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Mar 29, 2016 - polymer network coating on stainless steel was formed. ... The PDSHP film provides active catechol and primary amine groups. Branched ...
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A Novel Hybrid Polymer Network for Efficient Anticorrosive and Antibacterial Coatings Yaqi Fu,†,† Mengsha Cai,‡,† Eryong Zhang,‡ Simeng Cao,‡ and Peijun Ji*,‡ †

Department of Biochemical Engineering and ‡Department of Chemical Engineering, Beijing University of Chemical Technology, Beijing, 100029, China S Supporting Information *

ABSTRACT: By in situ simultaneous polymerization of dopamine and hydrolytic polycondensation of 3-aminopropyltriethoxysilane in an aqueous solution, a novel hybrid polymer network coating on stainless steel was formed. The polydopamine and silica hybrid polymer (PDSHP) adhered strongly on the surface of stainless steel. The PDSHP film provides active catechol and primary amine groups. Branched polyethylenimine was grafted based on the PDSHP film. The structure and morphology of the multilayer coating were characterized by attenuated total reflectance Fourier transform infrared spectroscopy reflectance, X-ray photoelectron spectroscopy, and atomic force microscopy and scanning electron microscopy images. The coatings on the stainless steel substrates exhibited anticorrosion of seawater. By making use of the primary amine groups on the multilayer coating, a biocidal agent 3chloro-2- hydroxypropyltrimethylammonium chloride (CHPTAC) was grafted. The grafted CHPTAC was effective in killing bacteria, extending the multilayer polymer coating with biocidal functionality. properties. The hybrid polymer film was grafted with polyethylenimine (PEI) to form a PEI layer. The multilayer was further functionalized with a biocidal functionality, by grafting 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC). Figure 1 illustrates the coating based on the PDSHP film. Herein we present simple yet efficient coatings on stainless steel by forming multilayer polymers possessing anticorrosive and antibacterial properties. On the other hand, the coating formation was carried out in aqueous solutions at room temperature without using catalysts, thus it can be easily carried out with potential application at a large scale.

1. INTRODUCTION Stainless steels have been widely used in packaging, medical equipment, food processing, and industrial and marine environments. To combat corrosion and biofouling, various materials for coating stainless steels have been investigated. Surface science plays an important role in the development of coating materials. Suitable choice of coating materials is essential for fabricating effective coatings. For anticorrosion, poly(pyrrole-co-bithiophene) copolymers were used to coat steel,1 thin film was formed on stainless steel by heat treatment of poly(vinyl alcohol) and zirconiumoxynitrate,2 polyelectrolyte multilayers with different polyelectrolyte compositions were formed and the multilayer exhibited very high corrosion protection,3 poly(N-methylpyrrole)-dodecylsulfate coating was electrosynthesized on stainless steels providing an effective protection against to corrosion.4 Epoxy−silica hybrid nanomaterial coatings5,6 and siloxane−PMMA hybrid coatings7 have been studied for anticorrosion. For combating biofouling, stainless steels were coated with catecholamine copolymers,8 sulfonated poly(etheretherketone) based composite,9 superhydrophobic polymer film,10 Ce3+/Eu3+ dual-substituted hydroxyapatite coating,11 polysulfobetaine brushes,12 poly(vinylbenzyl chloride)−polyaniline bilayers,13 and polymer brushes utilizing barnacle cement as surface anchor.14 The results help inspire further research on anticorrosive and antibacterial coatings on stainless steel. In this work, a novel hybrid polymer network coating has been formed by in situ simultaneous polymerization of dopamine and hydrolytic polycondensation of 3-aminopropyltriethoxysilane in alkaline solutions. The polydopamine and silica hybrid polymer (PDSHP) coatings can strongly adhere to a stainless surface and have mechanical and corrosive © 2016 American Chemical Society

2. METHODS 2.1. Materials. Type 304 stainless steel and 304 stainless steel sheet (#8 mirror) were purchased from Beijing Guangyanghuaxia Stainless Steel Co. The composition of the 304 stainless steel: Fe (ca. 68%), Cr (18−20%), Ni (8−11%). The green fluorescent protein (GFP)-expressing Escherichia coli were purchased from Takara Co. (Takara, Dalian, China). Dopamine hydrochloride (98%), branched polyethylenimine, 3-aminopropyltriethoxysilane (APTES), peptone, yeast extract, and 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC) were purchased from Sigma−Aldrich and used as received. Ethanol, acetone, H2SO4, H2O2, NaOH, isopropyl alcohol, NaCl, Na2SO4, Na2CO3, KCl, KBr, MgCl2·6H2O, CaCl2·6H2O,H3BO3, MgSO4·7H2O, NH4Cl, CaSO4, K2HPO4, NaO3C3H5, C6H5Na3O7·2H2O, and (NH4)2Fe(SO4)2 were Received: Revised: Accepted: Published: 4482

