Corrosion Science 140 (2018) 249-362 Content lists available a ScienceDicect Corrosion Science ELSEVIER journal homepage: www elsevier.com/locatelcorsei A one-step preparation of inhibitor-loaded silica nanocontainers for self- healing coatings Jun-Bo Xu, Yun-Qing Cao, Lu Fang, Ji-Ming Hu’ Depron of hen, rang Unbvety,Hangho $0027 PR Oia Keywords We present «simple one-step method of preparing inhbitrouded mesoporous sles nanoconainss without A copper fr steps sich a template removal or labors luda. The syathlle method i based an the high solubity som fergie inhibitors In hydrophobic cores of template mele, The resultant inhibiter(benzoraole) and fetytimethyl ammonium bromide (CTAB) eoloaded sea sanocootalners had high uptake of ishbitor (Cis wea and possessed 4 lon responsve inhibitor release property. When examined by seannig vibeatg tleerode technique, the coating doped with these nanocootlnes eahiblte effective coursion protection property. These resus suggest tha the one-step syathetie method was lent energyseing and organle folven-snceameng others 1, Introduction Metal corrosion protection is one ofthe most important issues for industries and daily life (1). To prevent or slow down corrosion ki netis, coating system isthe most effective and widespread strategy t0 date, However, conventional corrosion protective costings onthe metal surface only aet as pasive barriers sgainst corrosive media without any feedback active protection, To overcome this limitation, corrosion in- bibitors are often incorporated into the coating systems to provide them. ‘with active properties, in which chromate conversion coating is often used for this strategy. Nevertheless, the industrial application of chro sium compounds is restricted because they are highly toxic to human fang the environment. Therefore, numeracs innocuous inorganic and forganie corrosion inhibitors have been developed to design environ smental-riendly coating systems (2,3) However, the diretly doped corrosion inhibitors into eonsion protective coatings have several limitations [2,4-1 1]. Fiesty, the high ‘content or strong interaction between inhibitors and coating matrix pairs the integrity of the coating and thus compromise ts protective capacity. Secondly, free inhibitors within the cating matrix may leak ‘out ofthe matrix, thereby weaken its efficacy, In addition, the osmotic pressure generated by the dissolution of inhibitors drives water into the coating and further eauses blistering or delamination at the interface. ‘As a rerlt, indizect strategies of incorporating inhibitors have been studied to prepare coating systems which overcome the above-men- tioned drawbacks [712-18]. Namely, corrosion inhibitors are en ‘apsulated in micto- and nanocontainers before integrating them into Ena ers: obo cs GAL Hu. ‘vist olne 39 May 5018 (010-9584/ © 2018 Elsevier Lt, Al rights reserved the coatings, hence avoiding their direct interactions with coatings. Various micro and nanocontainers have been reported s0 fer, including layer-by-layer polyeleczolytes [6,19,20], polymer hollow spheres [11,21,22}, Beyelodextxin [5,23,24], mesoporous Si0> nanoparticles [5-10,25-28}, mesoporous TIO, nanoparticles [25,2830], halloysite rnanorubes [51-35], layered double hydroxides [5¢-37], montmor- ‘Monit [38,38], zeolites [40], hydroxyapatite [11], inorganic hollow spheres (50,42,8], carbon nanotubes [14,5], graphene oxide [46], cellulose nanofibers [47.48], porous sol-gel films [49-53], porous polymer films (54-56), porous oxide layers of metal matrix and so on [57-59]. The encapsulated inhibitors are released when micro- oF na- ocontainers receive corrosion initiated or artificial stimulations such as pH [10,28 35,50-62], ions [35,36,61,52], redox [63-56], enzyme 153}, ight [25,29,67), temperature and mechanical erack [22,53] ‘Among the various micro- and nanceontainers, mesoporous SiO ‘panopatieles have attracted much attention from researchers because they possess the following benefits: (D homogeneous distribution inthe sol-gel films or polymer eoatings because of their good compatiilits {high loading content of inhibitors because they have high surface areas and large pore