TAP CHi HOA HOC TAP 49(1), 79-83 THANG 2 NAM 2011
CONG NGHE MA XOA VOI NANO COMPOZIT Ni-TIOz, SiC
D^o Khanh Du, Nguyin Duy Ket, Nguyen Diic Hiing Viin Hda hpc - Vdt Hiu, Viin Khoa hpc Ky thudt Qudn su
Din Tda soan 31-5-2010
Abstract
The bmsh electroplating not only recovers defective areas of machine parts caused by abrasion but also improves the quality of plating surfaces better by using this composite plating solution with inert and rigid particles, especially the nanoparticles such as TiO:, SiC. The purpose of this article was to determine the solution compositions Ni-Ti02, Ni-SiC plating in order to enhance the efficiency and the physico-mechanical properties of plating layers. Results showed that using of solution NiCb, NH4CI, (NH4)3C6H507 with nanoparticle Ti02 (5.5 g/I), SiC (4.2 g/I) the plating rate can be increased to 100 mA/dm^ and the efficiency as well as the physico-mechanical properties of plating layers was improved.
I.MCJDAU
Cdc chi tilt mdy boat ddng thudng xuyin se bj hao mdn do ma sat [1] ldm gidm do chinh xdc vd chat lugng ciia thilt bj ciing nhu sdn phdm do thilt bj tao ra. Vi vdy din gidi ban hao mdn nhdt djnh se phdi thay thi hoac sira chiia phuc hdi nham gidm chi phi. So vdi cdc ky thudt phuc hdi chi tilt bj mai mdn bang cdng nghe co nhilt nhu hdn dap, phun phu,...
cong nghe ma diln hda, dac bilt cdng nghe ma
"khong phai su dyng b i ma" [2] cdn dugc ggi Id "ma xoa" [3] cd nhiiu lgi thi vi ddu tu, tiit kilm thdi gian thdo gid, khdng cdn van chuyin din xudng ma.
Vi vdy ma phuc hdi chi tiit mdy hu hdng bang cdc kim loai nhu ddng, niken, crdm da trd nin phd biln [3 - 5]. Dl tang tinh chdt ca ly cua ldp ma phyc hdi, ma td hgp vdi cdc hat tro, ciing, dac bilt cdc hat cd kich thudc nano nhu Si02 [6], Tib2 [7], AI2O3 [8]
cacbon graphit [9] hoac SiC [10] dang dugc nghiln ciiu bang cdng nghe ma xoa. Nham triln khai vdo thyc tien cho cdng nghe chl tao mdy d Viet Nam, bai bdo trinh bdy khd nang tang tdc do ma xoa bang dung djch composit Ni-SiC.
2. PHUONG P H A P NGHIEN CUtJ
Cac hod chdt tinh khiit phdn tich (PA):
NiCl2.6H20, NH4CI, (NH4)3C6H507, su dung dk nghiln cuu dugc nhap tii Trung Qudc cdn hat Ti02, Sic vdi kich thudc trung binh 10 nm dugc nhdp tir Merk. Diln cyc andt tra Ti/Ru02 dugc chi tao tir hoa chdt RuCls cua hang Mecrk [11]. Thdnh phdn cua dung djch ma xoa dugc chgn Id:
NiCb.dHzO: 250 - 550 g/I, -NH4CI:80-550g/I, - (NH4)3C6H507: 30 - 80 g/I,
Ti02, SiC: 1 - 6% (trgng lugng).
Cdc phuomg phdp nghiln ciiu:
- Do dudng cong phdn cyc (DCPC) dugc thyc hiln trin mdy Auto Lab 30 ciia Hd Lan vd chup dnh hiin vi diln tir quit (SEM) trin mdy Jenon 66110 cua Nhdt Ban tai Vien Hda hgc - Vdt lieu.
Xdc djnh thanh phdn cdc chat ciia bl mat vat ma bdng phi EDX bang may IEOL-JSM-6490LV tai Vien Khoa hgc Cdng nghe Viet Nam.
Do Cling tl vi dugc xdc djnh trin mdy do do Cling hiin vi quang hgc HX 1000 cua Trung Qudc tai Vien Cdng nghe Tdng cue CNQP.