December March 16, March 29, March 29,

17, 2015 2016 2016 2016 DOI: 10.1021/acs.iecr.5b04818 Ind. Eng. Chem. Res. 2016, 55, 4482−4489

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Industrial & Engineering Chemistry Research

Figure 1. Schematic presentation of coating stainless steel based on the PDSHP film: SS, stainless steel; PDSHP, polydopmine and silica hybrid polymer network; PEI, branched polyethylenimine.

operating pressure was 2 × 10−9 Pa, and Mg Ka X-ray was used as the excitation source. High resolution spectra were obtained by setting 10 eV for the analyzer pass energy. The background of the C 1s, O 1s, N 1s, and Si 2p spectra was subtracted using Shirley’s method. Thermo Avantage XPS software was used to analyze the data.16 The XPS spectra were fitted without setting constraints. The width at half-maximum varied between 0.8 and 1.9 eV. The subspectra were optimized with an accuracy of ±0.05 eV for the peak positions. FTIR Spectra Measurement. Infrared spectra were measured using a FTIR spectrometer (Bruker TENSOR 27), which is equipped with a temperature-controlled ATR with ZnSe Crystal (Pike Technology) and a specular reflectance accessory. A liquid-nitrogen-cooled mercury−cadmium−telluride detector was used. It collected 128 scans per spectrum at a resolution of 2 cm−1. The ATR element spectrum was used as background. Ultrapure nitrogen gas was introduced for purging water vapor. SEM Images. To evaluate the corrosion damage on the samples, SEM (Hitachi Su1510) imaging was carried out on the samples after 30 days of exposure in the solutions mimicking seawater. Six different surface locations on each sample were randomly chosen for SEM imaging. Atomic Force Microscopy (AFM). AFM images were measured on a SPM-9700 instrument. The scan was performed using a silicon cantilever (Nanoworld AG) with a spring constant 42 N/m and a resonance frequency 320 kHz. A tip with a radius of curvature ∼8 nm was used. A silicon cantilever (Nanoworld AG), Arrow-FMR) with a nominal spring constant of 2.8 N/m was used for all images, with a scan rate of 1.0 Hz and image resolution of 512 × 512 pixels. Film Thickness by Ellipsometry. The ellipsometry measurement was performed on an SE200BA ellipsometer. The film thickness on the SS surfaces was measured at angles 65°, 70°, and 75° and at wavelengths from 400 to 800 nm. The refractive indices of clean SS substrates (#8 mirror) were measured prior to preparing samples. The thickness of hybrid polymer film was determined with a three-layer optical model. The Cauchy layer model was used for fitting ellipsometric data. The refractive index of 1.6 was assumed to the PDSHP layer.17 Mean film thickness and standard deviation were obtained by measuring five separate spots for each sample. Corrosion Exposures. The pristine SS, SS-PDSHP, and SSPDSHP-CHPTAC samples with dimensions of 1.0 cm × 1.0 cm were used for corrosion investigation in artificial seawater, in triplicate for each exposure time. Artificial seawater was prepared according to the article.18 The artificial seawater composition (per liter) was as follows: 23.568 g of NaCl, 3.986 g of Na2SO4, 0.197 g of NaHCO3, 0.672 g of KCl, 0.097 g of KBr, 10.63 g of MgCl2·6H2O, 1.471 g of CaCl2·6H2O, 0.026 g

