this pigment on carbon steel and galvanized steel to replace chromates (Cr⁶⁺) as inhibitor pigment, but none has considered its performance on aluminum or aluminum alloys. In this research, alkyd coatings have been formulated with Si/Ca pigment at different concentrations and applied on aluminum 1050 (Al 99.5%) specimens. These specimens have then been subjected to accelerated tests (condensing humidity, salt spray, and Kesternich) and natural weathering in atmospheres of different aggressivity. Corrosion performance has been also evaluated in the laboratory by electrochemical impedance spectroscopy. The study has also considered an organic coating with zinc chromate anticorrosive pigment for comparative purposes. The results obtained with organic coatings formulated with Si/Ca pigments confirm that they provide corrosion protection of the underlying aluminum substrate, even improving the behavior of the reference zinc chromate in some environmental conditions.     

Comparison of the efficiency of inorganic nonmetal pigments with zinc powder in anticorrosion paints

This paper deals with the study of properties of anticorrosion pigments of varying chemical composition in epoxyester paints. Two type lines of paints were prepared. The first line comprised an anticorrosion pigment with a PVC concentration of 10% while the other line comprised an anticorrosion pigment with a PVC concentration = CPVC. The following nontoxic anticorrosion pigments were observed: zinc phosphate, zinc phosphomolybdate, calcium hydrogen phosphate, zinc phosphate modified with an organic corrosion inhibitor, strontium–aluminum polyphosphosilicate, zinc–aluminum polyphosphate, calcium metaborate, calcium ferrite, calcium borosolicate, and strontium chromate. The epoxyester primers were observed for the effect of the type of pigment on the anticorrosion properties. Anticorrosion efficiency was derived from tests in a condenser chamber and in a salt spray cabinet as well as from a test of chemical resistance of pigmented coatings. The evaluation of anticorrosion efficiency of inorganic nonmetal pigments was carried out by means of comparison with anticorrosion efficiency of metal dust.     

Sublayer assisted by hydrophilic and hydrophobic ZnO nanoparticles toward engineered osmosis process

Hydrophilic and hydrophobic polyethersulfone (PES)-zinc oxide (ZnO) sublayers were prepared by loading of ZnO nanoparticles into PES matrix. Both porosity and hydrophilicity of the hydrophilic sublayer were increased upon addition of hydrophilic ZnO, while these were decreased for the hydrophobic sublayer. In addition, the results demonstrated that the hydrophilic membrane exhibited smaller structural parameter (S value or S parameter or S), which is beneficial for improving pure water permeability and decreasing mass transfer resistance. In contrast, a higher S parameter was obtained for the hydrophobic membrane. With a 2M NaCl as DS and DI water as FS, the pure water flux of hydrophilic TFN0.5 membrane was increased from 21.02 L/m² h to 30.06 L/m² h and decreased for hydrophobic TFN0.5 membrane to 14.98 L/m² h, while the salt flux of hydrophilic membrane increased from 10.12 g/m² h to 17.31 g/m² h and decreased for hydrophobic TFN0.5 membrane to 3.12 g/m² h. The increment in pure water permeability can be ascribed to reduction in S parameter, which resulted in reduced internal concentration polarization (ICP). The current study provides a feasible and low cost procedure to decrease the ICP in FO processes.     

Synthesis and evaluation of several high absorbance black pigments for spacecraft thermal control coatings

Using black coatings and materials with high light absorbance that are capable of absorbing photons at visible and longer wavelengths is a very effective way to reduce unwanted stray light, also known as optical noise, within optical equipment. These lights can be greatly reduced to a reasonable level by functional and performable black coatings that are modified to absorb incident light as much as possible by their specific pigments. In the present work, several carbonaceous pigments were synthesized for the first time from wasteful materials and their optical properties in the visible and near‐infrared ranges studied. First, MCM‐48 and SBA‐15 were synthesized at different conditions and were then used as templates for carbonaceous products. SSS‐1 (the carbonic pigment synthesized by the mixture of sucrose and sodium silicate), SSS‐2 (the carbonic pigment synthesized by the mixture of sawdust and sodium silicate), and mesoporous carbon pigments (CMK‐3 and CMK‐1 with different levels of saturations) were synthesized. Finally, their structure, morphology, and optical properties were investigated by X‐ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FE‐SEM), and Diffuse Reflectance Spectroscopy (DRS). The results indicated that the SSS‐1 pigment had a lower reflectance (below 1%) than carbon black (about 2.5%) in the visible region despite it being more cost‐effective than carbon black. The mesoporous pigments showed very high light absorbance in the visible region (about 2.5%). Compared with other black pigments, the CMK‐1 was the blackest synthesized material with a very low reflectance (about 0.05% in visible region), making it an ideal candidate as a super black pigment for reducing unwanted stray light within optical equipment.     

The effect of benzimidazole and zinc acetylacetonate mixture on cathodic disbonding of epoxy coated mild steel

Electrochemical behavior of mild steel in the presence of zinc acetylacetonate (Zn(acac)₂) and benzimidazole (BIMIDA) was evaluated by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution and compared to zinc phosphate (ZP) pigment and zinc potassium chromate (ZPC) pigment extracts. Results showed superior performance of Zn(acac)₂ and BIMIDA mixture (ZBM) compared to ZP pigment, while it introduced inferior inhibitive action compared to ZPC pigment. The epoxy coatings were formulated with ZBM as anticorrosive additive, ZP and ZPC pigments. The disbonding rate of coated steel follows the order: Blank > ZP > ZBM > ZPC. EIS results showed a complex film could be formed at the hole area for the coatings formulated with ZP, ZBM and ZPC. It is concluded that the stronger the complex film on the surface, the lesser the cathodic disbonding rate would be.