Project's information
Project's title | Research and development of advanced materials and coating technologies for civilian and defense applications |
Project’s code | TĐVLTT00/21-23 |
Research hosting institution | Institute for Tropical Technology |
Project leader’s name | Prof. Dr. Tran Dai Lam |
Project duration | 01/01/2021 - 31/12/2023 |
Project’s budget | 42,000 million VND |
Classify | Grade A |
Goal and objectives of the project | • Develop materials, apply tropical techniques, new material technologies, and green technologies in the creation of advanced coatings for civil and defense applications.
• Promote scientific research and development of advanced, high-efficiency technologies focusing on the application of new material technologies and green technologies in practical implementations, contributing to enhancing economic efficiency and national defense security.
Specific objectives:
• Successfully create the following advanced coatings:
o Advanced coatings based on polymers and composites to protect against microbial corrosion and fouling for metallic materials operating in marine environments.
o Sun-reflective, waterproof, and weather-resistant coatings for weapon storage facilities, fuel tanks, and civil constructions.
o Environmentally friendly organic coatings using modified nano-sized particles combined with electrochemical protection methods to protect steel structures working in marine and atmospheric environments.
o Advanced inorganic coatings for both civil and defense applications. |
Main results | Scientific contributions
a. Research and Development of Antifouling Coating Systems:
- In-situ synthesis of various nano-additives used for antifouling paint systems, such as ZnO, Cu₂O, ZrO₂, TiO₂, and zeolite@Ag, was conducted with surfactants including TOPO, OLA, and OA. The nano-additives have a particle size ≤ 50 nm and are relatively uniform. The coupling efficiency of organic functional groups on the surface exceeds 90%, with an organic content of about 5-25%. The nano-additives remain well-dispersed and stable in organic solvents even after 12 months.
- The composition and proportions of the primer, intermediate paint, and topcoat for the anti-biofouling and antifouling paint system used on steel structures operating in seawater have been determined:
+ Organically modified ZnO nanoparticles exhibit good compatibility with the epoxy resin matrix, enhancing the mechanical properties and anti-corrosion protection of the primer film. The primer and primer film meet the technical requirements of TCVN 8789:2011.
+ Organically modified TiO₂ and ZrO₂ nanoparticles exhibit good compatibility with the base resin, enhancing the properties of the intermediate paint film. The intermediate paint and intermediate paint film meet the technical requirements of TCVN 8789:2011. The intermediate paint also improves compatibility and adhesion between the primer and topcoat.
+ Combining an Ag-Zn zeolite additive at a concentration of 1% by weight relative to the mass of the plastic with a nano Cu₂O additive at a concentration of 2% by weight relative to the mass of the plastic enhances the antibacterial properties and the ability to prevent biofilm formation of the coating film.
- Three technological processes have been developed and successfully used to produce paints on a scale of 100 kg per batch: an epoxy primer modified with nano ZnO, an epoxy intermediate paint modified with nano TiO₂ and nano ZrO₂, and a polysiloxane, vinyl ester, and fluorinated polymer basecoat reinforced with nano TiO₂ and nano ZrO₂ particles. These coatings incorporate commercial antibacterial additives (Irraguard B, Iragol, Rocima) and nano Cu₂O antifouling additives, all meeting the quality requirements specified in TCVN 8789:2011. Subsequently, 100 kg each of primer, intermediate paint, and topcoat were produced to evaluate their characteristics, properties, and performance in natural seawater.
- Laboratory test results indicate that the paint system with polysiloxane and vinyl ester resin coatings effectively resists biofilm adhesion, killing over 95% of the marine bacteria P. stutzeri B27 and sulfate-reducing marine bacteria. After 60 days of testing in natural seawater at Vung Oan, Ha Long City, Quang Ninh Province, the concentrations of Cu⁺ ions released from the coating of the 3-layer paint system were 0.122 mg/L for polysiloxane, 0.247 mg/L for vinyl ester, and 0.020 mg/L for polyfluor coatings. Salt spray and UV-humidity tests demonstrate that the 3-layer paint systems with vinyl ester and polysiloxane coatings exhibit greater durability against salt mist and UV-humidity exposure compared to the 3-layer paint system with fluorinated polymer coatings.
