ANT HA CNG CHO NHM V MT S HP KIM NHM

CI THIN CC TNH CHT B MT

HARD ANODIZING OF ALUMINIUM AND ITS ALLOYS TO
IMPROVE SURFACE PROPERTIES
Nguyn Thu i, Nguyn Thanh Lc, ng V Ngon
Khoa Cng Ngh Vt Liu, Trng i hc Bch Khoa Tp.H Ch Minh, Vit Nam
TM TT
Ant ha cng c bit n nh l mt qui trnh hiu qu to ra lp ph cng v chu mi mn
trn Al v hp kim ca n. Lp ph ny c b dy (75-100 m) ln hn cc lp ph ant ha thng
thng. Tuy nhin qui trnh ant ha cng li i hi mt s iu kin ring bit nh nhit rt thp,
mt dng cao v dung dch in phn c bit. Cc i hi ny gy kh khn cho vic thit k v
vn hnh qui trnh. Do vic tm ra mt qui trnh mi c th to ra lp ph cng hn nhng nhit
cao hn l rt cn thit. Trong bi bo ny, qui trnh ant ha cng trong hn hp dung dch axt
formic v axt oxalic c nghin cu trn Nhm sch k thut 99,8%, Hp kim Al-Mg-Si (6061)
i din cho nhm hp kim bin dng khng ha bn bng nhit luyn v Hp kim Al-Cu (ura) i
din cho nhm hp kim bin dng ha bn bng nhit, cha pha th hai ha bn. nh hng ca cc
thng s in ha n b dy, cng, xp, chu mi mn ca lp ph cng c kho st.
ABSTRACT
Hard anodizing is known as an efficient process to produce a hard and wear resistance coating
over aluminum and its alloys. The thickness of this coating is thicker (75-100 mm) than the one
obtained from normal anodizing. However the process requires some special conditions such as very
low temperature, high current density and particular electrolytes. That brings out a lot of difficulties in
process setting up and operation. Therefore, it is necessary to find a new process which can produce a
harder coating at higher temperature. In this paper, hard anodizing over aluminum, Duralumin and
6061 alloy in a mixture of oxalic acid and formic acid was studied. The effects of electrochemical
parameters on coating thickness, hardness, porosity and wear reasistance were also investigated.
1. T VN
Hin nay, th gii ang c xu hng thay th
dn cc hp kim st thp thng thng bng
vt liu nhm v nhng tnh nng u vit ca
loi vt liu ny (nh, bn n mn v d to
hnh, v.v.). c bit l trong cng ngh hng
khng, tu bin, t,v.vgip gim ng k
khi lng ca phng tin iu dn ti tit
kim c nhin liu, tng cng sut hot
ng v gim thiu cc tc nhn nhim mi
trng. Trong , ant ha l mt khu quan
trng x l cc sn phm nhm.
Nhng nm gn y, cng ngh ant ha c
c bit quan tm v pht trin mnh m
kha cnh cng ngh to ra nhng lp ph ant
ha c dy (>50 m) v cng kh cao
(trn 3500 MPa) khc vi cc lp ph ant ha

trc y thng rt mng khng c kh nng

chu mi mn. Lp ph ant ha cng: dy,
chu mi mn tt, c xp nht nh nn c
kh nng ngm du bi trn c ng dng
kh ph bin trong cc lnh vc k thut cng
nghip tng cng kh nng hot ng cho
nhng chi tit chu mi mn b mt nh
pitng, xylanh, bnh rng ca ng c hi
nc, v.v...
Cng ngh ant ha cng c p dng kh
thnh cng nhiu nc trn th gii nh:
Anh, M, Thy S, Hn Quc,v.v.Trong nc,
cng ngh ant ha cng c quan tm
nghin cu nhng cha ph bin v ng dng
rng ri. Cc nghin cu ch yu thc hin
trn dung dch sulfuric, vi cng trn di
4000 MPa v gp nhiu kh khn trong vic

phi lm lnh dung dch in phn xung ti 50C.

