Summary of Doctoral thesis in Materials science: Research on fabrication and characteristic properties of zirconium oxide film combination with silane on steel substrate as pretreatment for

Preparing of zirconia/silane combined films on steel subtrate for organic coatings to replace phosphate and chromate pretreatment. Proposing the mechanism of film formation process and assessing characteristics of morphology, composition, electrochemical properties and bonding of the zirconia/silane film.

MINISTRY OF VIETNAM ACADEMY OF EDUCATION AND TRAINING SCIENCE AND TECHNOLOGY GRADATE UNIVERSIY OF SCIENCE AND TECHNOLOGY NGUYEN VAN CHI RESEARCH ON FABRICATION AND CHARACTERISTIC PROPERTIES OF ZIRCONIUM OXIDE FILM COMBINATION WITH SILANE ON STEEL SUBSTRATE AS PRETREATMENT FOR ORGANIC COATING Major: Metal Code: 9.44.01.29 SUMMARY OF DOCTORAL THESIS IN MATERIALS SCIENCE Ha Noi – 2020 This thesis was done at: Graduate University of Science and Technology - Vietnam Academy of Science and Technology Supervisors 1: Dr PHAM Trung San Supervisors 2: Assoc.Prof Dr TO Thi Xuan Hang Reviewer 1: Reviewer 2: Reviewer 3: The dissertation will be defended at Graduate University of Science and Technology, 18 Hoang Quoc Viet street, Hanoi Time: ., , 2020 This thesis could be found at National Library of Vietnam, Library of Graduate University of Science and Technology, Library of Institute of Materials and Science, Library of Vietnam Academy of Science and Technology INTRODUCTION The urgency of the thesis Surface pretreatment of the steel substrate before painting had significant effect on coating adhesion and corrosion protection performance Pretreatment not only increases the adhesion between the paint and the substrate, but also improves the long-term corrosion protection Phosphate or chromate pretreatment has been widely used for this purpose However, these methods are often increasingly restricted by international conventions because of several drawbacks from environmental, energy and process points of view The trend of finding alternative methods has been interested in research and application recently These conversion coatings are usually transition metal oxides such as zirconium, titanium, vanadium, molybdenum Among them, A promising emerging pretreatment technique is one of potential replacements for phosphating and one of them is the application of zirconium oxide or organo-silane The outstanding advantage of zirconia is that the film is made of nano properties, environmentally friendly, cost-saving, simple technology, applicable on mutli-metal However, the disadvantage is that it is necessary to use deionized or ultrafiltration water because the formed film is quite sensitive to the ions in the washing water and easily forms rust during stages Besides, organo-silane is also considered as a promising surface pretreatment method because of its increased ability to bond between organic coating and metal substrate and effective corrosion protection However, the basic disadvantage of the silane is that it depends how the surface was treated, the cleanliness of the surface and the density of hydroxyl group Therefore, it is necessary to clean the surface well before pretreatment to promote the effectiveness A combination of Zr based and silane based pretreatment on metal substrates in different ways has been performed recently such as: The hot-dip galvanized steel surface was treated, firstly, with zirconium nitrate salt then silane; the doped silane pretreatment on galvanised steel subtrate; Ce-silane-ZrO2 composite coating on 1060 aluminum The results confirmed that the combined film had higher corrosion resistance, less porosity, less microscopic cracking and better pre-treatment than that of each component Several methods can be applied to combine between zirconia and silane Sol-gel is an atomic scale method which to form zirconia films with the advantage of high uniformity, the stages of the reaction can be controlled However, compared to the chemical dipping method, sol-gel method requires more stages, higher temperature, more by-products, it is limited in industrialization The zirconia/silane film could also be formed by two steps in two solutions, however, the one-solution method would allow a simpler process, at the same time, propose a mechanism for zirconia and silane to be together formed film on the substrate Factors directly related to films forming by the method of immersion