- The results of natural testing of 3-layer paint systems on a double-bottom steel-hulled ship model in Vung Oan, Ha Long City, Quang Ninh Province showed that the 3-layer paint systems with vinyl ester and polysiloxane coatings exhibited low levels of biofouling, with minimal or no fouling, and had an antifouling effectiveness lasting over 18 months (up to the end of December 2023), which is better than the 3-layer paint systems with fluorinated polymer coatings. The 3-layer paint systems with vinyl ester resin coatings, demonstrating antifouling effectiveness for up to 21 months (until the end of March 2024), show promise as marine paints with potential for extended antifouling performance.
b. Research and Development of Solar Heat Reflective, Waterproof, and Highly Weather-Resistant Coatings
- A variety of additives have been synthesized for heat-reflective, waterproof, and weather-resistant coating systems, including nano additives such as BaSO₄, TiO₂, ZrO₂, CaSiO₃, CaCO₃, CaSO₄, and nanocarriers like SiO₂@Ce³⁺, Fe₂O₃@Ce³⁺, ZnO@Ce³⁺, CeO₂-SiO₂, CeO₂-Fe₂O₃, and CeO₂-Fe₂O₃-SiO₂. The results indicate that the size of these additives ranges from 15 to 40 nm, with fairly uniform particles and an organic content of approximately 5-25%. Phase transitions have been successfully achieved using methods such as ligand exchange, amphiphilic polymer usage, or silanization reactions to modify the surface of the additives for compatibility with water-based paints.
- Successfully manufactured a heat-reflective, weather-resistant exterior wall paint system for construction projects, designed for wall surfaces and reinforced concrete, based on acrylic emulsion resin and incorporating micro- and nano-sized heat-reflective inorganic particles:
+ The composition and proportion of SiO₂ nanoparticles in the alkali-resistant primer have been determined. With an inclusion of approximately 2.5% by mass of SiO₂ nanoparticles, the alkali resistance of the primer film has been significantly increased.
+ The composition and proportion of the coating components were determined. Results of the evaluation of micro- and nano-sized heat-reflecting inorganic additives (hollow microspheres, TiO₂, BaSO₄, ZrO₂, CaSiO₃) on UV-Vis-NIR reflectivity indicated that nano-TiO₂ is the most effective heat-reflecting additive. The optimal content of nano-TiO₂ in the paint film is 2%. At this concentration, a paint film with a thickness of 60 µm achieves an average reflectivity of approximately 90-91% in the wavelength range λ = 700-1400 nm.
+ The optimal tinting content for solar heat reflective paint film has been determined. AXX yellow tinting achieves high reflectivity of over 80%. Other tinting colors can be mixed into the heat reflective paint at a mass ratio of 10-20% relative to the mass of white paint, while still maintaining a reflectivity of over 80%.
+ The heat-reflective, weather-resistant exterior wall paint system can reduce the concrete surface temperature by approximately 9.5°C with white color and by 7-8°C with other colors. It also lowers the air temperature in the simulation test chamber by about 4.5°C with white color and by 3-3.7°C with other colors, compared to the unpainted test chamber.
- A roof waterproofing paint system with heat-reflective and high-weather-resistance properties has been successfully manufactured. This system, including both primer and topcoat, is based on water-based polyurethane resin and incorporates micro- and nano-sized heat-reflective inorganic particles. Research results demonstrate that the paint film provides excellent waterproofing. A 60 µm thick paint film achieves an average reflectance of approximately 90-91% in the λ = 700-1400 nm range, reduces surface temperature by 9.12°C, and lowers the air temperature in the test chamber by 4.21°C compared to the test chamber without paint.