volumes; (ii) controllable stimlation-responsive release of inhibitors: Gv) high mechanical stability (8-10,25-28} However, traditional inhibitoroading methods for mesoporous SiO, ‘panopaticles have mult steps and are time-consuming. Such methods involve many successive steps, including synthesis of SiO,template composites, removal of templates by calcination or acid extraction, possible functionalization of SiO, nanopatiles and subsequent loading ‘of corrosion inhibitors. Therefore, iti necessary to develop a simpleJB Meal cas ene 140 2018 348-852 ae ee “ Present One-step Synthesis 4 rept cr my = Inhibitor-loaded Nanocontainers Fig 1. Schematic illustration of the synthesis of inibitertoaded mesoporous SiO; nanoconaicrs by the traditional mlstep method andthe one-step route presented in this work, ang efficient method of loading inhibitors to enhance industrial appl cation [68] In recent years, one-step synthetic methods of preparing inhibitors incorporated micro- and nanocontainers have been investigeted, gex- fray through an oibinowater microemulsion polymerization [22,58-7#]. However, there are wo main challenges to this technique, Firstly, the size ofthe particles obtained are often micrometers, which ‘may damage the integrity ofthe coating matrix according to literature [50,58,71-75], Secondly, as reported by Maia and Zheludkevich eta, the employment of poisoaous organic solvents is inevitable even when, preparing nanocontainers with a diameter less than 150mm (70-72,74,73) Herein, we report a novel one-step method, free of organic solvents, to simultaneously prepare mesoporous SiO, nanocontainers and load Inhibitors. Since hyérophobic inhibitors are highly soluble in hydro phobic micelles, the one-step method avoids utilization of organic 99.9%, thickness: 1 mm, Quanfu Metal Co, Le China) were cut to a dimension of 25cm x 4em. Prior to use, the plates were abraded by emery papers of 400 grade, chen washed with Aelonized water and ethanol, Alkyd resin (injiangdagiao Co, Ud China), tetraethoxyslane (TEOS, 98.9%, Aladdin), cetytrimethyl am- onium bromide (CTAB, 99.0%, Aladdin), 1-benzotriazole (BTA, 99%, Aladdin), were wed without farther purification, 2.2, Preparation of SiO, nanocontzners ‘Typical preparation procedure of Si0,-CTAB-BTA wat a¢ follows: (0.21 g of NaOH was first dissolved in 3831mL of deionized water at 80°C. 0.754 of surfactant CTAB was added inco the solution while sirving, and 1.25 of BEA was added Gniial CTAB/BTA unit molse ratio = 1/5), Then 3.75 ml of TEOS was added slowly, The reaction sminture was kept under vigorous magnete string at 80°C for 2h. The resaltant product was centrifuged, washed twice with deionized water fand dried a¢ 90°C for 6h, Several kinds of SiO;-CTAB-BTA nano- containers with differen intial CTAB/BTA unit molar ratios ranging. from 3/1 to 1/5 were prepared, and denoted 25 S1O;-CTAB-BTAGb (a/ bis the initial CTAB/BTA unit molar ratio}. Besides, SiO CTAB-BTA defaults to Si0,-CTAB-BT/ “The preparation process of S10,-CTAB was same as described above, ‘except that no inhibitor BTA was added. For comparison, nanocontal- ners without CTAB were fabricated using a one-step procedure. In ad Aiton, BTA Toaded mesoporous SiO, nanocontaners (enoted as SiO, BTA) prepared by multistep method were also synthesized for com- parison and the procedure was in accordance with previous report [8] 23. Inhbior release of SiO, nanocontaners ‘Toinvestgate inhibitor release kinetis from SiO, nanocontainers in aqueous solution with different pil values, a typeal procedure of re Tease experiment was a follows: 20.0 mg of $10,-CTAB-BTA (13 w% (of BTA corresponding to 2.6mg) was dispersed in 80 ml, of aqueoussolution and adjusted by HCl or NaOH to different pH valves (3.0, 70 fand 11.0), The mixture was transferred into a dialysis membrane (@tWCO: 8000-24000 gmol™', Shanghai Yuanye Biotechnology Co. Lid. China) and the dialysis membrane was immersed in 170mL of agueous solution ofa corresponding pH value. The suspension and re lease medium were kept under moderate magnetic sting at 25°C for ‘72h. 9.0m of solution outside the dialysis membrane was taken at given time intervals, followed by addition of 8.0m, of