3. KET QUA VA T H A O LUAN
Anh hudng ciia ndng do cdc thdnh phdn dugc su dyng trong dung djch ma niken tdc do cao vdi cdc chat NiCl2, NH4CI, (NH4)3C6H507 dugc tiinh bdy tai hinh 1. Kit qud tir hinh 1 cho thdy, khi ndng do cdc thdnh phdn tiong dung djch ma tang diu thay ddi phdn cyc catdt Id co sd dk diiu khiln kha ndng ma.
Khi ndng do NiCl2 nhd (250 g/l) lugng chdt tao phiic: NH4CI va (NH4)3C6H507 du, cdc phiic cua niken bin vimg, khd phdng diln nin do phdn cyc ldn. Khi tang ndng do NiCl2 trong khodng 350 din 450 g/l tuomg ling vdi do bin ciia phiic tuomg ddi dn djnh, cdc dudng cong phdn cyc thay ddi it.
Khi tdng ndng do NiCl2 tdi 550 g/l chdt tao phiic bj thiiu, phiic ciia niken kim bin nin do phdn cyc gidm, vi vay niu ma d ndng do ndy Idp ma se thd.
Tir vj tri cdc DCPC cho thdy ndng do NiCl2 phu hgp ndm trong khodng 450 -H 500 g/l.
Trong dung djch ma da chgn, Ni^"^ nam d 2 dang phuc vdi amoni vd xitrat, tiong dd hang sd bin cua phiic niken vdi xitiat cao hom nin ty II cua chiing tiong
TCHH, T.49 (1), 2011 Cdng nghi mg xoa vdi...
dung djch cunp cao hom. Trong khodng ndng do NH4CI tii 45 den 90 g/l do lugng xitiat chua du tao phirc hit vdi Ni nin mgt phdn ion Ni ndm d tiang thai ty do, cd do phdn cyc nhd nin tang ndng dg NH4CI se tang lugng phirc cua niken vdi amoni vd tang phan cyc. Khi tiip tyc tang nong dg NH4CI den khi
todn bg ion Ni^^ da tao phiic hit thi se xdy ra su chuyin djch ndng dg phiic gitta niken tiong phiic xitiat bin hom sang niken frong phirc amoni kim ben lam gidm phdn cyc. Ndng dg NH4CI cdng cao cdng lam gidm phdn cyc nen nong dg amoni clorua hgp ly dugc chgn Id 120 g/l img vdi ndng dg NiCl2 Id 500 g/l.
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-0.08 -0,07 -0,06 -0,05 -0,04 -0,03 -0.02 -0.01 0.00 0,01
• NH.CI 49
— NH.CI to NH.C1110 NH<CIMO
-0,14 -012
-0,10 -0,08 -0,06 -004 -0.02 0.00 0.02
• C.H.7N.O, 20
C,H,rN.O7 40 / c.H.,N,o,ao .•
C,H„N,0,120 . '
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a. NH4CI: 120 g/l (NH4)3C6H507:
60 g/l
-0.5 -0.6 -0.7 -0.8 -0 9 -1.0 -1 1
E, V (SCE)
b. NiCb: 500 g/l (NH4)3C6H507: 60 g/l
-0 5 -0.6 -0.7 -0.8 -0 9 -1.0
E, V (SCE)
c. NiClz: 500 g/l NH4CI: 120 g/l Hinh 1: Anh hudng ciia ndng do: a. NiCb, b. NH4CI vd c. (NH4)3C6H507 din qud trinh catdt cua dudng cong phdn cyc vdi tdc do quel thi 10mV/s Khi giu nguyin ndng do: NH4CI = 120 g/l, NiCl2
= 500 g/l, nhdn thdy irng vdi ndng do amoni xitrat tang tir 20 din 120 g/l se Idm tang phdn cyc vdi miic do khdc nhau. Trong khodng ndng do tir 20 din 40 g/l tang ndng do amoni xitrat ldm chuyin ion niken tir tiang thdi ty do sang trang thdi phiic vdi xitrat cd do bin cao nin do tang phdn cyc cua cdc DCPC tang manh. Khi ndng do amdni xitrat ldn hom 40 g/l sy tang ndng do amoni xitrat chi ldm chuyin djch can bang giura hai phiic cua niken nin mac dii tang ndng do do phdn cyc chuyin dich rdt it.