purchased from Sinopharm Chemical Reagent Co. The analytical grade chemicals were used as received without further purification. Deionized distilled water was used to prepare solutions. 2.2. Multilayer Polymer Functionalization of Stainless Steel Surface. P2500 silicon carbide papers were used to polish the 304 stainless steel (SS) substrates. To clean the SS samples, they were sonicated separately in deionized water, acetone, and ethanol, each for 10 min. Then the cleaned SS samples were rinsed with deionized water for 10 min. They were activated by immersing in H2SO4/H2O2 (3:1 by vol) for 30 min, generating hydroxyl groups on the surfaces.14,15 Dopamine hydrochloride was dissolved in ethanol/water (1:3 by vol) to prepare a solution. The concentration of dopamine hydrochloride was 1 mg/mL. APTES was added to the solution, the molar ratio of dopamine hydrochloride to APTES was 1:1. After stirring to form a homogeneous solution, NaOH (3 M) was added to the solution, and the solution pH was controlled at pH 10.5. Then SS substrates were immersed in the solution. After 48 h, polydopamine and silica hybrid polymer (PDSHP) coatings were formed on the SS samples. The hybrid polymer coupled samples (referred as SS-PDSHP) were then withdrawn from the solution. The SS-PDSHP samples were sonicated for 20 min, rinsed thoroughly with deionized water, and dried through nitrogen-blowing. The SS-PDSHP samples were immersed in the aqueous solution of branched polyethylenimine (PEI) (2.0 mg/mL). The reaction was carried out at 37 °C for 4 h, and then the samples were rinsed with distilled water to remove the unreacted EPI and dried by nitrogen-blowing. The dried samples were immersed in a solution of glutaraldehyde in ethanol (2.0 wt %), the reaction was carried out at 50 °C for 20 min. The prepared samples were designated as SS-PDSHP-PEI. The CHPTAC solution with a concentration of 31% (weight fraction) was prepared, and the pH condition was controlled at pH 10 by addition of NaOH (3 M). SS-PDSHP-PEI samples were immersed in the solution for 10 h at 60 °C. CHPTAC was grafted on the SS-PDSHP-PEI samples (referred to SSPDSHP-PEI-CHPTAC). The SS-PDSHP-PEI-CHPTAC samples were then sonicated for 20 min, rinsed with deionized water for 10 min, and dried through nitrogen-blowing. A 25 mL aliquot of the remaining solution was diluted with 75 mL of distilled water. Then 10 mL of the diluted remaining solution was further diluted with 35 mL of distilled water, and then 1.5 mL of chromate indicator was added. The sample was titrated with 0.1 M silver nitrate solution. Finally the reaction ratio of CHPTAC on the surface was determined to be 23.6 ± 0.8%. 2.3. Surface Characterization. X-ray Photoelectron Spectroscopy. A Thermo VG ESCALAB250 X-ray photoelectron spectrometer was used to measure XPS spectra. The 4483

DOI: 10.1021/acs.iecr.5b04818 Ind. Eng. Chem. Res. 2016, 55, 4482−4489

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Industrial & Engineering Chemistry Research

Figure 2. Hybrid polymer coating on the SS sample (a) and the proposed structure of polydopmine and silica hybrid polymer network (PDSHP) (b).

measured as 45 ± 2.6 nm. In the coating process, a series of reactions occurred in aqueous solutions. In the hydrolysis of APTES, the Si−C bond is hydrolytically stable and does not further hydrolyze, and the aminopropyl group is not cleaved.20 The hydrolysis of APTES produced trisilanols, the ethoxy groups were hydrolyzed, and the transient silanol groups condensed with other silanols to form network polymers.20 The polydopamine formation was achieved by autoxidation of dopamine,21 and the catechols of polydopamine reacted with the amines of the aminopropyl groups from APTES.22,23 Thus, a polydopamine−silica hybrid polymer (PDSHP) network was formed. The proposed structure of the PDSHP network is illustrated in Figure 2b. The formation of the PEI layer on the PDSHP film was accomplished via two steps. Through Schiff base formation, the catechol groups on the PDSHP film reacted with the primary amine groups of PEI; by glutaraldehyde (GA) cross-linking, the primary amine groups of PEI reacted with the primary amine groups on PDSHP, as illustrated in Figure 1. In the alkaline solution, CHPTAC was readily reacted with the primary amine groups of PEI, introducing the quaternary ammonium substituent (Figure 1).24−26 The SS-PDSHP-PEICHPTAC samples were sonicated for 1 h, in order to investigate whether sonication can peel off the hybrid polymer coating. XPS spectra and SEM images (not shown) confirmed that sonication had no effect on the hybrid polymer films. The pull-off adhesion test has also confirmed that the PDSHP coating adhered to the stainless steel surface very strongly (Figure S2). FTIR Results. Fourier transform infrared (FTIR) spectra were acquired from the PDSHP film deposited on SS substrates for 48 h as illustrated by Figure S3. Bands were assigned and listed in Table S1; the band assignment was based on the refs 27 and 28. Broad peaks centered at 3395 and 3433 cm−1 were attributed to N−H and O−H stretching; the peaks at 2941, 2945, 2982, 2886 cm−1 were assigned to aliphatic C−H stretching; and the peaks at 1661 and 1657 cm−1 were assigned to ring CO stretching29 from the quinone groups of dopamine. Two peaks at 1572 and 1563 cm−1 were assigned to ring CC stretching and ring CN stretching,30 indicating the presence of aromatic amine in the PDSHP film.27 The peak at 1343/1345 cm−1 was assigned to the C−N−C stretching of the indole ring;23 C−N stretching vibration at 1149, 1140 cm−1.29 The peak at 1089/1069 cm−1 was assigned to asymmetric Si−O−Si stretching or Si−O−C;23 Si−OH