Do , ti c t ra vi mc ch tm
kim nhng h dung dch c kh nng ant ha
su, to c nhng lp ph c cng cao
hn v c kh nng ant ha cng nhit
thng
Vit Nam, cng ngh ant ha cng c
ng dng rt nhiu trong vic tng bn v phc
hi cc chi tit t nhm v hp kim nhm. C
th nh sau:
Cng ngh ant ha cng c dng
nng cao tui th, ch to v phc hi cc bn
in offset thay v trc y phi nhp t nc
ngoi vi gi kh cao. Cc bn in c ant
ha c tui th tng ln r rt t 5000-10000
ln so vi 500-1000 ln so vi khi cha ant
ha [15].
i vi cc chi tit b i nh piston,
xecmng, xylanh, cc van trt ca phn t
kh nn, cc chi tit bc lt trong bm, v.v.th
ant ha l mt khu x l khng th thiu
to b mt chu mi mn tt v c kh nng t
bi trn.
t bit l trong cng nghip dt, si c rt
nhiu cc chi tit my bng nhm cn c
tng cng v tng bn nh: ti gp si, gng
ko si, b gp si, v.v.
2. PHNG PHP THC NGHIM
Cc thng s cng ngh ti u c chn theo
gi tr cng cao nht; gi tr dy ch
dng nh gi mc ph hp v dy
ca lp ph ant ha cng theo tiu chun
ASTM ( dy lp ant ha cng dng trong
k thut phi ln hn 50 m) v nhn xt quy
lut nh hng ca cc thng s in ha n
lp ph. Cc gi tr ti u a ra ch l nhng
s liu ph hp nht trong khong gi tr kho
st (c th hin bng s in m).
Chn vt liu lm mu
Mu ant ha c chn i din cho mt s
cc nhm hp kim tiu biu.
C th nh sau:
Nhm sch k thut 99,8%
Hp kim Al-Mg-Si (6061) i din cho
nhm hp kim bin dng khng ha bn bng
nhit luyn.
Hp kim Al-Cu (ura) i din cho nhm
hp kim bin dng ha bn bng nhit, cha
pha th hai ha bn.

Thnh phn cc nguyn t ha hc ca cc

mu nghin cu (phn tch bng my quang
ph pht x Spectromax) nh sau:
Bng 1: Thnh phn nhm sch k thut
Nguyn
Thnh
Nguyn
Thnh
t
phn %
t
phn %
Si
Fe
Cu
Mn
Mg
Zn
Ni
Cr
Pb
Sn

0,044
0,093
0,001
0,002
0,002
0,005
0,002
0.002
<0,002
<0,003

Ti
Ag
B
Bi
Cd
Zr
Co
V
Ga
Al

0,002
0,001
0,004
<0,003
<0,001
0,001
<0,001
0,004
0,009
99,8

Bng 2: Thnh phn hp kim 6061

Nguyn
Thnh
Nguyn
Thnh
t
phn %
t
phn %
Si
Fe
Cu
Mn
Mg
Zn
Ni
Cr
Pb
Sn

0,468
0,192
0,02
0,002
0,51
0,045
0,005
0,003
<0,002
<0,003

Ti
Na
B
Bi
Ca
Zr
Co
V
Ga
Al

0,013
0,001
0,002
0,004
0,001
0,001
<0,001
0,004
0,016
98,7

Bng 3: Thnh phn hp kim ura

Nguyn
Thnh
Nguyn
Thnh
t
phn %
t
phn %
Si
Fe
Cu
Mn
Mg
Zn
Ni
Cr

0,198
0,449
3,74
0,315
1,31
0,064
0,01
0.01

Ti
Ag
B
Bi
Ca
Zr
Co
V

0,037
0,001
0,001
<0,002
0
0,003
<0,001
0,003

Pb
Sn

0,003
0,009

Ga
Al

0,006
93,8

Cc th nghim ant ha c thc hin theo

quy trnh sau:
Mu (2x5x30)