in hexaflorozirconic acid solution could be mentioned as: temperature, pH, concentration and dipping time Several studies have shown that when the temperature of the solution was increased, the corrosion performance and properties of the zirconia film were reduced Solution pH and concentration are two directly correlated parameters However, a low concentration hexaflorozirconic acid solution (with pH of about to 4) usually leaded to a zirconia film with better pretreatment effect, and when the pH was changed, it would affect the forming film decisively Based on the above discusses, with the desire to manufacture a steel surface pretreatment film which is effective as phosphate and chromate, the topic of the thesis was chosen: "Research on fabrication and characteristic properties of zirconium oxide film combination with silane on steel substrate as pretreatment for organic coating” Goals of the thesis - Preparing of zirconia/silane combined films on steel subtrate for organic coatings to replace phosphate and chromate pretreatment; - Proposing the mechanism of film formation process and assessing characteristics of morphology, composition, electrochemical properties and bonding of the zirconia/silane film Main contents of the thesis - Research on preparation of zirconium oxide film on steel and selecting initial conditions on solution pH and dipping time as basis parameters for manufacturing zirconia/silane film; - Research on manufacturing zirconia/silane films on steel substrates; explain the process of formation and their characterization of morphology, composition, electrochemistry and bonding; - Study the role of zirconia/silane pretreatment film for powder coating Scientific and application of the thesis On the scientific side, the thesis has contributed new points in the research of steel surface treatment films for coatings to replace phosphates and chromate In practice, the results of the thesis are the basis for the development of technology for manufacturing steel surface treatment films for environmentally friendly coatings in Vietnam Detail goals of the thesis - Preparing of zirconium oxide and zirconium oxide/silane films on steel subtrate by chemical immersion method - Interpreting the mechanism of forming ZrO2/silane film and describing their characterization of morphology, composition, electrochemistry and bonding - Identifying some basic factors affecting the film forming process; selecting suitable conditions to form film - Manufacturing of zirconium oxide/silane film with high corrosion resistance, improved adhesion and long-term protection performance of powder coating compared to zinc phosphate CHAPTER OVERVIEW 1.1 The traditional method of steel surface treatment Overview of mechanical treatment methods Concept, development history, formation mechanism, properties and technological diagrams of chemical treatment methods: phosphate, chromate 1.2 Zirconia-based treatment method: Mechanism of formation, pretreatment efficiency, characterization and influencing factors; 1.3 Silane-based treatment method: Mechanism of formation, pretreatment efficiency, characterization and influencing factors; 1.4 Zirconia and silane combined treatment method: Presentation of several methods were applied to combine between zirconia and silane; The advantages of these combining methods compared to an individual method; CHAPTER EXPERIMENTAL AND METHODS 2.1 Research scheme Preparation of chemicals, samples and H2ZrF6 solution Fabrication of zirconium oxide films Determining the appropriate conditions of pH and dipping time according to corrosion resistance and adhesion Preparation of chemicals, samples and solution of H2ZrF6/silane Fabrication of zirconia/silane films Mechanism of film formation process Characterization of morphology, composition, electrochemistry and bonding The influence of dipping time and silane concentration on characteristic properties Adhesion and corrosion resistance under paint, long-term protection performance of coating Discussion, conclusion 2.2 Main materials and chemicals - Carbon steel samples (Quoc Viet Company) were abraded with SiC polishing paper, degreased, rusted and rinsed with distilled water and stored in a dehumidifier (bare samples) - ZrF4 crystal, 99,99% purity, white (Sigma), Silane A-1100: γAPS (China, 99% purity) 2.3 Preparation of surface treatment solution Preparation of H2ZrF6 solution: ZrF4 was completely dissolved