Dung djch phiic cho phIp ma vdi mat do ddng khd cao, tdc do ma nhanh. Khi tang mat do ddng ma qud cao hieu sudt ddng diln giam (hinh 2a) vd chat lugng ldp ma se kim (hinh 2b). Kit qua tiln hinh 2 cho thdy dung djch nghien cuu cd mat do ddng ma cho phIp cao hom nhilu so vdi dung dich ma niken thdng thudng (gdp 7 ldn). Trong khodng mat do ddng tir 10 H-20 A/dm" hieu sudt ddng diln cao vd on djnh trin 80%. Khi mat do ddng cao hom 25 A/dm^
hieu sudt ddng diln gidm, chdt lugng ldp ma kem, ldp ma bj thd vd xdp.
cn
TT 1 2 3 4 5 6
DK, A/dm^
5 10 15 20 25 30
Chdt lugng ldp ma Mjn, md Mjn sdng Mjn sdng, ban bdng Mjn sdng, ban bdng
Mjn sang Thd
?n ^n 40
a
Hinh 2: Anh hudng ciia mat do ddng din hieu sudt ma bi (a ) va chdt lugng ldp ma (b) Nhiimg kit qua trin cho thdy dung djch phiic vdi
thdnh phdn cdc chdt NiCl2, NH4CI, (NH4)3C6H507 cho tdc do ma cao thda man diiu kiln sir dung dk, ma xoa.
Hinh 3 cho thdy khi cho them vdo dung djch ma cdc hat tro Ti02 vd SiC dudng cong phan cyc catdt cua qud tiinh ma niken hau nhu khdng bj dnh hudng.
Anh hudng ciia ham lugng hat ran nano Ti02 va SiC trong dung djch ma niken nhanh din thanh phdn ciia chiing trong lap ma dugc frinh bay tai hinh 4. Tii hinh 4 ta nhdn thdy d cimg mdt chi do ma, khi tdng ndng do hat frong dung djch, ban ddu hdm lugng hat trong ldp ma tang nhanh sau dd cd xu hudng dn djnh (bao hod hat rdn frong ldp ma). Ham lugng bao hoa
TCHH, T. 49(1), 2011 Nguyin Due Hung vd cdng su khi sir dung hat Ti02 vdo khodng 5,5 g/l trong khi
cua SiC la 4,2 g/l. Khi tdng ndng do hat trong dung djch, cdc hat cd ca hdi din bi mat diln cyc nhiiu hom, do dd chiing cd nhieu khd ndng ddng kit tua va tang ham lugng cua chung frong ldp ma. Tuy nhiln sy thay ddi ham lugng hat trong ldp ma khdng ty ll vdi su thay ddi cua chiing trong dung djch. Diiu ndy CO thi dugc gidi thich do qud trinh ding kit tiia ciia cdc hat ran vdo ldp ma cdn phu thudc vdo qud trinh phdng diln cua ion Ni tiong dung djch tao thdnh kim loai niken dl chdn lap cdc hat. Niu cdc hat din
bl mat diln cue nhieu md tdc do tao thdnh niken khdng kjp dk chdn ldp thi chung sl lai rdi khdi bl mat diln cyc.
Nhu vdy dung djch ma niken tir dung dich phiic cho phIp tao dugc ldp ma td hgp kich thudc nano he Ni-SiC vd Ni-Ti02 Thanh phdn toi uu ciia hat Ti02 Id 5,5 g/l, cua hat SiC la 4,2 g/l cd thi sir dyng dk tao ldp ma t i hgp bdng phuomg phdp ma xoa.
Anh hudng ciia mat do ddng dien ma tdi thdnh phan va tinh chat ldp ma niken td hgp nano Ni-Ti02 va Ni-SiC dugc trinh bay trong hinh 5 vd bang 1.