Gia cng c
Ra sch bng nc
Ty du bng hn hp
Na3PO4+ NaSiO3

Ra sch bng nc
Hot ha bng hn hp
HNO3+H2SO4+H3PO 4

Ra sch bng nc
Ant ha
3. KT QU V NHN XT
3.1. nh hng ca t l mol formic/oxalic
Th nghim c kho st da trn s thay i
t l s mol ca hai cu t trong h bng cch
gi nguyn nng axt oxalic v thay i
nng fomic, c k hiu t C1(80-60) n
C5(80-140) tng ng vi nng axt oxalic
l 80g/l khng i cn nng axt formic
thay i t 60 n 140 g/l. Cc th nghim u
c thc hin mt dng 6A/dm2, nhit
300C, thi gian 60 pht. Cc khong gi tr
chn kho st c tham kho trn cc ti liu
nc ngoi [1,2,8,9].
Bng 4 : Gi tr o cng v dy lp
ant ha theo thnh phn axt formic
cng (HV)
T l HCOOH/
H2C2O4
( dy (m))
(mol/mol)
A
M
D
1,5
398
269
256
(48,68) (43,10) (14,48)
320
303
2
420
(57,12) (46,00) (25,49)
2,5
381
353
302
(67,30) (59,23) (40,56)
312
3
372
370
(75,40) (63,01) (35,78)

3,5

328
(66,60)

321
(64,50)

318
(55,26)

Ta thy rng, dy lp ant ha ca cc mu

u tng theo chiu tng t l mol
formic/oxalic v khi nng axt tng, qu
trnh to mng s xy ra nhanh hn, dy v
cng tng. Tuy nhin, n mt gi tr nng
nht nh do s ho tan ca lp mng xy
ra mnh dn n tng kch thc l xp nn
cng gim xung; gi tr cng ca cc mu
i qua mt im cc i.
3.2. Kho st s thay i gi tr pH ti t l
mol axt formic/axt oxalic ti u
Thay i ng thi khi lng axt oxalic v
axt formic sao cho t l mol khng i theo
hng gim gi tr pH ca dung dch. Gi
nguyn ch in phn: 6A/dm2, 300C, 60
pht.
Kt qu kho st c trnh by bng 3.2,
cho thy khi tng lng axt, khng c li cho
qu trnh to mng ca nhm sch v h hp
kim 6061. Tuy nhin, i vi hp kim ura th
qu trnh c thun li hn mt cht do ha tan
c phn ln cc pha th 2 nn c kh nng
to lp mng dy hn nhng gi tr cng
vn cha cao.
Bng 5: Gi tr o cng v dy lp
ant ha theo gi tr pH
pH

2,61
2,59
2,55
2,50
2,54
2,49
2,42
2,39
2,52

cng (HV)
( dy (m))
A
M
D
420
(57,12)
378
(63,40)
377
(60,17)
376
(60,90)
370
(63,01)
369
(64,45)
363
(70,30)
313
(66,19)
318
(55,26)

332
(58,50)
351
(71,50)
345
(73,49)

2,42
2,38

600
500
o cng (HV)

2,48

400
300

Nhom sach
6061
ura

200
100

3.3. nh hng ca nhit

0
5

Kt qu cho thy, khi gim nhit , dy

lp ant ha ca nhm sch v cc hp kim
u tng do gim c ng k kh nng ha
tan ca dung dch, lp mng t xp, cng
tng theo chiu gim nhit . Tuy nhin, vi
dy qu ln cng gim, do dy ca
lp mng ant ha pht trin trn c s tng
dy ca phn xp.
Bng 6: nh hng ca nhit n
dy v cng ca lp ant ha
cng (HV)
Nhit

( dy (m))
A
M
D
30
420
370
318
(57,12)
(63,01)
(55,26)
25
430
421
368
(80,39)
(78,50)
(71,35)
432
389
20
569
(95,06)
(86,80)
(70,64)
15
494
450
439
(99,57)
(88,50)
(81,35)
10
459
410
372
(103,70)
(94,50)
(85,05)