fresh aqueous solution, Then, the concentration of BTA inthe removed solution was measured by a UV-vis speetrophotometer (TU-1901, Purkinje Genel, China) at 259.0nm (pil = 3.0 and 7.0) of 273.5 nm (pH = 11.0) based ‘on the calibration curves of BIA in different medias. The cumulative release at diferent time was calelated from the forma: cumulative release (96) = My/Mo X 100, where Mis the cumulative amount of BTA, released at time t, and My is the amount of BTA loaded in the SiO, CTABBTA (Mp = Mya. 24. CTAB release of SiO, nanocontainers Due to the difficulties involved in the direct measurement of the ‘concentrations of CTAB in aqueous solutions, an indirect and ex site ‘method was applied in the present work to determine the amounts of CTAB released {rom SiO,-CIAB-BIA in solutions with different ptt values. The procedure was as follows: 500mg of SiO,-CTABBTA (13 wL.% of BIA) was dispersed in 80mL of aqueous solutions with diferent pH values (3.0, 7.0 and 11.0) adjusted by HCl or NaOH. The mixture war transferred to a dialysis membrane, And the dialysis membrane was immersed in 170m. of aqueous solution of a core sponding pH value. After a given duration, the suspension ligud inthe dialysis membrane was taken out and centrifuged. The separated solid ‘was then dried at 100°C for 6h. Flementary analysis (C and N ele rents) ofthe dry solid was conducted by an elementary analyzer (Vario Micro, Hlenemtar Analysensysteme GmbH, Germany). Weight fractions ‘of GTAB in the soaked Si0,-CTAB-BTA samples were calculated based fon the facts that C and N elements only distribute in BTA and CTAB. ‘compounds and the mass fraction of each element in a compound is constant. Amount of C and N elements in SiO,-CTAB-BTA composites, fits into the following system of linear equations: O% = mezan * Cerna + mara * Carat, NI = Moran * Nexanto + Mara” Marat where O¥ and NY are the weight percentages of C and N elements in ‘the soaked S10,-GTAB-BTA composites, mzay and Mara ae the weight percentages of CTAB and BTA in SiQ,-CTAB-BTA composites, and Cyt And N.S are the weight percentages of C and N elements in compound 2X Gs CTAB or BIA), For each type of soaked SI0,-CTAB-BTA sample, (C5 and N¥ are obtained through elementary analysis, and C.9% and 1N% are constants, Thus meray ad mara can be calculated using the abovementioned system of linear equations of wo unknowns. Specifically calculation ofthe weight fraction of CTAB in Si0;-CTAB. ‘BTA follows the formula: mcrag = (C86 ~ 1.71 x N¥/0.56, where O% fang N% ate the amounts of C and N elements in Si0,-CTAB-BTA ‘composites, respectively. Five different immersion time intervals (Smin, 30min, 6Omin, 180min and 720 min) were performed for ‘each solution ata specif pH values 25. Preparation and corrosion protection evaluation of elf healing coatings The commercial alkyd resin (AR) was coated on the copper plates by a brush, After coating, samples were pre-cured at 25°C for 12, and, then cured at 45°C for 7 days. For the purpose of comparison, four kinds of coatings with differen: dopants were prepared and denoted as follows: alkyd resin costing without any additives (AR), alkyd resin coating doped with 1.Owt SiO;-CTAB-BTA (AR-SCB), alkyd resin coating doped with 0.13 we86 BTA (AR-BTA) end alkyd resin coating oped with 1.0.8 Si0,-CTAB (ARSC). We chose OWES as the Toading content of nsnacontainets in this work because iis lose to the critical concentrations of S10, nanocontaner (27,77). The mass of BTA, {in Si0z-CTAB-BTA incorporated in the coating was almost similar (0 {hat of BTA dicecly doped into the coating, Mle curing, the thickness ofthe alkyd resin coating on copper was measured as 50 = Sym by an ‘eddy-current coating thickness gauge (Qnix 8500, Germany), Copper dissolution measurement was carried out on the line-seribed, (1.0m x 40um) alkyd resin coating samples. An atomic absorption spectrometer (AA800, Perkintlmer, USA) was used to measure the ‘pumber of dissolved copper ions in a 3.5 wt.% NaCl aqueous solution (@5'O. After the seratched alkyd resin coated copper plates were im- rmersed in 30ml, of 3.Swt.