of H3BO3, and 0.04 g of SrCl2·6H2O. The samples were transferred to the exposure vessels containing deoxygenated artificial seawater. During the exposure periods deoxygenation was achieved by putting the exposure vessels in an anaerobic chamber (ELECTROTEK) under an atmosphere containing 5% H2, 5% CO2, and 90% N2. Samples were immersed in the artificial seawater for 30 days. The morphology of the corroded surfaces was analyzed by visual observation and scanning electron microscopy (SEM). Antibacterial Activity Determination. Escherichia coli for expressing Green fluorescent protein (GFP) was used for the evaluation of the bactericidal efficacy. The GFP-expressing Escherichia coli was cultured in a broth medium at 37 °C for 5 h. The broth medium contained peptone (10 g/L), yeast extract (5 g/L), and NaCl (10 g/L) at pH 7.5. The Escherichia coli suspension was centrifuged after incubation. The precipitated bacterial cells were resuspended in PBS buffer. The samples were sterilized under UV-light for 1 h before the experiment. They were placed in 12-well plates, and 2 mL of the bacterial suspension was added to each well. Completely covering the samples surfaces with the bacterial suspension was guaranteed. The initial cell concentration was 6 × 107 cells/m, the incubation process was carried out at 37 °C for 12 h. Adhered and colonized bacterial cells were investigated under optical microscope (LEICA DM-1000 Microscope). Bacteria viability on samples was quantified by using the spread plate method.19 After 1 day exposure, the bacterial suspension was collected from the sample surfaces. The suspension was diluted, and 0.3 mL of the diluted suspension was plated onto solid agar. After incubation at 37 °C for 24 h, the number of viable cells on the SS-PDSHP-CHPTAC surfaces and on the SS surfaces were counted manually. The ratio of the number on the SS-PDSHPCHPTAC surfaces to the number on the SS surface was used to evaluate the bactericidal efficacy.

3. RESULTS AND DISCUSSION 3.1. Multilayer Polymer Coating on SS Samples. By immersing SS samples in the aqueous basic solution consisting of dopamine and APTES, the dopamine polymerization and hydrolytic polycondensation of APTES resulted in spontaneous deposition of an adherent PDSHP film (Figure 2a). The thickness of the hybrid polymer coating as a function of immersion time in the reaction solutions is shown in Supporting Information, Figure S1. The final thickness was 4484

DOI: 10.1021/acs.iecr.5b04818 Ind. Eng. Chem. Res. 2016, 55, 4482−4489

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Industrial & Engineering Chemistry Research

Figure 3. XPS spectra of the samples. (a) Wide scan spectra: black, SS-PDSHP; blue, SS-PDSHP-PEI; olive, SS-PDSHP-PEI-CHPTAC. (b, c) SSPDSHP; (d, e) SS-PDSHP-PEI; (f, g) SS-PDSHP-PEI-CHPTAC.

stretching vibration at 920 and 915 cm−1. The peaks at 843 and 766 cm−1 were attributed to Si−O−Si symmetric stretching.30,31 The proposed structure as illustrated in Figure 2b is supported by the FTIR spectra analyzed above for the PDSHP film. X-ray Photoelectron Spectroscopy (XPS). XPS analysis for the multilayer coatings is shown in Figure 3a. The peaks are for the C 1s, O 1s, N 1s, Cl 2p, and Si 2p and Si 2s regions. Table 1 lists the binding energies corresponding to the functional groups.