- Successfully manufactured an organic solvent-based paint system that offers anti-corrosion protection, heat reflection, and high weather resistance. This system includes both primer and topcoat and features heat-reflective inorganic particle additives:
+ The effect of nanocarrier@Ce³⁺ particles on the properties and corrosion resistance of epoxy-based primer films was evaluated. The results indicated that the paint film containing 1.5% SiO₂ particles modified with Ce³⁺ exhibited the best properties and highest corrosion resistance. After 30 days of immersion in NaCl solution, the total resistance of the paint film remained high, at 2.108 Ω·cm-².
+ The composition of the polyurethane-based coating was determined. The coating film had a thickness of 60 µm and a reflectivity of 90.16% in the region λ = 700-1400 nm.
+ The organic solvent paint system offers anti-corrosion protection, heat reflection, and high weather resistance. It can reduce surface temperatures by up to 19.31°C and air temperatures in the test tank by 15.75°C.
- The weather resistance of the paint films was determined by an accelerated weathering test. The results showed that after 1560 hours of testing, FE-SEM analysis revealed that although the paint film surface was eroded, forming micro-grooves, these defects could not be observed by the naked eye. The paint film containing nanoparticles exhibited chalking at level 2. The reflectance decreased slightly by about 2%. The color reduced the heat reflectance and cooling efficiency but slightly increased the weather resistance. The addition of TiO2 and SiO2 nanoparticles to the coating formulation significantly improved the paint’s properties, including reflectance, cooling insulation performance, and weather resistance.
c. Research and development of environmentally organic coatings
- Synthetized and modified several nanocomposites as CNT, nanoclay, nanocly/metallic oxide, GO and SiO2-polypyrrole as pigment in anticorrrosion protective coatings. The results obtained when CT3 steel substrate immersed in the electrolyte solution containing GO-PPy showed that the current corrosion density was decreased and the corrsion potential was deplaced towards more positive. The PU coating containing SiO2@Ce3+ nanoparticles showed a good resistance against UV while SiO2/Ppy nanocomposites help to increase the corrosion resistance of epoxy coating.ong khi nanocompozit SiO2/PPy có tác dụng làm tăng độ bền chống ăn mòn cho màng epoxy.
- 08 nanocomposites were selectively developed (based on No.1 component, commercial nanoproducts and self-synthetized nanopigments) in order to research the reinforcement effect in epoxy and polyurethane resins. The results showed that the anticorrosion properties, the adhesion behavior and the resistance against cathodic disbondment of epoxy coating were significantly increased in the presence of experimental nanopigments. The UV resistance, the water resistance of nanopartilces -based PU coatings were also reinforced. The optimal content of nanopigments in organic coatings varied from 0,1 – 3 % (depending on the type of nanoparticles).
- Researched and manufactured various epoxy primers and PU-top coatings by selected the optimal ratio of 08 nanocomposites (in the presence of other fillers and additives). According to international standards (ASTM-B117, ISO 12944, ASTM-G8-96, ISO 20340…), 04 nanocomposite-based paint systems were evaluated that presented the excellent and superior physical and mechanical properties, anticorrosion properties, UV weather resistance, resistance against cathodic disbondment compared to several commercial well-known paints in Vietnam.
- Selected to build 04 processes for manufacturing 02 types of primer coatings, 02 types of paint coatings that are resistant to cathodic peeling and marine atmosphere, and at the same time researched and promulgated 04 basic standards for the above paints based on based on international standards. Registered 01 intellectual property on synthesizing nanoparticles based on CePO4 and manufacturing anti-corrosion and cathodic peeling protective paint.
d. Research and development of advanced inorganic coatings
- Nano-sized particles of SiO2, Al2O3, CeO2, and a CeO2-TiO2 hybrid have been successfully manufactured for inorganic coatings. The results show that these nano additives have an average particle size of 50-100 nm and a large specific surface area, making them suitable for incorporation into inorganic coatings.