% NaCl solution for $ days, 20m. of 2.0 moll" H,S04 aqueous solution was added to ensure that all the corrosion products of copper were dissolved to the seid solution atthe same time copper matrix was unaltered. The scanning vibrating electrode technique (SVET) measurements were performed in 0,10mol1.~! NaCl soliton sing a VersaSean micro scanning electrochemical workstation (Ametck, USA). A line seratch (Lomm x 40um) of the coating was manufactured with a surgical ‘ife before immersion in the NaCl solution. The side and the back area ofthe coating sample were sealed and tightly immobilized by acrylic, ‘The only section of the sample exposed to the NaCl solution was the ‘coating surface containing a line setatch. The size of the probe tip used {platinun-iridium) was 1Oym and the vibration amplitude was 30 pm with a frequency of 80H. Local current densities were mapped 09 {rid of 21 = 21 points over an atea of 2.0 x 2.0mm? (each lateral step 1Was 100m). The distance between the probe tip and the sample sur- face was 100m, The scans were performed for 12h at gifferent time intervals. 26, Characterization ‘The morphologies of nanoparticles and coatings were characterized by SEM (GU 8010, Hitachi, Japan) at an accelerating voltage of 5 ORV coupled with energy dispersive spectroscopy. Coating samples with ‘ross sections were prepared with a cutoff machine, The morphologies and pore structures of nanoparticles were characterized by TEM (HT- 17700, Hitachi, Jepan) working at 100kV and HRTEM (JEM 2100F, SJEOL, Japan) operating et 200V with an energy dispersive spectro ‘scopy. Nz adsorption-desorption isotherms were obtained at 77K on a Micromerities ASAP 2020 analyzer. Samples (S1O,CTAB and SiO, CCTAB-BTA) were caleined at 600°C for 6h in ai to remove templates and inhibitors before charaterization. Their respective surface areas Were calculated by BET model and pore volumes and pore size dis. tributions were obtained according to the BJH method. Small-angle X- zy diffraction (SAXRD) measurements were conducted with a Rigaku ‘Uhimate VI Xray diffractometer (40 KV, 20 mA) using Cuga radiation source (& = 1.5406). The UV-vis absorption spectra of solid samples fand aqueous solutions of BTA were obtained by UV-vis spectro photometer (TV-1901, Purkinje General, China). The Avoreseence spectra of solid samples and BTA-contained aqueous solutions were obtained by afuorescence spectrophotometer (F-4600, Hitachi, Japan) withthe excitation wavelength at 327 nm. FT-R spectra of the slid samples were recorded using a FTAR spectrometer (Nicolet 6700, ‘Thermo Scientific, USA). Thermo gravimetric analysis (TGA) of the materials was performed wsing thermal analysis system (TGA/DSC 1 (SF 1100°C), Metter-Toledo, Switzerland) at a heating rate of 10°Gmin~ from room temperature 9 600"C in air. The surface to- pographs ofthe coatings were obtained by AFM (Multimode 8, Bruker, Germany) 4, Results and discussion 5.1, Symesis and characterization of SiO, nanocantainers (S10, CTAB Bra) The one-step method designed in the present study is inspired by rug delivery systems, which ste developed in one step using surfactantJB Meal cas ene 140 2018 348-852 f —sio,cras A Sio,-cTAB-BTA| a 2 — $i0,-CTAB = = si0,-crAB-BTA| 00 02 04 a6 0B 10 ia a Relative Pressure / P/P, 3 2 theta / deg. ig. 2, SEM (ab) 2nd TEM (, d images of Si0-CTAB (a © and SiO,-CTABABTA )nanocontanes (6 N asorpion-dsorption isotherms for Si0;-CTAB and ‘Si0,-CTAB-BTA afer ealeinaios. The inset in) shows the corresponding pore sue distribution eaves. Smalangle KAD patters of Si0,-CIAB and SO;-CTAB A micelles (templates of mesoporous Si0,) [78-88]. BTA molecules di solve in CTAB micelles through hyérophobic interaction. Meanwhile, ‘THOS transforms to SiO through hydrolysis and polyconcensstion, and assembles with positively charged CTAB micelles, yielding the one-step Tormation of Si0,-CTAB-BTA composice. [As shovin in the SEM images (Fg. 2a and b), nanoparticles of SiO, [CTAB (inthe absence of BTA) and Si0;-CTAB-BTA display a spherical shape and a near-spherieal shape, respectively. Apparently, less regular morphology was observed with S10;-CTAB-BTA compared with SiO, CTAB, More detailed information ofthe structural differences is shown, bby TEM images (Piz, 2c and 24). Highly