8128 eM SP Re SBT eH Vol. 12.No, 4 1992 $5 12 8 JOURNAL OF CHINESE SOCIETY OF CORROSION AND PROTECTION __Decenber 1992 FA XPS,FT-IR & Raman #2 OR ATMP-Fe 8 49h BRL F BP ety ELL? RRAX) °C LE BEY * zg SRA XPS FT-IR, Bk Raman Je MBER T eR I= HAG (ATP) AE ee TE A He TUBE. ASR OE ATMP Ze RTE FE TAT MIT OO ee Ae DRE RET AB (FY SE A A «A 7 Ae 8 AUR HCH CAC. 6992048. AK LP 28. 696 sFe 7.0% 3N 4.3% C11. 7%, ey AHEMR SEN ALTE AH Me WC FeCATMP),], -— hh of PE SF BAR KS EE FRE RE i LD Tg T FLFR — PAAR EAR" TALS ES SE — A EE A OS ROTH Jae TET PA Ab HE Pr AEF UA A. ELAM He SA XPS A AES HEFT A DUR ARE Ti LIE A EO AL A LER, LE RATMP UF RRM MP HL seat LE A XPSPT-IR B Raman Je HEE ATMP Ze eRe TL TIE AL AS eT A HE TRU =. RAR 1 RBS FA 10X10 2mm BY A3 SA AACBR IT » 26 7K BD CER AGH RM FE A ACT BR RS PLY TCL BAe Ae TET LAE A GM BRAN BAAS Le ET AO. BC a RAR ET MR. 2. POE TRIR IS SER REIL? = BEM TP HG ADEE A ER pI 3 ONC) AAC HL SO Bk REE. C2) Ai Fad AE ak PB A nA 4 0. Sem*) , FL ih OK SA SA BA i SEAR LL BG EA] OPED BBE HATA AL aT NRE A A RRR sO S AHO | 9A RC4M FL XPS FT-IR J Raman JGHPFFL ATMP-Fe FRE 4008 309 TSR TR ERIE 3 BF REST FACS2 ]PHI-550 HAF ABI MHEFT XPS SPT. A Al K.(1486. GeV EWM. XPS HEH TAAL Sh BEE BT FASE A 1 000V Fl S0eV, 5) HT EAE Hy 10-7 Pa, Art RAREST BM dV Ml 15mA, MARY 5X Smm, iA HEAD Cis (284. SV BEAT RM AEH LO. 1eV, 4A AE SEH BERET SP SEI D T FUCS¢]NICOLET 170SX FT-IR LiKE. BEATE: HER dem" TM 100 Ks BRAY INE SRR dem? URE 50 IK. 5. BIE Raman His} a FACS ISPEX1403 $434 Raman Jt ith {X UE » PEK 5145 cm™', Dae 0. 3W A AARSE 300um, = BRSitit 1, FRE A kB PE iMG AY CrP OLR LE TS ‘Structural formulas of tested organic phosphonic acids Taro ATMP CREED NOGLPOM, CH;PO.H: aa 1-BRZR ‘HEDP — H,0;P—C—PO,H; (4 vm) 1 on # GU POs, NN) -SRR i DMPG (Samzace) HOOC—CH,-N ‘CHPOH, _ H,O,P—CH, CH;PO;Hy EDIMP (*ahe SNe ot cH WN” H.0,p-cHy” ‘CH,POH, m exnr (:2BBzE) wor dsos, (CH, POH: FER TE 45°C .1. Omol/L 8 OLB PALS 20min, GEE RRA310 PER RS he HE 128 LEN RUD DAR LR 2, Table 2 The results of accelerating corrosion test ‘Salt watet Point test Indoor Treatment dipping exposure (ay) (second) (aay) Blank 0. 8(D)* 2 2D) 41, Omol/L. ATMP* 15(A) 240 30¢A) 1. Omol/L HEDP* 15(¢) 20 30(D) 1. Omol/L DMPG* 15). 30 30a) 1. Omol/L EDTMP* 15(€) 30 30(D) 1. Omol/L EEDP* 15(B) 80 30~D) “A= Slighly discolored 1B Moderately discolored. lustre decreased obviously (C— Severely discolored. darkened, corrosion point seattredD— Corraded completly 85S 2 WPA A, Ze AT MP BUS TE WL 9 TS HE CR, KE MPG, 3K BRSMRF LME—CHPOM, HE ARAM TAK. 2.XPS B AES $4RSR RR TE REA Bi a AS BLE ATMP ei LA EH XPS HLA 1, HYPE 1 BS BLA BRR ROR TEE. Ar MUNA RY XPS i GBR 1000 $60 &07 700 G00 500 400 300 200 100 0 700 600 500 400 700 600 500 400 Binding energy (eV) Binding energy(eV) Fig. | Survey