- The appropriate solution composition for the single-layer ZnNi alloy plating has been selected: KCl 170-230 g/l, NiCl2: 40 - 80 g/l, ZnCl2: 60 - 100 g/l. The resulting coating has a suitable alloy composition (10 - 15% Ni).
- The appropriate plating regime has been determined: pH 2-5, temperature 20-35oC, current density 1-5 A/dm2, plating time 20-40 minutes to produce plating layers with good quality, high protection and anti-corrosion ability for steel substrates.
- SiO2 nanoparticles, Al2O3 nanoparticles, and CeO2 nanoparticles have been dispersed into the plating solution, the particle size distribution has been investigated, the zeta potential has been measured in plating solutions containing nanoparticles. SiO2 nanoparticles, Al2O3 nanoparticles, and CeO2 nanoparticles have beeb successfully introduced into the coating layer. The influence of the concentration of SiO2 nanoparticles, Al2O3 nanoparticles, and CeO2 nanoparticles on the coating morphology, Tafel polarization curve, open circuit potential, and coating composition has been studied. SiO2 nanoparticles were selected for use in the ZnNi-composite alloy plating solution.
- The solution for making conversion coatings on the ZnNi plating layer based on Cr(III) has beeb prepared with the mass ratio of NH4HF2/Cr(III) from 2/5 to 4/5, the appropriate pH is in the range of 1.75-2.25. Salt spray test results for conversion coated samples were achieved over 312 hours (until white rust appeared).
- The (ZnNi)n and (ZnNi-nanosilica)n multilayer coatings have been fabricated with n = 1 and n = 3, and the thickness of each layer in the multilayer coating combinations has been determined.
- The influence of air-compressed pressure and distance from the nozzle to the sample surface on the surface roughness of the steel substrate has been studied, and a mathematical equation has been built to show the relationship between surface roughness Rz and air-compressed pressure P and abrasive spray distance L: Rz = -10.32 + 9.607P – 0.0456L with reliability of 96.33%.
- The optimal mode for abrasive blasting to create roughness on the steel surface is found: air air-compressed pressure is 8 bar, and an abrasive blasting distance is 100 mm.
- The influence of electric current intensity, compressed air pressure, and spray distance on the porosity and adhesion of the coating has been studied. A mathematical equation to show the relationship between the porosity of the Al-Mg coating and the technological parameters as electric current, compressed air pressure, and spray distance has been developed: Porosity = 18.116 – 0.008033* I – 1.5717*P + 0.0022*L with reliability of 98.92%. A mathematical equation was built to show the relationship between the adhesion of the Al-Mg coating with the technological parameters as electric current, compressed air pressure, and spray distance: Adhesion = -1.53 + 0.01775*I + 2.710*P + 0.00267*L with reliability of 97.25%.
- The optimal electric arc spraying mode has been found to produce an Al-Mg coating with low porosity and high adhesion: current intensity is 300 A, compressed air pressure is 5.5 bar and spray distance is 163 mm. The cross-sectional structure, elemental composition, phase composition, porosity, microhardness, and adhesion strength of the coatings were studied.
- The protection and corrosion resistance of Al-Mg coatings were studied using electrochemical methods and salt spray tests. Al-Mg coating achieves salt spray durability of > 3000 hours, and corrosion resistance in dry-wet cycles reaches > 110 days.
- 01 dry-wet cyclic corrosion testing system and 01 dynamic corrosion-abrasion testing system have been successfully researched and manufactured.
- The effect of nano SiO2 and nano Al2O3 content on the properties of Al-Mg/epoxy-nanocomposite coating has been researched and the nano content and type for a good quality coating of 1% nano Al2O3 was selected.
- The anti-corrosion protection ability of Al-Mg/epoxy-nanocomposite coating has been researched using electrochemical methods and salt spray testing. Al-Mg/epoxy-nanocomposite coating achieves salt spray durability > 6000 hours and dynamic abrasion corrosion resistance > 2700 hours.