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-100.0m -80.0m -60.0m -40.0m -20.0m 0.0-
m 4
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-0.4 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6 E, V (SCE)
Hmh 3: DCPC frong dung djch ma xoa he NiCl2, NH4CI, (NH4)3C6H507 vdi cdc hdm lugng hat SiC va Ti02 khdc nhau, tdc do quit 10mV/s
0 g/l, 1 g/l SiC 4 g/l SiC 1 g/l Ti02 4 g/l Ti02
6 5
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^ 2 1
4.4
4.0
3.6 3.2 2.8
I I I • I • I • I • I • I • I ' — I — • — I
0 1 2 3 4 5 6 7 8 9
Thanh phan TiO trong dung dich (g/l)
0 1 2 3 4
Thanh phin SiC trong dung dich (g/l)
a b . TTinh 4: Quan he giCira thdnh phdn hat rdn trong dung djch vd trong ldp ma
niken compozit (Dk = 15A/dm^). a. Hat Ti02 b. Hat SiC
Hinh 5 cho thdy d mat do ddng thdp tdc do tao thanh ldp ma niken nano composit cham nen khi cdc hat da bdm vdo bi mat ldp ma khdng thi giii dugc cac
hat va cac hat lai theo ddng chdy hoac bi khi day ra ngodi vi vay ham lugng hat frong ldp ma thdp. Khi tdng mat do ddng diln ma, kha ndng chdn ldp cac hat
TCHH, T.49 (1), 2011 Cdng nghi mg xoa vai..
vdo ldp ma tang nen ham lugng ciia chiing trong ldp ma Cling tdng. Khi mat do ddng qud ldn, kem theo hieu sudt ddng diln gidm manh, khi hydrd thodt ra tir bi mat ma rdt manh cd tdc dpng day cdc hat ra khdi bi mat nin lam gidm so hat dugc chdn ldp cdng vdi lugng niken vao nhiiu nen thdnh phdn ciia cdc hat trong ldp ma gidm. Hinh 5 cung cho thdy cimg che dg
ma thi hat SiC cd khd nang vao ldp ma cao han so vdi Tib2. Ldp ma Ni-SiC cd thi dat tdi 6,7% frong khi ldp m? Ni-Ti02 chi dat cao nhat Id 5%).
Anh hudng cua chi dg cdng nghg ma xoa din tinh chdt vd hinh thdi bi mat khi cd cac hat Ti02 va SiC kich thudc nano trong dung djch dugc trinh bdy tai bdng 1 vd hlnh 6.
O
20 40 60 80 100 120
Mat do ddng di|n ma xoa; A/dm
140
2
160 20 40 60 80 100 120 140 160
Mat do ddng diln ma xoa; A/dm^
Hinh 5: Anh hudng ciia mat dg ddng dien ma xoa tdi ham lugn hat Ti02 vd SiC trong ldp ma td hgp
Bdng 1: Anh hudng ciia mat do ddng diln ma xoa niken td hgp tdi tinh chat ldp ma
TT 1 2 3 4 5 6
Mat do ddng diln, A/dm^
40 60 80 100 120 140
Do Cling, Hv Ni-Ti02
400 450 480 570 560 550
Ni-SiC 450 485 535 650 640 580
Hinh dang bl ngodi Ni-Ti02
Mjn, md Sang Bdng Bdng Mjn, md
Md
Ni-SiC Mjn, md
Sdng Bdng Bdng Mjn, md
Md Bang 1 cho thdy khi cd mat cdc hat Ti02 vd SiC
kich thudc nano trong dung djch, ldp ma xoa cd do bdng mjn cao hom khi ma niken nguyen chdt. Cdc hat cd kich thudc nano lan vdo ldp ma da cdi thien dugc do bdng mjn cua be mat ma. So sdnh do ciing cua ldp ma td hgp vdi ldp ma niken nguyin chdt thu dugc theo cdng nghe ma xoa cho thdy do ciing da dugc cdi thiln rd ret: ldp ma Ni thdng thudng trong bi Id 270 Hv, ma Ni xoa Id 450 Hv, ma Ni td hgp vdi Ti02 la 570 Hv vd Ni to hgp vdi SiC cd do cirng cao nhdt la 650 Hv do cdc hat SiC cd do ciing rdt cao dugc phdn bd ddng diu trong ldp ma. Cdc hat Ti02 cung ldm tdng do cirng ldp ma so vdi khi ma niken nguyin chat nhung miic do tdng kRdng bdng hat SiC. Su cd mat ciia cdc hat nano trong ldp ma ciing cho khd ndng ma vdi mat do ddng cao din
100 A/dm^, ldp ma trd nen bdng mjn hom.
4. KET LUAN
Dung djch ma xoa niken frIn ca sd sur dung cdc chat tao phirc NH4CI vd amdni xifrat cho khd ndng tao ldp ma niken cd chdt lugng tdt vd tdc do ma nhanh, de su dyng.