in HF solution and then distilled water was added into H2ZrF6 acid solution obtained Zr4+ = 50 ppm Preparation of H2ZrF6/silane solution: Silane A-1100 with different concentration added to H2ZrF6 solution to form H2ZrF6/silane solution 2.4 Methods for substrate treatment of samples 2.4.1 Surface treatment in H2ZrF6 solution To form zirconia film, the bare samples were immersed in H2ZrF6 solution in a combination of pH varying from to 6, the division was and the time varying from to minutes, the division was 0,5 2.4.2 Surface treatment in H2ZrF6 solution combined with silane To form zirconia/silane film, the bare samples were immersed in H2ZrF6/silane solution in a combination of silane concentration varying from %  0,05 % (v/v), the division was 0,0125 %, the time varying from to minutes, the division was 0,5 2.4.3 Surface treatment with a two steps by immersion The bare samples were treated in H2ZrF6 solution to form zirconia film then in silane solution to form silane film (two steps) After surface treatments, the samples were dried with a dry air stream (70 ± °C) for about 15 minutes in the laboratory 2.5 Methods, equipments and technique EIS and DC were conducted using PGSTAT204N with 3electrode cell in 3,5% NaCl Frequency: 100kHz10mHz; ± 100 mV Scan rate of 1mV/s, step of mV The OCP were performed during film formation for minutes Surface morphology was investigated by FE-SEM on Jeol 7401F (Japan) Components and bonds in the film were studied by FT-IR on Bruker Alpha (Germany) in wave number of 3000500 cm-1, EDS was investigated by Jeol 7401F and XRD patterns in the following mode: 2: 20  80o; speed: 0,05o/giây; Cu (Kα) = 1,5406 Å To quickly assess the decrease in adhesion and the degree of corrosion under the incision, the samples were immersed in 3,5 % NaCl with different exposure time, according to ASTM D 1654-5 Adhesion was assessed by ASTM D3359 (X-shaped incision) and ASTM D4541 (PosiTest AT-M) The salt spray testing (JIS 8502:1999) was conducted on Q-FOG CCT600 (USA): pH: 6,5 ÷ 7,2; NaCl: 5%; pressure: 1,0Atm, temperature: 35 ÷ 37 oC; saturation temperature: 47 ÷ 49 oC; speed: mL/h Natural testing was conducted in accordance with ISO 4628: 2016 (Part 8) at the Marine research and testing station, Vietnam - Russia Tropical Center, Hon Tre Islands, Nha Trang city, Khanh Hoa province CHAPTER RESULTS AND DISCUSSION 3.1 Research on manufacturing zirconia film 3.1.1 Effect of pH of hexaflorozirconic acid solution 3.1.1.1 Effect of pH on corrosion resistance of samples EIS spectrum, polarization curve were at different pHs (Figure 3.1, 3.3) had similar shape but different radians Figure 3.1, 3.3 The EIS spectrum and PD curve at different pHs Nova 2.0 software, equivalent diagram, capacitance formula: and Tafel extrapolation were used to identify the typical parameters (Table 3.1, 3.2) The zirconia film formation has increased the corrosion resistance Rp value was higher (Jcorr was lower) when the pH was between and and reached the largest value at pH = When pH alkalinity increased, the anode reaction decreased, the cathode reaction slowed, so the pH at the surface-solution interface increased not enough to form Zr oxide Table 3.1 Electrochemical parameters of the film at different pHs Parameter Bare Rs (Ω.cm2) pH of H2ZrF6 solution 72,63 ± 0,34 72,86 ± 0,31 72,38 ± 0,64 74,63 ± 0,26 73,40 ± 0,49 73,59 ± 0,38 Rp (Ω.cm2) 664,29 ±14,88 947,04 ± 16,65 C (µF.cm-2) 970 660 Y0 (±%) 2177,68 3198,74 ± 37,23 ± 46,38 310 280 2438,82 1372,37± ± 41,46 30,31 306 536 0,003643 0,002487 0,000875 0,000993 0,001122 0,001959 ± 1,903 ± 1,546 ± 1,650 ± 0,952 ± 1,249 ± 1,700 n (±%) 0,8145 ± 0,881 0,8202 ± 0,663 0,7855 ± 0,596 0,7886 ± 0,356 0,8016 ± 0,486 0,8250 ± 0,708 χ² 0,02798 0,02239 0,02854 0,01311 0,03318 0,03287 Table 3.2 Tafel extrapolation results of samples at different pHs Parameter Bare E (- mV/SCE) Jcorr (µA/cm ) pH of H2ZrF6 solution 560,8 633,2 676,4 690,2 683,9 637,6 137 38,8 7,7 7,2 8,0 74 3.1.1.2 Effect of pH on the adhesion of powder coating Base sample pH=2 pH=4 pH=5 pH=3 pH=6 Figure 3.4 Adhesion of powder coating at different pHs 3.2.1 Process dynamics and film composition The trend of OCP (Figure 3.8) showed that the steel electrode was gradually moving toward the positive side during film formation The film was quickly formed within the first minutes, slowed down until minutes and stabilized to minutes Immersion time (mins) Figure 3.8 Trend of OCP value