- Exposure to marine atmosphere of Al-Mg and Al-Mg/epoxy-nanocomposite coating systems has been exposed at Nha Trang and Quang Ninh test stations. After 12 months, the coatings still have good protection for steel substrates.
- Electrode sensors have been successfully manufactured using 3D printing technology, using graphene-based ink and some conductive metal nanoparticles such as AuNPs, AgNPs, and CuNPs. Two-electrode resistance measurement systems with IC 555 and IC LM393 have been successfully developed to provide early warning of corrosion events, especially in highly corrosive tropical and marine environments. Test results for total resistance measurement in humid and corrosive gas environments show that Ag material sensors with serrated electrode structures are ideal for designing and manufacturing humidity sensors that determine water film formation by measuring total resistance.
Application contributions:
- Three antifouling paint systems were tested and applied on a double-bottomed ship model under seawater conditions at Vung Oan, Ha Long City, Quang Ninh Province. The 3-layer paint system, which includes polysiloxane and vinyl ester coating, demonstrated antifouling capabilities for more than 18 months.
- Heat-reflective exterior wall paint systems, heat-reflective roof waterproofing paint systems, and organic solvent paint systems for corrosion protection, heat reflection, and high weather resistance have been successfully manufactured. These products have been practically tested on various surfaces: 1000 m² of building exterior surface, 200 m² of roof area, and 1435 m² of oil tank surface. The effects include a reduction in the building exterior surface temperature by over 9°C, a tank surface temperature reduction of 9-19°C, and a decrease in the temperature inside the tank by more than 9°C.
- Conducted natural test painting of samples and on steel structure works working in marine environment and marine atmosphere. The exposed surface area is about 120m2 of iron and steel components of the test buoy of the Joint Vietnam-Russia Tropical Science and Technology Research Center in the Hon Tre Island area - Nha Trang (Vinh Nguyen, Nha Trang, Khanh Hoa). These buoys work in seawater splashing conditions and are subject to harsh climates, with cathodic protection. After 09 month of natural exposed, the protective coatings still work well, do not show any trace of corrosion, damage (verified by application confirmation document). The second test was about 200 m2 of steel structures for 08 microwave antenna towers working in marine climate conditions on Truong Sa Island. The coating layers of these projects have so far been evaluated well by the coordinating unit. The coating layers of these projects have so far been evaluated well by the coordinating unit.
- Experimental fabrication of coating systems: Zn/TĐ Cr(III); Zn-nanosilica/TĐ Cr(III); (ZnNi)n; (ZnNi-nanosilica)3/TĐ Cr(III); (ZnNi)3/Zn-nanosilica/TĐ Cr(III) with sizes 100x150x1mm and 100x50x1mm were conducted and these samples were exposed for natural testing at Quang Ninh and Nha Trang stations. The results after 20 months showed that the samples had not been rusted red.
- A total of 100 m2 of coatings on the hull of the steel ship Vietship 02 (registration number SG.6766) was fabricated, including 50 m2 of Al-Mg alloy coating and 50 m2 of Al-Mg/epoxy-nanocomposite coating ensuring quality according to the issued basic standards. After 15 months of operation at sea, the hull with thermal coatings remained intact and undamaged. Meanwhile, the hull without thermal coatings had areas of red rust. |
Novelty and actuality and scientific meaningfulness of the results | - Some nano additives have been successfully synthesized in-situ using surface-active agents such as TOPO, OLA, OA. These nano additives have particle sizes ≤ 50 nm and relatively uniform distribution. The grafting efficiency of organic functional groups on the surface is > 90% with an organic content ranging from 5-25%. These nano additives disperse well and remain stable in organic solvents, even after 12 months. |
Products of the project | Published/accepted scientific papers: |
Research region | - Cai Lan Petroleum Joint Stock Company (Gieng Day, Ha Long, Quang Ninh). |
Recommendations | After the implementation of the project, we would like to propose the following recommendations: |
Images of project | ![]() |