long-range ordered hexagonal array and streak structural features of SiO,-CTAB are shown in TEM lage (Fig. 20) corresponding to two different viewing direetions of crytals, while a leseordered and wormvlike type structure was ex hibited by Si0,-CTAB-BTA (Fig. 2d). Besides, the TEM image af SiO, CCTAB-BTA shoves that the nanoparticles varied in sizes and stuck to gether disorderly while a homogenous distribution with a size of = 90 nm was observed in $10,-CTAB nanoparticles. These results con. fiem that addition of inhibors altered the morphology, size and steueture of $10,-micelles composite We furthermore evaluated the ordered structures of SiO, nano- composites (S10;-CTAB and SiO,CTAB-BTA) by N, adsorptionsdeso- xption isotherms (after the removal of templates and inhibitors by ‘aleining) and small-angle XRD. Fig. 2¢ demonstrates that SiO,-CTAB, and SiO,-CTAB-BTA isotherms ate of typelV with hysteresis loops, ‘hich are typical characteristics of mesoporous materials. With regard {o pore diameter distributions analysis inset in Pig. 2), we found that Si0,-CTAB had a narcow pore size distribution (3.4m in average) hile i0,-CTAB.BTA had broader pore size (~5,5am) Table 1 illus ‘rates that Si0,-CTABBTA had a larger BJH volume of pores and a Tablet Structure information of i0,-CTAB and SiO,-CTAB-BTA afer clcnations de. temined fom the Nz adsorption desorption iatherms: OWEN alee’ SO;CTARSTA eked Barco pore diameter 348m Seono ov 4 giz] 2 3 i a ate, iS 309 : Eos 3? g 03 £1 2 oo KE °. 20” abo” 350 abo 450 250” 300 350 460 450 Wavelength / nm Wavelength / nm c . a Taal 746 2 5 3 wr € a Tal, z 5 fy i tH 350 400450 500 4000 3000 2000 1000 900 750 600 Wavelength / nim Wavenumber/ Fig 3. Solid UV-vis absorption spectra (a, Suoreeence spectra () and FIR spectra (of samples. Riht pat in (@ are the corresponding expanded spect. (5) ‘UVevi abrorption spectra of BTA in aqueous solutons with diferent pL (1: BTA, (2): S]OACTABABTA, (3 iO.-CTAB, (4): Si0,37A smaller BET surface (1.29 mg and 852 m* g~'), which is expected ‘considering there results of pore diameter distribution, These result are also corroborated by small-angle XRD patterns (Pig. 20. In agreement With the disordered structure of SiO,-CTAB-BTA, the intensity ofits fraction peaks i much weaker than that of SiO,-CTAR, In addition, the ditfraction angle of SiO, CTAB-BTA-31 corresponding to crystal face indexed a (100) (1.88 its fall diffraction spectrum not shown ‘here) is smaller than that of Si0,-CTAB (1.98°), probably due to the ‘increase in pore size. Therefore, i is reasonable to conclude that the ‘encapsulation of BTA causes the swelling of CTAB micelles, which en latges its pore diameter and broadens the pote size distribution, In addition, spectral characterizations were performed to confirm the encapsulation of BIA in SiO,-CIABBTA. In the UV-we spectra AR SC = ARBIA > AR-SCH (detailed results not shown here), an in ication ofthe degree of oxidation and corrosion of copper substrate. In brief, AR-SCB coating exhibited high corrosion protection for copper due to the controlled release of inhibitor from S10;-CTAB-BTA nano containers in comparison to control samples. To further investigate the celthealing and corresion protection properties of SiO;-CTAB-BTA nanocontainers doped coating, local, ‘corfesion current measurements were carried out uring the seanning vibrating electrode technique (SVET). The coreosion processes over the metal surface eause anodie and eathodie ionic currents, which generate potential differences in the electrolyte solution. Using SVE, these po tential diferences can be detected by scanning vibrating electrode and then be transformed into the local current densities on the metal si face. A scratch with a length of 1.0 mm was introduced in AR coatings, in order to accelerate the corrosion processes. Fg. 10 shows the current density mape and variation curves of maximum current densities during {immersion in 0.10 mol L~" NaCl solutions for different coating systems Significant diferences in miero-area corrosion eurrent densities were ‘observed among the four kinds of coatings. Since cathodie current ‘densities are always much smaller than anodie