Table 1. XPS Peak Binding Energy Assignments

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functional group

binding energy (eV)

C−Si C−H C−N C−O CO, CN, C−N+ C-NH2 C-NH−/N−C C−N+

283.6 284.6 285.6 286.2 287.4 398.7 399.7 402.3

DOI: 10.1021/acs.iecr.5b04818 Ind. Eng. Chem. Res. 2016, 55, 4482−4489

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Industrial & Engineering Chemistry Research

Figure 4. AFM images of SS (a), SS-PDSHP (b), SS-PDSHP-PEI (c), and SS-−PDSHP-PEI-CHPTAC (d) samples.

Figure 5. SEM micrographs of the samples for anticorrosive test: (a) SS after immersing in the artificial seawater for 30 days. (b) SS-PDSHP; (c) SSPDSHP-PEI; (d) SS-PDSHP-PEI-CHPTAC The SS-PDSHP, SS-PDSHP-PEI, and SS-PDSHP-PEI-CHPTAC samples were immersed in the artificial seawater for 90 days.

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DOI: 10.1021/acs.iecr.5b04818 Ind. Eng. Chem. Res. 2016, 55, 4482−4489

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Industrial & Engineering Chemistry Research In the wide scan spectrum, the peak for Cl 2p spectrum is ascribed to the grafted CHPTAC. The C 1s region can be fitted with five binding energies, at 283.6, 284.6, 285.6, 286.2, and 287.4 eV (Figure 3b), attributable to peaks assigned to C−Si, CH, C−N, C−O, and C−N+/CO/CN,14,27 respectively. They are in accordance with the functional groups as illustrated in Figure 2b for the hybrid polymer network. The N 1s region can be fitted with two binding energies at 398.7 and 399.7 eV assigned to C−NH2 and C−NH−/N−C (Figure 3c),11 respectively. C−NH2 is from APTES and dopamine, C−NH− is due to polydopamine,32,33 and N−C is from 5,6dihydroxyindole and 5,6-indolequinone.27,32,33 In the wide scan spectrum (Figure 3a), the peaks at 101.8 and 152.9 eV were assigned to Si 2p and Si 2s spectra,32 respectively. APTES hydrolyzed to form polysiloxanes.20 After grafting PEI, the peak area of C−NH2 (C 1s) at 285.6 eV (Figure 3d) and C−NH2 (N 1s) at 398.7 eV were relatively increased (Figure 3e), this is attributed to the primary amine groups from PEI. Further grafting CHPTAC relatively increased the peak area at 285.6 (Figure 3f), this is attributed to the C−N increment after the grafting reaction (as illustrated in Figure 1). For the N 1 s region, another peak at 402.3 ev for −N+ appeared (Figure 3g), confirming the grafting of CHPTAC.33 AFM Images. Figure 4 shows AFM images for the SS, SSPDSHP, SS-PDSHP-PEI, and SS-PDSHP-PEI-CHPTAC samples. Scratches on the surface of the SS sample were clearly observed (Figure 4a). For the SS-PDSHP samples, because of covering by the PDSHP film, the scratches could not be observed anymore (Figure 4b). After the formation of the PEI layer, the roughness value Rq (root-mean-square deviation) is changed from 2.642 (SS-PDSHP) to 1.458 (SS-PDSHP-PEI). 3.2. Anticorrosion of Seawater. The corrosion of the samples in the artificial seawater was studied. Figure 5 shows SEM images for the SS, SS-PDSHP, SS-PDSHP-PEI, and SSPDSHP-PEI-CHPTAC samples after immersing in the artificial seawater. The surface morphology of the pristine SS sample with 30 days of immersion time shows that severe corrosion occurred (Figure 5a). In the contrast images for the samples of SS-PDSHP (Figure 5b), SS-PDSHP-PEI (Figure 5c), SSPDSHP-PEI-CHPTAC (Figure 5d) samples, after 90 days of immersion time, no corrosion occurred during the immersion time. The anticorrosion property of the coatings was further confirmed by the results of electrochemical impedance spectroscopy and XPS spectra as shown in Figures S4 and S5. To have a comparison, we have coated SS samples with polydopamine, which was formed by the dopamine polymerization in the aqueous basic solution. After exposure of the SSpolydopamine samples in the artificial seawater for 30 days, the sample surfaces were covered with a layer formed by the salt deposit, as illustrated in Figure S6. It is indicated that the polydopamine coating had no anticorrosive properties. Thus, the anticorrosion functionality of the PDSHP coatings is ascribed to the hybrid polymer network. 3.3. Bactericidal Efficacy. Figure 6 shows optical micrographs for SS and SS-PDSHP-PEI-CHPTAC samples after immersing in Escherichia coli broth. The SS surface could not resist the adhesion and colonization of Escherichia coli, and the adhered and colonized Escherichia coli on the SS surface with a large amount were clearly observed (Figure 6a). In contrast, the SS-PDSHP-PEI-CHPTAC surface was more resistant to the adhesion and colonization of bacteria, and only a few bacteria cells were found on the SS-PDSHP-PEI-CHPTAC surface, indicating a significant reduction in bacterial population. The

