Objective: To follow the EN HP behavior trought the entire cycle of 0.0 MTO to 3 MTO.

1.- To follow deposition rate under laboratory conditions.

2.- Record of key characteristics in order to identify its influence on deposition rate (m/hour).
3.- Make the characterization on cupons and iron nut to verify thickness and % P content.

Date:
Responsible
Key characteristic of EN HP
EN HP make up:
Bath Volume (lts)
Niklad 811A (mililiters)
Niklad 811B (mililiters)
H2O (mililiters)
Ni MTO
Nickel (gr/l)
Temp. C
pH a temp del bao
pH at 25 C
Hypo.
Orto.
H2O Conductivity (S/cm^2)
Replenishment:
Niklad 811A (mililiters)
Niklad 811HA (mililiters)
Surface treated (dm^2) Cupon 1
Surface treated (dm^2) Cupon 2
Surface treated (dm^2) Nut 1
Surface treated (dm^2) Nut 2
339-20-543
Surface load (dm^2 / liter)
Ley de consumo
Total surface plated (dm^2)
Thickness 1 (m)
Thickness 2 (m)
Total thickness (mM)
% Phosphorous 1
% Phosphorous 1
% Phosphorous Average
Deposition rate 1 (m/hr)
Deposition rate 2 (m/hr)
Deposition Rate Average

6/28/2013
ER/JB/RM
Make up
measured
-2

113.4
283.5
1603.1
0
5.93
89
4.93
4.82
31.05

-0.8

--------Niklad 811A (mililiters / dm^2)

Niklad 811HA (mililiters / dm^2)
Niklad 811A (mililiters / m)
Niklad 811HA (mililiters / m)

---------

Observations

pH of the bath
5.05

4.95

4.9

4.85

4.8

4.75
0

0.09 0.19 0.26 0.32 0.38 0.47 0.57 0.74 0.78 0.9 0.97 1.15 1.24 1.32 1.38 1.63 1.67 1.8 2.03 2

TO to 3 MTO.

rate (m/hour).
% P content. See sheet "Cupons characterization"

30min

60 min

90 min

120 min

150 min

180 min

210 min

--

--

--

--

--

--

--

----

----

----

----

----

----

----

0.09
5.81
89
4.88
4.77

0.19
5.87
88.7
4.89
4.81

0.26
5.87
89.2
4.89
4.8

0.32
5.87
89
4.9
4.8

0.38
5.81
89
4.9
4.81

0.47
5.87
88.9
4.89
4.78

0.57
5.93
89.2
4.86
4.78

---

---

---

---

---

---

---

0.8

0.8

0.8

0.8

0.8

0.8

0.8

--

--

--

--

--

--

--

20
40
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

25
50
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

16
32
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

15
30
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

15
30
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

15
30
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

23
46
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

2.264514
5.06
5.06

2.264514
5.09
5.12

2.264514
4.89
5.25

2.264514
5.19
5.28

2.264514
4.83
4.9

2.264514
4.75
4.41

2.264514
5.233
5.088

5.06

5.105

5.07

5.235

4.865

4.58

5.1605

6.22
5
2
5.16
0.88
3.28
4.68
5.25
1.97
1.25
4.85
1.18
2.15
4.93
5.735
3.485
1.625
5.005
1.03
2.715
4.805
15.18
15.27
14.67
15.57
14.49
14.25
15.70
15.18
15.36
15.75
15.84
14.7
13.23
15.26
15.18
15.315
15.21
15.705
14.595
13.74
15.4815
15.3690321429 15.36903214 15.36903214 15.36903214 15.36903214 15.36903214 15.36903214

