Tiiu ban Khoa hoc vdi lieu

ISBN: 978-604-91.

TONG HOfP PHU GIA iTC CHE AN MON TREN CO SO HYDROXIT LOP KEP
To Thi Xuan HJng. Nguyen Thiiy Duong, Trjnh Anh True Viin Ky thudt nhiit ddt 18 - Hoang Qudc Viet Ciu Giay, Ha Ndi Email: hang'gvnd.vast.ac.vn Tom tat: Hydroxit lap kep mang ire ehi dn mdn 2-benzolhiazolyl-siieeinie axit (LDHBTSA) dugc tdng hgp bdng phuang phdp ddng kit lua. LDH-BTSA chi tgo dugc phdn tieh bdng phd hdng ngggi vd kinh hiin vi diin lir quel. Hdm lugng BTSA trgng LDH-BTSA dirge xdc dinh bdng phd UV-VIS. Sir gicd phdng BTSA lu LDHBTSA trong dung dich NaCl 3%, Na2S04 i % va hdn hgp cdn/mtdc dugc nghien citu. Kit qud thu dugc cho thdy hdm lugng BTSA Irong LDH-BTSA Id 32,2%. Su giai phdng BTSA tir LDH-BTSA phu thude vgg logi anion trong dung dich, li li BTSA gidi phdng ra vdi sir cd mdt eug cinign S04'' cao han vdi sir cd mdt cita anion CT. Abstract: In this paper layered double hydroxide intercalated with corrosion inhibitor 2benzothiazolyl-succinic acid (LDH-BTSA) was prepared using the coprecipitation method. The LDH-BTSA obtained was chargcterized by infrgred spectroscopy and scanning electronic microscopy. The BTSA loading in the LDHBTSA M>as determined by UV-VIS spectroscopy. The release of BTSA from LDHBTSA in NaCl 3%, Na2S04 3% solution and in the mixture of ethanol and water was investigated. The results obtained show that the BTSA M'as intercalated in the layered double hydroxide and Us loading in LDH-BTSA was 32.2%. The release of BTSA from LDH-BTSA depends on the type of electrolyte and the release of BTSA in the presence of anion SO4'' is higher than in the presence of anion Ci.

MO DAU Ldp phii bao ve hiru ca ddng vai trd quan trpng trong bao ve chdng an mdn cac cdng trinh kim loai. Cromat la pigment cd hieu qua bao ve cao, nhung rat ddc hai, vi vay cd nhieu cdng trinh nghien cim cac chat ire che an mdn khdng dpc thay the cromat. Mpt trong cac hudng nghien cim dugc quan tam la che tao cac piment ire che an mdn tren ca sd cac hydroxit ldp kep. Ung dung ciia hydroxit ldp kep dua tren kha nang hap thu va kha nang trao ddi anion, tinh linh dpng ciia cac anion giira cac ldp. Cac hydroxit ldp kep chira decavanadat, molybdat da dugc nghien cim irng dung trong ldp phu bao ve chdng an mdn cho hgp kim nhdm [1-4]. Tuy nhien ldp phii chu'a hydroxit ldp kep Al-Zn-decavanadat van chua cd kha nang bao ve tuong duang ldp phii chira cromat. Ben canh dd cac ldp phu chiia hydroxit ldp kep mang cac anion hiru ca nhu benzotriazolat etyl xanthat va oxalat cung dirge nghien ciru [5]. Ket qua cho thay hieu suat ire che phu thupc \'ao cau true ciia anion hiru ca va hieu suit ire cbl tang theo thii tu sau: ethyl xanthat "^ oxalat< benzotriazolat, trong do dac biet benzotriazolat cd tuong tac vdi be mat hgp kim nhdm. Trong cac cdng trinh da nghien ciru trudc day. chiing tdi da nghien ciru irng diing ire che an mdn gdc benzothiazol trong mani:i san lot bao \'e chong an mdn cho thep, cac chat ire che an mdn nay cho mang san cd hieu qu . bao ve cao [6, 7]. 244

Hoi nghi Khoa hoc ky niem 35 ndm Viin KH&CNVN - Hd Noi -10/2010

Trong cdng trinh nay chiing tdi nghien ciiu tdng hgp phu gia mang ire che an mdn tren ca sd hydroxit ldp kep va nghien ciiu sir giai phdng lic che an mdn trong cac mdi tardng khac nhau. Hydroxit ldp kep dugc tdng hgp bang phuong phap tn^c tiep, cau true \'a tinli chat cua hydrotalcit biln tinh dugc phan tich bang phd hdng ngoai, phd tir ngoai-kha kiln (UV-VIS) va kinh hien vi dien tir quet. THUC NGHIEM + Nguyen lieu Mg(N03)2.6H20 su dung loai Merck A1(N03)3.9H20 sir dung loai Merck LTC ehl an mdn, 2-benzothiazolyl-succinic axit (BTSA) do hang Ciba cung cap cd cdng thiic nhu sau: / \ . ^ ^ . ^ N x.^
S-CH-CH2-COOH COOH