of bare sample in H2ZrF6/silane Initially, when the bare sample was immersed in H2ZrF6/silane, Fe was oxidized into the solution by anode reaction (Fe-2e→Fe2+) The Fe2+ ion would combine with ZrF6-2 to release Zr4+ into the solution (Fe2+ + ZrF6-2 → Zr4+ + FeF6-4) H+ ions were reduced by local cathode reaction on the surface, releasing H2 (2H+ + 2e → H2↑) The local pH result on the sample surface increased, resulting in precipitation of hydrated zirconium oxide The crystal is germinated and then spread to the entire surface to form a zirconia film according to the equation (Zr4++ 3H2O→ ZrO2·H2O +4H+) Siloxane network formation reactions could also occur: In silane solution, ethoxy groups switch to silanol group (– Si(OC2H5)3+3H2O→–Si(OH)3+3C2H5OH) The silanol group was adsorbed by (Fe-OH) through hydrogen bonding to metal-siloxane (Si-O-Fe) bonds according to (–Si(OH)3+Fe-OH→H2N(CH2)3 Si(OH)2-O-Fe) Si-OH groups also formed stable siloxane (Si-O-Si) network by the equation (SiOH+SiOH→Si-O-Si+H2O) 11 The presence of Zr (fig 3.9b) and Zr, Si (fig 3.9c) from EDS spectra proved the phase formation of Zr and Si in the film The presence of O also indicated the presence of oxide or hydroxide of zirconium and the siloxane network Other peaks may come from the substrate due to the very thin film a) b) c) Figure 3.9 EDS spectrum of bare sample (a), sample treated after minutes in H2ZrF6 (b) and H2ZrF6/silane (c) Table 3.5 The percentage of atoms in the zirconia/silane film was determined from the EDS spectrum Percentage Fe O C Zr Si Al Cu By atoms 77,34 12,65 6,99 2,05 0,76 0,12 0,09 By mass 90,09 1,59 3,85 0,35 0,06 0,11 3,95 The ratio of Zr and Si in the film composition may represent the formation of zirconia and silane phases (Figure 3.10) Initially, ZrO2 formation speed was very fast, silane film formation speed was very slow This result was due to the rapid electrochemical reaction to form ZrO2 at the beginning, which inhibited the covalent reaction to form 12 silane film on the sample surface By the time, the ZrO2 film gradually completed covering the surface, the electrochemical reaction slowed down and the reaction of form covalent bonds between silane and metal became easier Between and minutes, both Zr and Si concentrations increased, indicating that the two films were formed in parallel This meant that silane both competed with Zr in forming film on steel substrate and created bonds around the newly formed ZrO2 Figure 3.10 Variations of Zr and Si ratio in ZrO2/silane film 3.2.2 Surface morphology of zirconium oxide/silane film The FE-SEM images of the samples (Figure 3.11) showed that zirconia film was morphologically arranged with spherical or elliptical particle structure, tens of nanoscale and irregularly shaped particles groups randomly distributed on the surface (Figure 3.11b) Figure 3.11c showed that zirconia/silane film had a finer, more tightly sealed characteristic a) b) c) Figure 3.11 FE-SEM image of the untreated substrate (a), treated in H2ZrF6 (b) and H2ZrF6/silane (c) 13 3.2.3 Bonding in zirconium oxide/silane film In FT-IR spectra (Figure 3.12), peak at in 500-600 cm-1 indicated OZr-O bonds It was reported that Si-O-Zr bonds were usually at 964 cm-1 wavenumber Affected by the high positive charge of ZrO2, this bond could be elevated at 1050 cm-1 The peak in the range of 1000-1130 cm-1 was created by the Si-O-Si asymmetric bond, the long vibration and the separation of this peak showed the laminated structure and confirmed Transmittance (%) the bridging role of O between Zr and Si together Wavenumber (cm-1) Figure 3.12 FT-IR spectra in ZrO2/silane film The peak around the wavenumber of 1400 and 2900 cm-1 could represent deformation and asymmetric fluctuations of the –CH group (-CH2, -CH3) A peak of about 1600 cm-1 was typical for the valence of the N-H group in silane The X-ray pattern (Figure 3.13) showed that one main peak at 2θ = 44,38 and the second peak at 2θ = 64,70 on both the bare sample and the ZrO2/silane film, which were from steel The pic at 2θ = 35,26 in Figure 3.13b was typical for ZrO2 in the film Only one peak of ZrO2 was obtained because of either the film was too thin, the dominance of the measurement belonged to Fe From the Scherrer equation, the average particle size of ZrO2 was 81,27 nm This result was quite similar to the particle parameters achieved by FE-SEM image 14 Fe ZrO2 Fe Fe Fe Figure 3.13 XRD pattetn (a-bare, b- ZrO2/silane