the bath
91

90.5

90

89.5

pH a temp del bao

Temp. C

89

88.5

88

87.5
1.63 1.67 1.8 2.03 2.25 2.37 2.54 2.66 2.77 2.97 3.1 3.18 3.35

Samples send to MacDermid for SEM

Samples send to Voreppe for SEM
Samples for cross-section

240 min

270 min

300 min

330 min

360 min

390 min

420 min

--

--

--

--

--

--

--

----

----

----

----

----

----

----

0.74
5.46
88.7
4.9
4.8
33.07

0.78
5.93
89
4.88
4.77

0.9
5.64
88.9
4.91
4.82

0.97
5.87
89
4.91
4.8

1.24
5.87
89.5
5.02
4.91

1.32
5.81
89.5
4.97
4.86

--

---

---

---

1.15
5.87
90
5.02
4.92
31.6

--

---

---

0.8

0.8

0.8

0.8

0.8

0.8

0.8

--

--

--

--

--

--

--

40
80
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

10
20
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

30
60
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

15
30
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

25
50
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

20
40
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

20
40
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

2.264514
4.956
5.172

2.264514
4.6
4.56

2.264514
5.31
5.17

2.264514
5.14
5.15

2.264514
4.81
4.59

2.264514
5.33
5.79

2.264514
5.36
5.32

5.064

4.58

5.24

5.145

4.7

5.56

5.34

7.18
3.11
3.71
6.07
1.5
4.97
3.21
5.62
3.49
3.19
6.77
1.88
4.54
4.7
6.40
3.3
3.45
6.42
1.69
4.755
3.955
14.87
13.80
15.93
15.42
14.43
15.99
16.08
15.52
13.68
15.51
15.45
13.77
17.37
15.96
15.192
13.74
15.72
15.435
14.1
16.68
16.02
15.369032143 15.36903214 15.36903214 15.36903214 15.369032143 15.36903214 15.36903214

Filtration
Treatment

Filtration
Treatment

% Phosphorous Average
12

10

0
0.09 0.19 0.26 0.32 0.38 0.47 0.57 0.74 0.78 0.9 0.97 1.15 1.24 1.32 1.38 1.63 1.67 1.8 2.03 2.25 2.37 2.54 2.

mples send to MacDermid for SEM

mples send to Voreppe for SEM
mples for cross-section

450 min

480 min

510 min

540 min

570 min

600 min

630 min

--

--

--

--

--

--

--

----

----

----

----

----

----

----

1.38
5.87
90.1
4.9
4.8

1.63
5.4
90
4.93
4.83

1.67
5.87
89.5
4.93
4.82

2.03
6.1
90.1
4.9
4.81

2.25
5.99
89.9
4.9
4.81

2.37
5.52
90.1
4.89
4.81

---

---

---

1.8
5.69
90
4.89
4.8
32.5

--

---

34.8
63

---

0.8

0.8

0.8

0.8

0.8

0.8

0.8

--

--

--

--

--

--

--

15
30
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

60
120
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

10
20
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

30
60
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

55
110
0.241126
0.241126
0.296981
0.296981
1.1883
0.5661285

45
90
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

30
0
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

2.264514
5.01
5.04

2.264514
3.4
3.38

2.264514
5.01
4.86

2.264514
4.74
4.91

2.264514
4.45
4.5

2.559714
5.07
4.354

2.559714
6.735
6.51

5.025

3.39

4.935

4.825

4.475

4.712

6.6225

2.67
3.25
3.462
1.53
5.87
--3.33
3.91
7.45
1.39
6.39
--3
3.58
5.456
1.46
6.13
--15.03
15.674
15.03
14.22
13.35
15.21
20.205
15.12
15.5818
14.58
14.73
13.5
13.062
19.53
15.075
15.6279
14.805
14.475
13.425
14.136
19.8675
15.36903214 15.3690321429 15.36903214 15.369032143 15.3690321429 15.3690321429 15.3690321429