+ Tong hop hydroxit lop kep mang lie che an mon Hydroxit ldp kep nitrat magie-nhdm chira BTSA (LDH-BTSA) dugc tdng hgp bang phuang phap ddng ket tiia trong mdi trudng nita de loai bd CO2 cd the dan den chen cacbonat vao hydroxit ldp kep. Dung dich chira 0,125 niol Mg(N03)2.6H20 va 0,0625 moi A1(N03)3.9H20 trong 125 ml nude da loai bd khi CO2 dugc nhd dan dan vao dung dich chira 0,313 moi BTSA va 0,313 moi NaOH trong 145 ml nude cat. Dung dich giir d pH=8-10 bang each bd sung dung dich NaOH 1 M. Phan iing dugc giir d 65 C trong 24 gid, sau dd Ipc va rira nhieu lan bang hdn hgp cdn/nudc cat va say d 50 C trong chan khdng. + Xac djnh ham luong ire che an mon trong LDH-BTSA Can 0,0316 gam LDH-BTSA cho vao binh dinh miic 25 ml ciing vdi 2 ml FINO3 IM , sau 1 gid cho them etanol den vach dinh mirc 25ml. Khuay dung dich trong 24 gid, sau dd dung dich dugc do phd UV-VIS. Ndng dp BTSA dupe xac dinh va tinh ham lugng BTSA trong mau LDH-BTSA. + Xac djnh ham luong uc che an mon giai phong vao moi truong xam thuc Sir giai phdng lic che an mdn tir LDH-BTSA dugc xac dinh trong 3 mdi trudng: hdn hgp cdh/nudc (20/80), dung dich NaCl 3% va dung dich Na2S04 3%) pha trong hdn hgp cdn/nudc (20/80). Can 0,05 g LDH-BTSA cho vao 250ml hon hgp cdn/nudc (20/80) hay dung dich NaCl 3% hay dung dich Na2S04 3% pha trong hdn hgp cdn/nudc (20/80). Dung djch dugc khuay va mau dugc lay ra, Ipc va do phd UV-VIS theo thdi gian. + Phuong phap pho hong ngoai Cau true cua hydroxit ldp kep dugc phan tich bang phd hdng ngoai tren may Nicolet Nexus 670 d viing budc sdng tir 4000 cm"' den 400 cm"' cua Vien Ky thuat nhiet ddi. Hydroxit ldp kep dugc do d dang ep vien vdi KBr. + Phuong phap pho tir ngoai-kha kien Phd tir ngoai-kha kiln (UV-VIS) dugc do tren may CINTRA 40, GBC (My) tai Vien Ky thuat nhiet ddi. + Phuong phap kinh hien vi dien tu quet 245

Tiiu ban Khoa hoc vdt lieu

ISBN: 978-604-'-) 13-0 11-3

Cau tnic cua cac hat hydroxit ldp kep dugc phan tich bang kinh hien vi dien tu quet (SEM) tren may HITACHI S4800 tai Vien Khoa hpc Vat lieu, Vien Khoa hpc va Cdng nghe Viet Nam. KET QUA VA THAO LUAN Hydroxit ldp kep mang ire cbl an mdn BTSA (LDH-BTSA) dugc tdng hpp bang phuong phap true tilp. Ciu true ciia LDH-BTSA dugc phan tich bang phd hdng ngoai. phd nhieu xa tia X va kinh biln vi dien tir quet (SEM). Ham lugng ire che trong LDH-BTSA dugc xac dinh bang phd UV-VIS. + Phd hdng ngoai Phd hdng ngoai ciia hydroxit ldp kep (LDH). lie cbl an mdn 2-benzothiazolyl-succinic axit (BTSA) va hydroxit ldp kep chira BTSA (LDH-BTSA) dugc trinh bay tren hinh 1. Phd hdng ngoai ciia LDH cd cac pic dac trung tai 1383 cm"' va 3441 cm"' tirong ung vdi lien ket cua -NO3, -OH. Vdi phd hdng ngoai ciia BTSA ta thay cd cac pic dac trung cho nhdm COOH tai 1721cm"' va pic 1402 cm" dac trung cho lien ket ddi C=C. Phd hdng ngoai ciia LDH-BTSA cd cac pic dac trung cho LDH tai 1376 cm" va 3431 cm"'. Ben canh dd ta thay xuat hien pic tai 1586 cm"', dac trung cho nhdm -COO". Cac ket qua tren cho thay BTSA da dugc chen vao trong hydroxit ldp kep va trong cau true cua LDHBTSA, BTSA d dang carboxylat.