X-ray photoelectron spectra Fig. 2. XPS spectra of Fe-ATMP surface film of the Fe-ATMP surface film. sputtered for different time. (a) before sputtering (b) sputtering for 20 min FE 2228 Art RAS 20min Ja ATMP $4 HT NAP TRIGA WK RRR,i) JA XPS. FT-IR J Raman BES, ATMP-Fe BE A 49 311 RRL a EL 3, HE PH 3 BY ROR RY Fe O\NP.C HAIER EF BL PE Pe A, PE TAT TARE AG Ny ok EE A Re RIG RTL. AS REY Omin RRA TRF BE FEF RE MH iin GETRKHARE BRS. RIL 8~ min FMB ERS SSF L(A Ae 7 TR 9 ALR Ae 3 AR SS AY CR MS [PeCATMP) 2 JBC Bat SRF AD STH. Table 3. XPS quantitative analysis of the [Fe(ATMP),] and ATMP surface film on the iron Content of composition element (A.C. %) Specimen ° P Fe N c [Fe(ATMP)] 40.8 26.3 15.8 4.0 10.2 [FecaTMP>] 44.3 28.6 8.6 43 11.0 ATMP Surf. Film 48.4 28.6 7.0 43 4.7 ‘on Iron FEDEICATA DH TL FAY ALARA EY . BEAT BLE DH = 0. 23 wy BRAY FN HEE DH EYRCR BCE TRE RE. CT) AEE pH FEES ATMP Hh — OT PERO RE IE RAY JE AX fr A [Fe (ATMP) 2 FE SFE F ARTE DA BE A BE ACHE Hit 9% hh MERE Ne [Fe(ATMP)2]*. ° (DRT ATMP AMAA: EMRE P PART AANA OBR ECS ARRG FUE RM AMO NEI iT PM < Shee Fla Sat we SAH. | = Be. A3 AK ATMP 3 ia ATMP HA) NRF Al O IRF AEE FS Fett 0 204.6 8 10 12 14 16 48 BY So SPE RAC eR. Hy TT RR Sporting time min) RMET FOR ALAR MVEA 2G TIE 3 AES composition depth profile of the RRA surface film. Hh ae 4 TY LAE a Bh a ARS Pe 2p" A924 Erik tb FeSO, f+ Fe2p’*48 2 AE BENE T 1. 7eV, TG Os Nis AEH ATMP HAY O.sFl NisdP BUHL T 0. eV Ail 0. 7eV, AVE BA BETH Fe*+ 45 ATMP Hit OLN f)W8 Ste TBC EL. Fe 2 Ef ME EAN OLN 25-4 FEF 08 DR JE ATMP Ff By O AD 5 FEF Ze BBY Ht I] Fe? $6 , Fe? 09 ft HF Zs Me BES Son SPB Se EE A TCA Jat) OF0N GFA EME, CA 1S REESE MR WBA MET. Hee mS Fea Fe, (ATMP) JRC A 2A EAB AT A AS RTO BUTE T RG ATMP RES 99 ft.312 ilk elak aeaid 12 Table 4 Bonding energy of the elements concerned on the ATMP-Fe coordination compounds and ATMP surface film , Feaptt Os Nu ATMP-Fe before spat. 712.10 531.2 401.6 fim spat, for 20min 710.4 531.8 401.9 TRATED" 02 531.2 401.9 710.8 51.7 401.8 CrecaTM) 712.8 531.9 402.2 (ResATMP)* 710.8 532.0 402.3 [Pey(ATMP) ]* 712.0 ~ yo F280, - 531.2 401.2 ‘ATM “Synthetic solid coordination compounds according to different mole ratio. 3280 969 99007 160! roa? 400 4000 500 3200 240012999 12000” 400 (a3 ATMP ‘Wave number /em (b) Surface: Fig. 4 Refeiction IR spectra of ATMP and surface film formed in |. Omol/L ATMP solution. 