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电镀工艺学. 第九章 电镀铬. Plating technology Chapter Ⅸ Chromium Plating. 电镀铬及代铬镀层 1 电 镀 铬 概述 镀铬在电镀工业中占有极其重要的地位,并被列为三大镀种之一。电镀铬属于单金属电镀,与其它单金属电镀相比,有许多共同之处。但是,它又有一些其它单金属电镀所没有的特点,故镀铬是电镀单金属中较为特殊的镀层。

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电镀工艺学

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Plating technologyChapter Chromium Plating

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1

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1.

(Cr)

51.994

6.98cm3~7.219cm3

1875~1920

0Cr3+/Cr=0.74V

0Cr3+/Cr2+=0.41V

0Cr2O72-/Cr2+=1.33V

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(HV400~1200)500

400 500

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()

65(88)(55)

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2

(1) 0.25m~1m

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(2) ()1 mmm

(3)

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(4)

(5) ()

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1) CrO3H2SO4100/1150gL450gLCrO3 250gLH2SO4 2.5gL

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2) 20

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3) KspSO42SiF62SO42SiF62SrSO4K2SiF6SO42SiF62SrSO4K2SiF6SO42SiF62

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SO42SiF62(27)(100Adm2)(50mh)

4)

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5) Cr3+(3037)24

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6)

7) (Cr3+)

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3

(1) ()818

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(2) SO42 SiF62 FCr3+

(3)12V8V

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(4)(PbSbPbSn)

(5)

(6)

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4

Cr6+(H2Cr3O10)(H2Cr4O13)(HCrO4)(CrO3150gL400gL)

2CrO3+H2OH2Cr2O7 (151)

CrO3+H2O H2Cr2O4 (152)

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H2CrO4 HCrO4 H+ K4.1 (153)

HCrO CrO42 H+ K106 (154)

pH<1Cr2O72

pH2~6Cr2O72HCrO4

Cr2O72H2O 2HCrO4 2H+2CrO42(155)

2 pH 6

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pH>6 CrO42CrO42` HCrO4 ` Cr2O72 ` H+ ` Cr3+ `SO42 Cr2O72HCrO4pH(155)pHCrO42HCrO4

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(1)?

(2)??

(3)?

(4)CrO3

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  • Kasper(Cr51)CoughlinCrO31/2Cr2O3506.14KJ529.46KJ

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F.MullerR.Weiner

()151(1)(2)

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H2

Cr3

Cr3H2

Cr3

Cr

151

1250g/L CrO3

2--250g/L CrO35g/L H2SO4

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abpH1Cr2O72

Cr2O7214H+6e 2Cr3+7H2O (156)

b

bCr2O72CrO3+

2H+2e H2 (157)

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bcCr2O72 Cr3+ H+ H2Cr3+

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pH(155) Cr2O72HCrO4 HCrO4cHCrO4

HCrO46e+ 3H+ Cr4OH (158)

cd(15 6)(15 7)(15 8)cd1315

HCrO4?151

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bpHCr2O72 HCrO4 pH3Cr(OH)3Cr(OH)3Cr(OH)CrO4

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15-12bCr3+pHbc1VCr6+Cr0HHCrO4

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SO42SO42HCrO4

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SO42 Cr3+SO42 (156)(158)(157)SO42 (15 6)

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  • Cr3+Cr3+

  • (6-8)(6-8)(PbCrO4).

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(6-8)(6-8)(PbCrO4)

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2H2O 4e O2 + 4H+ (1510)

2Cr3++7H2O 6e Cr2O72+ 14H+ (1511)

Pb+7H2O 4e PbO2 + 4H+ (1512)

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Cr3+2:13:2(1512)

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5

1.

(<0.5/m)

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(Cr2HCrH2)CrHCrH215

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2m13500MPa2200MPa0~240MPa

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CrO3/SO425060 CrO3SO42

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  • HV900 1000-50g~100g 30m

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500

Wahl15240HV400~900HV90020~40EilenderHV750~800(153)

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15-2

Wahl

15-3

Eilender

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151

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  • 50Adm235 55800.070.050.03

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20070982002h~3h3003h~5h

20 508510.40.1

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30m()

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6

1)

(FSiF62)15-2Sargent

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50gL~400gL

15-4

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154

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15-515-615-54520Adm2250gL1915-655 45Adm2CrO3/SO42 =1001150gL400gL5~6