2500

2000

S6 song (cm')

ITmh 1: Phd hdng ngogi cua LDH (a), BTSA (b) vd LDH- BTSA (c) + Kinh hien vi diin tir quet Hinh thai hpc ciia LDH va LDH-BTSA dugc quan sat bing kinh hien vi dien tu quet. Hinh 2 trinh bay anh kinh hien vi dien tir quet ciia LDH va LDH-BTSA. Anh kinh hiin vi dien tir quet cho thay LDH cd ciu tnic tinh thi, dang tim. Kich tbudc ciia cac tinh thi LDH nhd. cd micromet LDH-BTSA cd ciu true la, khdng cd ciu true tinh thi. Dilu nay cd thi dugc giai thich do cd sir chen va bam ciia BTSA vao LDH.

Hinh 2: Anh kinh hien vi diin tu quel cua LDH (a) vd LDH-BTSA (b) 246

Hoi nghi Khoa hoc ky niim 35 ndm Viin KH&CNVN - Hd Noi -10 2010

+ Xdc dinh hdm hrgng BTSA trong LDH-BTSA Flam lupng BTSA trong LDH-BTSA dugc xac dinh bang phuong phap UV-VIS. Trudc het dudng chuan bilu dien sir phu thupc ciia ndng dp BTSA va cudng dp hip thu tai budc sdng 282.5 nm ciia phd UV-VIS dugc xac dinh: C = 0,8518.A (trong dd C la ndng dp BTSA vdi don vi la 10 M. A la cudng dp hap thu tai budc sdng 282,5 nm). Ham luang BTSA trong LDH-BTSA xac dinh dugc la 33,2%. + Sir gidi phdng ire che dn mon tir hydroxit lap kep Dd thi bieu dien ti le BTSA dugc giai phdng tir LDH-BTSA \'ao dung dich con'nudc, dung dich con'nudc chira 3 % NaCl va dung dich cdn/nudc chiia 3 % Na2S04 theo thdi gian dugc trinh bay tren hinli 3. Hinh 4 trinh bay anh hudng ciia ndng dp dung dich din sir giai phdng BTSA.
S^ 100 100

jz

10

20

30

40

50

60

70

80

2 N6ng do dung dich (%)

Thai gian ngam (gib")

Hinh 3: Su giai phdng BTSA lir LDH-BTSA vdo ITmh 4: Anh hudng cua ndng do dung dich dung dich Na2S04 3%. NaCl 3% vd hdn hgp din sir giai phdng BTSA tu LDH-BTSA vdo cdn nude theg ihdi gian dung dich Na2S04 vd NaCl Quan sat do thi tren hinh 3 ta thiy, khi ngam LDH-BTSA trong dung dich NaCl thi BTSA dupe giai phdng ra tir LDH-BTSA rit nhanh trong khoang thdi gian 8 gid diu tien. sau dd BTSA dupe giai phdng ra cham. Trong dung dich Na2S04 3% lugng BTSA dugc giai phdng ra cao hon lugng BTSA giai phdng ra trong dung dich NaCl 3 %. So vdi dung dich NaCl 3% va dung dich Na2S04 3%, ti le BTSA giai phdng tir LDH-BTSA trong dung djcb cdn/nudc thap ban rat nhilu. Sau 72 gid ngam, lugng BTSA dugc giai phdng ra tir LDHBTSA la 81.3% trong dung djch Na2S04 3%. la 61,2% trong dung dich NaCl 3%. trong khi lugng BTSA dugc giai phdng ra tir LDH-BTSA la 19.7% trong hon hgp cdn/nudc. Cac kit qua cho thay lugng BTSA dugc giai phdng cao khi cd mat anion S04-", Cl". Dilu nay cd thi dugc giai thich bdi sir tham gia ciia anion 504"" va Cl" vao phan iing trao ddi anion vdi anion cacboxylat chen trong LDH. Ti le BTSA giai phdng ra cao ban khi cd mat anion SO4-" cd thi dugc giai thich do kich tbudc anion SO4-" Idn han anion Cl". Cac kit qua tren da khang dinh sir nha ire che BTSA tir LDH-BTSA khi cd mat ion S04-" va Cl", dilu nav md ra triln vong ung dung h)droxit ldp kep bien tinh LDH-BTSA lam phu gia ire chi an mdn trong ldp phu bao ve. Dd thi tren hinh 4 cho thiy vdi ca 2 dung dich Na2S04 va dung dich NaCl d ndna do 1%, ti le BTSA giai phdng ra tuong ddi cao (53,3% vdi NaCl va 68^6% vdi Na.S04), U le BTSA giai phong ra tang khi ndng dp dung dich tang tir 1 % len 3%