film) 3.2.4 Effect of silan concentration on morphology, composition and corrosion resistance of zirconia/silane film 3.2.4.1 Effect of silane concentration on surface morphology 0,0 0,0125 0,05 0,025 steps silane Figure 3.14 FE-SEM image at different silane concentration FE-SEM image showed that the presence of silane significantly improved surface smoothness compared to the case without silane 3.2.4.2 Effect of silane concentration on film component The atom ratio of Si/Zr was shown in Figure 3.15 Si/Zr ratio in the case of steps (0,025%) was approximately equal to case of 1-solution (0,0125%) and lower than 1-solution (0,025%) 15 proved that combined film formed simultaneously during film formation This ratio increased as the concentration of silane in the solution increased, reflecting the competition in forming the link between Zr, Si and steel substrate 3.2.4.3 The effect of silan concentration on corrosion resistance The EIS spectra electrochemical and parameters of the film at different silane concentrations (Figure 3.16 and Table 3.9) showed that silane doped H2ZrF6 solution at different concentrations Figure 3.16 Nyquist spectra at different silane concentration polarization resistance and capacitance of combined film Table 3.6 Electrochemical parameters of samples at silane concentration leading to an increase in both Silane concentration (v/v) Paramete r 0,0125 0,025 0,05 Rp (Ω.cm2) 3198,74 ± 46,38 5279,68 ± 111,40 9116,37 ± 279,57 7830,15 ± 219,24 7152,84 ± 305,43 C (µF.cm-2) 280 422 327 413 321 steps 3.2.5 Effect of immersion time on morphology, composition and corrosion resistance of zirconia/silan film 3.2.5.1 Effect of immersion time on surface morphology FE-SEM images of the samples with different time (Figure 3.17) showed that, from to minutes, the film was mainly zirconia, the surface was still porous and characterized by ZrO2 film 16 a b c d e f Figure 3.17 FE-SEM image of samples with different time:: mins (a), mins (b), mins (c), mins (d), mins (e), silane only (f) After minutes the ZrO2/silane film was almost complete, however, the silane could still be formed, resulting surface morphology had silane characterization (Figure 3.17de) 3.2.5.2 Effect of immersion time on film components Figure 3.18 showed that the Si/Zr ratio in the forming combined film increased by immersion time At minutes, this ratio was very low (about 23/100), increased rapidly over time and reached about 36/100 Figure 3.18 Ratio of Si/Zr with different immersion time and 38/100 respectively with and minutes In the range of to minutes, this rate increased less, confirming the mutual competition during film formation 3.2.5.2 Effect of immersion time on corrosion resistance The impedance spectrum and electrochemical parameters of the samples (Figure 3.19 and Table 3.7) showed that the arc's magnitude corresponded to the polarizing resistance of the film, which increased with immersion time from to minutes 17 Figure 3.19 EIS spectra with different immersion time Table 3.7 Electrochemical parameters of samples according to immersion time Parameter Immersion time mins mins mins mins mins Rp (Ω.cm2) 3198,74 ± 46,38 6851,81 ± 144,57 9116,37 ± 279,57 9080,63 ± 277,43 9078,74 ± 286,89 C (µF.cm-2) 312 374 327 413 486 3.3 The protection performance of fully painted samples 3.3.1 Adhesion measurement 3.3.1.1 Dry adhesion The adhesion of the paint film according to the different options (Table 3.8) proves that all the treated samples have a higher adhesion than steel The result is that the zirconia membrane is tightly bound to the substrate while the silane outside plays a good role as a double bonding agent Table 3.8 The result determines the adhesion of powder coating Parameters Bond strength values (MPa) Bare sample 3,04 ± 0,23 Treated in H2ZrF6 after mins 4,20 ± 0,50 18 ... effective as phosphate and chromate, the topic of the thesis was chosen: "Research on fabrication and characteristic properties of zirconium oxide film combination with silane on steel substrate as pretreatment. .. preparation of zirconium oxide film on steel and selecting initial conditions on solution pH and dipping time as basis parameters for manufacturing zirconia /silane film; - Research on manufacturing... of film formation process and assessing characteristics of morphology, composition, electrochemical properties and bonding of the zirconia /silane film Main contents of the thesis - Research on