Rough
coupons

pH
adjustment/filtrati
on due
metalization
signs

Filtration
Treatment

A nut will be
taken every 60
min

orous Average

3 1.67 1.8 2.03 2.25 2.37 2.54 2.66 2.77 2.97 3.1 3.18 3.35

% Phosphorous Average

660 min

690 min

720 min

750 min

780 min

810 min

--

--

--

--

--

--

----

----

----

----

----

----

2.54
6.1
89.7
4.89
4.81

2.66
6.1
89.4
4.92
4.81

2.77
5.81
89.6
4.91
4.8

2.97
6.05
89.5
4.91
4.8

3.1
6.05
89.7
4.93
4.82

3.18
6.16
90.5
4.89
4.8

---

---

32
--

---

---

---

0.8

0.8

0.8

0.8

0.8

0.8

--

--

--

--

--

--

10
20
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

60
120
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

35
70
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

45
90
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

40
80
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

20
40
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

2.559714
5.139
5.56

2.559714
2.836
2.903

2.559714
5.368
5.256

2.559714
4.59
4.327

2.559714
4.382
4.392

2.559714
5.125
5.377

5.3495

2.8695

5.312

4.4585

4.387

5.251

10.5
-----10.6
-----10.55
-----15.417
17.016
16.104
13.77
13.146
15.375
16.68
17.418
15.768
12.981
13.176
16.131
16.0485
17.217
15.936
13.3755
13.161
15.753
15.3690321429 15.3690321429 15.3690321429 15.3690321429 15.3690321429 15.3690321429

840 min
20

--

18

----

Deposition Rate

14

3.35
6.22
90
4.91
4.82

12
0

--0.8

-40
80
0.241126
0.241126
0.296981
0.296981
1.4835
0.6399285

2.559714
6.343
6.535

6.439
7.62
5.76
6.69
19.029
19.605
19.317
15.3690321429

16

6.4
6.2
6

6.4
6.2

End of baths life

due to
precipitation

6
5.8
5.6
5.4

Filtrat
treat

5.2
5
4.8

0 0.09 0.19 0.26 0.32 0.3

Deposition Rate
20
18
Deposition Rate

16
14
12
0

0.5

1.5

2.5

MTO

Nickel (gr/l)
6.4
6.2
6

3.5

Nickel (gr/l)
6.4
6.2
6

Filtration
treatment

5.8
5.6
5.4

Filtration
treatment

Filtration
treatment
Filtration treatment

5.2
5
4.8

0 0.09 0.19 0.26 0.32 0.38 0.47 0.57 0.74 0.78 0.9 0.97 1.15 1.24 1.32 1.38 1.63 1.67 1.8 2.03 2.25 2.37 2.54 2.66 2.77

ate

2.5

5.1
5
4.9
4.8
3

3.5

4.7

Deposition Rate
pH a temp del bao

nt
Nickel (gr/l)

1.8 2.03 2.25 2.37 2.54 2.66 2.77 2.97 3.1 3.18 3.35

Sample

EDTA 0.1 M (ml) Nickel Concentration (g/L)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44

10.0
10.0
10.3
10.1
9.5
10.5
10.4
10.4
10.0
10.0
10.5
10.0
9.6
10.4
10.2
10
10.3
10.2
10
10.3
10.2
10.1
10.3
10
10.3
10
10.4
10
10.3
10.3
10
10.4
9.9
9.5
10.6
10.4
10.2
10.3
10
9.7
10.3
10.2
10
10

5.87
5.87
6.05
5.93
5.58
6.16
6.10
6.10
5.87
5.87
6.16
5.87
5.64
6.10
5.99
5.87
6.05
5.99
5.87
6.05
5.99
5.93
6.05
5.87
6.05
5.87
6.10
5.87
6.05
6.05
5.87
6.10
5.81
5.58
6.22
6.10
5.99
6.05
5.87
5.69
6.05
5.99
5.87
5.87