Dung djch ma xoa niken khi them cdc hat SiC va Ti02 cd kich thudc cd 10 mn vdi ndng do tuong ling Id 4,2 va 5,5 g/l cho phep tao dugc ldp ma niken td hgp Ni-SiC vd Ni-Ti02 bdng cdng nghe ma xoa.
Cdc ldp ma niken vd niken td hgp theo cdng nghe ma xoa cd tinh chdt ca, ly tdt hom ldp ma niken thdng thudng, dac bilt cd do ciing cao hom nin hoan todn cd thi su dung d l ma phuc hdi chi tiit ldm viec trong dilu kiln chju ma sdt ldn.
Ldp ma Ni-SiC ed do cung cao hom so vdi ldp ma Ni-Ti02 phu hgp cho muc dich chdng mai mon, cho chi tiit ca khi. Thanh phdn dung dich va chi do
TCHH, T. 49(1), 2011 Nguyin Dice Himg vd cdng su
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N I K S I K C K Totals
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80.x 9.59 9.59
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///n/z d: Anh SEM b i mat (Trin, phdi), mat cdt ngang (trin, trdi, vdi ndi hat Ti02 da bj chdn ldp (a), dang chdn dd (b) vd bj bong ra (c) vd anh SEM cua b l mat vdi do phdng dai khdc nhau (giura) va kit qua EDX cua
ldp ma Ni-SiC tai vj tri danh ddu (dudi trdi vd phdi) ma xoa niken td hgp Ni-SiC toi uu: NiCl2 500 g/l;
NH4CI: 120 g/l; amoni xitrat: 60 g/l; hat SiC 4,2 g/l, mat do ddng ma 100 A/dm^
T A I LIEU THAM K H A O
1. Nguyin Anh Tuan, Pham Van Hung. Ma sat hoc, Nxb. Khoa hpc va Ky thuat. Ha Noi (2007).
2. Nguyin Diic Hung, Nguyin Duy Kit. Tap chi Khoa hpc va Cong nghe, T. 44 (2), 70 - 75 (2006).
3. Dao Khanh Du. Nang cao tinh nang ma sat cua ldp ma xoa ding va niken, Luan an tien s7 ky thuat, DHBK HN (2007).
4. P. Gyftou, M. Stroumbouli, A.E. Pavlatou, P.
Asimidis, N. Spyrellis. Surface and Coatings Technology, Vol. 156, 214 - 223 (2002).
5. Tai lieu ciia hang Diamond composite technology:
Diamond chromium composite plating, Div. UK Abrasives Inc., 2006.
6. V. B. Singh, Pinky Pandey. Joumal of New Materials for Electrochemical Systems, Vol. 8, 299 303 (2005).
7. Denny Thiemig, Andreas Bund. Surface and Coating Technology, Vol. 202, 2976 - 2984 (2008).
8. Bin Wu, Bin-shi Xu, Bin Zhang, Yao-hui Lii. Surface and Coating Technology, Vol. 201, pp 6933-6939, 2007.
9. Bin Wu, Xu hua Yu, Bin Zhang, Bin-shi Xu. Surface and Coating Technology, Vol. 202, 1975 1979 (2008).
10. Ming-Der Ger. Materials Chemistry and Physics, Vol. 87, 67 74 (2004).
11. Nguyen Due Hung, Pham Thi Phuong, Nguyen Duy Ket, Nguyen Nhi Tm, Hoang Minh Due:
Electrochemical characterization of Ti/Ru20-Mn02 Electrode, VAST-Proceedings: Intemational scientific conference on chemistry for development and intergration, Hanoi, 838 H- 845 (2008).