Figure 6. Fluorescence micrographs of GFP recombinant Escherichia coli on the samples: (a) pristine SS; (b) SS-PDSHP-PEI-CHPTAC. The scale bar is 50 μm.

spread plate method was used for quantitative in vitro antibacterial assay. The spread plate method was used for antibacterial assay. The SS-PDSHP-PEI-CHPTAC samples were incubated with Escherichia coli broth. The bactericidal function of the multilayer coating was studied by counting the number of viable Escherichia coli cells on the SS-PDSHP-PEI-CHPTAC surfaces. As illustrated in Figure 7, viable Escherichia coli cells on

Figure 7. Viable cells on the surfaces of SS (a) and SS-HPDSHP-PEICHPTAC (b) after a 24 h incubation period.

the SS-PDSHP-PEI-CHPTAC surfaces were 0.15 cells/cm2, in comparison to 4.9 cells/cm2 for the SS surfaces. It is indicated that the survival rate (3.1%) for the Escherichia coli cells on the SS-PDSHP-PEI-CHPTAC surface was low. The number of viable cells adhered on the SS-PDSHP-PEI-CHPTAC surface was significantly decreased, confirming the effectiveness of the coating in killing Escherichia coli cells.

4. CONCLUSIONS By in situ simultaneous polymerization of dopamine and hydrolytic polycondensation of 3-aminopropyltriethoxysilane in an alkaline solution, a hybrid polymer network coating on stainless steel was formed. The coating adhered strongly on the surface of stainless steel and exhibited an anticorrosive property. Further coating with polyethylenimine provides active primary amine groups. By making use of the primary amine groups on the multilayer coating, a biocidal agent 3chloro-2-hydroxypropyltrimethylammonium chloride was grafted, and the multilayer coatings were demonstrated to be effective in killing bacteria. This work demonstrated that the PDSHP coating can be taken as a solid substrate with anticorrosion properties. Depending on the substrate, multilayer coatings can be carried out to have other functionalities, such as biocidal functionality. 4487