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155 45 20Adm2

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15 6 150gLCrO3---- 250gLCrO3----400g LCrO3

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15-3

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CrO3SO42200gL~300gL

250gLH2SO42.5gL

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2)

()

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15-7CrO3SO42100:1

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15-7

45C---60 C

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CrO3SO42100:1

CrO3SO4250:1

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CrO3SO421001 SO42200:1 SO42

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(F SiF62BF4 )1.5~415-815-9250gL CrO31~3SO4218SiF6225SiF62BF4

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15-8 ()250gL CrO3

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15-9

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3

Cr3+ Cr6+Cr3+ Cr3+Cr6+

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Cr3+Cr3+Cr3+ Cr3+2gL~4gL8gLCr3+SO42Cr3+SO42

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(1)(15-6)Cr6+15-11

(2)(98)0.5mL/L

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(3) 10~3060~801.8~2.0Adm21h0.3gL

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4

15-1015-11

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15-10 250gL CrO3 , 2.5gL H2SO4

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15-11

400gL CrO34gL H2SO4

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:

k=a log D+b (15-13)

k

D

ab

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15-12 240gLCrO32.4gLH2SO4

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15-13

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15-13 2502.55005.0

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15-1415-4

(1~2)

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15-14 ()

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5

Fe<10gLCu 4gLZn 2gL

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(1)

Fe3+3gL5gL10gL

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CrO3<130gL732Fe3+Cu2+Zn2+Cr3+CrO30.5mLL 98Cr3+

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15-15 Cr6+Cr3+pHCr3+Cr3+Cr6+pH100gL~150gL

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15-15

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(2)

C1 > 0.1gLPbO2C1 C1

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2Cl + 2e Cl2 >40Adm260~70

C1AgAgCl C1

2HCl+Ag2CO3 = 2AgCl +CO2 +H2O (15-13)

2AgNO3+Na2CO3 = Ag2CO3+2NaNO3

3~5NO3

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(3)

NO3>0.1gL;NO31gL

BaCO3SO42NO365 ~70 10Adm2~20Adm2

NO3 +10H++8eNH3++3H2O (15-15)

NH3+

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15 . 1.5

(1)0.25m~0.5 m

(2)

(3)

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1.

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300gL

CrO3SO421000.9

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(1 m)

()

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2

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?(Microdiscontinuous Chromium)155156

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(1)

ASTM456760.8m15-7

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20601mo.25 mPNS(Poet Nickel strike)30mm10015-16

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15-16 (a)(b)

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CrO3 80~100gL 2~2.5Adm2

H2SO4 80~100gL 2~3min

CuSO4 200~250gL 0.5~1.0Adm2

H2SO4 50 ~100gL 2min

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(2)

(Nickel Seal)0.5 m0.5m50gL~100gL2~3

ASTM4566710000/ cm214.1.50

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3.

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40 30Cr3+

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4

5m~50m200m~800m15-8

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()()()

15-2

(1)Ra0.8m

(2)

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15-17

15181511915201521

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15-17

A B

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1518 (a)(b)

1519

12

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1520

1

2

1521

A

B

(3)

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(4) 2()

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(5)

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C(C)Cr6Cr3

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H912310Adm2~30Adm215-9

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(6)

180 ~200 2h~4h

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(7)

(65~75)(15Adm2~25Adm2)20m58~6040Adm2~60Adm2

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15.1.7

1

()()2-4(0.5~1.0)

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()

CrO3 240gL~260gL 60C 1C

H2SO4 2.1gL~2.5gL 50Adm2

Cr3+ 1.5gL~6.0gL

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()

100m 320Amindm2

100~150m 400Amindm2

150m 480Amindm2

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12~13100m

20Adm2~30Adm2

6min~4min

120Amindm2

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100(1522)(a)(b)(c)(d)(e)

1522 x100

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CrO3SO42

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2.

()()2~3300

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(CrO3)

(Cr) 56.1 (H) 1.25

(N) 0.4 (O) >26.0

(C) 0.1

HVl30~3501510

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200gL~400gLCrO3

5gl20gL

30gL

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SO42C1SO42BaCO3SO42BaSO4ClCu21gL

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25Adm275Adm245Adm2~60Adm240C

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15min20min4m~5m15min~20min

7

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(1)()

(2)

(3)

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15.1.8

1.

(1)

1)

NaOH 90gL 2Adm2

2) .