15

20

Nhiet o 0C

25

30

35

3.4. nh hng ca mt dng in

Kho st nh hng ca mt dng ti nng
, nhit ti u ca tng loi hp kim.
Bng 7: nh hng ca mt dng n
cng v dy lp mng ant ha
cng (HV)
Mt
dng
( dy (m))
(A/dm2)
A
M
D
4
398
339
306
(47,50) (44,45) (37,10)
5
534
385
370
(64,18) (58,38) (58,55)
450
6
569
439
(95,06) (79,50) (75,50)
383
7
458
510
(97,03) (84,78) (83,70)
8
440
432
298
(98,74) (89,57) (87,05)
120

100

100
80
60
40

Nhom sach
6061
ura

20
0
3

80
60

5
6
7
Mat o dong (A/dm2)

600

40

Nhom sach
6061
ura

20

500

0
5

10

15

20

Nhiet o C

25

30

35

o cng (HV)

o day (micromets)

120

10

Hnh 1: nh hng ca nhit n

cng v dy lp ant ha.

o day (micromets)

Kt qu nghin cu nh hng ca nhit

n qu trnh ant ha c thc hin ti nng
ti u mt dng 6A/dm2, thi gian 60
pht v nhit thay i t 300C n 100C.

400
300
200

Nhom sach
6061
ura

100
0
3

5
6
7
Mat o dong (A/dm2)

Hnh 2: nh hng ca mt dng in

n dy v cng lp ant ha

120
o day (micromets)

100
80
60
40

Nhom sach
6061
ura

20
0
30

45

600

60

75
90
Thi gian (phut)

105

120

500
o cng (HV)

Ta thy rng tn ti mt vng bo ha gn

nh nm ngang ng vi gi tr mt dng
nm trong khong 6-7 A/dm2 c gi l gi
tr mt dng ti hn jth (hnh 3.2). Vi gi
tr mt dng j>jth th dy tng rt chm
v hu nh khng tng do hiu ng tng nhit
Jun-Lenx, sinh nhit cc b lm cho qu trnh
ha tan mng xy ra nhanh hn. Ti thi im
qu trnh pht trin cc ct oxt xp v ha tan
chng cn bng nhau th tc mng ant pht
trin chm li v t chiu dy gn nh bo
ha; cng tng ng gim dn khi tng j
vt qu gi tr jth.

400
300
200

Nhom sach ky thuat

Hp kim 6061
Hp kim ura

100
0

3.5. nh hng ca thi gian n qu trnh

ant ha
Bng 7: nh hng ca thi gian n
cng v dy lp ant ha
Thi
gian
(pht)
45
60
75
90
105

cng (HV)
( dy (m))
A
M
380
346
(72,21)
(52,58)
569
510
(95,06)
(89,80)
502
476
(101,45)
(90,36)
453
423
(104,63)
(98,12)
371
357
(107,88) (100,23)

D
328
(52,77)
439
(81,35)
467
(85,02)
409
(94,32)
319
(98,36)

Theo di nh hng ca thi gian n dy

ca lp ph cho thy dy lp ph tng dn
theo thi gian, mu sc chuyn t vng sang
vng nu, nhng tc pht trin lp mng
gim dn. cng qua im cc i sau
gim dn theo thi gian v tng chiu dy
lp mng.
Qua kho st nh hng ca iu kin khuy
trn (sc kh) cho thy vic khuy trn lm
ng u ha nhit v thnh phn dung dch
nn dy v cng tng mt cht. Nhng
do axit formic l cu t d bay hi nn vic
khuy trn lm mt tnh n nh ca dung
dch.