3. ESCH SEHRAT Sh iE BT BAG AR RY HA SL RTM BGT T NL NAR IE 5 ono 1440 AUoRME ATMP PEAY IR SEE TT RRL A a ATMP 481 AP CE SCA A TERR RE PRR HB von 1145em~" iz B Hl 1105em~"; Yeo HH 1002cm~"#$B] 976em—", HEAL AEA ARN RFA OF OI Fede Ht HAF CN BAL P-O BRIE] AY HL ZEBRA EAL EAR I BE Fig.5 Raman spectra of specimens. (a) AB steel (b) Surface film (@)ATMP 100 300 600 700 900 1100 1800 1500 1700 1900 2100 Raman shift/em1% FA XPS,PT-IR 3 Raman ENDER, ATMP-Fe FE 245 BE 313 BRR TN AO MF STAAL ATMP fh HEH GEMM HM : 7990m™! (ypc) »1432em~" (cw) + 1232cm~* Cypo) SFE BR LAB A LS (LF i FA EG A CE He RH 4. BCH Rit AB SCH ATMP th FEDA 2 22 TH RAY Raman SET 5. ee PET LB ATMP Shit ay AS HAC TE 715em™', 765em™!, 1440em~" hb 5-3] HH BLT $82 0H SB 9 He Bh BC AFG ATMP fy SHERI RAL— HCO, (ABI AE 101 0cm™ Yh AT RU EH ATMP ZE 965em™" Cye—on) 2 BA TE 20cm! Wh 9 RUN i A AB BS TY AE AR Hy Ae PIE RT Pe-O-P BR fA Da AY RRA TRB. Hb 96Sem™'P-OH MEE ATMP H7R BK TEPER HA A SS BS 2B BH} OW BY Fe RG(iL. RAZE 390em™ ‘ab Hy BLAS RU 5 SARC STR N Fe-N BRISA. A LE RY Fe! 5 ATMP ERT RMAC. Oe 1. 45 HEDP .DMPG ,EDTMP, EEDP 9% 4 SLIM AR AH EL» ATMP Aj SRF M5 FE wt Be OT Ob a HE HBR. 2. FL XPS 28 Art PSE ALE A Ae TY AAR RAT 20min JEP NAP TORO EVR RRS. 3. XPS WN APART NP GS2R ab Le ATMP tPA SE RE Fe ANSE A ABEL FeSO. 489 MG. A Ra- man Hii BEF ARETE Fe-N GRA] ATMP BARRE RT A. 4. SA RAY 7G Aw AOL HL SE DO AY AD a AG Pe CATMP) 2) FB PD IE HEDRT ARR OT fk i Le (ATP): ei LG. eskm (2) Michel,D. , Corrasion, 37(5),262(1989) (2) Eur. Pat. . 10.486 (3) UL S. Pat. 4,276,089. 4,409,121,4.717,541 CD) WAL, BMHAEL. (7). 42201980) (5) Fang Jingli. Wu Naijun, Wang Zhanwen,Li Ying, Corrosion, 47(3).169(1991) 527% »7(2). 9(1990) (8) Pang Jingli, Cai Zi, Plat. & Surf. Finist. , 77(2),58(1988) (7) Fang Jingli, Wu Naijun, Plat. & Surf, Finist. .77(2).54(1990) 8) WRAL ROPE RMR. (4), 121991) (9) F. R. G. Standard Din 50,942(1970) (10) Weber. J. Prace Inst. Mech. Precyg. «16, 191956) CLI Reywennos B. Th 5 Casuponay A. A. 9K. TIX.» 19,2119(1988) (2}Canter, Re PL, Inorg. Chem. <6, 393967) (iSISmith. T. D. J. Inorg. Nucl Chem.» 8,150(1953) (1d) Moedritzer. K. . Syn. Inorg. Metal-Org. Chem. ,2(4), 137(1972) (1S}Goggin. P. Li. Woodwand, L. A. , Trans Faraday Soc. $8,1495(1962)314 BB BG 8S eH 12 XPS, FT-IR AND RAMAN SPECTRUM STUDIES OF ATMP-Fe COORDINATION COMPOUND FILM Fang Jinli} , Li Ying, Ye Xiangrong!and Wang Zhanwen® 1 (Nanjing University) * (Nanjing Institute of Chemical Technology ) Abstract The protective surface film formed of carbon steel after a treatment in 1. 0 mol/L amino-trimethylidenephosphonic acid (ATMP) solution was analysed by XPS, FT-IR and Raman spectrometer. The restlts showed that an anticorrosive coordination compound film was formed on the steel surface. By Ar~ sputtering, the composition depth profile of the film was determind. The relative atomic percent contents (A. C. %) of the film, as obtained from the element composition constant region of the profile curves, were 48.4% Os 28.6% Ps 7.0% Fey 4.3% Ny 11.7% C. The structure of the coordina- tion compound film was deducted from the above results, as probably [Fe(ATMP)2}.