NaOH l0~20 60C~70C 10Adm2~20Adm2

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(2)

HCl(d=1.19) 1LSb2O3 20g

2.

HCI (d=1.19) 530C~40C

3.

Cr2O3 10gL~30gL

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4.

(HCl) (d=1.19) 1:1 30C~40C

5.

Na2S8H2O 30gL NaOH 20gL

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15 . 2

(1)13~18

(2)150gL~350gL15

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(3)

(4)

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15.2.1

Alecra3(Alpright&wilson)EnviroChrome(Caning)TriChrome()

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Cr3+Cr6+

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1512Caning10

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(1)(5gL~20gL)

(2)

(3)3Adm2~12Adm221~25

(4)

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(1)3m

(2)Fe2+Cu2+Ni2+Zn2+

(3)

(4)

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15.2.2

2070207050gL100gL

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1523250gL100gL50gL18V~20VCrO3 100gL

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1523

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5gL

()5

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15.2.3

(1) SO42FSiF6SeO32BO32ClO4BrO3IO3

()

(2)

(3) La3+Ce3+Nd3+()Pr3+Sm3+

(4) Sr2+Mg2+

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Romanowski1967

20801987~1988CS

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15-15CS14

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2.

(1)CrO3120gL~200gL10C~50C5Adm2~30Adm218~25

(2)30~6060~8520~3030~50

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(3) 5Adm24Adm26V~8V

(4)

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3.

?X

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(1) 15-1(12)(aa')(15-24)1Cr6+Cr3+Cr3+ 2aa'

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(2)

Y2O3

15-26(a)15-26(b)1CrO42

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1524

1525

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1526

(a)

(b)4.0gL La2O3

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(3)X

4.

(1)5minF-

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(2)

(3)1gL~2gL

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15.2.4

2050M&T

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80(U.S.P3,505,183)Edgar(93C60Adm2):CnH2n+1COOMMHRSO3MRRMH

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8060C150Adm225minHV135075m28~48

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200gL~300gL 1gL~10gL

2gL~3gL 1gL~5gL

55C~65C 20~80Adm2

HV ll00S /C>127

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80

200gL~350gL

3gL~15gL

80gL~120gL

2gL~3gL

1gL~3gL

50C ~ 60C

20~80Adm2

20

2-3-

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1984M&THEEF(High Efficiency Etch Free)HEEF25

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HEEF 25

HEEF 25G 550mLL

2.7gL

55C~60C4h~6h(6V15:1)

225gL~275gL

55C~60C

2.5gL~4.0gL

30Adm2~75Adm2

HEEF25R350mL(kAh)

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HEEF 25

(1)22~26HEEF2515-1615-2715-28

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1527

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1528

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1529 2h

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1530

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(2)HEEF25HV900100015292h

(3)2025

(4)400cm1530

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(5)70Adm

(6)

(7)HEEF25

HEEF25CanningCSIKC50ANKORll27NFT,PALDO

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Ly2000ST926ST627CHSHC25CSHEEF25

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15.3

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1518

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15.3.1

1.

0.2Pm (HV300400)1519

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8040gL60gL2mlL5mlL30s60s

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6535HV4006001520

(72732728)lmmin

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2.

65355102065

108L-25SL55gL150gL10mlLpH8.7-9.570C0.5Adm210Adm232HV450500HVl0001200

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10gL25gL30gL75gL()30gL80gL10gL20gL00.400.3pH7.50.5Adm25Adm22060

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15.3.2

1.

3032HV450500350 400HVl000120025

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300C1hHV100030gLHVl200814

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59.539.51HV600315 1hHV9501050

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2.

0.3molL10gL0.2molL~0.56molL50CpH3.0~4.52Adm2~10Adm2>85>8HV490~570400C1hHVll50

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20HV500600I1521

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3.X

3s(shining Surface Systems)METTE 6x()HV820HV12002-6180mh2

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96METTEX6

200gL~280gL

20gL~80gL 50C~55C

30gL~80gL

2Adm2~10Adm2

20gL~50gL SS(1.0~1.5):5.0

50mLL~100mLL

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NiCo5nm20nm

4.

(NiPNiBNiW)

Al2O380gl~100gL A12060nm

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08

1

2

3

4

5

6

7

8

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08

9

10

10

11

12 52

13 67

14 79

15

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08

16 5

17 113118

18

19

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082

a

b

c

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