30

45

60
75
90
Thi gian (phut)

105

120

Hnh 3: nh hng ca thi gian ti dy

v cng lp ant ha

Hnh 4: nh hng ca thi gian n mu

sc lp ph ant ha.
3.6. Kho st xp theo thi gian
Theo thi gian ant ha, mt mt pht trin
dy lp xp ca mng nhng mt khc lm
tng kch thc l xp, do xp tng,
cng gim. xp ca lp ant ha trong h
dung dch oxalic-formic nm trong khong 2550% thp hn xp t c trong h dung
dch sulfuric t 43-69% (hnh 5). T gc s
dng vt liu cho thy, gi tr xp t 2550% kh ph hp i vi tiu chun v xp
th tch ca hp kim trc h bcbt ( xp
35-45%) theo yu cu lm vic ca cc b i,
trt, lm vic trong iu kin ma st trt
c bi trn.

55
50

o xop (%)

45
40
35
30

Nhom sach
6061
ura

25
20
30

45

60

75

Thi gian (phut)

90

105

120

Hnh 5: nh hng ca thi gian n

xp ca lp ph ant ha
3.7. Kim tra kh nng chu mi mn ca
lp ant ha cng
Nhn thy rng, khi lng kim loi b mt i
ca nhm sch l ln nht, k n l hp kim
6061 v hp kim ura tng ng vi kh nng
chu mi mn ca hp kim tng dn. Tuy nhin
lp ph ant ha trn nhm sch li c kh
nng chu mi mn cao hn c, ph hp vi
kt qu o cng, do lp oxt trn nhm sch
st cht hn. iu cng cho thy rng s c
mt ca nhng nguyn t hp kim trong lp
ph lm nh hng rt ln n cu trc hnh
thnh ca lp ph ant. T biu so snh
(hnh 6) ta thy khi c ant ha kh nng
chu mi mn ca chi tit tng ln gp 20 ln.

Khoi lng b mat (g/mm2)

70
cha anot hoa
a anot hoa

60
50
40
30
20
10
0

Nhom sach

6061

ura

Hnh 6: Biu so snh kh nng chu mi

mn ca vt liu nhm v lp ant ha
Tm li, iu kin ant ha ti u theo
cng c trnh by trong bng sau:
Bng 8: iu kin ant ha ti u cho nhm
v hp kim.
iu kin ant
Nhm
Hp
Hp
ha v tnh cht
sch
kim
kim
ca lp ph
6061
ura

Nng axt
axt oxalic (g/l)
Nng axt
axt formic (g/l)
Mt dng
(A/dm2)
Nhit (oC)
Thi gian (pht)
cng (MPa)
dy tng
ng (mm)

80

80

112

80

120

196

20
60
5690
95,06

15
60
5200
89,8

15
75
5080
85,02

4. KT LUN
So vi cc kt qu nghin cu trn h sulfuric
ph gia axt oxalic c cng b vo nm
1996 th kt qu cng ca lp ph ant ha
t trn cng mt loi nhm sch k thut
99,8% trong h hn hp axt oxalic v axt
formic cao hn, t 5690 MPa so vi trong h
sulfuric l 4640 MPa [15].
Tuy nhin, mi ch ant ha u c nhng
u im v khuyt im ring ca n. Mi
cng ngh ph hp vi tng c tnh ring ca
sn phm. H sulfuric tuy kinh t hn v mt
vt t ha cht nhng ngc li phi thc hin
nhit m. Thm vo , nhng chi tit cn
cng cao th phng php ny khng t
yu cu hay i vi nhng chi tit cn bt kn,
nhum en th cng ngh ny khng ph hp
v xp kh cao, mu sc sng. H axt
oxalic v axt formic tuy chi ph cho vt t ha
cht cao hn mt cht nhng ngc li c kh
nng ant ha cng nhit cao hn, gim
ng k chi ph cho thit b lm lnh, nng
lng. Thm vo gi tr cng t c
cao hn nhiu.
Gi tr cng v dy trn nhm sch t
c nhit thng trong iu kin kh hu
Vit Nam (nhit trung bnh l 270C) l 4200
MPa v 72 m t yu cu v cng v
dy theo tiu chun ASTM B 580-79 (phin
bn 2000).
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