Niklad ELV A
Addition (ml)
5.2
5.2
-1.8
2.9
16.9
-6.5
-4.2
-4.2
5.2
5.2
-6.5
5.2
14.6
-4.2
0.5
5.2
-1.8
0.5
5.2
-1.8
0.5
2.9
-1.8
5.2
-1.8
5.2
-4.2
5.2
-1.8
-1.8
5.2
-4.2
7.5
16.9
-8.9
-4.2
0.5
-1.8
5.2
12.2
-1.8
0.5
5.2
5.2

45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74

MAKE UP:
Niklad ELV 811 A
Niklad ELV 811 B

10.3
10
10.9
10.6
10.3
10.1
10.4
10.1
10.3
9.9
8.9
10.6
10.8

6.05
5.87
6.40
6.22
6.05
5.93
6.10
5.93
6.05
5.81
5.22
6.22
6.34
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
TOTAL

-1.8
5.2
-15.9
-8.9
-1.8
2.9
-4.2
2.9
-1.8
7.5
31.0
-8.9
-13.6
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
240.0
65.1

240
480

Niklad ELV HA
Addition (ml)
10.4
10.4
-3.7
5.7
33.9
-13.1
-8.4
-8.4
10.4
10.4
-13.1
10.4
29.2
-8.4
1.0
10.4
-3.7
1.0
10.40
-3.69
1.01
5.70
0.00
10.40
-3.69
10.40
-8.38
10.40
-3.69
-3.69
10.40
-8.38
15.10
33.88
-17.78
-8.38
1.01
-3.69
10.40
24.49
-3.69
1.01
10.40
10.40

MTO

1.06

COMMENTS

Niklad ELV A
Addition (ml)
6.0
6.0
0.0
3.0
20.0
0.0
0.0
0.0
6.0
6.0
0.0
6.0
15.0
0.0
0.0
6.0
0.0
0.0
6.0
0.0
0.0
3.0
0.0
6.0
0.0
6.0
0.0
6.0
0.0
0.0
6.0
0.0
8.0
17.0
0.0
0.0
0.0
0.0
6.0
12.0
0.0
0.0
6.0
6.0

-3.69
10.40
-31.86
-17.78
-3.69
5.70
-8.38
5.70
-3.69
15.10
62.06
-17.78
-27.17
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
480.00
133.9

ml/L
ml/L

0.0
10.4
0.0
0.0
3.0
6.0
0.0
6.0
2.0
15.0
50.0
0.0
0.0

SUBTOTAL
TOTAL

254.4
254.4

Niklad ELV HA
Addition (ml)
12.0
12.0
0.0
6.0
40.0
0.0
0.0
0.0 50 min
12.0 60min
12.0 80min
0.0
12.0 100min
30.0 120min
0.0 120min
0.0 120min
12.0
0.0
0.0 140min
12.0 140min
0.0 140min
0.0 160min
6.0
0.0 180min
12.0 180min
0.0 180min
12.0 200min
0.0 200min
12.0 220min
0.0 240min
0.0 240min
12.0 240min
0.0 240min
16.0 240min
34.0
0.0 260min
0.0 260min
0.0 280min
0.0 280min
12.0 300min
24.0 320min
0.0
12.0 320min
12.0
12.0 340min

6.6

6.4

6.2

6
Nickel (g/L)
5.8

5.6

5.4

5.2

0 1 2 3 4 5 6 7 8 9 1011121314151617181920212223

0.0
20.8 360min
0.0 380min
0.0 380min
6.0 380min
12.0 380min
0.0 400min
12.0 400min
4.0 400min
30.0 420min
100.0 440min
0.0
0.0 460MIN
0.0
0.0 460MIN
0.0
0.0 480min
0.0 480min
0.0 480min
0.0 500min
0.0 500min
0.0 500min
0.0 520min
0.0 520min
0.0 520min
0.0 520min
0.0 540min
0.0
0.0 560min
0.0
520.8
520.8

Nickel Concentration of beaker bath (g/L)

1112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960616263646566676
Sample