247

Tieu ban Khoa hgc vdt lieu

ISBN: 978-604-913-t'

KET LUAN Da nghien ciiu tdng hgp hydroxit ldp kep mang lie che an mdn BTSA. Ket qua phan tich cho thay BTSA da chen vao hydroxit ldp kep, ham lupng BTSA chen vao la 33.2%. Da nghien cim kha nang giai phdng lic che an mdn ciia LDH-BTSA trong dung dich NaCl 3%, Na2S04 3% va trong hdn hgp cdn/nudc Kit qua thu dugc cho thiy lupng BTSA giai phdng ra phu thupc vao loai anion va ndng dp ciia anion trong dung dich. Trong ba loai dung dich khao sat, lugng BTSA giai phdng ra cao nhit trong dung dich Na2S04. ti le BTSA giai phdng ra tang khi nong dp dung djch tang. Sau 72 gid ngam, lupng BTSA dupe giai phdng ra tir LDHBTSA la 81,3%, 61,2% va 19,7% trong cac dung dich tuong img Na2S04 3%. NaCl 3% va hon hgp con/nude Cac kit qua nghien cuu md ra triln vpng iing dung hydroxit ldp kep mang BTSA lam phu gia ire che an mdn trong ldp phu bao ve. Loi cam on: Cdng trinh dugc hoan thanh vdi sir tai trg cua Quy phat trien khoa hpc va cdng nghe qudc gia (dl tai ma so 104.01.47.09).

TAI LIEU THAM KHAO 1. G. Williams and H.N. McMurray, Anion-Exchange Inhibition of Filiform Corrosion on Organic Coated AA2024-T3 Aluminum Alloy by Hydrotalcite-Like Pigments,Electrochemical and Solid-State Letters, 6 (2003), B9-B11. 2. H.N. McMurray and G. Williams, Inhibition of Filiform Corrosion on OrganicCoated Aluminum Alloy by Hydrotalcite-Like Anion-Exchange Pigments, Corrosion, 60(2004), 219. 3. S. Chrisanti, K.A. Ralston, R.C. Buchheit. Corrosion protection from inhibitors and inhibitor combinations delivred by synthetic ion exchange compound pigments in organic coatings. Corrosion science and Technology. Vol. 7, No. 4 (2008), P. 212218. 4. B. Chico. J. Simancas, J.M. Vega, N. Granizo, I. D'laz, D. de la Fuente, M. Morcillo. Anticorrosive behaviour of alkyd paints formulated with ion-exchange pigments. Progress in Organic Coatings 61 (2008), 283-290. 5. Geraint Williams and H. Neil McMurray. Inhibition of Filiform Corrosion on Polymer Coated AA2024-T3 by Hydrotalcite-Like Pigments Incorporating Organic Anions. Electrochem, Solid-State Lett., Volume 7, Issue 5, (2004) B13-B15. 6. Trinh Anh True, Td Xuan Hing, Vu K I Oanh , Nguyen Tuin Dung, Biii Thi An. Nghien cim sir dung ire che an mdn gdc benzothiazol trong son Idt, Tap chi khoa hpc va cdng nghe, T36, No 5 (1998), 36-40. 7. Trinh Anh Tmc, To Xuan Hang, Vu Ke Oanh, Nguyen Tuan Dung. Improvement of Protective Properties of Top Coatings Applied on Zinc-Rich Primer by 3Aminopropyl-Triethoxysilan and 2-(Benzothialylthio) Succinic Acid, Corrosion Science and Technology, V.3, N.3 (2004), 107-111. 8. Calistor Nyambo, Dan Chen, Shengpei Su, Charies A. Wilkie. Variation of benzyl anions in MgAl-layered double hydroxides: Fire and thermal properties in PMMA, Polymer Degradation and Stability, Vol. 94, 4 (2009) 496-505.

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