current éensities [98], we ploted the changes of maximum anodie curent densities as func tions of immersion time (Pig. 10, right). After immersion for 4b, high Anodic current peaks for the AR and AR-SC coatings appeared at the center of the scratched regions, reaching 787 and 25.64iAcm™* ft, Hig. 10a and b), respectively. After immersion for 10h, the anodic ccarrents became higher with prolonged immersion time (middle, ig. 10a and b). Conversely, after immersion for 4h, anodic current Desks of AR-ETA and AR-SCE were both less than 10jAem”” (left, Fig. L0e and d), which were almost negligible when compared withthe ‘wo former control samples without BTA. However, the anodic eurent (of AR-BTA increased to 147 yAcm? after immersion for 10h (mile, Fig. 10e) while the value of anodie current pesk of AR-SCR was lower than 20 nA.m™# after further immersion in 0.10 moll." NaCI (middle, Fig. 104), The maximum anodic eurent densities as functions of ime rmersion time (eight, Tig. 10) clearly showed the persistent corrosion inhibition effect of Si0,-CTABTA nanocontainers-Joaded coatings. ‘A schematic representation of the self-healing mechanism i pre- sented in Fig. 11. Once corrosion is triggered by permeation of corre sive meéia along defects, many corrosive miero-anodic or eathodic re gions are generated over the metal surface (middle, Fg. 11). In the ‘mean time, corrosion reactions generally cause localized pH increase rear cathodes due tothe reduction of oxidants (eg. Oy 1 2H,0 + 4e = 40H") while pH decease near anodes via the hydrolysis of corrosion products (e4. Cu" + H,0 = CuOH +H", Cu? + 21,0 = uOrD, ‘+ 24"). Particlaty, areas with significanily low pl (2.5~ 4) near the anodic sites of corroded copper are formed [99]. This concept can be confirmed by calculations based on precipitation and acli-base eauill- bria similar with the classical literature (100). Considering the Ky value of CuOH (1.0 x 10"), the corresponding maximum values of Hin the anodic area are ~ 1.0 and 40, when [Cu"} = 0.1 and 0.0001 soll", respectively. In the case of Cu(OH),, pH values are predicted to be 47 and 6.5, when [Cu®*] = 0.1 and 0.0001 moll.~', respec- tively. In the latter eizeumstance, K, value of 2.2 x 10 was used in the calculation. Therefore pHi value at anodic sites during copper cor- sion was acide, approximately lower than 4.0, sshich matched with the pl sensitivity of SiO-CTABBIA (the release of BTA), When st mulated by acidification near miro anodic regions, the inhibitor was released from H” ionesponsive Si0;-CTAB-BTA nanocontaners near active corrosion sites, The released inhibitor formed compact chelates ‘vith metal ions that covered the metal surface and stopped the corro- sive processes (ight, ig. 10), 4. Conclusion In this work, a novel one-step preparation of BTA-Joaded SiOz me- soporous nanocontainess was developed and utlized for ative corro- sion protection of metals. Using this simple method, containers of in- Inbitors are easily incorporated at nanoscales and the whole preparation proces i fee of organic solvents. The release of BTA in- hnbitor in nanocontainers is responsive to pH, tha is, inhibitor releases ‘along with the dissolution of CTAB micelles in acid condition. Such a p-zesponsive release property makes S10,-CIAB-BTA nanocontainers suitable fr incorporation into coating for corrosion protection, because ff its on-demand release induced by metal corrosion reactions. In conclusion, ths work presents & new onestep approach for preparing ‘nhibitorleaded nanocontainers. It ean he extended to various ine Inbitors and templates which display diferent stimulation-rexponse properties, This simple and efficent method may lead to the generation ‘of new inbibitor-loaded nanocontaness that can be applied in diverse selthealing coatings Acknowledgements ‘This work was supported by National Key R&D Program of China (2017¥F1200800) and National Natural Science Foundation of China (No. 51371159 and 51671174) and Natural Science Foundation of ‘Zhejang Province (1276010001), References 1H) 80s UX ta 6 aD Zhang, Me Zheng WX, DL Fa The ot tay Nh Vocvdin Wi tetas WS Son Fs Arad ES. 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