5657585960616263646566676869707172737475

Deposition Rate
11.75036

Temp
pH

88
4.78

MTO
Thickness (m) %P Radiall OBR
%P Radiall VOP
0.09
5.06
5.735
10.36
0.26
5.07
1.625
0.38
4.865
1.03
0.74
5.064
6.4
0.97
5.145
6.42
1.15
4.7
1.69
10.47
1.32
5.34
3.955
1.63
3.39
3.58
9.83
1.67
4.935
7.45
10.09
1.8
4.825
1.46
10.06
2.03
4.475
6.13
11.83
2.54
5.349
10.55
3.1
4.387
3.35
6.439
6.69

%P MacDermid
10.1

10.6
9.9

11.0
8.7
9.6
11.1

Ni MTO
0
0.09
0.19
0.26
0.32
0.38
0.47
0.57
0.74
0.78
0.9
0.97
1.15
1.24
1.32
1.38
1.63
1.67
1.8
2.03
2.25
2.37
2.54
2.66
2.77
2.97
3.1
3.18
3.35

Nickel

Temp

pH

Rate

5.93
5.81
5.87
5.87
5.87
5.81
5.87
5.93
5.46
5.93
5.64
5.87
5.87
5.87
5.81
5.87
5.4
5.87
5.69
6.1
5.99
5.52
6.1
6.1
5.81
6.05
6.05
6.16
6.22

89
89
88.7
89.2
89
89
88.9
89.2
88.7
89
88.9
89
90
89.5
89.5
90.1
90
89.5
90
90.1
89.9
90.1
89.7
89.4
89.6
89.5
89.7
90.5
90

4.93
4.88
4.89
4.89
4.9
4.9
4.89
4.86
4.9
4.88
4.91
4.91
5.02
5.02
4.97
4.9
4.93
4.93
4.89
4.9
4.9
4.89
4.89
4.92
4.91
4.91
4.93
4.89
4.91

-15.18
15.32
15.21
15.71
14.60
13.74
15.48
15.19
13.74
15.72
15.44
14.10
16.68
16.02
15.08
15.63
14.81
14.48
13.43
14.14
19.87
16.05
17.22
15.94
13.38
13.16
15.75
19.32

Done
Done
Done
Done
Done
Done
Done
Done

Done

Done
Done
Done
Done
Done
Done

Done

Term
Constant
Temperature
pH
Nickel
MTO
Temp*pH
Temp*Ni
Temp*MTO
pH*Ni
pH*MTO
Ni*MTO
Temp*pH*Ni
Temp*pH*MTO
Temp*Ni*MTO
pH*Ni*MTO
Temp*pH*Ni*MTO

Coef
-44458.2
493.689
8642.24
7518.82
90061.4
-95.9317
-83.4947
-1011.86
-1463.06
-18555.6
-14673.5
16.2467
208.489
164.811
3025.61
-33.9854

Deposition Rate
14.3591632088
14.4712166484
14.8574070258
14.792810604
14.597259168
14.7267839558
14.8942287155
12.7864720992
15.0325990688
14.2230953024
15.1402308706
17.90746244
17.2378762292
16.6644986358
15.5829270224
19.06424164
16.043362275
15.99062942
14.240364682
14.9968303451
17.2929124365
14.5277396392
15.6270505408
16.2600873888
15.4051687696
15.5532998179
11.6025248016
12.7749286802

Term
Coef
Constant
1.6894
pH
2.71875
MTO
-36.4484
pH*MTO
7.45312

Deposition Rate
14.949954304
14.983585292
14.983400268
15.03427916
15.03859244
14.982845196
14.773570024
15.06447212
14.896703968
15.17023978
15.180489124
16.44872676
16.535690376
15.985147948
15.11048044
15.574472508
15.586291772
14.97932974
15.15720764
15.173023
14.977823116
14.977373772
15.653378064
15.444043684
15.473327524
16.00883046
14.975682124
15.52896682