DOI: 10.1021/acs.iecr.5b04818 Ind. Eng. Chem. Res. 2016, 55, 4482−4489

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(12) Sin, M. C.; Sun, Y. M.; Chang, Y. Zwitterionic-Based Stainless Steel with Well-Defined Polysulfobetaine Brushes for General Bioadhesive Control. ACS Appl. Mater. Interfaces 2014, 6, 861. (13) Lv, Li.; Yuan, S. J.; Zheng, Y.; Liang, B.; Pehkonen, S. O. Surface Modification of Mild Steel with Thermally Cured Antibacterial Poly(vinylbenzyl chloride)−Polyaniline Bilayers for Effective Protection against Sulfate Reducing Bacteria Induced Corrosion. Ind. Eng. Chem. Res. 2014, 53, 12363. (14) Yang, W. J.; Cai, T.; Neoh, K. G.; Kang, E. T.; Teo, S. L. M.; Rittschof, D. Barnacle Cement as Surface Anchor for “Clicking” of Antifouling and Antimicrobial Polymer Brushes on Stainless Steel. Biomacromolecules 2013, 14, 2041. (15) Yang, W. J.; Cai, T.; Neoh, K. G.; Kang, E. T.; Dickinson, G. H.; Teo, S. L. M.; Rittschof, D. Biomimetic Anchors for Antifouling and Antibacterial Polymer Brushes on Stainless Steel. Langmuir 2011, 27, 7065. (16) Parry, K. L.; Shard, A. G.; Short, R. D.; White, R. G.; Whittle, J. D.; Wright, A. Characterisation of Plasma Polymerised Surface Chemical Gradients. Surf. Interface Anal. 2006, 38, 1497. (17) Zhu, B.; Edmondson, S. Polydopamine-Melanin Initiators for Surface-Initiated ATRP. Polymer 2011, 52, 2141. (18) Kester, D. R.; Duedall, I. W.; Connors, D. N.; Pytkowicz, R. M. Preparation of Artificial Seawater. Limnol. Oceanogr. 1967, 12, 176. (19) Yuan, S. J.; Pehkonen, S. O.; Ting, Y. P.; Neoh, K. G.; Kang, E. T. Inorganic-Organic Hybrid Coatings on Stainless Steel by Layer-byLayer Deposition and Surface-Initiated Atom-Transfer-Radical Polymerization for Combating Biocorrosion. ACS Appl. Mater. Interfaces 2009, 1, 640. (20) Minier, M.; Salmain, M.; Yacoubi, N.; Barbes, L.; Méthivier, C.; Zanna, S.; Pradier, C. M. Covalent Immobilization of Lysozyme on Stainless Steel. Interface Spectroscopic Characterization and Measurement of Enzymatic Activity. Langmuir 2005, 21, 5957. (21) Lee, H.; Dellatore, S. M.; Miller, W. M.; Messersmith, P. B. Mussel-Inspired Surface Chemistry for Multifunctional Coatings. Science 2007, 318, 426−430. (22) Faure, E.; Falentin-Daudré, C.; Jérôme, C.; Lyskawa, J.; Fournier, D.; Woisel, P.; Detrembleur, C. Catechols as Versatile Platforms in Polymer Chemistry. Prog. Polym. Sci. 2013, 38, 236. (23) Pop-Georgievski, O.; Verreault, D.; Diesner, M. O.; Proks, V.; Heissler, S.; Rypacek, F.; Koelsch, P. Nonfouling Poly(ethylene oxide) Layers End-Tethered to Polydopamine. Langmuir 2012, 28, 14273. (24) Sajomsang, W.; Gonil, P.; Tantayanon, S. Antibacterial Activity of Quaternary Ammonium Chitosan Containing Mono or Disaccharide Moieties: Preparation and Characterization. Int. J. Biol. Macromol. 2009, 44, 419. (25) Geresh, S.; Dawadi, R. P.; Arad, S. M. Chemical Modifications of Biopolymers: Quaternization of the Extracellular Polysaccharide of the Red Microalga Porphyridium sp. Carbohydr. Polym. 2000, 63, 75. (26) Song, Y.; Sun, Y.; Zhang, X.; Zhou, J.; Zhang, L. Homogeneous Quaternization of Cellulose in NaOH/Urea Aqueous Solutions as Gene Carriers. Biomacromolecules 2008, 9, 2259. (27) Zangmeister, R. A.; Morris, T. A.; Tarlov, M. J. Characterization of Polydopamine Thin Films Deposited at Short Times by Autoxidation of Dopamine. Langmuir 2013, 29, 8619. (28) Silverstein, R.; Bassler, G.; Morrill, R. Spectrometric Identification of Organic Compounds; John Wiley & Sons: New York, 1981. (29) Tsuboi, M.; Takahashi, S.; Harda, J. Infrared and Raman spectra of nucleic acids. Vibration in the base residues. In Physicochemical Properties of Nucleic Acids, 2nd ed.; Academic Press: New York, 1973; p 91. (30) De, G.; Karmakar, B.; Ganguli, D. Hydrolysis-Condensation Reactions of TEOS in the Presence of Acetic Acid Leading to the Generation of Glass-Like Silica Microspheres in Solution at Room Temperature. J. Mater. Chem. 2000, 10, 2289. (31) Innocenzi, P.; Brusatin, G.; Guglielmi, M.; Bertani, R. New Synthetic Route to (3-Glycidoxypropyl)trimethoxysilane-based Hybrid Organic-Inorganic Materials. Chem. Mater. 1999, 11, 1672.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.iecr.5b04818. Table for infrared bands of the hybrid polymer coatings on SS sample surfaces, FTIR spectra of SS-PDSHP, figures for pull-off test for the PDSHP coated SS samples, thickness of the hybrid polymer PDSHP, and Nyquist plot of SS-PDSHP-PEI-CHPAC; SEM image of the SSpolydopamine sample (PDF)



AUTHOR INFORMATION

Corresponding Author

*Tel.: +86 10 64446249. E-mail: [email protected]. Author Contributions †

Y.F. and M.C. contributed equally to this work.

Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS This work was supported by the National Science Foundation of China (21176025, 21476023).



REFERENCES

(1) Pekmez, N.Ö .; Cınkıllı, K.; Zeybek, B. The electrochemical copolymerization of pyrrole and bithiophene onstainless steel in the presence of SDS in aqueous medium and itsanticorrosive performance. Prog. Org. Coat. 2014, 77, 1277. (2) Lee, P. J.; Ho, C. C.; Hwang, C. S.; Ding, S. J. Improved physicochemical properties and biocompatibility of stainless steel implants by PVA/ZrO2-based composite coatings. Surf. Coat. Technol. 2014, 258, 374. (3) Andreeva, D. V.; Skorb, E. V.; Shchukin, D. G. Layer-by-layer polyelectrolyte/ inhibitor nanostructures for metal corrosion protection. ACS Appl. Mater. Interfaces 2010, 2, 1954. (4) Zeybek, B.; Aksun, E. Electrodeposition of poly(N-methylpyrrole) on stainless steel in the presence of sodium dodecylsulfate and its corrosion performance. Prog. Org. Coat. 2015, 81, 1. (5) Abdollahi, H.; Ershad-Langroudi, A.; Salimi, A.; Rahimi, A. Anticorrosive Coatings Prepared Using Epoxy−Silica Hybrid Nanocomposite Materials. Ind. Eng. Chem. Res. 2014, 53, 10858. (6) Suleiman, R.; Dafalla, H.; El Ali, B. Novel Hybrid Epoxy Silicone Materials as Efficient Anticorrosive Coatings for Mild Steel. RSC Adv. 2015, 5, 39155. (7) Harb, S. V.; dos Santos, F. C.; Caetano, B. L.; Pulcinelli, S. H.; Santilli, C. V.; Hammer, P. Structural Properties of Cerium Doped Siloxane−PMMA Hybrid Coatings with High Anticorrosive Performance. RSC Adv. 2015, 5, 15414. (8) Xu, L. Q.; Pranantyo, D.; Ng, Y. X.; Teo, S. L. M.; Neoh, K. G.; Kang, E. T.; Fu, G. D. Antifouling Coatings of Catecholamine Copolymers on Stainless Steel. Ind. Eng. Chem. Res. 2015, 54, 5959. (9) Rajeswari, D.; Gopi, D.; Ramya, S.; Kavitha, L. Investigation of Anticorrosive, Antibacterial and in Vitro Biological Properties of a Sulphonated Poly(Etheretherketone)/Strontium, Cerium Cosubstituted Hydroxyapatite Composite Coating Developed on Surface Treated Surgical Grade Stainless Steel for Orthopedic Applications. RSC Adv. 2014, 4, 61525. (10) Li, L.; Breedveld, V.; Hess, D. W. Creation of Superhydrophobic Stainless Steel Surfaces by Acid Treatments and Hydrophobic Film Deposition. ACS Appl. Mater. Interfaces 2012, 4, 4549. (11) Gopi, D.; Sathishkumar, S.; Karthika, A.; Kavitha, L. Development of Ce3+/Eu3+ Dual-Substituted Hydroxyapatite Coating on Surgical Grade Stainless Steel for Improved Antimicrobial and Bioactive Properties. Ind. Eng. Chem. Res. 2014, 53, 20145. 4488

DOI: 10.1021/acs.iecr.5b04818 Ind. Eng. Chem. Res. 2016, 55, 4482−4489

Article

Industrial & Engineering Chemistry Research (32) Dreyer, D. R.; Miller, D. J.; Freeman, B. D.; Paul, D. R.; Bielawski, C. W. Elucidating the Structure of Poly(dopamine). Langmuir 2012, 28, 6428. (33) Wang, J. S.; Matyjaszewski, K. Controlled/″Living″ Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition-Metal Complexes. J. Am. Chem. Soc. 1995, 117, 5614.

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DOI: 10.1021/acs.iecr.5b04818 Ind. Eng. Chem. Res. 2016, 55, 4482−4489